CN113308084B - Polyether ketone composite material and preparation method thereof - Google Patents
Polyether ketone composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyether ketone composite material and a preparation method thereof, wherein the preparation method of the polyether ketone composite material comprises the following steps: adding thermotropic liquid crystal polymer with the particle size less than 100nm in the in-situ polymerization process of the polyether ketone so as to compound the polyether ketone and the thermotropic liquid crystal polymer to obtain a reactant; and separating the reactants to remove free thermotropic liquid crystal polymer and polyether ketone to obtain the polyether ketone composite material. The preparation method of the polyether ketone composite material can improve the composite compatibility of the polyether ketone and the thermotropic liquid crystal polymer, so that the polyether ketone composite material does not split phases and the melt viscosity is obviously reduced.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a polyether ketone composite material and a preparation method thereof.
Background
Polyether ketone (PEKK) is a novel special engineering plastic, is known as a material of a pyramid tip, has excellent mechanical property, self-lubricating property, chemical corrosion resistance, high temperature resistance, radiation resistance and the like, is a thermoplastic semi-crystalline material, has multiple forming and processing modes and strong plasticity, and has extremely high requirements in the fields of chemical corrosion resistance, aerospace, electronic and electrical appliances, automobiles, medical appliances and the like. However, the chemical structure of the polyether ketone determines that the polyether ketone has high viscosity in a molten state, so that the forming and processing of the polyether ketone are difficult, and the application of the polyether ketone is limited to a certain extent.
Thermotropic Liquid Crystal Polymer (TLCP) is high-strength and high-modulus engineering plastic developed in the later 70 years of the last century, has a plurality of excellent properties, is usually compounded with thermoplastic materials to improve the properties of the thermoplastic materials, however, the thermotropic liquid crystal polymer has the problem of poor compatibility when compounded with the thermoplastic materials, is easy to generate phase separation, and is difficult to exert the modification effect of the thermotropic liquid crystal polymer on the thermoplastic materials.
Disclosure of Invention
Therefore, the polyether ketone composite material and the preparation method thereof are needed to provide the polyether ketone composite material which can improve the compatibility of the polyether ketone and the thermotropic liquid crystal polymer composite, ensure that the polyether ketone composite material does not phase separate and obviously reduce the melt viscosity.
A preparation method of a polyether ketone composite material comprises the following steps:
mixing a thermotropic liquid crystal polymer with a reaction monomer of polyether ketone for in-situ polymerization to obtain a reactant, wherein the particle size of the thermotropic liquid crystal polymer is less than 100nm;
and separating the reactants to remove the free thermotropic liquid crystal polymer and the free polyether ketone to obtain the polyether ketone composite material.
In one embodiment, the method further comprises the step of performing superfine treatment on the thermotropic liquid crystal polymer to obtain the thermotropic liquid crystal polymer with the particle size of less than 100nm.
In one embodiment, the thermotropic liquid crystal polymer is ultrafined by at least one of jet milling, colloid milling and emulsification.
In one embodiment, the step of mixing the thermotropic liquid crystalline polymer with the reactive monomer of polyetherketoneketone for in situ polymerization comprises: mixing a catalyst, a solvent and the thermotropic liquid crystal polymer, cooling to-10 to-15 ℃, adding terephthaloyl chloride, isophthaloyl chloride and diphenyl ether, reacting for 1 to 2 hours, heating to 10 to 30 ℃, and continuing to react for 10 to 20 hours.
In one embodiment, the step of separating the reactants is performed by settling separation.
In one embodiment, the step of separating the reactants comprises:
providing a separation solution, wherein the separation solution is not reactive with both the polyetherketoneketone and the thermotropic liquid crystal polymer, and the density of the separation solution is between the density of the polyetherketoneketone and the density of the thermotropic liquid crystal polymer;
and (3) placing the reactant into the separation solution, stirring, standing for layering, and removing the free thermotropic liquid crystal polymer and the free polyether ketone.
In one embodiment, the separation solution is selected from at least one of an aqueous sodium hydroxide solution and an aqueous sodium chloride solution.
In one embodiment, in the polyether ketone composite material, the thermotropic liquid crystal polymer accounts for 1-50% by mass; and/or the presence of a catalyst in the reaction mixture,
the melting point temperature of the polyether ketone is in the liquid crystal state temperature interval of the thermotropic liquid crystal polymer; and/or the presence of a catalyst in the reaction mixture,
the thermotropic liquid crystal polymer has a density of 1.4g/cm 3 ～1.7g/cm 3 The density of the polyether ketone is 1.2g/cm 3 ～1.3g/cm 3 。
In one embodiment, the method further comprises the following steps: and extruding and granulating the polyether ketone composite material.
In one embodiment, before the step of separating the reactants, the method further comprises: and a step of pulverizing the reactant.
In one embodiment, the method further comprises the step of purifying the polyether ketone composite material.
In one embodiment, the step of purifying comprises: and respectively cleaning the polyether ketone composite material by adopting methanol and water, and then drying.
The polyether ketone composite material is prepared by the preparation method of the polyether ketone composite material.
The preparation method of the polyether ketone composite material comprises the steps of mixing the thermotropic liquid crystal polymer with the particle size smaller than 100nm with the reaction monomer of polyether ketone for in-situ polymerization, enabling the polymerization reaction to occur on the surface of the thermotropic liquid crystal polymer, and enabling the polyether ketone to deposit on the surface of the thermotropic liquid crystal polymer, so that the thermotropic liquid crystal polymer and the polyether ketone are compounded at the molecular level, the compatibility of the composite material is improved, and phase splitting is avoided. And then separating reactants, and removing free polyether ketone and free thermotropic liquid crystal polymer in the reaction, so as to avoid phase separation of the free polyether ketone and the free thermotropic liquid crystal polymer in the composite material and influence on the performance of the composite material, thereby utilizing the excellent melt fluidity of the thermotropic liquid crystal polymer, greatly reducing the melt viscosity of the whole composite material and improving the processing performance of the composite material. Therefore, the preparation method of the polyether ketone composite material can improve the compatibility of the polyether ketone and the thermotropic liquid crystal polymer, so that the polyether ketone composite material does not split phases and the melt viscosity is obviously reduced.
Drawings
FIG. 1 is a process flow diagram of one embodiment of a method for making a polyetherketoneketone composite;
FIG. 2 is a picture of the polyetherketoneketone composites prepared in example 4 and comparative example 2 under a fidica microscope of super field depth;
FIG. 3 is a graph of the rheology of the polyetherketoneketone prepared in example 2 and the polyetherketoneketone composites prepared in examples 4-6, example 10, and comparative examples 1-3 at different shear rates;
FIG. 4 is a graph of the rheology of the polyetherketoneketone prepared in example 3 and the polyetherketoneketone composites prepared in examples 7-9 at different shear rates.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description taken in conjunction with the accompanying drawings. The detailed description sets forth the preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The thermotropic liquid crystal polymer is an engineering plastic with high strength and high modulus, the melt viscosity is low in a liquid crystal area, a molecular chain has high orientation, and the performance of the polymer is improved. Thermotropic liquid crystal polymers are thermoplastic, and the thermotropic liquid crystal polymers and thermoplastic materials are compounded to prepare the composite material, so that the fluidity of a polymer melt can be greatly improved, and simultaneously, the thermotropic liquid crystal polymers and the thermoplastic materials can form orientation and fiber formation to a certain extent under the action of external force in the processing processes of extrusion, injection molding and the like, thereby improving the processing performance and mechanical property of a matrix material.
However, when the thermotropic liquid crystal polymer and the polyether ketone are blended to prepare the composite material, the problems of poor compatibility and easy phase separation exist, so that the performance of the prepared composite material is poor. Therefore, in this embodiment, the inventors improve the method of compounding the thermotropic liquid crystal polymer with the polyetherketoneketone, so that the thermotropic liquid crystal polymer can be uniformly mixed and dispersed with the polyetherketoneketone, and the performance of the composite material is improved.
Specifically, referring to fig. 1, a preparation method of a polyetherketoneketone composite material according to an embodiment includes the following steps:
step S110: mixing the thermotropic liquid crystal polymer with a reaction monomer of polyether ketone for in-situ polymerization to obtain a reactant.
Wherein the particle size of the thermotropic liquid crystal polymer is less than 100nm.
Specifically, the step of mixing the thermotropic liquid crystal polymer and the reaction monomer of polyether ketone for in-situ polymerization comprises the following steps: mixing a catalyst, a solvent and a thermotropic liquid crystal polymer, cooling to-10 to-15 ℃, then adding terephthaloyl chloride, isophthaloyl chloride and diphenyl ether, reacting for 1 to 2 hours, heating to 10 to 30 ℃, and continuing to react for 10 to 20 hours.
In one embodiment, the catalyst is aluminum chloride. The solvent is a mixture of dichloroethane and N-methylpyrrolidone. Furthermore, the mass ratio of the terephthaloyl chloride to the isophthaloyl chloride is 80-60. For example, the mass ratio of terephthaloyl chloride to isophthaloyl chloride is 80, 70, 30, 60. The crystallization behavior, the processing temperature, the melting point, the use temperature and the like of the material are changed by adjusting the mass ratio of the terephthaloyl chloride to the isophthaloyl chloride so as to meet different requirements.
Specifically, before step S110, the method further includes: the thermotropic liquid crystal polymer is subjected to superfine treatment to obtain the thermotropic liquid crystal polymer with the particle size less than 100nm. In the in-situ polymerization, reaction monomers, a catalyst and the like are all added into a disperse phase, and the monomers or prepolymers are soluble in a single phase, but polymers of the monomers or prepolymers are insoluble in the whole system, so that the polymerization reaction occurs on the disperse phase, and the polymers are deposited on the surface of the disperse phase.
Specifically, the thermotropic liquid crystal polymer is subjected to ultrafine processing by at least one of a jet milling method, a colloid mill method and an emulsification method. For example, the ultrafine treatment is carried out in a jet mill or an emulsifying machine. Preferably, the thermotropic liquid crystal polymer is subjected to superfine treatment by adopting a jet milling mode.
Further, the method further comprises a drying step after the step of performing ultrafine processing on the thermotropic liquid crystal polymer. Further, it was dried to constant weight.
The thermotropic liquid crystal polymer and polyether ketone composite material prepared by the in-situ polymerization method is compounded on a molecular level instead of the traditional physical blending, solves the problem of poor compatibility when the thermotropic liquid crystal polymer and a thermoplastic material are blended, avoids phase splitting, greatly reduces the melt viscosity of the whole composite material, improves the processing performance of the composite material, reduces the abrasion and energy consumption on equipment, greatly reduces the cost in molding processing, improves the mechanical property of the composite material, and has wide application prospect.
Step S120: and (4) crushing the reactant.
The reactant is crushed, so that on one hand, the composite material, the free polyether ketone and the free thermotropic liquid crystal polymer can be conveniently separated by a sedimentation method in the subsequent process, and on the other hand, impurities in the reactant can be conveniently removed by cleaning in the subsequent process, and the composite material can be conveniently purified.
Specifically, the reactant is pulverized until the particle size is 100nm or less.
Further, the pulverization method is at least one of colloid milling and emulsification.
Step S130: and separating the reactants to remove the free thermotropic liquid crystal polymer and the free polyether ketone to obtain the polyether ketone composite material.
In the step of separating the mixture, a sedimentation separation method is adopted. Specifically, the sedimentation separation method may be gravity sedimentation or centrifugal sedimentation, and among them, gravity sedimentation is preferred.
Specifically, the step of separating the reactants comprises:
providing a separation solution, wherein the separation solution is not reacted with the polyether ketone and the thermotropic liquid crystal polymer, and the density of the separation solution is between that of the polyether ketone and that of the thermotropic liquid crystal polymer;
and (3) placing the reactants into a separation solution, stirring, standing for layering, and separating the free thermotropic liquid crystal polymer and the polyether ketone.
The settling separation method is to prepare a solution which does not react with two resins, control the density of the solution to be between the two pure resins and to be close to the density of the composite material resin, and then separate the resin according to the phenomena of floating, suspending and settling caused by different densities.
Specifically, the thermotropic liquid crystalline polymer had a density of 1.4g/cm 3 ～1.7g/cm 3 . Preferably, the thermotropic liquid crystalline polymer has a density of 1.7g/cm 3 . The density of the polyether ketone is 1.2g/cm 3 ～1.3g/cm 3 . The density difference between the thermotropic liquid crystal polymer with the density and the polyether ketone is large, and the thermotropic liquid crystal polymer with the density is convenient to separate by a sedimentation method.
In one embodiment, the polyetherketoneketone has a density of 1.3g/cm 3 The density of the thermotropic liquid crystal polymer used is 1.7g/cm 3 The density of the composite material is 1.5g/cm 3 And the density of the composite material resin can be changed according to the mass percent of the thermotropic liquid crystal polymer in the composite material, but is always positioned between the two polymers.
Specifically, the separation solution is at least one selected from an aqueous sodium hydroxide solution and an aqueous sodium chloride solution. Wherein the density of the separation solution can be changed by adjusting the content of the solute in the solution so that the density of the separation solution is similar to that of the composite material.
Step S140: and purifying the polyether ketone composite material.
Wherein, the purification step comprises: and respectively cleaning the polyether ketone composite material by adopting methanol and water, and then drying. Impurities such as a catalyst remaining in the reaction can be removed by the purification treatment.
Step S150: and extruding and granulating the polyether ketone composite material.
Specifically, a twin-screw extruder is used for melt blending.
The polyether ketone composite material prepared by the steps S110 to S140 is a powder material, and the powder material has the problems of difficulty in transportation, difficulty in storage and the like, so that the granular composite material is obtained by extruding and granulating the polyether ketone composite material, and the problems of storage and transportation of the composite material are solved. In addition, the thermotropic liquid crystal polymer in the polyether ketone composite material is oriented and arranged orderly in the extrusion process, so that the mechanical property of the prepared composite material can be further improved. In addition, as the polyether ketone and the thermotropic liquid crystal polymer in the polyether ketone composite material are blended in a molecular level, the polyether ketone and the thermotropic liquid crystal polymer are directly melted and blended, and the problem of phase separation can not occur.
Specifically, the thermotropic liquid crystal polymer accounts for 1-50% of the composite material by mass percent. Preferably, the thermotropic liquid crystal polymer accounts for 20-30% of the composite material by mass percent.
Furthermore, the melting point temperature of the polyether ketone is in the liquid crystal state temperature interval of the thermotropic liquid crystal polymer, so that the thermotropic liquid crystal polymer is in a liquid crystal state in the melting and extruding process, and is oriented and regularly arranged, and the mechanical property of the composite material is improved. For example, in the raw materials for preparing the polyether ketone, the mass ratio of the terephthaloyl chloride to the isophthaloyl chloride is 80; in the raw materials for preparing the polyether ketone, the mass ratio of the terephthaloyl chloride to the isophthaloyl chloride is 70; in the raw materials for preparing the polyether ketone, the mass ratio of the terephthaloyl chloride to the isophthaloyl chloride is 60.
The preparation method of the polyether ketone composite material at least has the following advantages:
(1) The method adopts an in-situ polymerization method to prepare the thermotropic liquid crystal polymer and polyether ketone composite material, is a composite material on the molecular level rather than the traditional physical blending, solves the problem of poor compatibility when the thermotropic liquid crystal polymer and a thermoplastic material are blended, and avoids phase splitting.
(2) The preparation method of the polyether ketone composite material compounds polyether ketone and thermotropic liquid crystal polymer, utilizes the excellent melt fluidity of the thermotropic liquid crystal polymer, greatly reduces the melt viscosity of the whole composite material, improves the processing performance of the composite material, reduces the abrasion and energy consumption to equipment, and greatly reduces the cost in molding processing.
(3) The preparation method of the polyether ketone composite material can improve the mechanical property of the composite material and has wide application prospect.
The invention also provides the polyether ketone composite material of the embodiment, which is prepared by the preparation method of the polyether ketone composite material. The polyether ketone composite material has good uniformity, is not easy to phase split, has improved melt fluidity and processability, has excellent mechanical property, and has wide application prospect.
The following are specific examples:
the thermotropic liquid crystalline polymer used in the examples was obtained from Jiangsu Wott Special materials manufacturing Co., ltd, and was of type KH or KDI.
Example 1
The embodiment provides a preparation method of an ultrafine thermotropic liquid crystal polymer, which comprises the following steps:
weighing thermotropic liquid crystal polymer (TLCP, the mark of which is KH), and performing superfine treatment by using an air flow pulverizer to obtain superfine thermotropic liquid crystal polymer, wherein the particle size of the superfine thermotropic liquid crystal polymer is less than 100nm.
And weighing the KDI thermotropic liquid crystal polymer by the same method, and performing superfine treatment to obtain the superfine thermotropic liquid crystal polymer (KDI) with the particle size of less than 100nm.
Example 2
The embodiment provides a preparation method of polyether ketone powder, which comprises the following steps:
500g of AlCl are respectively added into a 1000mL three-neck bottle with a magnetic stirring and nitrogen guide pipe 3 500mL of dichloroethane and 125mL of N-methylpyrrolidone, cooling to-12 ℃ at low temperature, adding 162.4g of terephthaloyl chloride, 40.6g of isophthaloyl chloride and 160mL of diphenyl ether while stirring, reacting at the temperature for 1.5 hours, then heating to room temperature for reacting for 15 hours, and after the reaction is finished, adding 100mL of methanol to quench so as to obtain a white colloid. And (3) crushing the white colloid, sequentially cleaning the white colloid with methanol and deionized water, and finally placing the product in a drying oven to be dried to constant weight at 60 ℃ to obtain polyether ketone powder (T/I = 80/20).
Example 3
The embodiment provides a preparation method of polyether ketone powder, which comprises the following steps:
500g of AlCl are respectively added into a 1000mL three-neck bottle with a magnetic stirring and nitrogen guide pipe 3 500mL of dichloroethane and 125mL of N-methylpyrrolidone, cooling to-12 ℃ at low temperature, adding 142.1g of terephthaloyl chloride, 60.9g of isophthaloyl chloride and 160mL of diphenyl ether while stirring, reacting at the temperature for 1.5 hours, then heating to room temperature for reacting for 15 hours, and after the reaction is finished, adding 100mL of methanol to quench so as to obtain a white colloid. Crushing the white colloid, sequentially washing with methanol and deionized water, and finally placing the product in an oven to dry to constant weight at 60 ℃ to obtain polyether ketone powder (T/I = 70/30).
Example 4
The embodiment provides a preparation method of a polyether ketone composite material, which comprises the following steps:
41.4g of the ultrafine thermotropic liquid crystalline polymer (having a trade name of KH) prepared in example 1 and 500g of AlCl were charged into a 1000mL three-necked flask equipped with a magnetic stirrer and a nitrogen gas introduction tube, respectively 3 500mL of dichloroethane and 125mL of N-methylpyrrolidone, cooling to-12 ℃ at low temperature, adding 162.4g of terephthaloyl chloride, 40.6g of isophthaloyl chloride and 160mL of diphenyl ether while stirring, reacting at the temperature for 1.5 hours, then heating to room temperature for reacting for 15 hours, and after the reaction is finished, adding 100mL of methanol to quench so as to obtain a white colloid. And crushing the white colloid to obtain mixture powder.
The powder of the mixture is put into the mixer with a density of 1.5g/cm 3 The sodium hydroxide solution of (2) is separated by a sedimentation separation method, specifically, the mixture powder is put into a solution having a density of 1.5g/cm 3 Stirring and dispersing the mixture in a sodium hydroxide aqueous solution, and then standing to generate layering: floating on the upper layer was a density of 1.29g/cm 3 The middle layer is suspended with the density of 1.29g/cm 3 To 1.7g/cm 3 The lower layer is sinking and floating, and the density is 1.7g/cm 3 The thermotropic liquid crystal polymer and polyether ketone (TLCP/PEKK) composite material alloy is obtained after the thermotropic liquid crystal polymer powder is obtained, the thermotropic liquid crystal polymer and polyether ketone composite material powder is sequentially washed by methanol and deionized water, filtered, placed in a drying oven to be dried to constant weight at 120 ℃, finally melted and blended by a double-screw extruder and granulated.
Example 5
The embodiment provides a preparation method of a polyether ketone composite material, which comprises the following steps:
93.3g of the ultrafine thermotropic liquid crystalline polymer (having a trade name of KH) prepared in example 1 and 500g of AlCl were charged into a 1000mL three-necked flask equipped with a magnetic stirrer and a nitrogen gas introduction tube, respectively 3 500mL of dichloroethane, 125mL of N-methylpyrrolidone, and 162.4g of terephthaloyl chloride, 40.6g of isophthaloyl chloride and 160mL of diphenyl ether were added while stirring at a low temperature of-12 ℃ to react at this temperature for 1.5 hours, and then the temperature was raisedThe reaction was allowed to warm to room temperature for 15 hours, and after completion of the reaction, 100mL of methanol was added and the reaction was quenched to give a white colloid. And crushing the white colloid to obtain mixture powder.
The powder of the mixture is put into the mixer with a density of 1.5g/cm 3 The sodium hydroxide solution of (2) is separated by a sedimentation separation method, specifically, the mixture powder is put into a solution having a density of 1.5g/cm 3 Stirring and dispersing the sodium hydroxide aqueous solution, and standing to generate layering: floating on the upper layer was a density of 1.29g/cm 3 The middle layer is suspended with the density of 1.29g/cm 3 To 1.7g/cm 3 The lower layer is sinking and floating, and the density is 1.7g/cm 3 The thermotropic liquid crystal polymer and polyether ketone composite material alloy is obtained by obtaining pure thermotropic liquid crystal polymer and polyether ketone composite material powder, sequentially cleaning with methanol and deionized water, filtering, placing the powder in an oven to be dried to constant weight at 120 ℃, finally melting and blending by a double-screw extruder, and granulating to obtain the thermotropic liquid crystal polymer and polyether ketone (TLCP/PEKK) composite material alloy.
Example 6
The embodiment provides a preparation method of a polyether ketone composite material, which comprises the following steps:
159.9g of the ultrafine thermotropic liquid crystalline polymer (having a trade name of KH) prepared in example 1 and 500g of AlCl were charged into a 1000mL three-necked flask equipped with a magnetic stirrer and a nitrogen gas introduction tube, respectively 3 500mL of dichloroethane and 125mL of N-methylpyrrolidone, reducing the temperature to-12 ℃ while stirring, adding 162.4g of terephthaloyl chloride, 40.6g of isophthaloyl chloride and 160mL of diphenyl ether, reacting at the temperature for 1.5 hours, then heating to room temperature for reacting for 15 hours, and after the reaction is finished, adding 100mL of methanol to quench so as to obtain a white colloid. The white colloid is smashed to obtain the reactant powder.
The reactant powder was charged to a density of 1.5g/cm 3 The reaction mixture was separated by sedimentation separation, and specifically, the reaction mixture powder was poured into a solution having a density of 1.5g/cm 3 Stirring and dispersing the sodium hydroxide aqueous solution, and standing to generate layering: floating on the upper layer was density 1.29g/cm 3 The middle layer is suspended with the density of 1.29g/cm 3 To 1.7g/cm 3 The lower layer is sinking and floating, and the density is 1.7g/cm 3 Separating the thermotropic liquid crystal polymer powder to obtain pure thermotropic liquid crystal polymer and polyether ketone composite material powder, sequentially cleaning with methanol and deionized water, carrying out suction filtration, placing the powder in a drying oven, drying to constant weight at 120 ℃, finally carrying out melt blending by using a double-screw extruder, and granulating to obtain the thermotropic liquid crystal polymer and polyether ketone (TLCP/PEKK) composite material alloy.
Example 7
The embodiment provides a preparation method of a polyether ketone composite material, which is similar to the preparation method of the polyether ketone composite material in the embodiment 4, and is different in that the mass of terephthaloyl chloride and isophthaloyl chloride is 142.1g and 60.9g respectively, the thermotropic liquid crystal polymer used is the superfine thermotropic liquid crystal polymer (with the brand name of KDI) prepared in the embodiment 1, and in the obtained polyether ketone composite material, T/I =70/30.
Example 8
This example provides a preparation method of a polyetherketoneketone composite material, which is similar to the preparation method of the polyetherketoneketone composite material in example 5, except that the mass of terephthaloyl chloride and isophthaloyl chloride is 142.1g and 60.9g, respectively, the thermotropic liquid crystal polymer used is the ultrafine thermotropic liquid crystal polymer (brand KDI) prepared in example 1, and in the obtained polyetherketoneketone composite material, T/I =70/30.
Example 9
The present example provides a preparation method of a polyetherketoneketone composite material, which is similar to the preparation method of the polyetherketoneketone composite material in example 6, except that the mass of terephthaloyl chloride and isophthaloyl chloride is 142.1g and 60.9g, respectively, the thermotropic liquid crystal polymer used is the ultrafine thermotropic liquid crystal polymer (brand No. KDI) prepared in example 1, and T/I =70/30 in the obtained polyetherketoneketone composite material.
Example 10
This example provides a preparation method of a polyetherketoneketone composite material, which is similar to the preparation method of the polyetherketoneketone composite material in example 4, except that the polyetherketoneketone composite material powder is purified and dried, and then is not subjected to extrusion granulation. The method comprises the following specific steps:
41.4g of the ultrafine thermotropic liquid crystalline polymer (having a trade name of KH) prepared in example 1 and 500g of AlCl were charged into a 1000mL three-necked flask equipped with a magnetic stirrer and a nitrogen gas introduction tube, respectively 3 500mL of dichloroethane and 125mL of N-methylpyrrolidone, cooling to-12 ℃ at low temperature, adding 162.4g of terephthaloyl chloride, 40.6g of isophthaloyl chloride and 160mL of diphenyl ether while stirring, reacting at the temperature for 1.5 hours, then heating to room temperature for reacting for 15 hours, and after the reaction is finished, adding 100mL of methanol to quench so as to obtain a white colloid. The white colloid is smashed to obtain the reactant powder.
The reactant powder is put into the reactor with the density of 1.5g/cm 3 The reaction mixture was separated by sedimentation separation, and specifically, the reaction mixture powder was put into a reactor having a density of 1.5g/cm 3 Stirring and dispersing the sodium hydroxide aqueous solution, and standing to generate layering: floating on the upper layer was a density of 1.29g/cm 3 The middle layer is suspended with the density of 1.29g/cm 3 To 1.7g/cm 3 The lower layer is sinking and floating, and the density is 1.7g/cm 3 Separating the thermotropic liquid crystal polymer powder to obtain pure thermotropic liquid crystal polymer and polyether ketone composite material powder, sequentially cleaning the powder by using methanol and deionized water, performing suction filtration, and placing the powder in a drying oven to dry the powder to constant weight at 120 ℃ to obtain the thermotropic liquid crystal polymer and polyether ketone (TLCP/PEKK) composite material.
Comparative example 1
Comparative example 1 provides a preparation method of a polyetherketoneketone composite material, similar to the preparation method of the polyetherketoneketone composite material of example 4, except that the thermotropic liquid crystalline polymer (having a trade name of KH) used in this example was not ultrafinely treated and had a particle size of 300 to 500 μm.
Comparative example 2
Comparative example 2 provides a method of preparing a polyetherketoneketone composite comprising the steps of:
373.24g of the polyether ketone powder prepared in example 2 and 41.4g of the superfine thermotropic liquid crystal polymer (with the grade of KH) prepared in example 1 were melted and blended by a twin-screw extruder, and granulated to obtain a thermotropic liquid crystal polymer and polyether ketone (TLCP/PEKK) composite material alloy.
Comparative example 3
Comparative example 3 provides a method of preparing a polyetherketoneketone composite comprising the steps of:
41.4g of the ultrafine thermotropic liquid crystalline polymer (having a trade name of KH) prepared in example 1 and 500g of AlCl were charged into a 1000mL three-necked flask equipped with a magnetic stirrer and a nitrogen gas introduction tube, respectively 3 500mL of dichloroethane and 125mL of N-methylpyrrolidone, cooling to-12 ℃ at low temperature, adding 162.4g of terephthaloyl chloride, 40.6g of isophthaloyl chloride and 160mL of diphenyl ether while stirring, reacting at the temperature for 1.5 hours, then heating to room temperature for reacting for 15 hours, and after the reaction is finished, adding 100mL of methanol to quench so as to obtain a white colloid. Crushing the white colloid to obtain reactant powder, sequentially cleaning with methanol and deionized water, performing suction filtration, placing the powder in an oven, drying to constant weight at 120 ℃, finally performing melt blending by using a double-screw extruder, and granulating to obtain the thermotropic liquid crystal polymer and polyether ketone (TLCP/PEKK) composite material alloy.
The following are test sections:
(1) The compatibility of the polyetherketoneketone composite materials prepared in example 4 and comparative example 2 was tested at 3000 times magnification using a superfield come microscope, and the experimental data shown in fig. 2 were obtained.
From the two photographs in fig. 2, it can be seen that the left side of the TLCP/PEKK composite material manufactured by the embodiment 4 of the present invention has particularly good compatibility, and the TLCP is arranged in the PEKK resin in an oriented state and has no phase separation structure; the right side of the TLCP/PEKK composite material prepared by adopting the conventional industrial physical blending in the comparative example 2 has an obvious two-phase structure and poor compatibility.
(2) Rheological property tests were performed at different shear rates using 10 thermotropic liquid crystal polymer and polyether ketone composite materials prepared in examples 4 to 10 and comparative examples 1 to 3 and 2 samples of different grades of polyether ketone (PEKK, T/I =80/20 and T/I = 70/30) pure resin in examples 2 to 3, the test data are shown in tables 1 and 2 below, and the test data in tables 1 and 2 are plotted to obtain the rheological curves of the PEKK and the TLCP/PEKK composite materials at different shear rates as shown in fig. 3 and 4. The test conditions were: the temperature is 390 ℃; the shear rates were 100/s, 200/s, 500 1/s, 800 1/s, 1000 1/s and 1500 1/s, respectively.
TABLE 1
TABLE 2
As can be seen from fig. 3 and 4, in the polyetherketoneketone composite materials prepared in the examples, as the mass percentage of the TLCP in the composite material increases, the viscosity of the composite material has a significantly decreasing tendency.
(3) The thermotropic liquid crystal polymer and polyetherketoneketone composite materials prepared in examples 4 to 10 and comparative examples 1 to 3 and 2 samples of different grades of polyetherketoneketone (PEKK, T/I =80/20 and T/I =70/30, respectively) pure resin in examples 2 to 3 were subjected to tensile property test, bending property test and heat distortion temperature test to obtain experimental data shown in tables 3 and 4.
TABLE 3
TABLE 4
It can be seen from the table that as the mass percentage of the TLCP in the composite material increases, the tensile strength, tensile modulus, flexural strength, flexural modulus, and heat distortion temperature of the composite material all increase significantly, and the elongation at break decreases slightly.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, which is convenient for specific and detailed understanding of the technical solutions of the present invention, but the present invention should not be construed as being limited to the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present patent shall be subject to the content of the appended claims, and the description and drawings can be used to explain the content of the claims.
Claims (12)
1. The preparation method of the polyether ketone composite material is characterized by comprising the following steps:
mixing a thermotropic liquid crystal polymer with a reaction monomer of polyether ketone for in-situ polymerization to obtain a reactant, wherein the particle size of the thermotropic liquid crystal polymer is less than 100nm;
separating the reactants to remove free thermotropic liquid crystal polymer and free polyether ketone to obtain polyether ketone composite material;
in the step of separating the reactants, a sedimentation separation method is adopted;
the step of separating the reactants comprises:
providing a separation solution, wherein the separation solution is not reacted with both the polyetherketoneketone and the thermotropic liquid crystalline polymer, and the density of the separation solution is between the density of the polyetherketoneketone and the density of the thermotropic liquid crystalline polymer;
placing the reactant in the separation solution, stirring, standing for layering, and removing free thermotropic liquid crystal polymer and free polyether ketone;
the separation solution is an aqueous sodium hydroxide solution.
2. The method of claim 1, further comprising the step of ultrafining the thermotropic liquid crystalline polymer to obtain a thermotropic liquid crystalline polymer having a particle size of less than 100nm.
3. The method of claim 2, wherein the thermotropic liquid crystalline polymer is ultrafined by at least one of jet milling, colloid milling and emulsification.
4. The method for preparing the polyetherketoneketone composite material as claimed in claim 1, wherein the step of mixing the thermotropic liquid crystal polymer with the reaction monomer of polyetherketoneketone for in situ polymerization comprises: mixing a catalyst, a solvent and the thermotropic liquid crystal polymer, cooling to-10 ℃ to-15 ℃, adding terephthaloyl chloride, isophthaloyl chloride and diphenyl ether, reacting for 1h to 2h, and heating to 10-30 ℃ to continue reacting for 10h to 20h.
5. The preparation method of the polyether ketone composite material as claimed in any one of claims 1 to 4, wherein the mass percent of the thermotropic liquid crystal polymer in the polyether ketone composite material is 1-50%.
6. The method for preparing the polyether ketone composite material as claimed in any one of claims 1 to 4, wherein the melting point temperature of the polyether ketone is within the liquid crystal state temperature interval of the thermotropic liquid crystal polymer.
7. The method for preparing the polyether ketone composite material as claimed in any one of claims 1 to 4, wherein the thermotropic liquid crystal polymer has a density of 1.4g/cm 3 ~1.7g/cm 3 The density of the polyether ketone is 1.2g/cm 3 ~1.3g/cm 3 。
8. The method for preparing the polyether ketone composite material as claimed in any one of claims 1 to 4, further comprising: and extruding and granulating the polyether ketone composite material.
9. The method for preparing the polyether ketone composite material as claimed in any one of claims 1 to 4, wherein before the step of separating the reactants, the method further comprises the following steps: and a step of pulverizing the reactant.
10. The method for preparing the polyether ketone composite material as claimed in any one of claims 1 to 4, further comprising a step of purifying the polyether ketone composite material.
11. The method of claim 10, wherein the step of purifying comprises: and respectively cleaning the polyether ketone composite material by adopting methanol and water, and then drying.
12. A polyether ketone composite material, which is prepared by the preparation method of the polyether ketone composite material as claimed in any one of claims 1 to 11.
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| US5006402A (en) * | 1989-04-28 | 1991-04-09 | The University Of Akron | Wholly aromatic polyester fiber-reinforced high performance thermoplastic and process for preparing same |
| CN1073601C (en) * | 1997-05-05 | 2001-10-24 | 中国科学院化学研究所 | Polyether ether ketone compound material modified by thermotropic liquid crystal polymer |
| WO2008123449A1 (en) * | 2007-03-29 | 2008-10-16 | Asahi Kasei Chemicals Corporation | Resin pellet reinforced with long-fiber filler |
| WO2014130275A2 (en) * | 2013-02-22 | 2014-08-28 | Ticona Llc | High performance polymer composition with improved flow properties |
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