阅读说明：本技术 一种阻燃吸波的聚丙烯发泡珠粒及其制备方法 (Flame-retardant wave-absorbing polypropylene foamed bead and preparation method thereof ) 是由 陈奕镔 于 2021-07-13 设计创作，主要内容包括：本发明公开了一种阻燃吸波的聚丙烯发泡珠粒,具体涉及聚丙烯发泡珠粒技术领域,包括以下原料：阻燃改性聚丙烯、复合导电填料、改性发泡成核剂、分散剂和抗氧剂,所述复合导电填料包括以下原料：导电炭黑、碳纳米管、镀银导电玻璃纤维、云母和偶联剂。本发明通过添加有镀银导电玻璃纤维能够有效提高聚丙烯发泡珠粒的导电性能,而且镀银导电玻璃纤维具有优异的电磁屏蔽性能,通过阻燃改性聚丙烯、复合导电填料和改性发泡成核剂的混合能够在聚丙烯发泡珠粒内部形成稳定的导电阻燃网络,极大的提高了聚丙烯发泡珠粒的导电性能,对微波具有良好的反射率,吸波效果更好。(The invention discloses a flame-retardant wave-absorbing polypropylene foamed bead, and particularly relates to the technical field of polypropylene foamed beads, which comprises the following raw materials: the flame-retardant modified polypropylene composite conductive filler comprises flame-retardant modified polypropylene, a composite conductive filler, a modified foaming nucleating agent, a dispersing agent and an antioxidant, wherein the composite conductive filler comprises the following raw materials: conductive carbon black, carbon nanotubes, silver-plated conductive glass fibers, mica and a coupling agent. The conductive performance of the polypropylene foam beads can be effectively improved by adding the silver-plated conductive glass fibers, the silver-plated conductive glass fibers have excellent electromagnetic shielding performance, a stable conductive flame-retardant network can be formed in the polypropylene foam beads by mixing the flame-retardant modified polypropylene, the composite conductive filler and the modified foaming nucleating agent, the conductive performance of the polypropylene foam beads is greatly improved, the composite conductive glass beads have good reflectivity to microwaves, and the wave-absorbing effect is better.)

1. The flame-retardant wave-absorbing polypropylene foaming bead is characterized in that: the feed comprises the following raw materials in parts by weight: 60-80 parts of flame-retardant modified polypropylene, 20-40 parts of composite conductive filler, 1-3 parts of modified foaming nucleating agent, 1-3 parts of dispersant and 1-3 parts of antioxidant, wherein the composite conductive filler comprises the following raw materials in percentage by mass: 40-50% of conductive carbon black, 10-20% of carbon nano tube, 15-25% of silver-plated conductive glass fiber, 15-25% of mica and 1-5% of coupling agent.

2. The flame-retardant wave-absorbing polypropylene expanded bead as claimed in claim 1, wherein: the feed comprises the following raw materials in parts by weight: 65-75 parts of flame-retardant modified polypropylene, 25-35 parts of composite conductive filler, 2-3 parts of modified foaming nucleating agent, 1.5-2.5 parts of dispersant and 1.5-2.5 parts of antioxidant, wherein the composite conductive filler comprises the following raw materials in percentage by mass: 43-47% of conductive carbon black, 13-17% of carbon nano tube, 18-22% of silver-plated conductive glass fiber, 18-22% of mica and 2-4% of coupling agent.

3. The flame-retardant wave-absorbing polypropylene expanded bead as claimed in claim 1, wherein: the feed comprises the following raw materials in parts by weight: 70 parts of flame-retardant modified polypropylene, 30 parts of composite conductive filler, 2 parts of modified foaming nucleating agent, 2 parts of dispersant and 2 parts of antioxidant, wherein the composite conductive filler comprises the following raw materials in percentage by mass: 45% of conductive carbon black, 15% of carbon nano tube, 18% of silver-plated conductive glass fiber, 19% of mica and 3% of coupling agent.

4. The flame-retardant wave-absorbing polypropylene expanded bead as claimed in claim 1, wherein: the dispersing agent is polyethylene glycol, the antioxidant is one of an antioxidant 1010, an antioxidant 300 and an antioxidant 168, the conductive carbon black is HG-4 conductive carbon black, the mica is flake mica powder, and the coupling agent is a silane coupling agent.

5. The preparation method of the flame-retardant wave-absorbing polypropylene expanded beads according to any one of claims 1 to 4, characterized by comprising the following steps: the preparation method comprises the following specific steps:

the method comprises the following steps: preparing flame-retardant modified polypropylene, namely weighing a certain amount of polypropylene, a toughening agent, a polyolefin silsesquioxane flame retardant, magnesium hydroxide, phosphate and an antioxidant, placing the weighed raw materials in a high-speed mixer for premixing at 80-90 ℃ for 20-40min, and placing the premixed raw materials in a double-screw extruder for extrusion granulation to obtain the flame-retardant modified polypropylene for later use;

step two: preparing a composite conductive filler, namely weighing conductive carbon black, a carbon nano tube, silver-plated conductive glass fiber, mica and a coupling agent according to the proportion of the composite conductive filler, placing the weighed conductive carbon black, the carbon nano tube, the silver-plated conductive glass fiber, the mica and the coupling agent in a high-speed mixer for premixing at room temperature for 20-40min, and placing the mixture in a double-screw extruder for extrusion granulation after premixing to obtain the composite conductive filler for later use;

step three: preparing a modified foaming nucleating agent, weighing a certain amount of nano mesoporous silica, reaming by using a salt soaking method, adding a copolymer for grafting reaction after reaming is finished, adding n-octanol into a grafted product for heating reflux treatment, extracting by using acetone after heating reflux is finished, and drying at 60-70 ℃ for 10-12 hours after extraction is finished to obtain the modified foaming nucleating agent for later use;

step four: weighing the flame-retardant modified polypropylene obtained in the step one, the composite conductive filler obtained in the step two, the modified foaming nucleating agent obtained in the step three, the dispersing agent and the antioxidant in parts by weight, uniformly mixing and stirring, then putting into a closed reaction kettle, heating and pressurizing the reaction kettle under the stirring action, generating internal pressure expanding outwards under high temperature and high pressure to form a dispersion body, fully impregnating the polypropylene particles with the modified foaming nucleating agent, and discharging the dispersion body into the atmosphere to obtain the foaming beads.

6. The preparation method of the flame-retardant wave-absorbing polypropylene expanded bead according to claim 5, characterized in that: the extrusion granulation of the double-screw extruder in the first step comprises nine temperature zones which are sequentially distributed, wherein the temperature of the first zone is 190-.

7. The preparation method of the flame-retardant wave-absorbing polypropylene expanded bead according to claim 5, characterized in that: the extrusion granulation of the double-screw extruder in the second step comprises nine temperature zones which are sequentially distributed, wherein the temperature of the first zone is 190-.

8. The preparation method of the flame-retardant wave-absorbing polypropylene expanded bead according to claim 5, characterized in that: and the pore-expanding treatment in the third step is to add the nano mesoporous silicon dioxide into a salt solution and then calcine the nano mesoporous silicon dioxide by a programmed heating method, wherein the heating reflux temperature in the third step is 65-75 ℃, and the heating reflux time is 4-6 h.

9. The preparation method of the flame-retardant wave-absorbing polypropylene expanded bead according to claim 8, characterized in that: the temperature programming process comprises the following steps: (1) raising the temperature from room temperature to a first calcining temperature, and keeping the temperature for 40-60 minutes; (2) raising the temperature from a first calcining temperature to a second calcining temperature, and keeping the temperature for 3-5h, wherein the first calcining temperature is 250-350 ℃, and the second calcining temperature is 450-600 ℃.

10. The preparation method of the flame-retardant wave-absorbing polypropylene expanded bead according to claim 5, characterized in that: and in the fourth step, carbon dioxide is injected into the reaction kettle when the reaction kettle is heated and pressurized, so that the internal pressure of the reaction kettle is 1.8-2.2 and the temperature is 140-.

Technical Field

The invention relates to the technical field of polypropylene foamed beads, in particular to a flame-retardant wave-absorbing polypropylene foamed bead and a preparation method thereof.

Background

Polypropylene expanded beads (EPP) products have excellent mechanical properties, high dimensional accuracy and are easy to degrade and recover, gradually replace traditional Polyethylene (PE), Polystyrene (PS) and Polyurethane (PU) expanded materials, have increasingly wide application fields, and besides the industries of electronic packaging, transportation and automobile parts, some functionalized EPP materials are also gradually applied to special fields, such as semiconductive EPP materials for absorbing microwaves.

The foaming material applied to the microwave absorption field is mostly PU foam internally adsorbed with conductive filler, and as the PU foam is in an open-cell structure, the adsorbed conductive filler can gradually run off in the using process, and finally the conductive performance of the PU foam is deteriorated and the electromagnetic shielding function of microwave absorption is lost. The semiconductive EPP beads are produced by adopting an intermittent reaction kettle foaming method, and then are fused into a use part by a steam molding method, the closed pore rate is high, and the conductive filler is coated in a PP matrix to form a conductive network, so that the use time is long; and to produce expanded beads: the polypropylene resin particles, the aqueous dispersion medium, the dispersing agent and the foaming agent are put into a closed autoclave together, the dispersion in the autoclave is heated to a temperature higher than the Vicat softening point of polypropylene by a heating device under the action of stirring, so that the foaming agent is fully impregnated in the polypropylene resin particles, and then the dispersion is discharged into the atmosphere to obtain foaming beads without any toxic substances; the EPP bead forming process is to introduce water vapor into a closed die, uniformly fuse the foamed beads into a used part by means of rapid diffusion and high temperature of the steam, and have no toxic substances in the whole process; compared with toxic substances such as isocyanate and the like remained in the PU foam processing process, the wave-absorbing EPP is more green and environment-friendly. The process that electrically conductive EPP absorbs the electromagnetic wave, it is the loss that utilizes electrically conductive network to turn into the electromagnetic wave heat energy, leads to EPP's temperature to rise, and can contact the electric wire when absorbing the wave material and use, in order to prevent that electric wire electric leakage or material are heated excessively and ignite, it needs to possess high fire behaviour to absorb the wave EPP.

The existing polypropylene foaming beads have single function, and are difficult to simultaneously meet high flame retardance and high wave-absorbing performance.

Disclosure of Invention

In order to overcome the defects in the prior art, the embodiment of the invention provides a flame-retardant wave-absorbing polypropylene expanded bead and a preparation method thereof, and the invention aims to solve the following problems: how to improve the flame retardant property and the wave absorbing property of the polypropylene foaming bead.

In order to achieve the purpose, the invention provides the following technical scheme: the flame-retardant wave-absorbing polypropylene foaming bead comprises the following raw materials in parts by weight: 60-80 parts of flame-retardant modified polypropylene, 20-40 parts of composite conductive filler, 1-3 parts of modified foaming nucleating agent, 1-3 parts of dispersant and 1-3 parts of antioxidant, wherein the composite conductive filler comprises the following raw materials in percentage by mass: 40-50% of conductive carbon black, 10-20% of carbon nano tube, 15-25% of silver-plated conductive glass fiber, 15-25% of mica and 1-5% of coupling agent.

In a preferred embodiment, the feed comprises the following raw materials in parts by weight: 65-75 parts of flame-retardant modified polypropylene, 25-35 parts of composite conductive filler, 2-3 parts of modified foaming nucleating agent, 1.5-2.5 parts of dispersant and 1.5-2.5 parts of antioxidant, wherein the composite conductive filler comprises the following raw materials in percentage by mass: 43-47% of conductive carbon black, 13-17% of carbon nano tube, 18-22% of silver-plated conductive glass fiber, 18-22% of mica and 2-4% of coupling agent.

In a preferred embodiment, the feed comprises the following raw materials in parts by weight: 70 parts of flame-retardant modified polypropylene, 30 parts of composite conductive filler, 2 parts of modified foaming nucleating agent, 2 parts of dispersant and 2 parts of antioxidant, wherein the composite conductive filler comprises the following raw materials in percentage by mass: 45% of conductive carbon black, 15% of carbon nano tube, 18% of silver-plated conductive glass fiber, 19% of mica and 3% of coupling agent.

In a preferred embodiment, the dispersant is polyethylene glycol, the antioxidant is one of antioxidant 1010, antioxidant 300 and antioxidant 168, the conductive carbon black is HG-4 conductive carbon black, the mica is flake mica powder, and the coupling agent is a silane coupling agent.

The invention also provides a preparation method of the flame-retardant wave-absorbing polypropylene foaming bead, which comprises the following specific preparation steps:

the method comprises the following steps: preparing flame-retardant modified polypropylene, namely weighing a certain amount of polypropylene, a toughening agent, a polyolefin silsesquioxane flame retardant, magnesium hydroxide, phosphate and an antioxidant, placing the weighed raw materials in a high-speed mixer for premixing at 80-90 ℃ for 20-40min, and placing the premixed raw materials in a double-screw extruder for extrusion granulation to obtain the flame-retardant modified polypropylene for later use;

step two: preparing a composite conductive filler, namely weighing conductive carbon black, a carbon nano tube, silver-plated conductive glass fiber, mica and a coupling agent according to the proportion of the composite conductive filler, placing the weighed conductive carbon black, the carbon nano tube, the silver-plated conductive glass fiber, the mica and the coupling agent in a high-speed mixer for premixing at room temperature for 20-40min, and placing the mixture in a double-screw extruder for extrusion granulation after premixing to obtain the composite conductive filler for later use;

step three: preparing a modified foaming nucleating agent, weighing a certain amount of nano mesoporous silica, reaming by using a salt soaking method, adding a copolymer for grafting reaction after reaming is finished, adding n-octanol into a grafted product for heating reflux treatment, extracting by using acetone after heating reflux is finished, and drying at 60-70 ℃ for 10-12 hours after extraction is finished to obtain the modified foaming nucleating agent for later use;

step four: weighing the flame-retardant modified polypropylene obtained in the step one, the composite conductive filler obtained in the step two, the modified foaming nucleating agent obtained in the step three, the dispersing agent and the antioxidant in parts by weight, uniformly mixing and stirring, then putting into a closed reaction kettle, heating and pressurizing the reaction kettle under the stirring action, generating internal pressure expanding outwards under high temperature and high pressure to form a dispersion body, fully impregnating the polypropylene particles with the modified foaming nucleating agent, and discharging the dispersion body into the atmosphere to obtain the foaming beads.

In a preferred embodiment, the extrusion granulation of the twin-screw extruder in the first step includes nine temperature zones sequentially arranged, wherein the temperature of the first zone is 190-.

In a preferred embodiment, the extrusion granulation of the twin-screw extruder in the second step includes nine temperature zones sequentially arranged, wherein the temperature of the first zone is 190-.

In a preferred embodiment, the pore-expanding treatment in the third step is to add the nano mesoporous silica into a salt solution, and then calcine the nano mesoporous silica by a programmed heating method, wherein the heating reflux temperature in the third step is 65-75 ℃, and the heating reflux time is 4-6 h.

In a preferred embodiment, the temperature programming process comprises the steps of: (1) raising the temperature from room temperature to a first calcining temperature, and keeping the temperature for 40-60 minutes; (2) raising the temperature from a first calcining temperature to a second calcining temperature, and keeping the temperature for 3-5h, wherein the first calcining temperature is 250-350 ℃, and the second calcining temperature is 450-600 ℃.

In a preferred embodiment, when the reaction kettle in the fourth step is heated and pressurized, carbon dioxide is injected into the reaction kettle, so that the internal pressure of the reaction kettle is 1.8-2.2 and the temperature is 140-.

The invention has the technical effects and advantages that:

1. the flame-retardant wave-absorbing polypropylene foaming bead prepared by adopting the raw material formula of the invention is composed of flame-retardant modified polypropylene, composite conductive filler and modified foaming nucleating agent, the polypropylene is subjected to flame-retardant modification by utilizing polyolefin silsesquioxane flame retardant, magnesium hydroxide and phosphate, so that polypropylene particles have good conductivity, the composite conductive filler comprises conductive carbon black, carbon nano tubes, silver-plated conductive glass fibers, mica and coupling agent, the composition of the conductive carbon black, the carbon nano tubes and the mica can obtain the ideal grape string-shaped conductive filler, the conductivity of the polypropylene foaming bead can be effectively improved by adding the silver-plated conductive glass fibers, the silver-plated conductive glass fibers have excellent electromagnetic shielding performance, the foaming nucleating agent adopts modified mesoporous silica, and polymer grafting reaction is carried out after the nanometer mesoporous silica is subjected to hole expanding treatment, the nano mesoporous silica has excellent dispersibility and good interface compatibility, so that the polypropylene particles can be better treated by the foaming nucleating agent, and the conductivity and the wave-absorbing performance of the polypropylene foaming beads can be effectively improved;

2. according to the invention, the flame-retardant modified polypropylene, the composite conductive filler and the modified foaming nucleating agent are mixed to form a stable conductive flame-retardant network in the polypropylene foaming beads, so that the conductivity of the polypropylene foaming beads is greatly improved, the polypropylene foaming beads have good reflectivity to microwaves, and the wave-absorbing effect is better.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

the invention provides a flame-retardant wave-absorbing polypropylene foaming bead which comprises the following raw materials in parts by weight: 60 parts of flame-retardant modified polypropylene, 20 parts of composite conductive filler, 1 part of modified foaming nucleating agent, 1 part of dispersant and 1 part of antioxidant, wherein the composite conductive filler comprises the following raw materials in percentage by mass: 45% of conductive carbon black, 15% of carbon nano tube, 18% of silver-plated conductive glass fiber, 19% of mica and 3% of coupling agent.

In a preferred embodiment, the dispersant is polyethylene glycol, the antioxidant is one of antioxidant 1010, antioxidant 300 and antioxidant 168, the conductive carbon black is HG-4 conductive carbon black, the mica is flake mica powder, and the coupling agent is a silane coupling agent.

The invention also provides a preparation method of the flame-retardant wave-absorbing polypropylene foaming bead, which comprises the following specific preparation steps:

the method comprises the following steps: preparing flame-retardant modified polypropylene, namely weighing a certain amount of polypropylene, a toughening agent, a polyolefin silsesquioxane flame retardant, magnesium hydroxide, phosphate and an antioxidant, placing the weighed raw materials in a high-speed mixer for premixing at 85 ℃ for 30min, and placing the premixed raw materials in a double-screw extruder for extrusion granulation to obtain the flame-retardant modified polypropylene for later use;

step two: preparing a composite conductive filler, namely weighing conductive carbon black, a carbon nano tube, silver-plated conductive glass fiber, mica and a coupling agent according to the proportion of the composite conductive filler, placing the weighed conductive carbon black, the carbon nano tube, the silver-plated conductive glass fiber, the mica and the coupling agent in a high-speed mixer for premixing at room temperature for 30min, and placing the mixture in a double-screw extruder for extrusion granulation after premixing to obtain the composite conductive filler for later use;

step three: preparing a modified foaming nucleating agent, weighing a certain amount of nano mesoporous silica, reaming by using a salt soaking method, adding a copolymer for grafting reaction after reaming is finished, adding n-octanol into a grafted product for heating reflux treatment, extracting by using acetone after heating reflux is finished, and drying at 65 ℃ for 12 hours after extraction is finished to obtain the modified foaming nucleating agent for later use;

step four: weighing the flame-retardant modified polypropylene obtained in the step one, the composite conductive filler obtained in the step two, the modified foaming nucleating agent obtained in the step three, the dispersing agent and the antioxidant in parts by weight, uniformly mixing and stirring, then putting into a closed reaction kettle, heating and pressurizing the reaction kettle under the stirring action, generating internal pressure expanding outwards under high temperature and high pressure to form a dispersion body, fully impregnating the polypropylene particles with the modified foaming nucleating agent, and discharging the dispersion body into the atmosphere to obtain the foaming beads.

In a preferred embodiment, the extrusion granulation of the twin-screw extruder in the first step comprises nine temperature zones arranged in sequence, wherein the temperature of the first zone is 185 ℃, the temperature of the second zone and the third zone is 195 ℃, the temperature of the fourth zone to the seventh zone is 200 ℃, the temperature of the eighth zone and the nine zone is 195 ℃, and the temperature of the head of the twin-screw extruder is 190 ℃.

In a preferred embodiment, the extrusion granulation of the twin-screw extruder in the second step comprises nine temperature zones arranged in sequence, wherein the temperature of the first zone is 195 ℃, the temperature of the second zone and the temperature of the third zone are 215 ℃, the temperature of the fourth zone to the seventh zone is 225 ℃, the temperature of the eighth zone and the temperature of the ninth zone are 215 ℃, and the temperature of the head of the twin-screw extruder is 210 ℃.

In a preferred embodiment, the pore-expanding treatment in the third step is to add the nano mesoporous silica into a salt solution, and then calcine the nano mesoporous silica by a programmed heating method, wherein the heating reflux temperature in the third step is 70 ℃, and the heating reflux time is 5 hours.

In a preferred embodiment, the temperature programming process comprises the steps of: (1) raising the temperature from room temperature to the first calcining temperature, and keeping the temperature for 50 minutes; (2) and (3) raising the temperature from a first calcining temperature to a second calcining temperature, keeping the temperature for 4 hours, wherein the first calcining temperature is 290 ℃, and the second calcining temperature is 550 ℃.

In a preferred embodiment, in the fourth step, carbon dioxide is injected into the reaction kettle while the reaction kettle is heated and pressurized, so that the internal pressure of the reaction kettle is 2.0 and the temperature is 150 ℃.

Example 2:

different from the embodiment 1, the invention provides a flame-retardant wave-absorbing polypropylene expanded bead, which comprises the following raw materials in parts by weight in a preferred embodiment: 70 parts of flame-retardant modified polypropylene, 30 parts of composite conductive filler, 2 parts of modified foaming nucleating agent, 2 parts of dispersant and 2 parts of antioxidant, wherein the composite conductive filler comprises the following raw materials in percentage by mass: 45% of conductive carbon black, 15% of carbon nano tube, 18% of silver-plated conductive glass fiber, 19% of mica and 3% of coupling agent.

Example 3:

different from the embodiment 1-2, the invention provides a flame-retardant wave-absorbing polypropylene foaming bead, which comprises the following raw materials in parts by weight: 80 parts of flame-retardant modified polypropylene, 40 parts of composite conductive filler, 3 parts of modified foaming nucleating agent, 3 parts of dispersant and 3 parts of antioxidant, wherein the composite conductive filler comprises the following raw materials in percentage by mass: 45% of conductive carbon black, 15% of carbon nano tube, 18% of silver-plated conductive glass fiber, 19% of mica and 3% of coupling agent.

Example 4:

the invention provides a flame-retardant wave-absorbing polypropylene foaming bead which comprises the following raw materials in parts by weight: 60 parts of flame-retardant modified polypropylene, 20 parts of composite conductive filler, 1 part of modified foaming nucleating agent, 1 part of dispersant and 1 part of antioxidant, wherein the composite conductive filler comprises the following raw materials in percentage by mass: 40% of conductive carbon black, 15% of carbon nano tube, 20% of silver-plated conductive glass fiber, 20% of mica and 5% of coupling agent.

In a preferred embodiment, the dispersant is polyethylene glycol, the antioxidant is one of antioxidant 1010, antioxidant 300 and antioxidant 168, the conductive carbon black is HG-4 conductive carbon black, the mica is flake mica powder, and the coupling agent is a silane coupling agent.

The invention also provides a preparation method of the flame-retardant wave-absorbing polypropylene foaming bead, which comprises the following specific preparation steps:

the method comprises the following steps: preparing flame-retardant modified polypropylene, namely weighing a certain amount of polypropylene, a toughening agent, a polyolefin silsesquioxane flame retardant, magnesium hydroxide, phosphate and an antioxidant, placing the weighed raw materials in a high-speed mixer for premixing at 85 ℃ for 30min, and placing the premixed raw materials in a double-screw extruder for extrusion granulation to obtain the flame-retardant modified polypropylene for later use;

step two: preparing a composite conductive filler, namely weighing conductive carbon black, a carbon nano tube, silver-plated conductive glass fiber, mica and a coupling agent according to the proportion of the composite conductive filler, placing the weighed conductive carbon black, the carbon nano tube, the silver-plated conductive glass fiber, the mica and the coupling agent in a high-speed mixer for premixing at room temperature for 30min, and placing the mixture in a double-screw extruder for extrusion granulation after premixing to obtain the composite conductive filler for later use;

step three: preparing a modified foaming nucleating agent, weighing a certain amount of nano mesoporous silica, reaming by using a salt soaking method, adding a copolymer for grafting reaction after reaming is finished, adding n-octanol into a grafted product for heating reflux treatment, extracting by using acetone after heating reflux is finished, and drying at 65 ℃ for 12 hours after extraction is finished to obtain the modified foaming nucleating agent for later use;

step four: weighing the flame-retardant modified polypropylene obtained in the step one, the composite conductive filler obtained in the step two, the modified foaming nucleating agent obtained in the step three, the dispersing agent and the antioxidant in parts by weight, uniformly mixing and stirring, then putting into a closed reaction kettle, heating and pressurizing the reaction kettle under the stirring action, generating internal pressure expanding outwards under high temperature and high pressure to form a dispersion body, fully impregnating the polypropylene particles with the modified foaming nucleating agent, and discharging the dispersion body into the atmosphere to obtain the foaming beads.

In a preferred embodiment, the extrusion granulation of the twin-screw extruder in the first step comprises nine temperature zones arranged in sequence, wherein the temperature of the first zone is 185 ℃, the temperature of the second zone and the third zone is 195 ℃, the temperature of the fourth zone to the seventh zone is 200 ℃, the temperature of the eighth zone and the nine zone is 195 ℃, and the temperature of the head of the twin-screw extruder is 190 ℃.

In a preferred embodiment, the extrusion granulation of the twin-screw extruder in the second step comprises nine temperature zones arranged in sequence, wherein the temperature of the first zone is 195 ℃, the temperature of the second zone and the temperature of the third zone are 215 ℃, the temperature of the fourth zone to the seventh zone is 225 ℃, the temperature of the eighth zone and the temperature of the ninth zone are 215 ℃, and the temperature of the head of the twin-screw extruder is 210 ℃.

In a preferred embodiment, the pore-expanding treatment in the third step is to add the nano mesoporous silica into a salt solution, and then calcine the nano mesoporous silica by a programmed heating method, wherein the heating reflux temperature in the third step is 70 ℃, and the heating reflux time is 5 hours.

In a preferred embodiment, the temperature programming process comprises the steps of: (1) raising the temperature from room temperature to the first calcining temperature, and keeping the temperature for 50 minutes; (2) and (3) raising the temperature from a first calcining temperature to a second calcining temperature, keeping the temperature for 4 hours, wherein the first calcining temperature is 290 ℃, and the second calcining temperature is 550 ℃.

In a preferred embodiment, in the fourth step, carbon dioxide is injected into the reaction kettle while the reaction kettle is heated and pressurized, so that the internal pressure of the reaction kettle is 2.0 and the temperature is 150 ℃.

Example 5:

different from the embodiment 4, the flame-retardant wave-absorbing polypropylene foaming bead comprises the following raw materials in parts by weight: 60 parts of flame-retardant modified polypropylene, 20 parts of composite conductive filler, 1 part of modified foaming nucleating agent, 1 part of dispersant and 1 part of antioxidant, wherein the composite conductive filler comprises the following raw materials in percentage by mass: 48% of conductive carbon black, 18% of carbon nano tube, 15% of silver-plated conductive glass fiber, 15% of mica and 4% of coupling agent.

The flame-retardant and wave-absorbing polypropylene foam beads prepared in the above examples 1 to 5 were prepared into plates by an EPP forming machine, and the plates were used as experimental group 1, experimental group 2, experimental group 3, experimental group 4, and experimental group 5, respectively, and the plate prepared from the conventional polypropylene foam beads was used as a control group, and the surface resistance, the electromagnetic wave absorption performance, and the vertical combustion level of the selected plate were first detected. The test results are shown in table one:

watch 1

As can be seen from the table I, compared with the plate produced by the traditional polypropylene expanded bead, the plate produced by the polypropylene expanded bead of the invention has better conductivity, enhanced wave-absorbing effect and better flame-retardant effect, the proportion of the composite conductive filler is changed in the embodiment 4 and the embodiment 5, the conductivity is better when the conductive carbon black is more, the wave-absorbing performance is better when the silver-plated conductive glass fiber is more, the plate is composed of flame-retardant modified polypropylene, the composite conductive filler and the modified foaming nucleating agent, the polypropylene is subjected to flame-retardant modification by using the polyolefin-based silsesquioxane flame retardant, the magnesium hydroxide and the phosphate, so that the polypropylene particles have good conductivity, the composite conductive filler comprises conductive carbon black, carbon nano tubes, silver-plated conductive glass fibers, mica and a coupling agent, and the ideal grape string-shaped conductive filler can be obtained by compounding the conductive carbon black, the carbon nano tubes and the mica, the conductive performance of the polypropylene foaming beads can be effectively improved by adding the silver-plated conductive glass fibers, the silver-plated conductive glass fibers have excellent electromagnetic shielding performance, the foaming nucleating agent adopts modified mesoporous silica, and polymer grafting reaction is carried out on the nano mesoporous silica after hole expanding treatment, so that the nano mesoporous silica has excellent dispersibility and good interface compatibility, the processing effect of the foaming nucleating agent on polypropylene particles is better, and the conductive performance and the wave absorbing performance of the polypropylene foaming beads are effectively improved.

And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.