Biomodification preparation method of degradable polypropylene composite material
By combining lignin with composite compatible agent and lignin-based expanded flame retardant, the polypropylene material is solved, and the problem of poor degradation and insufficient flame retardant performance of the polypropylene composite in the prior art is achieved, and the efficient degradation of the material and the enhanced flame retardant performance are achieved.
Patent Information
- Application Number
- CN202510495383.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-21
- Publication Date
- 2025-06-03
AI Technical Summary
The existing biomodification technology process for polypropylene composite materials is cumbersome, the raw materials are costly and difficult to degrade, causing environmental pollution.
Lignin is used as a natural organic polymer material, and the polypropylene material is modified by combining with composite compatible agents and lignin-based expansion flame retardant to improve its degradability and flame retardant properties.
It effectively improves the degradability of polypropylene materials, promotes macromolecules decomposition, enhances the melt strength, toughness and heat resistance of the material, and forms an expanded carbon layer during combustion, which plays a flame retardant role.
Smart Images
Figure CN120082136A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of composite material modification, and particularly relates to a method for biologically modifying a degradable polypropylene composite material. Background Art
[0002] At present, the process of biologically modifying polypropylene composite materials is relatively cumbersome during preparation, and the raw material costs involved are also high. At the same time, they are not easily degraded, causing irreversible effects on the environment. Summary of the Invention
[0003] The purpose of the present invention is to provide a method for biologically modifying a degradable polypropylene composite material in view of the defects and deficiencies of the prior art. Lignin, as a natural organic polymer material, is biodegradable. After degradation, it can increase the degradable area of the polypropylene material, promote the decomposition of the macromolecular polypropylene material, effectively improve the modification efficiency, and be more environmentally friendly.
[0004] To achieve the above object, the present invention adopts the following technical solutions: Its operation steps are as follows: Step 1: Mix polypropylene, 2-isocyanatoethyl acrylate, and an initiator, pour them into a polymerization kettle, raise the temperature in the polymerization kettle to 160 - 170 °C, and perform melt grafting for 4 - 8 minutes. Pour the product into xylene for dissolution and filtration, use acetone for sedimentation, repeat the dissolution and sedimentation processes 2 - 3 times, and perform vacuum drying to obtain an intermediate; Step 2: Mix the intermediate, p-aminophenyl POSS, and toluene, add a catalyst dropwise, stir well, and then stir at a temperature of 60 - 70 °C for 4 - 12 hours. Remove the solvent by vacuum distillation, filter out the solid material, wash it again, and perform vacuum drying to obtain a composite compatibilizer; Step 3: Mix lignin with tetrahydrofuran, add phosphorus pentoxide, stir at room temperature for 2 - 6 hours, remove the solvent by vacuum distillation, pour in purified water to precipitate the solid material, centrifuge to separate the solid sample, and perform vacuum drying to obtain phosphorus-containing lignin. The mass ratio of lignin to phosphorus pentoxide is 1:2 - 5; Step 4: Dissolve the phosphorus-containing lignin in 1,4-dioxane, raise the temperature of the system to 60 - 80 °C, add piperazine, stir for 4 - 8 hours, remove the solvent by vacuum distillation, wash the solid material with ethanol 2 - 3 times, perform vacuum drying, grind and sieve to 10 - 20 mesh to obtain a lignin-based intumescent flame retardant; Step 5: Add 70 - 80 parts by weight of a polypropylene matrix, 20 - 30 parts by weight of the composite compatibilizer, 0.2 - 0.5 parts by weight of antioxidant 1010, and 0.3 - 0.6 parts by weight of polyethylene wax to a mixer, and stir until a uniform premix is formed; Step 6: Add the premix into the twin-screw extruder through the main feeding hopper, and add 2-6 parts by weight of the lignin-based intumescent flame retardant into the twin-screw extruder from the side feeding hopper, then carry out extrusion granulation. Wait for the material to cool naturally to obtain the biodegradable modified polypropylene material.
[0005] Further, the initiator is one of benzoyl peroxide or dicumyl peroxide.
[0006] Further, the rotation speed of the polymerization reactor is 50-60 r / min.
[0007] Further, the mass ratio of the polypropylene, 2-isocyanatoethyl acrylate and the initiator is 95:4:1.
[0008] Further, the catalyst is one of dibutyltin dilaurate or stannous octoate.
[0009] Further, the mass ratio of the intermediate and p-aminophenyl POSS is 10:0.5-1.5.
[0010] Further, the mass ratio of the phosphorus-containing lignin and piperazine is 5:1.
[0011] Further, the stirring speed of the mixer is 500-600 r / min.
[0012] Further, the temperature at the main feeding hopper is 200-240 °C, the temperature at the side feeding hopper is 180-200 °C, and the screw rotation speed is 300-400 r / min.
[0013] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention provides a method for biologically modifying a degradable polypropylene composite material. Lignin, as a natural organic polymer material, is biodegradable. After degradation, it can increase the degradable area of the polypropylene material and promote the decomposition of the macromolecular polypropylene material. At the same time, the composite compatibilizer can increase the crosslinking density of the polypropylene matrix, enhance the melt strength, toughness and heat resistance. The lignin-based intumescent flame retardant can form an intumescent carbon layer during the combustion of polypropylene, playing a flame retardant role, and has a synergistic flame retardant effect with the composite compatibilizer. BRIEF DESCRIPTION OF THE DRAWINGS
[0014] Figure 1 It is a data table for testing the product performance of Examples 1 to 4. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0015] The technical solutions in the present invention will be clearly and completely described below. The preferred embodiments described are only for illustration. All other embodiments obtained by those skilled in the art without creative efforts fall within the protection scope of the present invention.
[0016] Example 1: This example includes the following operating steps: Step 1: Mix polypropylene, 2-isocyanatoethyl acrylate, and benzoyl peroxide, pour them into a polymerization kettle, raise the temperature in the polymerization kettle to 160 °C, and carry out melt grafting at a rotation speed of 60 r / min for 8 min. Pour the product into xylene for dissolution and filtration, carry out sedimentation using acetone, repeat the dissolution and sedimentation process 3 times, and carry out vacuum drying to obtain an intermediate. Among them, the mass ratio of polypropylene, 2-isocyanatoethyl acrylate, and benzoyl peroxide is 95:4:1; Step 2: Mix the intermediate, p-aminophenyl POSS, and toluene, dropwise add dibutyltin dilaurate, stir well, and stir at a temperature of 70 °C for 10 h. Remove the solvent by vacuum distillation, filter out the solid material, wash it again, and carry out vacuum drying to obtain a composite compatibilizer. Among them, the mass ratio of the intermediate and p-aminophenyl POSS is 10:0.5; Step 3: Mix lignin with tetrahydrofuran, add phosphorus pentoxide, stir at room temperature for 6 h, remove the solvent by vacuum distillation, pour into purified water to precipitate the solid material, centrifuge to separate the solid sample, and carry out vacuum drying to obtain phosphorus-containing lignin. The mass ratio of lignin to phosphorus pentoxide is 1:5; Step 4: Dissolve the phosphorus-containing lignin in 1,4-dioxane, raise the system temperature to 70 °C, add piperazine, stir for 5 h, remove the solvent by vacuum distillation, wash the solid material with ethanol 3 times, carry out vacuum drying, grind and sieve to 20 mesh to obtain a lignin-based intumescent flame retardant. Among them, the mass ratio of phosphorus-containing lignin to piperazine is 5:1; Step 5: Add 70 parts by weight of polypropylene matrix, 20 parts by weight of composite compatibilizer, 0.2 part by weight of antioxidant 1010, and 0.3 part by weight of polyethylene wax to a mixer, set the stirring speed to 600 r / min, and stir until a uniform premix is formed; Step 6: Add the premix to a twin-screw extruder through the main feeding hopper, and add 2 parts by weight of the lignin-based intumescent flame retardant to the twin-screw extruder from the side feeding hopper. The temperature at the main feeding hopper is 240 °C, the temperature at the side feeding hopper is 200 °C, the screw rotation speed is 400 r / min, and extrusion granulation is carried out. Wait for the material to cool naturally to obtain a biodegradable modified polypropylene material.
[0017] Example 2: This example includes the following operating steps: Step 1: Mix polypropylene, 2-isocyanatoethyl acrylate, and benzoyl peroxide, pour them into a polymerization kettle, raise the temperature in the polymerization kettle to 165 °C, carry out melt grafting at a rotation speed of 60 r / min for 5 min, pour the product into xylene for dissolution and filtration, carry out sedimentation using acetone, repeat the dissolution and sedimentation processes 3 times, and carry out vacuum drying to obtain an intermediate. Among them, the mass ratio of polypropylene, 2-isocyanatoethyl acrylate, and benzoyl peroxide is 95:4:1; Step 2: Mix the intermediate, p-aminophenyl POSS, and toluene, dropwise add dibutyltin dilaurate, stir well, and stir at a temperature of 65 °C for 8 h, carry out reduced-pressure distillation to remove the solvent, filter out the solid material, wash it again, and carry out vacuum drying to obtain a composite compatibilizer. Among them, the mass ratio of the intermediate and p-aminophenyl POSS is 10:0.5; Step 3: Mix lignin with tetrahydrofuran, add phosphorus pentoxide, stir at room temperature for 6 h, carry out reduced-pressure distillation to remove the solvent, pour purified water to precipitate the solid material, centrifuge to separate out the solid sample, and carry out vacuum drying to obtain phosphorus-containing lignin. The mass ratio of lignin to phosphorus pentoxide is 1:5; Step 4: Dissolve the phosphorus-containing lignin in 1,4-dioxane, raise the temperature of the system to 70 °C, add piperazine, stir for 5 h, carry out reduced-pressure distillation to remove the solvent, wash the solid material with ethanol 3 times, carry out vacuum drying, and grind and sieve to 20 mesh to obtain a lignin-based intumescent flame retardant. Among them, the mass ratio of the phosphorus-containing lignin and piperazine is 5:1; Step 5: Add 70 parts by weight of polypropylene matrix, 20 parts by weight of composite compatibilizer, 0.2 part by weight of antioxidant 1010, and 0.3 part by weight of polyethylene wax to a mixer, set the stirring speed to 600 r / min, and stir until a uniform premix is formed; Step 6: Add the premix to a twin-screw extruder through the main feeding hopper, and add 2 parts by weight of the lignin-based intumescent flame retardant to the twin-screw extruder from the side feeding hopper. The temperature at the main feeding hopper is 200 °C, the temperature at the side feeding hopper is 180 °C, the screw rotation speed is 400 r / min, carry out extrusion granulation, and wait for the material to cool naturally to obtain a biodegradable modified polypropylene material.
[0018] Example 3: This example includes the following operating steps: Step 1: Mix polypropylene, 2-isocyanatoethyl acrylate, and benzoyl peroxide, pour them into a polymerization kettle, raise the temperature in the polymerization kettle to 170 °C, carry out melt grafting at a rotation speed of 50 r / min for 5 min, pour the product into xylene for dissolution and filtration, carry out sedimentation using acetone, repeat the dissolution and sedimentation processes 3 times, and carry out vacuum drying to obtain an intermediate. Among them, the mass ratio of polypropylene, 2-isocyanatoethyl acrylate, and benzoyl peroxide is 95:4:1; Step 2: Mix the intermediate, p-aminophenyl POSS and toluene, add dibutyltin dilaurate dropwise, stir well, then stir at 60 °C for 8 h, remove the solvent by vacuum distillation, filter out the solid material, wash it, and dry it under vacuum to obtain a composite compatibilizer, where the mass ratio of the intermediate to p-aminophenyl POSS is 10:1.5; Step 3: Mix lignin with tetrahydrofuran, add phosphorus pentoxide, stir at room temperature for 6 h, remove the solvent by vacuum distillation, pour into purified water to precipitate the solid material, centrifuge to separate the solid sample, and dry it under vacuum to obtain phosphorus-containing lignin, where the mass ratio of lignin to phosphorus pentoxide is 1:2; Step 4: Dissolve the phosphorus-containing lignin in 1,4-dioxane, raise the system temperature to 80 °C, add piperazine, stir for 5 h, remove the solvent by vacuum distillation, wash the solid material with ethanol 3 times, dry it under vacuum, grind and sieve it to 20 mesh to obtain a lignin-based intumescent flame retardant, where the mass ratio of phosphorus-containing lignin to piperazine is 5:1; Step 5: Add 75 parts by weight of polypropylene matrix, 25 parts by weight of composite compatibilizer, 0.3 part by weight of antioxidant 1010 and 0.5 part by weight of polyethylene wax to a mixer, set the stirring speed to 600 r / min, and stir until a uniform premix is formed; Step 6: Add the premix to a twin-screw extruder through the main feed hopper, and add 4 parts by weight of the lignin-based intumescent flame retardant to the twin-screw extruder through the side feed hopper. The temperature at the main feed hopper is 220 °C, the temperature at the side feed hopper is 180 °C, the screw speed is 350 r / min, and extrusion granulation is carried out. Wait for the material to cool naturally to obtain a biodegradable modified polypropylene material.
[0019] Example 4: This example includes the following operating steps: Step 1: Mix polypropylene, 2-isocyanatoethyl acrylate and diisopropylbenzene peroxide, pour them into a polymerization kettle, raise the temperature in the polymerization kettle to 170 °C, and carry out melt grafting at a rotation speed of 50 r / min for 5 min. Pour the product into xylene for dissolution and filtration, and carry out precipitation with acetone. Repeat the dissolution and precipitation process 3 times, and dry it under vacuum to obtain an intermediate, where the mass ratio of polypropylene, 2-isocyanatoethyl acrylate and diisopropylbenzene peroxide is 95:4:1; Step 2: Mix the intermediate, p-aminophenyl POSS and toluene, add stannous octoate dropwise, stir well, then stir at 60 °C for 8 h, remove the solvent by vacuum distillation, filter out the solid material, wash it, and dry it under vacuum to obtain a composite compatibilizer, where the mass ratio of the intermediate to p-aminophenyl POSS is 10:1.5; Step 3: Mix lignin with tetrahydrofuran, add phosphorus pentoxide, stir at room temperature for 6 h, remove the solvent by vacuum distillation, pour purified water to precipitate the solid material, centrifuge to separate the solid sample, and dry it under vacuum to obtain phosphorus-containing lignin. The mass ratio of lignin to phosphorus pentoxide is 1:2. Step 4: Dissolve the phosphorus-containing lignin in 1,4-dioxane, raise the system temperature to 80 °C, add piperazine, stir for 5 h, remove the solvent by vacuum distillation, wash the solid material with ethanol three times, dry it under vacuum, and grind and sieve it to 20 mesh to obtain a lignin-based intumescent flame retardant. The mass ratio of phosphorus-containing lignin to piperazine is 5:1. Step 5: Add 75 parts by weight of polypropylene matrix, 25 parts by weight of composite compatibilizer, 0.3 parts by weight of antioxidant 1010, and 0.5 parts by weight of polyethylene wax to a mixer, set the stirring speed to 600 r / min, and stir until a uniform premix is formed. Step 6: Add the premix to a twin-screw extruder through the main feeding hopper, and add 4 parts by weight of the lignin-based intumescent flame retardant to the twin-screw extruder through the side feeding hopper. The temperature at the main feeding hopper is 220 °C, the temperature at the side feeding hopper is 180 °C, and the screw speed is 350 r / min. Carry out extrusion granulation, and wait for the material to cool naturally to obtain a biodegradable modified polypropylene material.
[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: Lignin, as a natural organic polymer material, is biodegradable. After degradation, it can increase the biodegradable area of the polypropylene material and promote the decomposition of the macromolecular polypropylene material. The composite compatibilizer can increase the crosslinking density of the polypropylene matrix, enhance the melt strength, toughness, and heat resistance. The lignin-based intumescent flame retardant can form an intumescent carbon layer during the combustion of polypropylene, playing a flame retardant role, and has a synergistic flame retardant effect with the composite compatibilizer.
[0021] For those skilled in the art, they can modify the technical solutions recorded in the foregoing embodiments and perform equivalent substitutions for some technical features. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
Claims
1. A biodegradable polypropylene composite material biomodification preparation method, characterized in that: its operating steps are as follows: Step (i), mixing polypropylene, 2-isocyanatoethyl acrylate and an initiator, pouring into a polymerization kettle, raising the temperature in the polymerization kettle to 160-170° C., melt grafting for 4-8 minutes, pouring the product into xylene for dissolution and filtration, using acetone for sedimentation, repeating the dissolution and sedimentation process 2-3 times, and vacuum drying to obtain an intermediate; Step (ii), mixing the intermediate, p-aminophenyl poss and toluene, adding a catalyst dropwise, stirring evenly, stirring at 60-70°C for 4-12h, removing the solvent by vacuum distillation, filtering out the solid material, washing it, and vacuum drying it to obtain a composite compatibilizer; Step (iii), mixing lignin with tetrahydrofuran, adding phosphorus pentoxide, stirring at room temperature for 2-6 hours, removing the solvent by distillation under reduced pressure, pouring purified water to precipitate solid materials, centrifuging to separate the solid sample, and vacuum drying to obtain phosphorus-containing lignin, wherein the mass ratio of lignin to phosphorus pentoxide is 1:2-5; Step (iv), dissolving the phosphorus-containing lignin in 1,4-dioxane, raising the system temperature to 60-80° C., adding piperazine, stirring for 4-8 hours, removing the solvent by vacuum distillation, washing the solid material with ethanol for 2-3 times, vacuum drying, grinding and sieving to 10-20 mesh, to obtain a lignin-based intumescent flame retardant; Step (V), adding 70-80 parts by weight of a polypropylene matrix, 20-30 parts by weight of a composite compatibilizer, 0.2-0.5 parts by weight of an antioxidant 1010 and 0.3-0.6 parts by weight of a polyethylene wax into a mixer, and stirring until a uniform premix is formed; Step (six), adding the premix into the twin-screw extruder through the main feeding hopper, and adding 2-6 parts by weight of lignin-based intumescent flame retardant into the twin-screw extruder from the side feeding hopper, performing extrusion granulation, and allowing the material to cool naturally to obtain a biodegradable modified polypropylene material.
2. The method for preparing a biodegradable polypropylene composite material by biomodification according to claim 1, characterized in that: The initiator is one of benzoyl peroxide or dicumyl peroxide.
3. The method for preparing a biodegradable polypropylene composite material by biomodification according to claim 1, characterized in that: The rotation speed of the polymerization reactor is 50-60r / min.
4. The method for preparing a biodegradable polypropylene composite material by biomodification according to claim 1, characterized in that: The mass ratio of the polypropylene, 2-isocyanatoethyl acrylate and the initiator is 95:4:
1.
5. The method for preparing a biodegradable polypropylene composite material by biomodification according to claim 1, characterized in that: The catalyst is one of dibutyltin dilaurate or stannous octoate.
6. The method for preparing a biodegradable polypropylene composite material by biomodification according to claim 1, characterized in that: The mass ratio of the intermediate to p-aminophenyl poss is 10:0.5-1.
5.
7. The method for preparing a biodegradable polypropylene composite material by biomodification according to claim 1, characterized in that: The mass ratio of the phosphorus-containing lignin to piperazine is 5:
1.
8. The method for preparing a biodegradable polypropylene composite material by biomodification according to claim 1, characterized in that: The stirring speed of the mixer is 500-600r / min.
9. The method for preparing a biodegradable polypropylene composite material by biomodification according to claim 1, characterized in that: The temperature at the main feeding hopper is 200-240°C, the temperature at the side feeding hopper is 180-200°C, and the screw speed is 300-400r / min.