MOFs-based low-odor regenerated PP highly-doped polypropylene composite material and preparation method thereof

Abstract

The invention discloses a low-odor regenerated PP (polypropylene) highly-doped polypropylene composite material based on MOFs (metal organic frameworks) and a preparation method of the low-odor regenerated PP highly-doped polypropylene composite material, and the low-odor regenerated PP highly-doped polypropylene composite material is characterized by comprising the following components in percentage by weight: 10-50% of brand-new polypropylene; 20-40% of daily mixed recycled polypropylene; 1-15% of an elastomer toughening agent; 10-20% of an inorganic filler; 0.1 to 1% of a modified MOFs composite material; 0.1 to 2.0 percent of a stabilizer; and 0-5% of other additives. Firstly, an in-situ self-assembly method is utilized to realize in-situ compounding of MIL-101 (Cr) and macroporous polyacrylate, so that the composite material has excellent adsorption performance. The method comprises the following steps: adding an MIF-101 (Cr)-polyacrylate composite material into a modified polypropylene composite material in which recycled polypropylene is added in a high proportion, and effectively adsorbing and recycling ketone, phenol and amine odor substances in polypropylene by utilizing the high specific surface area, abundant pore structure and excellent adsorption performance of the MIF-101 (Cr)-polyacrylate composite material; the smell of the modified polypropylene finished product material is obviously improved.

Description

Technical Field

[0001] The present invention relates to a regenerated PP high-doped polypropylene composite material with low odor based on MOFs and a preparation method thereof, belonging to the technical field of polymer material processing and modification. Background Art

[0002] In recent years, environmental issues have increasingly become the focus of global attention, especially in plastic pollution and resource recycling. Modified polypropylene (PP), as one of the most widely used general plastics globally, its recycling problem has also received extensive attention from the industry. With the continuous progress of waste PP recycling technology and the improvement of processes, the demand for automotive recycled PP materials has also increased.

[0003] Currently, the recycled PP used in automotive modified PP materials mainly comes from various PP plastics in daily necessities and the casings of white household appliances. After processing and long-term use, these materials often have a strong odor and a decline in mechanical properties. If recycled PP is directly and highly proportionally added to the formulation for modification, it may lead to a reduction in the performance of the final product and be accompanied by an unpleasant odor. Therefore, the application of recycled PP in automotive interior parts is restricted and is usually added to the modified material at a relatively low proportion (0 - 10%) and through post-treatment processes to ensure that the material odor meets the standards required by the vehicle manufacturers. In order to increase the addition proportion of recycled PP in interior PP modified materials with strict requirements for odor and emission, the primary task is to effectively reduce its intolerable odor.

[0004] Metal-organic framework materials (MOFs) are a new type of porous three-dimensional crystal framework material formed by the self-assembly of organic ligands and metal ions, known for their huge specific surface area, adjustable pore size, ordered microporous structure, and diverse pore sizes and framework structures. The unsaturated metal coordination sites of MOFs materials can perform functional modification on the pore surface, making them superior to traditional zeolite and activated carbon materials in terms of odor and VOCs treatment, specific surface area, pore distribution, and adsorption performance. The MOF material MIL-101(Cr) is famous for its huge specific surface area, rich pore structure, and excellent adsorption performance, especially showing a strong adsorption capacity for common VOCs, especially aromatic substances. By impregnating MIL-101(Cr) into the interior of polyacrylate using the impregnation method, and utilizing the confinement space characteristics and the characteristics of large pore nano-scale roughness inside polyacrylate, the MIL-101(Cr)@polyacrylate composite material is prepared to further improve the adsorption performance of MOFs materials. Summary of the Invention

[0005] The object of the present invention is to develop a regenerated PP high-filled polypropylene composite material with low odor based on MOFs. The obtained composite material can be used in automotive interior parts such as door panels, lower instrument panels, and side seat panels. Under the action of the MIF-101(Cr)@polyacrylate composite material, the odor of the regenerated high-filled polypropylene composite material is effectively improved.

[0006] Another object of the present invention is to provide a preparation method for this polypropylene material.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] A regenerated PP high-filled polypropylene composite material with low odor based on MOFs and its preparation method, characterized in that it is composed of the following raw materials by weight percentage:

[0009] Brand-new polypropylene: 10 - 50%;

[0010] Recycled polypropylene from sundries: 20 - 40%;

[0011] Elastomer toughening agent: 1 - 15%;

[0012] Inorganic filler: 10 - 20%;

[0013] Modified MOFs composite material: 0.1 - 1%;

[0014] Stabilizer: 0.1 - 2.0%;

[0015] Other additives: 0 - 5%.

[0016] Among them,

[0017] The melt flow rate of the brand-new polypropylene is 10 - 60 g / 10 min; the melt flow rate of the recycled polypropylene from sundries is 20 - 30 g / 10 min;

[0018] The toughening agent is ethylene-octene copolymer or ethylene-butene copolymer or a combination of both, with a density of 0.88 - 0.91 g / cm3 and a melt flow rate of 0.5 - 15 g / 10 min;

[0019] The inorganic filler is at least one or a combination of several of talc powder, calcium carbonate, montmorillonite, wollastonite;

[0020] The modified MOFs composite material is MIF-101(Cr)@polyacrylate composite material;

[0021] The stabilizer is the main antioxidant and auxiliary antioxidant considered necessary by those skilled in the art. Among them, the main antioxidant is a hindered phenol or a thioester antioxidant, and the auxiliary antioxidant is a phosphite or a lipid antioxidant;

[0022] The other additives described above are one or several compositions of toner, antistatic agent, surfactant, plasticizer, coupling agent, and anti-scratch agent that are considered necessary by those skilled in the art;

[0023] The preparation method of the above-mentioned MOF-based low-odor recycled PP high-fill polypropylene composite material is as follows:

[0024] Step 1: Preparation of porous polyacrylate. Weigh appropriate monomers TBA, TBMA, TMPTA, emulsifier, toluene, and oxidant BPO and mix them into an oil phase in a 50 ml beaker. Use a high-speed disperser to mix the oil phase evenly, and slowly drop 15 ml of deionized water into the oil phase. Continue stirring to disperse the emulsion evenly. Add 150 ml of deionized water to a 250 ml three-necked flask, place it in an oil bath at 65 °C, then add an appropriate amount of dispersant PVA and initiator APS. Then pour the prepared emulsion into the flask and drop an appropriate amount of TMEDA. After reacting for 10 minutes, filter it out and place it in an oven at 60 °C to dry for 4H to obtain porous polyacrylate spherical particles;

[0025] Step 2: Preparation of MIF-101(Cr)@polyacrylate composite material. Weigh 0.2 g of porous polyacrylate and place it in a 25 ml round-bottom flask equipped with a vacuum device. Evacuate at room temperature for 30 minutes. Weigh appropriate H 2 BDC and DMF and heat and dissolve them into a ligand solution in a beaker. Weigh Cr(NO 3 ) 3 ·9H 2 O and methanol and stir to dissolve them into a metal salt solution. Pour the ligand solution and the metal salt solution into a constant pressure funnel respectively while maintaining the vacuum. Under the action of the pressure difference, they are completely impregnated into the carrier. Put the above-impregnated microspheres into a reaction kettle with deionized water and a growth regulator solution, react at 220 °C for 8 hours, take it out after natural cooling and obtain green powder by centrifugation. Soak the powder in DMF for 48H, displace DMF with methanol, centrifuge again and dry for 12H to obtain MIF-101(Cr)@polyacrylate composite material;

[0026] Step 3: Mix brand-new polypropylene, recycled polypropylene from daily sundries, elastomer toughening agent, inorganic filler, stabilizer, and other additives in proportion in a high-speed mixer, and then add them to a twin-screw extruder from the main screw feeding port. Add the MIF-101(Cr)@polyacrylate composite material to the side feeding port of the twin-screw extruder, and cool and pelletize after melt extrusion. The process is as follows: Zone 1: 190 - 200 °C, Zone 2: 200 - 210 °C, Zone 3: 210 - 220 °C, Zone 4: 205 - 215 °C; Residence time: 1 - 2 min, Pressure: 12 - 18 MPa.

[0027] The advantages of the present invention are as follows:

[0028] 1. A high proportion of recycled polypropylene from daily sundries is introduced into the modified polypropylene finished material, and at the same time, brand-new polypropylene and an elastomer toughening agent are added, ensuring the rigidity and toughness of the material, thus significantly improving the utilization rate of recycled polypropylene from daily sundries and guaranteeing the mechanical properties of the product.

[0029] 2. MIL-101(Cr) is selected as the main adsorption material. Due to its large specific surface area and rich pore structure, this MOF material exhibits excellent adsorption capacity for common volatile organic compounds (VOCs), especially aromatic substances. This enables MIL-101(Cr) to effectively adsorb odor substances such as ketones, phenols, and amines in recycled polypropylene, effectively solving the odor problem of the recycled PP high-doped polypropylene composite material and enhancing the environmental friendliness of the material.

[0030] 3. Considering that the high water vapor environment during the production process of polypropylene materials may reduce the adsorption efficiency of MIL-101(Cr), the present invention conducts hydrophobic modification on MIL-101(Cr) by introducing polyacrylate to prepare the MIL-101(Cr)@polyacrylate composite material. This modification not only maintains the high adsorption performance of MIL-101(Cr) but also enhances its adsorption capacity for odor substances in the industrial production environment. Even under high humidity conditions, it can maintain excellent adsorption effects, ensuring the odor control performance of the composite material. Specific embodiments

[0031] The present invention will be further described in detail below through examples and comparative examples, and the present invention is not limited to the scope of the described examples.

[0032] In the composite material formulations of Examples 1 - 5, the preparation method of the porous polyacrylate used is as follows: Weigh appropriate monomers TBA, TBMA, TMPTA, emulsifier, toluene, and oxidant BPO and mix them into an oil phase in a 50 ml beaker. Use a high-speed disperser to mix the oil phase evenly, and slowly drip 15 ml of deionized water into the oil phase, and continue stirring to disperse the emulsion evenly. Add 150 ml of deionized water to a 250 ml three-necked flask, place it in an oil bath at 65 °C, then add an appropriate amount of dispersant PVA and initiator APS. Subsequently, pour the prepared emulsion into the flask, and drip an appropriate amount of TMEDA. After reacting for 10 minutes, filter it out and place it in an oven at 60 °C for drying for 4H to obtain porous polyacrylate spherical particles.

[0033] The preparation method of the used MIF-101(Cr)@polyacrylate composite material is as follows: Weigh 0.2 g of porous polyacrylate and place it in a 25 ml round-bottom flask equipped with a vacuum device. Evacuate at room temperature for 30 minutes. Weigh an appropriate amount of H 2 BDC and DMF are heated and dissolved in a beaker to form a ligand solution. Weigh Cr(NO 3 ) 3 ·9H 2 O and methanol are stirred and dissolved to form a metal salt solution. The ligand solution and the metal salt solution are respectively poured into a constant-pressure funnel while maintaining the vacuum. Under the action of the pressure difference, they are completely impregnated into the interior of the carrier. The above-impregnated microspheres are placed in a reaction kettle containing deionized water and a growth regulator solution, and reacted at 220 °C for 8 hours. After natural cooling, they are taken out and centrifuged to obtain a green powder. The powder is soaked in DMF for 48H, DMF is replaced with methanol, and centrifuged again and dried for 12H to obtain the MIF-101(Cr)@polyacrylate composite material;

[0034] Example 1

[0035] (1) Weigh 38 parts of brand-new polypropylene, 30 parts of recycled polypropylene from daily sundries, 14 parts of an elastomeric toughening agent, 16 parts of an inorganic filler, 0.5 part of a stabilizer, and 2 parts of other additives by weight percentage, and dry-mix in a high-speed mixer for 8 minutes to obtain a premix; Weigh 0.2 part of the MIF-101(Cr)@polyacrylate composite material by weight percentage;

[0036] (2) Add the premix into a twin-screw extruder from the main screw feeding port, and add the MIF-101(Cr)@polyacrylate composite material into the twin-screw extruder from the side feeding port. After melting and extrusion, it is cooled and pelletized. The process is as follows: Zone 1: 190 - 200 °C, Zone 2: 200 - 210 °C, Zone 3: 210 - 220 °C, Zone 4: 205 - 215 °C; Residence time: 1 - 2 min, Pressure: 12 - 18 MPa; The post-treatment baking process is set to bake at 140 °C for 8H.

[0037] Example 2

[0038] (1) Weigh 38 parts of brand-new polypropylene, 30 parts of recycled polypropylene from daily sundries, 14 parts of an elastomeric toughening agent, 16 parts of an inorganic filler, 0.5 part of a stabilizer, and 2 parts of other additives by weight percentage, and dry-mix in a high-speed mixer for 8 minutes to obtain a premix; Weigh 0.4 part of the MIF-101(Cr)@polyacrylate composite material by weight percentage;

[0039] (2) Add the premix into the twin-screw extruder from the main screw feeding port, and add the MIF-101(Cr)@polyacrylate composite material into the twin-screw extruder from the side feeding port. After melting and extrusion, it is cooled and pelletized. The process is as follows: Zone 1: 190 - 200 °C, Zone 2: 200 - 210 °C, Zone 3: 210 - 220 °C, Zone 4: 205 - 215 °C; residence time: 1 - 2 min, pressure: 12 - 18 MPa; the post-treatment baking process is set to bake at 140 °C for 8 h.

[0040] Example 3

[0041] (1) Weigh 38 parts of brand-new polypropylene, 30 parts of recycled polypropylene from sundries, 14 parts of elastomeric toughening agent, 16 parts of inorganic filler, 0.5 part of stabilizer, and 2 parts of other additives by weight percentage, and dry mix them in a high-speed mixer for 8 minutes to obtain a premix; weigh 0.6 part of MIF-101(Cr)@polyacrylate composite material by weight percentage;

[0042] (2) Add the premix into the twin-screw extruder from the main screw feeding port, and add the MIF-101(Cr)@polyacrylate composite material into the twin-screw extruder from the side feeding port. After melting and extrusion, it is cooled and pelletized. The process is as follows: Zone 1: 190 - 200 °C, Zone 2: 200 - 210 °C, Zone 3: 210 - 220 °C, Zone 4: 205 - 215 °C; residence time: 1 - 2 min, pressure: 12 - 18 MPa; the post-treatment baking process is set to bake at 140 °C for 8 h.

[0043] Example 4

[0044] (1) Weigh 38 parts of brand-new polypropylene, 30 parts of recycled polypropylene from sundries, 14 parts of elastomeric toughening agent, 16 parts of inorganic filler, 0.5 part of stabilizer, and 2 parts of other additives by weight percentage, and dry mix them in a high-speed mixer for 8 minutes to obtain a premix; weigh 0.8 part of MIF-101(Cr)@polyacrylate composite material by weight percentage;

[0045] (2) Add the premix into the twin-screw extruder from the main screw feeding port, and add the MIF-101(Cr)@polyacrylate composite material into the twin-screw extruder from the side feeding port. After melting and extrusion, it is cooled and pelletized. The process is as follows: Zone 1: 190 - 200 °C, Zone 2: 200 - 210 °C, Zone 3: 210 - 220 °C, Zone 4: 205 - 215 °C; residence time: 1 - 2 min, pressure: 12 - 18 MPa; the post-treatment baking process is set to bake at 140 °C for 8 h.

[0046] Example 5

[0047] (1) Weigh 38 parts of brand-new polypropylene, 30 parts of polypropylene recycled from sundries, 14 parts of elastomer toughening agent, 16 parts of inorganic filler, 0.5 part of stabilizer, and 2 parts of other additives by weight percentage, and dry-mix them in a high-speed mixer for 8 minutes to obtain a premix; Weigh 1.0 part of MIF-101(Cr)@polyacrylate composite material by weight percentage;

[0048] (2) Add the premix into a twin-screw extruder from the main screw feeding port, and add the MIF-101(Cr)@polyacrylate composite material into the twin-screw extruder from the side feeding port. After melting and extrusion, cool and pelletize. The process is as follows: zone 1 at 190 - 200 °C, zone 2 at 200 - 210 °C, zone 3 at 210 - 220 °C, zone 4 at 205 - 215 °C; residence time 1 - 2 min, pressure 12 - 18 MPa; the post-treatment baking process is set to bake at 140 °C for 8 h.

[0049] Comparative Example 1

[0050] (1) Weigh 48 parts of brand-new polypropylene, 20 parts of polypropylene recycled from sundries, 14 parts of elastomer toughening agent, 16 parts of inorganic filler, 0.5 part of stabilizer, and 2 parts of other additives by weight percentage, and dry-mix them in a high-speed mixer for 8 minutes to obtain a premix;

[0051] (2) Add the premix into a twin-screw extruder from the main screw feeding port, and after melting and extrusion, cool and pelletize. The process is as follows: zone 1 at 190 - 200 °C, zone 2 at 200 - 210 °C, zone 3 at 210 - 220 °C, zone 4 at 205 - 215 °C; residence time 1 - 2 min, pressure 12 - 18 MPa; the post-treatment baking process is set to bake at 140 °C for 8 h.

[0052] Comparative Example 2

[0053] (1) Weigh 38 parts of brand-new polypropylene, 30 parts of polypropylene recycled from sundries, 14 parts of elastomer toughening agent, 16 parts of inorganic filler, 0.5 part of stabilizer, and 2 parts of other additives by weight percentage, and dry-mix them in a high-speed mixer for 8 minutes to obtain a premix;

[0054] (2) Add the premix into a twin-screw extruder from the main screw feeding port, and after melting and extrusion, cool and pelletize. The process is as follows: zone 1 at 190 - 200 °C, zone 2 at 200 - 210 °C, zone 3 at 210 - 220 °C, zone 4 at 205 - 215 °C; residence time 1 - 2 min, pressure 12 - 18 MPa; the post-treatment baking process is set to bake at 140 °C for 8 h.

[0055] Comparative Example 3

[0056] (1) Weigh 28 parts of brand-new polypropylene, 40 parts of recycled polypropylene from sundries, 14 parts of elastomer toughening agent, 16 parts of inorganic filler, 0.5 part of stabilizer, and 2 parts of other additives by weight percentage, and dry-mix them in a high-speed mixer for 8 minutes to obtain a premix;

[0057] (2) Add the premix into a twin-screw extruder from the main screw feeding port, and after melting and extrusion, cool and pelletize. The process is as follows: zone 1: 190 - 200 °C, zone 2: 200 - 210 °C, zone 3: 210 - 220 °C, zone 4: 205 - 215 °C; residence time 1 - 2 min, pressure 12 - 18 MPa; the post-treatment baking process is set to bake at 140 °C for 8 h.

[0058] Table 1 Material formulation table of Comparative Examples 1 - 3 and Examples 1 - 5 (weight %)

[0059]

[0060] Performance evaluation method and implementation standard:

[0061] According to relevant testing standards, test the recycled PP high-doped polypropylene composites prepared from Specific Examples 1 - 5 and Comparative Examples 1 - 3. The main physical property indexes to be tested are as follows: density, tensile strength, flexural strength, flexural modulus, Izod notched impact strength, and odor test.

[0062] Among them, the odor test is carried out according to the Volkswagen PV3900 standard. The method is as follows: The specimen in a sealed container is stored at 80 °C for 2 hours, cooled to 60 °C, and then judged according to the rating score level of the PV3900 standard. More than 5 people participate in the evaluation to obtain a statistical overall judgment. Level 1 is no odor, level 2 has an odor but no irritation; level 3 has an obvious odor but no irritation; level 4 has an irritating odor; level 5 has a strong irritating odor; level 6 has an unbearable odor. Those with a rating score less than or equal to 3.5 are qualified.

[0063] Table 2 Performance test standard

[0064] Physical properties Test standard Unit Density GB / T1033.1 <![CDATA[g / cm 3 > Tensile strength GB / T1040.2 MPa Flexural strength GB / T9341 MPa Flexural modulus GB / T9341 MPa Notched Izod impact strength GB / T1843 <![CDATA[kJ / m 2 > Odor PV3900 Grade

[0065] Table 3 Material performance table of Comparative Examples 1 - 3 and Examples 1 - 5

[0066]

[0067] It can be clearly seen from the material property test results of Comparative Examples 1-3 that when the filling ratio of household waste recycled polypropylene increases from 20 parts to 30 parts and 40 parts, even with the post-treatment process of baking at 140 °C for 8 hours, it is impossible to ensure that the odor of the PP material meets the 3.5-level qualified standard recognized by the public. Moreover, the higher the filling ratio, the more serious the odor problem. Therefore, the odor problem caused by high-ratio filling of household waste recycled polypropylene cannot be solved only by the post-treatment baking process.

[0068] Further observing the material property test results of Examples 1-5 and Comparative Example 2, it can be seen that when the MIF-101(Cr)@polyacrylate composite material is introduced, the odor of the recycled PP high-doped polypropylene composite material is significantly improved. As the content of the MIF-101(Cr)@polyacrylate composite material gradually increases, its adsorption capacity for odor substances such as ketones, phenols, and amines in recycled polypropylene also increases. However, when the content of the MIF-101(Cr)@polyacrylate composite material reaches a certain critical point, its adsorption capacity will tend to be saturated, and at this time, continuing to increase its content will no longer significantly improve the odor of the modified finished material. Among them, the odor levels of the recycled high-doped polypropylene composite materials in Examples 3-5 can all meet the 3.5-level qualified standard recognized by the public and maintain the rigid-flexible balance performance of the materials.

[0069] As described above, the above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope defined by the claims.

Claims

1. A low-odor recycled PP high-doped polypropylene composite material based on MOFs, characterized in that: The following weight percentages of raw materials Composition: New polypropylene: 10-50%; Daily recycled polypropylene: 20-40%; Elastomer toughening agent: 1-15%; Inorganic filler: 10-20%; Modified MOFs composite material: 0.1-1; Stabilizer: 0.1-2.0%; Other additives: 0-5%.

2. The low-odor recycled PP high-doped polypropylene composite material based on MOFs according to claim 1, characterized in that: The melt flow rate of the new polypropylene is 10-60 g / 10 min; the melt flow rate of the recycled polypropylene is 20-30 g / 10 min.

3. The low-odor recycled PP high-doped polypropylene composite material based on MOFs according to claim 1, characterized in that: The toughening agent is ethylene-octene copolymer or ethylene-butene copolymer or a combination of the two, with a density of 0.88-0.91 g / cm3 and a melt flow rate of 0.5-15 g / 10 min.

4. The low-odor recycled PP high-doped polypropylene composite material based on MOFs according to claim 1, characterized in that: The inorganic filler is at least one of talcum powder, calcium carbonate, montmorillonite and wollastonite or a combination of several thereof.

5. The low-odor recycled PP high-doped polypropylene composite material based on MOFs according to claim 1, characterized in that: The modified MOFs composite material is a MIF-101(Cr)@polyacrylate composite material.

6. The low-odor recycled PP high-doped polypropylene composite material based on MOFs according to claim 1, characterized in that: The stabilizer is a primary antioxidant and a secondary antioxidant that are considered necessary by those skilled in the art, wherein the primary antioxidant is a hindered phenol or thioester antioxidant, and the secondary antioxidant is a phosphite or lipid antioxidant.

7. The low-odor recycled PP high-doped polypropylene composite material based on MOFs according to claim 1, characterized in that: The other additives are one or a combination of toner, antistatic additive, surfactant, plasticizer, and anti-scratch additive that are considered necessary by those skilled in the art.

8. The method for preparing a low-odor recycled PP high-doped polypropylene composite material based on MOFs according to any one of claims 1 to 7, characterized in that: The specific method is as follows: Step 1: Preparation of porous polyacrylate: weigh appropriate monomers TBA, TBMA, TMPTA, emulsifier, toluene and oxidant BPO and mix them into an oil phase in a 50 ml beaker. Use a high-speed disperser to mix the oil phase evenly, and slowly drop 15 ml of deionized water into the oil phase, and continue stirring to disperse the emulsion evenly; add 150 ml of deionized water to a 250 ml three-necked flask, place it in an oil bath at 65°C, then add appropriate amounts of dispersant PVA and initiator APS, then pour the prepared emulsion into the flask, drop appropriate amounts of TMEDA, react for 10 minutes, filter it out, put it in a 60°C oven and dry it for 4 hours to obtain porous polyacrylate spherical particles; Step 2: Preparation of MIF-101(Cr)@polyacrylate composite material: weigh 0.2g of porous polyacrylate and place it in a 25ml round-bottom flask equipped with a vacuum device, vacuum at room temperature for 30 minutes, weigh appropriate H2BDC and DMF and heat and dissolve them in a beaker to form a ligand solution, weigh Cr(NO3)3·9H2O and methanol and stir and dissolve them into a metal salt solution, pour the ligand solution and the metal salt solution into a constant pressure funnel while maintaining vacuum, and completely impregnate them into the carrier under the action of pressure difference. The impregnated microspheres are placed in a reactor with deionized water and growth regulator solution, react at 220°C for 8 hours, take out after natural cooling and centrifuge to obtain green powder, soak the powder in DMF for 48 hours, replace DMF with methanol, centrifuge again and dry for 12 hours to obtain MIF-101(Cr)@polyacrylate composite material; Step 3: Mix new polypropylene, recycled polypropylene, elastomer toughening agent, inorganic filler, modified MOFs composite material, stabilizer and other additives in a high-speed mixer in proportion, and then add them to the twin-screw extruder from the main feed port of the screw. Add the MIF-101(Cr)@polyacrylate composite material to the twin-screw extruder through the side feed port. After melt extrusion, cool and granulate. The process is: zone 1 190-200℃, zone 2 200-210℃, zone 3 210-220℃, zone 4 205-215℃; residence time 1-2min, pressure 12-18MPa.

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