Polypropylene composition, polypropylene material and preparation method and application thereof

Abstract

The invention relates to the field of polypropylene composite materials, and discloses a polypropylene composition, a polypropylene material and a preparation method and application thereof. The polypropylene composition comprises the following components in parts by weight: 100-200 parts of modified polypropylene resin, 80-120 parts of a modified flame retardant, 13-35 parts of a stabilizer and 8-20 parts of a plasticizer, wherein the modified polypropylene resin is castor oil-epoxy resin composite modified polypropylene resin; wherein the modified flame retardant is a glass bead modified ZIF-8 material. The polypropylene material prepared from the composition has excellent flame retardant property and mechanical property, and has long-term aging resistance.

Description

Technical Field

[0001] The present invention relates to the field of polypropylene composite materials, and in particular to a polypropylene composition, a polypropylene material, and a preparation method and application thereof. Background Art

[0002] Polypropylene is a general-purpose plastic with excellent comprehensive performance. It has good processing performance and excellent mechanical, physical and chemical properties. It has low specific gravity, light weight and low price. It is widely used in electronic and electrical engineering, home decoration, aerospace and other fields. However, polypropylene is very easy to burn. Its oxygen index is low. It cannot extinguish itself after catching fire in the air, which can easily cause fire accidents. This greatly limits the application field of polypropylene materials. Therefore, it needs to be flame-retardant modified.

[0003] Flame-retardant polypropylene is an important direction in polypropylene modification. Compared with ordinary polypropylene, flame-retardant polypropylene has better flame retardant properties. When a fire occurs, it can slow down the spread of fire and reduce the harm of fire to people and the environment. It also has the advantages of good heat resistance and processing performance.

[0004] CN1420909A discloses a flame retardant polypropylene resin composition, which is prepared by adding decabromodiphenyl ether and antimony oxide as flame retardants, and adding polytetrafluoroethylene to prevent melting and dripping during the combustion process. This flame retardant polypropylene resin has good flame retardant properties and processing properties, but its aging resistance is poor, and it is difficult to be exposed to outdoor products. In addition, the amount of smoke generated during the combustion process is large, which brings various disadvantages to disaster relief.

[0005] CN1479803A discloses a polypropylene resin composition, wherein the polypropylene resin is enhanced in anti-aging and flame retardant effects by adding a low melting point flame retardant, antimony oxide and UV light stabilizer. However, the low melting point flame retardant and UV light stabilizer are easily precipitated from the polymer surface, and long-term use will lead to a decrease in its performance, and the heat resistance is poor.

[0006] Therefore, it is urgent to develop a polypropylene composition with excellent aging resistance and flame retardancy to solve the above problems. Summary of the invention

[0007] The purpose of the present invention is to overcome the problem of poor flame retardancy and aging resistance of polypropylene materials in the prior art, and to provide a polypropylene composition, a polypropylene material, a preparation method and application thereof. The modified polypropylene material has excellent flame retardancy and mechanical properties, and has long-term aging resistance.

[0008] In order to achieve the above object, the first aspect of the present invention provides a polypropylene composition, wherein the composition comprises the following components: 100-200 parts by weight of a modified polypropylene resin, 80-120 parts by weight of a modified flame retardant, 13-35 parts by weight of a stabilizer and 8-20 parts by weight of a plasticizer;

[0009] Wherein, the modified polypropylene resin is castor oil-epoxy resin composite modified polypropylene resin;

[0010] Wherein, the modified flame retardant is a glass microsphere modified ZIF-8 material.

[0011] The second aspect of the present invention provides a method for preparing a polypropylene material from the composition described in the first aspect, the method comprising: melt-extruding the composition under vacuum conditions to obtain the polypropylene material.

[0012] The third aspect of the present invention provides a polypropylene material prepared by the method described in the second aspect.

[0013] The fourth aspect of the present invention provides an application of the polypropylene material described in the third aspect in construction, electrical and electronic equipment, transportation or home furnishing.

[0014] Through the above technical solution, the present invention has the following beneficial effects:

[0015] (1) The polypropylene composition provided by the present invention adopts castor oil-epoxy resin double modified polypropylene resin as modified polypropylene resin, the fatty acid in castor oil reacts with the functional group in epoxy resin to produce covalent bonds, unsaturated fatty acids are introduced into the double bond structure, the toughness of epoxy resin is increased, and the fatty acid in castor oil has a high melting point and thermal stability, which improves the heat resistance and thermal stability of epoxy resin; the double bond structure in polypropylene resin and the functional group structure in epoxy resin can react quickly, introduce a cross-linking structure, realize double modified polypropylene resin, thereby improving the toughness, heat resistance and chemical resistance of modified polypropylene resin, and improving the aging resistance of modified polypropylene resin.

[0016] (2) The polypropylene composition provided by the present invention adopts a glass microsphere-modified ZIF-8 material as a modified flame retardant. The ZIF-8 material itself has a relatively high decomposition enthalpy and generates oxides, free radicals and non-flammable gases after decomposition, so that it has good flame retardancy. The porous structure of ZIF-8 can load some small molecule glass microspheres. The glass microspheres have low thermal conductivity, thereby playing a synergistic flame retardant role. The glass microspheres have excellent mechanical properties and aging resistance, thereby improving the flame retardancy, mechanical properties and aging resistance of the polypropylene material.

[0017] (3) The polypropylene composition provided by the present invention adopts castor oil-epoxy resin dual-modified polypropylene resin and glass microsphere modified ZIF-8 material flame retardant, and is supplemented with an appropriate amount of stabilizer and plasticizer. Through the coordination of the components, the prepared polypropylene material has a combustion grade of V-0 to V-1, an impact strength of greater than 12MPa, an initial tensile strength of ≥63MPa, a tensile strength of 36.9-65MPa after aging treatment for 500h, and a tensile strength of 28.7-65.5MPa after aging treatment for 1000h. The material has high flame retardancy, mechanical properties and long-term aging resistance. DETAILED DESCRIPTION

[0018] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0019] The first aspect of the present invention provides a polypropylene composition, wherein the composition comprises the following components: 100-200 parts by weight of a modified polypropylene resin, 80-120 parts by weight of a modified flame retardant, 13-35 parts by weight of a stabilizer, and 8-20 parts by weight of a plasticizer;

[0020] Wherein, the modified polypropylene resin is castor oil-epoxy resin composite modified polypropylene resin;

[0021] Wherein, the modified flame retardant is a glass microsphere modified ZIF-8 material.

[0022] In some embodiments of the present invention, preferably, the composition comprises the following components: 110-180 parts by weight of modified polypropylene resin, 100-115 parts by weight of modified flame retardant, 20-25 parts by weight of stabilizer and 10-15 parts by weight of plasticizer.

[0023] In some embodiments of the present invention, preferably, the weight ratio of the modified polypropylene resin to the modified flame retardant is 1-1.8:1, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, and any value in the range of any two values, preferably 1.2-1.6:1. Controlling the weight ratio of the modified polypropylene resin to the modified flame retardant within the above range is conducive to making the polypropylene material have excellent flame retardant properties, mechanical properties and long-term aging resistance. When controlled within the preferred range, the polypropylene material has more excellent flame retardant properties, mechanical properties and long-term aging resistance.

[0024] In some embodiments of the present invention, preferably, the castor oil-epoxy resin composite modified polypropylene resin is prepared by mixing castor oil, polypropylene resin and epoxy resin.

[0025] In some embodiments of the present invention, preferably, the weight ratio of castor oil, polypropylene resin and epoxy resin is 1: 0.9-1.5: 0.8-1.4, preferably 1: 1-1.4: 0.9-1.2. In the present invention, controlling the weight ratio of castor oil, polypropylene resin and epoxy resin within the above range is conducive to making the polypropylene material have excellent flame retardant properties, mechanical properties and long-term aging resistance. When controlled within the preferred range, the polypropylene material has more excellent properties.

[0026] In some embodiments of the present invention, preferably, the castor oil-epoxy resin composite modified polypropylene resin is made from the following raw materials in parts by weight: 60-80 parts by weight of castor oil, 50-120 parts by weight of polypropylene resin, 50-100 parts by weight of epoxy resin, 2-6 parts by weight of succinic acid, 2-8 parts by weight of polyvinyl alcohol, 5-15 parts by weight of solvent and 10-30 parts by weight of water.

[0027] In some embodiments of the present invention, preferably, the solvent is selected from C 1 -C 3 The monohydric alcohol is preferably at least one selected from ethanol, butanol and isopropanol, more preferably isopropanol.

[0028] The present invention has no particular limitation on the sources of the castor oil, polypropylene resin, epoxy resin and polyvinyl alcohol, and they can be purchased from commercial sources or prepared by existing methods.

[0029] In the present invention, the effective component of the castor oil is ≥99%; the weight average molecular weight of the polypropylene resin is 8-15g / mol, and the total solid content is ≥52%; the weight average molecular weight of the epoxy resin is 1.1-20g / mol, and the total solid content is ≥80%; the content of succinic acid is ≥99%; the weight average molecular weight of the polyvinyl alcohol is 16000-20000g / mol, and the content is ≥99%.

[0030] In the present invention, there is no particular limitation on the specific manner of mixing the above raw materials. The raw materials may be added sequentially, or some of the raw materials may be mixed first and then mixed with the remaining raw materials. In the present invention, preferably, the preparation method of the castor oil-epoxy resin composite modified polypropylene resin specifically comprises the following steps: first mixing castor oil, polypropylene resin and isopropanol, then adding epoxy resin emulsion, succinic acid, polyvinyl alcohol and deionized water for second mixing to obtain castor oil-epoxy resin composite modified polypropylene resin.

[0031] In the present invention, there is no particular limitation on the first mixing method, as long as castor oil and polypropylene resin can be fully dissolved, preferably, mixing is carried out by stirring at a temperature of 65-70°C for 30-40 minutes; there is no particular limitation on the second mixing method, preferably, mixing is carried out by stirring at the first mixing temperature for 30-40 minutes.

[0032] In the present invention, the polyvinyl alcohol is beneficial to improving the stability of the epoxy resin emulsion and preventing the epoxy resin emulsion from phase separation or coagulation; the succinic acid is beneficial to promoting the uniform dispersion of the epoxy resin emulsion, preventing sedimentation, making the emulsion uniformly dispersed and increasing the viscosity of the modified emulsion, which is beneficial to obtaining the castor oil-polypropylene resin double-modified epoxy resin emulsion.

[0033] In the present invention, the fatty acid in the castor oil used in the castor oil-epoxy resin composite modified polypropylene resin reacts with the functional group in the epoxy resin to generate a covalent bond, and the unsaturated fatty acid is introduced into the double bond structure, thereby increasing the toughness of the epoxy resin. The fatty acid in the castor oil has a high melting point and thermal stability, thereby improving the heat resistance and thermal stability of the epoxy resin. The double bond structure in the polypropylene resin can react quickly with the functional group in the epoxy resin, thereby introducing a cross-linking structure, thereby increasing the cross-linking density and durability of the polypropylene resin. The double modified polypropylene resin is achieved, thereby improving the toughness, heat resistance and chemical resistance of the modified polypropylene resin, thereby improving the flame retardant properties, mechanical properties and long-term aging resistance of the modified polypropylene material.

[0034] In some embodiments of the present invention, preferably, the glass microsphere-modified ZIF-8 material is prepared by mixing ZIF-8 material, glass microspheres and polyurethane.

[0035] In some embodiments of the present invention, preferably, the weight ratio of the ZIF-8 material, glass microspheres and polyurethane is 1.5-3.5: 1.25-1.75: 1, preferably 2-3: 1.4-1.6: 1. In the present invention, the weight ratio of the ZIF-8 material, glass microspheres and polyurethane is controlled within the above range, which is conducive to making the polypropylene material have excellent flame retardant properties, mechanical properties and long-term aging resistance. When controlled within the preferred range, the polypropylene material has more excellent performance.

[0036] In some embodiments of the present invention, preferably, the glass microsphere modified ZIF-8 material is made of the following raw materials in parts by weight: 40-180 parts by weight of ZIF-8 material, 50-80 parts by weight of glass microspheres, 30-50 parts by weight of polyurethane, 10-30 parts by weight of silane coupling agent, 5-10 parts by weight of ammonia water, 10-20 parts by weight of solvent and 8-16 parts by weight of water.

[0037] In some embodiments of the present invention, preferably, the solvent is selected from at least one of acetone, butanone, ether and anhydrous ethanol, preferably acetone.

[0038] The present invention has no particular limitation on the sources of the ZIF-8 material, glass microbeads, polyurethane and silane coupling agent, and they can be purchased commercially or prepared by existing methods.

[0039] In the present invention, the purity of the ZIF-8 material is ≥99%, the pore size is 0.34nm×1.1nm-0.4nm×1.4nm, and the pore volume is 0.6-0.7cm 3 / g, BET specific surface area is 1300-1500m 2 / g, particle size is 100-300nm; density of glass microspheres is 2.2-2.65g / cm 3 , particle size is 250-300 mesh; the solid content of polyurethane is 30-33%, viscosity is greater than 300cP, pH is 5-6, elongation is 300-500%, and resilience is 70-90%; the silane coupling agent is at least one of KH-540, KH550 and KH560, and the effective substance is ≥98%; the mass concentration of ammonia water is 20-30%.

[0040] In the present invention, there is no particular limitation on the specific method of mixing the above raw materials, and they can be added sequentially, or some of the raw materials can be mixed first and then mixed with the remaining raw materials. Preferably, the glass microspheres are silane-modified glass microspheres, and the preparation method thereof comprises: mixing the glass microspheres and the silane coupling agent in the presence of a solvent, and then washing and drying.

[0041] In the present invention, the preparation method of the glass microsphere modified ZIF-8 material specifically includes the following contents: after mixing the glass microspheres and ammonia water, adding a silane coupling agent and acetone for a third mixing, and then washing and drying the obtained mixture to obtain silane modified glass microspheres; and mixing the silane glass microspheres with the ZIF-8 material, polyurethane and deionized water for a fourth time to obtain the glass microsphere modified ZIF-8 material.

[0042] In the present invention, the third mixing method is not particularly limited, and it is preferably mixed by stirring and reacted at 50-60°C for 30-40min; the fourth mixing method is not particularly limited, and it is preferably first ultrasonically dispersed at 15-20Hz for 0.8-1.2h, and then stirred at 40-50°C for 1.5-2h.

[0043] In the present invention, the washing conditions are not particularly limited, and deionized water is preferably used for washing; the drying conditions are not specifically limited, and drying is preferably carried out in a vacuum drying oven at 50-60° C. for 8-12 hours.

[0044] In the present invention, the surface of the glass microspheres is activated by ammonia water, which is beneficial to remove oxides and other impurities on the surface of the glass microspheres and expose more active sites.

[0045] In the present invention, the glass microspheres used in the glass microsphere-modified ZIF-8 material have low thermal conductivity, which can prevent heat transfer in the material; the ZIF-8 material has a high decomposition enthalpy and will produce oxides, free radicals and non-combustible gases after decomposition, and its oxides can isolate oxygen and heat, while the imidazole ligands will produce free radicals, including -CH and -NH, in the pyrolysis process, which can neutralize the free radicals released by the polymer in the gas phase and the free O in the air. 2 , the released NH 3 and CO 2 It can dilute oxygen, thus making it have good flame retardant ability. And the porous structure of ZIF-8 can load some small molecule glass microbeads, the two play a synergistic flame retardant role, and the glass microbeads have excellent mechanical properties and aging resistance, which is beneficial to improve the flame retardant properties, mechanical properties and aging resistance of polypropylene materials.

[0046] In some embodiments of the present invention, preferably, the stabilizer is tris(1,3-dichloroisopropyl) phosphate.

[0047] The present invention has no particular limitation on the source of tris(1,3-dichloroisopropyl) phosphate, which can be purchased commercially or prepared by existing methods. In the present invention, the effective ingredient content of tris(1,3-dichloroisopropyl) phosphate is ≥99%.

[0048] In the present invention, the tris(1,3-dichloroisopropyl) phosphate has high thermal stability and antioxidant properties. It decomposes at high temperature to produce carbon-like residues and can form a carbonized layer. The carbonized layer has permeability, can isolate the combustion area and provide an additional barrier layer, delay the spread of flames, and release phosphate phosphate gas. These gases can inhibit the combustion reaction. In addition, the phosphate phosphate gas can also react with free radicals generated during the combustion process, capture and consume free radicals, and reduce the combustion rate, which is beneficial to improve the flame retardant properties and heat-oxidation aging resistance of the polypropylene material.

[0049] In the present invention, the plasticizer is beneficial to improving the flame retardant effect of the polypropylene material, and improving the heat resistance and processing performance of the polypropylene resin material. The present invention has a wide range of selection of the type of the plasticizer, as long as it can achieve the above purpose, and can be various plasticizers conventionally used in the art. Preferably, the plasticizer is dioctyl adipate and / or dioctyl adipate, more preferably dioctyl adipate. The plasticizer of this preferred embodiment is beneficial to further improving the flame retardant effect of the polypropylene material, and improving the heat resistance and processing performance of the polypropylene resin material.

[0050] In some embodiments of the present invention, preferably, the composition further comprises 5-35 parts by weight of polyetheretherketone and 15-25 parts by weight of carbon fiber polyetherketone.

[0051] The present invention has no particular limitation on the sources of the polyetheretherketone and carbon fiber polyetherketone, which can be purchased from commercial sources or prepared by existing methods. In the present invention, the density of the polyetheretherketone is 1.2-1.4 g / cm 3 ; Carbon fiber polyetherketone is reinforced with 30% carbon fiber; Length is 3-7mm.

[0052] In the present invention, the carbon fiber polyetherketone has good mechanical and flame retardant properties, which is beneficial to increase the strength and rigidity of the polypropylene material, prevent it from melting or deforming at high temperature, and effectively prevent oxygen penetration, thereby slowing down the aging rate of the polypropylene material; polyetheretherketone is beneficial to improve the dispersion uniformity of the carbon fiber polyetherketone in the polypropylene composition. Polyetheretherketone and carbon fiber polyetherketone form a blending system to improve compatibility, and the synergistic effect of the two is beneficial to further improve the flame retardant properties, mechanical properties and aging resistance of the polypropylene material.

[0053] In some embodiments of the present invention, preferably, the weight ratio of the polyetheretherketone to the carbon fiber polyetheretherketone is 0.5-1.5: 1, preferably 0.6-1.4: 1. In the present invention, controlling the weight ratio of the polyetheretherketone to the carbon fiber polyetheretherketone within the above range is conducive to making the polypropylene material have excellent flame retardant properties, mechanical properties and long-term aging resistance. When controlled within the preferred range, the polypropylene material has more excellent properties.

[0054] The second aspect of the present invention provides a method for preparing a polypropylene material from the composition described in the first aspect, the method comprising: melt-extruding the composition under vacuum conditions to obtain the polypropylene material.

[0055] In some embodiments of the present invention, preferably, the melt extrusion is carried out in a twin-screw extruder, the screw temperature of the twin-screw extruder is 170-270° C., and the screw speed is 2400-2600 rpm.

[0056] In some embodiments of the present invention, preferably, the vacuum degree of the vacuum condition is 65-70 cmHg.

[0057] According to a preferred embodiment of the present invention, modified polypropylene resin, modified flame retardant, stabilizer and plasticizer are added to a high-speed mixer according to corresponding weight parts, and mixed for 3-5 minutes at 2000-2200rpm to obtain a premix; the premix is ​​fed from the main feeding port of a twin-screw extruder, melted, plasticized, sheared and dispersed under vacuum conditions, and then extruded, pulled, cooled, granulated, dried and homogenized to obtain a polypropylene material.

[0058] There is no particular limitation on the conditions and specific methods of each operation step in the above preparation process, and those skilled in the art can carry out the steps according to conventional technical means.

[0059] The third aspect of the present invention provides a polypropylene material prepared by the method described in the second aspect.

[0060] In some embodiments of the present invention, preferably, the flammability rating UL-94 of the polypropylene material is V-0 to V-1; the impact strength is 12-16 MPa; the initial tensile strength is 63-68 MPa, preferably 64.1-67.5 MPa; the tensile strength after aging treatment for 500 h is 36.9-65 MPa, preferably 43.6-65.5 MPa; the tensile strength after aging treatment for 1000 h is 28.7-65 MPa, preferably 37.2-64.2 MPa.

[0061] In the present invention, the combustion grade of the polypropylene material is tested according to the UL-94V standard. A test piece with a sample size of 130mm×13mm×1.6mm is held vertically, and the lower end is ignited with a burner for 10 seconds, and then the flame is removed, and the time for the fire on the test piece to go out is measured; then, while the fire is extinguished, the second ignition is performed for 10 seconds, and the time for the ignition to go out is measured in the same way as the first time. At the same time, it is evaluated whether the cotton under the test piece is ignited by the falling fire. The impact strength of the polypropylene material is tested according to the GB / T1843-2008 standard, and the tensile rate is 5mm / min. The testing method for the long-term aging resistance of the polypropylene material is as follows: placing a notched impact strength test piece in a forced ventilation heat aging test box, the test temperature is 150°C, the ventilation efficiency is 100±50%, the aging time is 500h and 1000h respectively, during which the test piece is taken out at the sampling point to observe the surface integrity and characterize the tensile strength, wherein the tensile strength is tested according to the ASTM D638 standard, the test piece is type I, the test piece is molded in an environment of 23±2°C, 50±10%RH for 48h and then tested, and the traction speed is 5mm / min.

[0062] In the present invention, the polypropylene material has a higher combustion grade, impact strength and aging resistance than the traditional flame-retardant polypropylene material, and has excellent flame-retardant properties, mechanical properties and long-term aging resistance.

[0063] The fourth aspect of the present invention provides an application of the polypropylene material described in the third aspect in construction, electrical and electronic equipment, transportation or home furnishing.

[0064] The present invention will be described in detail below through examples.

[0065] The testing methods for the combustion grade, impact strength, long-term aging resistance and tensile strength of the polypropylene material in the following examples and comparative examples are the same as those in the specific implementation method, and will not be repeated here.

[0066] The raw materials used in the following examples and comparative examples are respectively:

[0067] The purity of ZIF-8 material is 99.9%, the pore size is 0.34nm×1.1nm, and the pore volume is 0.66cm 3 / g, BET specific surface area is 1500m 2 / g, particle size is 200nm; density of glass microspheres is 2.2-2.65g / cm 3 , particle size is 250-300 mesh; the solid content of polyurethane is 32%, viscosity is >300cP, pH value is 5-6, elongation is 400%, and resilience is 80%; silane coupling agent uses KH-540, and the effective substance is ≥98%; the concentration of ammonia water is 25wt%, industrial grade; the total solid content of polypropylene resin is ≥52%, and the weight average molecular weight is 10g / mol; the effective ingredient content of castor oil is 99%; the total solid content of epoxy resin is ≥80%, and the weight average molecular weight is 10g / mol; the content of isopropanol is 99.9%, industrial grade; the content of succinic acid is 99%, industrial grade; the content of polyvinyl alcohol is ≥99%, the weight average molecular weight is 16000g / mol, industrial grade; the effective ingredient content of tris(1,3-dichloroisopropyl) phosphate is 99%, industrial grade; the plasticizer uses dioctyl ester, and the effective ingredient content is 99%; the density of polyetheretherketone is 1.3g / cm 3 ; Carbon fiber polyetherketone is reinforced with 30% carbon fiber and has a length of 5mm.

[0068] Preparation Example 1-5

[0069] The modified flame retardant was prepared by adding materials according to Table 1. The steps are as follows:

[0070] (1) After mixing glass microspheres and ammonia water, adding a silane coupling agent and acetone, heating to 50° C. and stirring for 30 minutes to obtain a silane-modified glass microsphere precursor, and washing and drying to obtain a silane-modified glass microsphere;

[0071] (2) The silane-modified glass microspheres obtained in step (1) are mixed with ZIF-8 material, polyurethane and deionized water, and after ultrasonic dispersion for 1 hour, the mixture is heated to 40° C. and stirred for 2 hours to obtain a glass microsphere-modified ZIF-8 material.

[0072] Table 1 Components and weight parts in Preparation Examples 1-5

[0073] serial number ZIF-8 Glass beads Polyurethane Silane coupling agent ammonia water acetone Preparation Example 1 60 50 40 20 7.5 12 15 Preparation Example 2 80 56 40 20 7.5 12 15 Preparation Example 3 100 60 40 20 7.5 12 15 Preparation Example 4 120 64 40 20 7.5 12 15 Preparation Example 5 140 70 40 20 7.5 12 15

[0074] Preparation Example 6-10

[0075] According to the materials in Table 2, the modified polypropylene resin was prepared. The steps are as follows:

[0076] Castor oil, polypropylene resin and isopropyl alcohol were mixed, heated to 70° C. and stirred for 30 minutes, then epoxy resin, succinic acid, polyvinyl alcohol and deionized water were added, and stirring was continued for 30 minutes to obtain castor oil-epoxy resin composite modified polypropylene resin.

[0077] Table 2 Components and weight parts in Preparation Examples 6-10

[0078]

[0079] Examples 1-5

[0080] The polypropylene material was prepared by adding materials as shown in Table 3. The steps are as follows:

[0081] (1) adding modified polypropylene resin, modified flame retardant, tris(1,3-dichloroisopropyl) phosphate and plasticizer according to the weight parts in Table 3 into a high-speed mixer, and mixing at a speed of 2000 rpm for 5 minutes to obtain a premix;

[0082] (2) feeding the premix obtained in step (1) from the main feeding port of a twin-screw extruder, controlling the vacuum degree to 70 cmHg, melting, plasticizing, shearing, and dispersing the premix in an extruder, and then extruding, pulling and drawing, cooling, granulating, drying, and homogenizing to obtain a polypropylene material, wherein the screw speed is set to 2500 rpm and the screw temperature is set to 200° C.;

[0083] Wherein, the modified polypropylene resin is the castor oil-epoxy resin composite modified polypropylene resin obtained in Preparation Example 6; and the modified flame retardant is the glass microsphere modified ZIF-8 material obtained in Preparation Example 1.

[0084] Embodiment 6-10

[0085] The method of Example 1 is followed, except that

[0086] In step (1), polyetheretherketone and carbon fiber polyetherketone are also added to obtain a polypropylene material, and the components and their weight parts are shown in Table 3.

[0087] Embodiment 11

[0088] The method of Example 8 was followed, except that

[0089] In step (1), the modified flame retardant is the glass microsphere modified ZIF-8 material obtained in Preparation Example 2, and the components and their weight parts are shown in Table 3.

[0090] Example 12

[0091] The method of Example 8 was followed, except that

[0092] In step (1), the modified flame retardant is the glass microsphere modified ZIF-8 material obtained in Preparation Example 3, and the components and their weight parts are shown in Table 3.

[0093] Embodiment 13

[0094] The method of Example 8 was followed, except that

[0095] In step (1), the modified flame retardant is the glass microsphere modified ZIF-8 material obtained in Preparation Example 4, and the components and their weight parts are shown in Table 3.

[0096] Embodiment 14

[0097] The method of Example 8 was followed, except that

[0098] In step (1), the modified flame retardant is the glass microsphere modified ZIF-8 material obtained in Preparation Example 5, and the components and their weight parts are shown in Table 3.

[0099] Embodiment 15

[0100] The method of Example 12 is followed, except that

[0101] In step (1), the modified polypropylene resin is the castor oil-epoxy resin composite modified polypropylene resin obtained in Preparation Example 7, and the components and their weight parts are shown in Table 3.

[0102] Example 16

[0103] The method of Example 12 is followed, except that

[0104] In step (1), the modified polypropylene resin is the castor oil-epoxy resin composite modified polypropylene resin obtained in Preparation Example 8, and the components and their weight parts are shown in Table 3.

[0105] Embodiment 17

[0106] The method of Example 12 is followed, except that

[0107] In step (1), the modified polypropylene resin is the castor oil-epoxy resin composite modified polypropylene resin obtained in Preparation Example 9, and the components and their weight parts are shown in Table 3.

[0108] Embodiment 18

[0109] The method of Example 12 is followed, except that

[0110] In step (1), the modified polypropylene resin is the castor oil-epoxy resin composite modified polypropylene resin obtained in Preparation Example 10, and the components and their weight parts are shown in Table 3.

[0111] Comparative Example 1

[0112] The method of Example 1 is followed, except that

[0113] In step (1), the modified flame retardant is replaced by an equal amount of ZIF-8 material, that is, the ZIF-8 material is not modified, and the remaining components and component amounts are the same as in Example 1.

[0114] Comparative Example 2

[0115] The method of Example 1 is followed, except that

[0116] In step (1), an equal amount of polypropylene resin replaces the modified polypropylene resin, that is, the polypropylene resin is not modified, and the remaining components and their amounts are the same as in Example 1.

[0117] Comparative Example 3

[0118] The method of Example 1 is followed, except that

[0119] In step (1), an epoxy resin-modified polypropylene resin is used to replace the modified polypropylene resin in an equal amount, that is, the polypropylene resin is only modified with the epoxy resin, and the remaining components and their amounts are the same as those in Example 1;

[0120] Wherein, the preparation method of the epoxy resin modified polypropylene resin comprises the following steps:

[0121] Weigh 63 parts by weight of polypropylene resin, 10 parts by weight of isopropanol, 56 parts by weight of epoxy resin, 4 parts by weight of succinic acid, 6 parts by weight of polyvinyl alcohol and 20 parts by weight of deionized water, mix the polypropylene resin and isopropanol, heat to 70°C and stir for 30 minutes, then add the epoxy resin, succinic acid, polyvinyl alcohol and deionized water, and continue stirring for 30 minutes to obtain epoxy resin-modified polypropylene resin.

[0122] Comparative Example 4

[0123] The method of Example 1 is followed, except that

[0124] In step (1), the modified polypropylene resin is replaced by an equal amount of castor oil-modified polypropylene resin, that is, the polypropylene resin is modified only with castor oil, and the remaining components and their amounts are the same as those in Example 1;

[0125] Wherein, the preparation method of the castor oil modified polypropylene resin comprises the following steps:

[0126] Weigh 70 parts by weight of castor oil, 63 parts by weight of polypropylene resin, 10 parts by weight of isopropanol, 4 parts by weight of succinic acid, 6 parts by weight of polyvinyl alcohol and 20 parts by weight of deionized water, mix the castor oil, polypropylene resin and isopropanol, heat to 70° C. and stir for 30 min, then add succinic acid, polyvinyl alcohol and deionized water, and continue stirring for 30 min to obtain castor oil-modified polypropylene resin.

[0127] Table 3 Components and weight parts in the examples

[0128]

[0129]

[0130] Test Case

[0131] The properties of the polypropylene materials prepared in the examples and comparative examples were tested, and the results are shown in Table 4.

[0132] Table 4

[0133]

[0134]

[0135] It can be seen from the results in Table 4 that the polypropylene material provided by the present invention has a high flame retardant grade, mechanical properties and long-term aging resistance. Combining Examples 1-5 and Table 4, it can be seen that compared with Examples 2-4, the amounts of the raw material components in Examples 1 and 5 do not adopt the preferred range of the present invention, and the flame retardant properties, mechanical properties and long-term aging resistance of the polypropylene materials described in Examples 1 and 5 are slightly lower than those in Examples 2-4.

[0136] From Examples 2-4, 6-10 and Table 4, it can be seen that due to the addition of polyetheretherketone and carbon fiber polyetherketone in Example 6-10, it has better flame retardant properties, mechanical properties and long-term aging resistance than Examples 2-4; compared with Examples 7-9, the amounts of polyetheretherketone and carbon fiber polyetherketone in Examples 6 and 10 do not adopt the further preferred range of the present invention, and the flame retardant properties, mechanical properties and long-term aging resistance of the polypropylene materials described in Examples 6 and 10 are slightly lower than those in Examples 7-9.

[0137] It can be seen from Examples 7-9, 11-14 and Table 4 that, compared with Examples 11-13, the amounts of ZIF-8, glass microbeads and polyurethane in the modified flame retardants added in Examples 7-9 and 14 did not adopt the further preferred range of the present invention, and the flame retardant properties, mechanical properties and long-term aging resistance of the polypropylene materials described in Examples 7-9 and 14 were slightly lower than those in Examples 11-13.

[0138] It can be seen from Examples 11-13, Examples 15-18 and Table 4 that, compared with Examples 15-17, the amounts of castor oil, polypropylene resin and epoxy resin added to the modified polypropylene resin in Examples 11-13 and Example 18 do not fall within the further preferred range of the present invention, and the flame retardant properties, mechanical properties and long-term aging resistance of the polypropylene materials described in Examples 11-13 and Example 18 are slightly lower than those in Examples 15-17.

[0139] Combining Example 1, Comparative Examples 1-4 and Table 4, it can be seen that Comparative Example 1 does not use the modified flame retardant defined in the present invention, and Comparative Examples 2-4 do not use the modified polypropylene resin defined in the present invention, and the flame retardant properties, mechanical properties and long-term aging resistance of the prepared polypropylene material are greatly reduced. The polypropylene material provided by the present invention has a UL-94 combustion grade of V-0 to V-1, an impact strength of 12-16Mpa, an initial tensile strength of 63-68Mpa, a tensile strength of 36.9-65MPa after aging treatment for 500h, and a tensile strength of 28.7-65MPa after aging treatment for 1000h, and has excellent flame retardant grade, mechanical properties and long-term aging resistance.

[0140] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A polypropylene composition, It is characterized in that The composition comprises the following components: 100-200 parts by weight of modified polypropylene resin, 80-120 parts by weight of modified flame retardant, 13-35 parts by weight of stabilizer and 8-20 parts by weight of plasticizer; Wherein, the modified polypropylene resin is castor oil-epoxy resin composite modified polypropylene resin; Wherein, the modified flame retardant is a glass microsphere modified ZIF-8 material.

2. The composition according to claim 1, in, The composition comprises the following components: 110-180 parts by weight of modified polypropylene resin, 100-115 parts by weight of modified flame retardant, 20-25 parts by weight of stabilizer and 10-15 parts by weight of plasticizer; Preferably, the weight ratio of the modified polypropylene resin to the modified flame retardant is 1-1.8:1, preferably 1.2-1.6:

1.

3. The composition according to claim 1 or 2, in, The castor oil-epoxy resin composite modified polypropylene resin is prepared by mixing castor oil, polypropylene resin and epoxy resin; Preferably, the weight ratio of castor oil, polypropylene resin and epoxy resin is 1:0.9-1.5:0.8-1.4, preferably 1:1-1.4:0.9-1.2; Preferably, the castor oil-epoxy resin composite modified polypropylene resin is made from the following raw materials in parts by weight: 60-80 parts by weight of castor oil, 50-120 parts by weight of polypropylene resin, 50-100 parts by weight of epoxy resin, 2-6 parts by weight of succinic acid, 2-8 parts by weight of polyvinyl alcohol, 5-15 parts by weight of solvent and 10-30 parts by weight of water; Preferably, the solvent is selected from C 1 -C 3 The monohydric alcohol is preferably at least one selected from ethanol, butanol and isopropanol, more preferably isopropanol.

4. The composition according to claim 1 or 2, in, The glass microsphere-modified ZIF-8 material is prepared by mixing ZIF-8 material, glass microspheres and polyurethane; Preferably, the weight ratio of the ZIF-8 material, glass microspheres and polyurethane is 1.5-3.5:1.25-1.75:1, preferably 2-3:1.4-1.6:1; Preferably, the glass microsphere-modified ZIF-8 material is made of the following raw materials in parts by weight: 40-180 parts by weight of ZIF-8 material, 50-80 parts by weight of glass microspheres, 30-50 parts by weight of polyurethane, 10-30 parts by weight of silane coupling agent, 5-10 parts by weight of ammonia water, 10-20 parts by weight of solvent and 8-16 parts by weight of water; Preferably, the solvent is selected from at least one of acetone, butanone, ether and anhydrous ethanol, preferably acetone.

5. The composition according to claim 1, in, The stabilizer is tris(1,3-dichloroisopropyl) phosphate; Preferably, the plasticizer is dioctyl adipate and / or dioctyl adipate, preferably dioctyl adipate.

6. A composition according to any one of claims 1 to 5, in, The composition further comprises 5-35 parts by weight of polyetheretherketone and 15-25 parts by weight of carbon fiber polyetherketone; Preferably, the weight ratio of the polyetheretherketone to the carbon fiber polyetheretherketone is 0.5-1.5:1, preferably 0.6-1.4:

1.

7. A method for preparing a polypropylene material from the composition according to any one of claims 1 to 6, in, The method comprises: subjecting the composition to melt extrusion under vacuum conditions to obtain the polypropylene material.

8. The method according to claim 7, in, The melt extrusion is carried out in a twin-screw extruder, the screw temperature of the twin-screw extruder is 170-270° C., and the screw speed is 2400-2600 rpm; Preferably, the vacuum degree of the vacuum condition is 65-70 cmHg.

9. A polypropylene material prepared by the method according to claim 7 or 8; Preferably, the UL-94 combustion grade of the polypropylene material is V-0 to V-1; the impact strength is 12-16 MPa; the initial tensile strength is 63-68 MPa, preferably 64.1-67.5 MPa; the tensile strength after aging treatment for 500 h is 36.9-65 MPa, preferably 43.6-65 MPa; the tensile strength after aging treatment for 1000 h is 28.7-65 MPa, preferably 37.2-64.2 MPa.

10. Use of the polypropylene material according to claim 9 in construction, electrical and electronic equipment, transportation or home furnishing.

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