CN110527129B - Polyether-ether-ketone porous foam material and preparation method thereof - Google Patents
Polyether-ether-ketone porous foam material and preparation method thereof Download PDFInfo
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Abstract
A porous foam material of polyether-ether-ketone and a preparation method thereof belong to the technical field of polymer material preparation. Uniformly mixing polyether-ether-ketone powder, a reinforcing filler and a foaming agent under high-speed stirring, putting the mixture into a mold cavity and preheating the mixture on a vulcanizing instrument; then applying pressure to the mold cavity, controlling proper foaming temperature for foaming, keeping the pressure, and cooling; and cooling to a certain temperature to obtain the porous polyether-ether-ketone foam material. The method can regulate and control the foaming rate by controlling the foaming temperature, properly improve the foaming temperature, accelerate the diffusion of gas generated by the foaming agent in the polymer, reduce the foaming time and improve the foaming efficiency. The invention has simple process, convenient operation, mild processing conditions and easy popularization.
Description
Technical Field
The invention belongs to the technical field of high polymer material preparation, and particularly relates to a high-performance polyether-ether-ketone porous foam material and a preparation method thereof.
Background
The special engineering plastic is a polymer material which has higher comprehensive performance and long-term use temperature of more than 150 ℃ and is mainly applied to the high-technology field, so the special engineering plastic is also called high-performance engineering plastic or heat-resistant engineering plastic, and polyether-ether-ketone is an important class of the high-performance engineering plastic or the heat-resistant engineering plastic. The polyetheretherketone serving as a crystalline polymer material has the advantages of high heat resistance, radiation resistance, chemical resistance, impact resistance, creep resistance, good flame retardance, excellent electrical property and the like, and is widely applied to the technical fields of high-speed rail transit systems, low-energy-consumption and new-energy automobiles, high-efficiency transportation technologies and equipment, aerospace, electronics, information, national defense and the like.
The foam material is composed of a rigid skeleton and internal holes, and has a plurality of excellent properties since the 20 th century and the 40 th era, such as: the composite material has the advantages of high specific strength, light weight, material saving, good heat insulation, capability of absorbing impact load, low heat conductivity, excellent shock absorption performance, sound insulation, heat insulation and other performances, and is applied to the aspects of household appliances, material packaging, insulating materials, daily trips, sports equipment, chemical industry and the like. The polymer foaming material with excellent performance plays an important role in the field of national defense. In order to further expand the application range of the polyether-ether-ketone material, the preparation of the polyether-ether-ketone foamed plastic has very important significance.
Whatever foaming process is adopted, the required foaming product can be prepared only by completing the following steps: (1) forming a polymer/gas system; (2) initiating nucleation by bubbles; (3) bubble growth and control. The three steps are the basis of the processing theory of the polymer foaming plastic.
The foaming method of foamed product is mainly physical foaming method and chemical foaming method, the chemical foaming is a method of adding chemical foaming agent to be heated and decomposed or making chemical reaction between raw material components to produce gas to make plastic melt full of foam holes, the physical foaming is a method of dissolving gas or liquid in high molecular plastic and then making it expand or vaporize and foam, but this method needs special injection moulding machine and other auxiliary equipment, the technical requirement is very high, and it is not convenient for industrialization.
There are many kinds of forming processes for foamed products, and the forming methods for industrially producing foamed sheets mainly include extrusion, injection and molding, but the extrusion and injection have the disadvantage that it is difficult to produce foamed products having a large thickness. At present, the most common method for industrially preparing the foamed sheet with larger thickness is a die pressing method, and the die pressing method has the following advantages: the method can prepare the high polymer plastic foaming plate with larger thickness, is convenient and easy to operate, has low equipment cost, and can also prepare high polymer plastic foaming materials which can not be realized by other processes.
Chinese patent CN102924743A discloses a crystallinePreparation method of hard polyether-ether-ketone porous foam material by using supercritical CO2The foaming agent is used for preparing the polyether-ether-ketone foam, but the method has the disadvantages of complicated equipment, difficult operation, high technical requirement and inconvenience for industrialization. Chinese patent CN105367994A discloses a light wear-resistant micro-foamed polyether-ether-ketone composite material, a preparation method and application thereof, wherein a high-temperature foaming agent is used for preparing a micro-foamed polyether-ether-ketone material, but the foaming ratio of the obtained material is too small, and the apparent density of the material is 1.35g/cm3The above. Chinese patent 03118818.4 discloses a method for producing microcellular engineering plastics by using a molding method and combining a chemical foaming agent, but the plastic matrix used in the method is limited to sheet materials and a foaming agent substrate needs to be prepared first, which greatly limits the popularization of the method. In conclusion, for preparing the porous foam material of polyether-ether-ketone, the existing method has either limited foaming ratio or complex process.
Disclosure of Invention
The invention aims to provide a porous foam material of polyetheretherketone and a preparation method thereof, aiming at the defects of the prior art.
The invention relates to a preparation method of a porous polyether-ether-ketone foam material, which comprises the following steps:
1) mixing polyether-ether-ketone powder, a reinforcement filler and a foaming agent for 0.5-2 min under high-speed stirring at 20000-30000 r/min to obtain a polyether-ether-ketone mixture;
2) putting the polyether-ether-ketone mixture obtained in the step 1) into a mold cavity, then placing the mold cavity on a vulcanizer with a certain temperature, and preheating for a certain time;
3) applying pressure to the die cavity in the step 2), controlling proper foaming temperature, foaming for a period of time, keeping the pressure, and cooling;
4) after cooling to a certain temperature, the porous foam material of polyetheretherketone of the invention is obtained.
The polyether-ether-ketone powder in the step 1) is 50-1000 meshes, and the melt index of the polyether-ether-ketone powder is 16-120 g/10min (the test temperature is 400 ℃, and the load is 5 Kg);
the reinforcement filler in the step 1) comprises but is not limited to carbon nano tubes, graphite, graphene, carbon black, carbon fiber powder, boron nitride, aluminum nitride, copper powder, silver powder, nickel powder and the like, and the mass amount of the reinforcement filler is 0-40% of that of polyether-ether-ketone powder;
the foaming agent in the step 1) is one of hindered amine light stabilizer 3346, hindered amine light stabilizer 196 and light stabilizer 610, and the mass amount of the foaming agent is 1-20% of polyether-ether-ketone powder;
preheating temperature of the vulcanizer in the step 2) is 350-390 ℃, and preheating time is 5-10 min;
in the step 3), the pressure applied to the mold cavity is 3-50 MPa, the temperatures of the heating upper plate and the heating lower plate of the vulcanizing instrument are 360-410 ℃, the temperatures of the heating upper plate and the heating lower plate can be kept consistent or have a certain temperature difference, the temperature difference range is 0-30 ℃, and the foaming time is 10-20 min;
the cooling temperature in step 4) is 200 ℃ or below.
Compared with the existing preparation method of the polyether-ether-ketone foam plastic, the preparation method has the following advantages:
the method can directly foam and form the powder without the process of preparing a polymer sheet, and can also be used for plastic which is not easy to foam by adopting an extrusion method and an injection molding method. The used equipment is a conventional vulcanizer (HY 4016 of Anhui Huabiao detection apparatus Co., Ltd.) with a heating upper plate and a heating lower plate and a die without special sealing, and the equipment cost is low and the cost is low. The method can regulate and control the foaming rate by controlling the foaming temperature, properly improve the foaming temperature, accelerate the diffusion of gas generated by the foaming agent in the polymer, reduce the foaming time and improve the foaming efficiency. The invention has simple process, convenient operation, mild processing conditions and easy popularization.
Drawings
FIG. 1: scanning electron micrographs of the polyetheretherketone porous foam obtained in example 1;
FIG. 2: the compression set curve of the porous peek foam material obtained in example 1 (compression set on the abscissa and compression stress on the ordinate);
FIG. 1 shows a scanning electron micrograph of a porous foam of polyetheretherketone. From a scanning electron microscope, the hard polyetheretherketone porous foam material has a uniform porous structure, and the pore size is about 420 μm.
Fig. 2 shows the compression set curve of the prepared porous foam material of polyetheretherketone. When the compression set is 10%, the maximum compressive strength of the foam material is 9.89 MPa.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
Example 1:
placing 16.0g of polyether-ether-ketone powder (100 meshes) with a melt index of 20g/10min and 33460.4 g of hindered amine light stabilizer into a high-speed stirrer, stirring at 25000r/min for 1.5min to obtain a polyether-ether-ketone mixture, placing the polyether-ether-ketone mixture into a stainless steel mold cavity, placing the mold cavity on a vulcanizer with an upper heating plate and a lower heating plate both having a temperature of 365 ℃, preheating for 6min, applying a pressure of 20MPa to the mold cavity, controlling the temperatures of the upper heating plate and the lower heating plate to be 370 ℃, foaming for 15min, maintaining the pressure of 20MPa, cooling to 200 ℃, and taking out a polyether-ether-ketone foaming sample from the mold cavity to obtain the polyether-ether-ketone porous foam material, wherein the average pore diameter of the polyether-ether-ketone porous foam material is 420 micrometers, and the cell density is 7.86 multiplied by 107Per cm3The maximum compressive strength was 9.89 MPa.
Example 2:
placing 16.0g of polyether-ether-ketone powder (400 meshes) with a melt index of 30g/10min and 1960.4 g of hindered amine light stabilizer into a high-speed stirrer at 25000r/min, mixing for 1.5min to obtain polyether-ether-ketone mixture, placing the polyether-ether-ketone mixture into a stainless steel mold cavity, placing the mold on a vulcanizer with an upper heating plate and a lower heating plate at 370 ℃, preheating for 7min, applying a pressure of 10MPa to the mold cavity, controlling the temperatures of the upper heating plate and the lower heating plate to be 380 ℃, foaming for 17min, maintaining the pressure of 10MPa, cooling to 190 ℃, and allowing polyether-ether-ketone to foamTaking the foam sample out of the die cavity to obtain the porous foam material of the polyether-ether-ketone, wherein the average pore diameter of the porous foam material of the polyether-ether-ketone is 487 mu m, and the cell density is 2.93 multiplied by 107Per cm3The maximum compressive strength was 8.0 MPa.
Example 3:
placing 16.0g of polyether-ether-ketone powder (600 meshes) with a melt index of 40g/10min, 0.70g of graphene and 6100.8 g of light stabilizer into a high-speed stirrer at a stirring speed of 25000r/min, mixing for 1.5min to obtain a polyether-ether-ketone mixture, placing the polyether-ether-ketone mixture into a stainless steel mold cavity, placing the mold on a vulcanizer with a heating upper plate and a heating lower plate at a temperature of 370 ℃, preheating for 8min, applying a pressure of 40MPa to the mold cavity, controlling the temperature of the heating upper plate to be 390 ℃, heating the temperature of the heating lower plate to be 380 ℃, foaming for 17min, maintaining the pressure of 40MPa, cooling to 190 ℃, and taking out a polyether-ether-ketone foaming sample from the mold cavity to obtain the polyether-ether-ketone porous foam material, wherein the average pore diameter of the polyether-ether-ketone porous foam material is 400 mu m, and the cell density is 4.7Per cm3The maximum compressive strength was 5.3 MPa.
Example 4:
placing 16.0g of polyether-ether-ketone powder (800 meshes) with a melt index of 90g/10min, 4.0g of graphite and 33461.12 g of hindered amine light stabilizer into a high-speed stirrer at a stirring speed of 25000r/min, mixing for 1.5min to obtain a polyether-ether-ketone mixture, placing the polyether-ether-ketone mixture into a stainless steel mold cavity, placing the mold on a vulcanizer with an upper heating plate and a lower heating plate both at 385 ℃, preheating for 9min, applying 25MPa of pressure to the mold cavity, controlling the temperature of the upper heating plate to be 390 ℃, heating the lower heating plate to be 370 ℃, foaming for 19min, maintaining the pressure of 25MPa, cooling to 180 ℃, taking out a polyether-ether-ketone foaming sample from the mold cavity to obtain the polyether-ether-ketone porous foam material, wherein the average pore diameter of the polyether-ether-ketone porous foam material is 328 mu m, and the cell density is 7.84X 107Per cm3The maximum compressive strength was 7.4 MPa.
Example 5:
polymerizing at a melt index of 20g/10minPlacing 16.0g of polyetheretherketone powder (900 meshes) and 33460.4 g of hindered amine light stabilizer into a high-speed stirrer, stirring at 25000r/min for 1.5min to obtain a polyetheretherketone mixture, placing the polyetheretherketone mixture into a stainless steel mold cavity, placing the mold on a vulcanizer with an upper heating plate and a lower heating plate at 390 ℃, preheating for 10min, applying a pressure of 19MPa to the mold cavity, controlling the temperature of the upper heating plate to 380 ℃, the temperature of the lower heating plate to 400 ℃, foaming for 20min, keeping the pressure of 19MPa, cooling to 170 ℃, taking a polyetheretherketone foaming sample out of the mold cavity to obtain the polyetheretherketone porous foam material, wherein the mean pore diameter of the polyetheretherketone porous foam material is 388 mu m, and the cell density is 4.6 multiplied by 107Per cm3The maximum compressive strength was 8.1 MPa.
Example 6:
16.0g of polyether-ether-ketone powder (700 meshes) with the melt index of 30g/10min, 1.50g of boron nitride and 33463.2 g of hindered amine light stabilizer are placed in a high-speed stirrer, the stirring speed is 25000r/min, the mixture is mixed for 1.5min to obtain a polyether-ether-ketone mixture, the polyether-ether-ketone mixture is placed in a stainless steel mold cavity, the mold is placed on a vulcanizer with the temperature of 380 ℃ for heating an upper plate and a lower plate, the preheating is carried out for 8min, the pressure of 10MPa is applied to the mold cavity, the temperature of the upper plate is controlled to be 370 ℃, the temperature of the lower plate is heated to be 380 ℃, the foaming is carried out for 12min, the pressure of 10MPa is kept, the temperature is cooled to be 180 ℃, and a polyether-ether-ketone foaming sample is taken out of the mold cavity, so that a polyether-ether7Per cm3The maximum compressive strength was 6.6 MPa.
Example 7:
placing 16.0g of polyether-ether-ketone powder (60 meshes) with a melt index of 30g/10min, 2.50g of copper powder and 33460.4 g of hindered amine light stabilizer into a high-speed stirrer at 25000r/min, mixing for 1.5min to obtain a polyether-ether-ketone mixture, placing the polyether-ether-ketone mixture into a stainless steel mold cavity, placing the mold on a vulcanizer with an upper plate and a lower plate heated at 385 ℃, preheating for 7min, and applying a pressure of 9MPa to the mold cavityControlling the temperature of the upper heating plate to be 360 ℃, the temperature of the lower heating plate to be 370 ℃, foaming for 10min, maintaining the pressure of 9MPa, cooling to 185 ℃, taking out a polyether-ether-ketone foaming sample from the die cavity, and obtaining the polyether-ether-ketone porous foam material, wherein the average pore diameter of the polyether-ether-ketone porous foam material is 498 mu m, and the cell density is 2.65 multiplied by 107Per cm3The maximum compressive strength was 6.5 MPa.
Example 8:
placing 16.0g of polyether-ether-ketone powder (700 meshes) with a melt index of 80g/10min and 33460.4 g of hindered amine light stabilizer into a high-speed stirrer, stirring at 25000r/min for 1.5min to obtain a polyether-ether-ketone mixture, placing the polyether-ether-ketone mixture into a stainless steel mold cavity, placing the mold on a vulcanizer with an upper plate and a lower plate heated at 350 ℃, preheating for 7min, applying a pressure of 45MPa to the mold cavity, controlling the temperature of the upper plate at 375 ℃, heating the lower plate at 370 ℃, foaming for 15min, maintaining the pressure of 45MPa, cooling to 50 ℃, and taking out a polyether-ether-ketone foaming sample from the mold cavity to obtain the polyether-ether-ketone porous foam material, wherein the average pore diameter of the polyether-ether-ketone porous material is 430 mu m, and the cell density is 5.64 multiplied by 107Per cm3The maximum compressive strength was 7.5 MPa.
Example 9:
placing 16.0g of polyether-ether-ketone powder (500 meshes) with a melt index of 19g/10min, 6.4g of carbon fiber powder and 33461.60 g of hindered amine light stabilizer into a high-speed stirrer at a stirring speed of 25000r/min, mixing for 1.5min to obtain a polyether-ether-ketone mixture, placing the polyether-ether-ketone mixture into a stainless steel mold cavity, placing the mold on a vulcanizer with an upper heating plate and a lower heating plate both at 375 ℃, preheating for 5min, applying a pressure of 10MPa to the mold cavity, controlling the temperature of the upper heating plate at 375 ℃, the temperature of the lower heating plate at 375 ℃, foaming for 17min, maintaining the pressure of 10MPa, cooling to 150 ℃, and taking out a polyether-ether-ketone foaming sample from the mold cavity to obtain the polyether-ether-ketone porous foam material, wherein the average pore diameter of the polyether-ether-ketone porous foam material is 328 mu m, and the cell density is 7.37Per cm3Maximum pressure ofThe compressive strength was 7.89 MPa.
Claims (4)
1. A preparation method of a porous polyether-ether-ketone foam material comprises the following steps:
1) uniformly mixing polyether-ether-ketone powder, a reinforcement filler and a foaming agent under high-speed stirring to obtain a polyether-ether-ketone mixture; the foaming agent is a hindered amine light stabilizer 3346, a hindered amine light stabilizer 196 or a light stabilizer 610, and the mass amount of the foaming agent is 1-20% of that of the polyether-ether-ketone powder;
2) putting the polyether-ether-ketone mixture obtained in the step 1) into a mold cavity, then placing the mold cavity on a vulcanizer at 350-390 ℃, and preheating for 5-10 min;
3) applying pressure of 3-50 MPa to the die cavity in the step 2), enabling the temperatures of the heating upper plate and the heating lower plate of the vulcanizing instrument to be 360-410 ℃, enabling the temperatures of the heating upper plate and the heating lower plate to be consistent or enabling the heating upper plate and the heating lower plate to have a certain temperature difference for foaming, enabling the temperature difference range to be 0-30 ℃, enabling the foaming time to be 10-20 min, keeping the pressure, and cooling;
4) after cooling to 200 ℃ or below, thereby obtaining the porous foam material of polyetheretherketone.
2. The method for preparing porous foam material of polyetheretherketone according to claim 1, wherein the method comprises the following steps: the polyether-ether-ketone powder in the step 1) is 50-1000 meshes, the melt index of the powder is 16-120 g/10min, the test temperature is 400 ℃, and the load is 5 Kg.
3. The method for preparing porous foam material of polyetheretherketone according to claim 1, wherein the method comprises the following steps: the reinforcement filler in the step 1) is carbon nano tube, graphite, graphene, carbon black, carbon fiber powder, boron nitride, aluminum nitride, copper powder, silver powder or nickel powder, and the mass amount of the reinforcement filler is 0-40% of that of the polyether-ether-ketone powder.
4. A porous foam material of polyetheretherketone, characterized in that: is prepared by the method of any one of claims 1 to 3.
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| CN112454949B (en) * | 2020-11-12 | 2022-12-02 | 湖南欧亚碳纤维复合材料有限公司 | Preparation process of carbon fiber part with built-in foaming mold |
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| CN1438104A (en) * | 2003-03-21 | 2003-08-27 | 湖北大学 | Method for making microporous foamed engineering plastic by mould pressing |
| CN101229682A (en) * | 2008-02-22 | 2008-07-30 | 四川大学 | Method of semi-vitreous extrusion molding manufacturing for portiforium type millipore plastics extrusions |
| WO2013092682A2 (en) * | 2011-12-22 | 2013-06-27 | Designergy Sa | Structurally integrated solar building element |
| CN107857891A (en) * | 2017-09-30 | 2018-03-30 | 中国科学院长春应用化学研究所 | The preparation method of polymer foams |
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| CN102167840B (en) * | 2011-04-12 | 2012-09-05 | 姜修磊 | Method for preparing polymer microporous foaming material by supercritical mould foaming |
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|---|---|---|---|---|
| CN1438104A (en) * | 2003-03-21 | 2003-08-27 | 湖北大学 | Method for making microporous foamed engineering plastic by mould pressing |
| CN101229682A (en) * | 2008-02-22 | 2008-07-30 | 四川大学 | Method of semi-vitreous extrusion molding manufacturing for portiforium type millipore plastics extrusions |
| WO2013092682A2 (en) * | 2011-12-22 | 2013-06-27 | Designergy Sa | Structurally integrated solar building element |
| CN107857891A (en) * | 2017-09-30 | 2018-03-30 | 中国科学院长春应用化学研究所 | The preparation method of polymer foams |
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