CN105838086B - Preparation method of sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material - Google Patents
Preparation method of sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material, which comprises the following steps: performing surface modification on the polyether-ether-ketone to reduce carbonyl on the surface of the polyether-ether-ketone into hydroxyl to form hydroxylated polyether-ether-ketone; oxidizing the carbon nano tube to obtain an oxidized carbon nano tube containing carboxyl, and sulfonating the oxidized carbon nano tube containing carboxyl to obtain a sulfonated carbon nano tube; the sulfonic acid group on the surface of the sulfonated carbon nanotube reacts with the hydroxyl on the surface of the hydroxylated polyether-ether-ketone to generate sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone; uniformly mixing sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone and polyether-ether-ketone to form a mixed raw material, and performing hot press molding to prepare the sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material, wherein the mass fraction of the sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone in the mixed raw material is 2-5%. The composite material prepared by the invention has high strength, high modulus, high hardness and high heat deformation temperature.
Description
Technical Field
The invention belongs to the technical field of new materials, relates to a preparation method of a composite material for carbon nano tube reinforced polyether ether, and particularly relates to a preparation method of a sulfonated carbon nano tube grafted hydroxylated polyether ether ketone/polyether ether ketone composite material.
Background
The polyether-ether-ketone resin is a thermoplastic special engineering plastic, has the characteristics of high heat resistance level, radiation resistance, high impact strength, good friction resistance and fatigue resistance, flame retardance, excellent electrical property and the like, and has been widely applied in the fields of aerospace, automobiles, electronics and electrical, chemical industry, machinery, medical treatment and the like. However, the pure polyether-ether-ketone resin has the glass transition temperature of 143 ℃, the melting point of 334 ℃, high brittleness and poor shearing performance, and limits the application range of the pure polyether-ether-ketone resin.
CN104804373A discloses an aminated carbon nanotube/polyetheretherketone composite material, which uses aminated carbon nanotubes and original polyetheretherketone to combine together by simple intermolecular forces, but has poor compatibility. Meanwhile, the patent adopts a solution mixing method to prepare the composite material, the aminated carbon nano tube and a DMF solution dissolved with a certain amount of polyether-ether-ketone are mixed and ultrasonically dispersed, and the solvent volatilization is reduced at a certain temperature to obtain the composite material. However, the solution mixing method easily causes the deposition of the aminated carbon nanotube at the bottom, so that the dispersibility of the aminated carbon nanotube is poor, and simultaneously, along with the volatilization of the solvent, the prepared material has smaller holes inside, so that the mechanical property and the thermal stability of the material are reduced.
Disclosure of Invention
In order to solve the defects in the prior art, the invention discloses a preparation method of a sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material, and aims to provide a composite material with high strength, high modulus, high hardness, high heat deformation temperature and high corrosion resistance.
The invention is realized by the following technical scheme:
a preparation method of sulfonated carbon nanotube grafted hydroxylated polyether ether ketone/polyether ether ketone composite material comprises the following steps:
(1) performing surface modification on the polyether-ether-ketone to reduce carbonyl on the surface of the polyether-ether-ketone into hydroxyl to form hydroxylated polyether-ether-ketone;
(2) oxidizing the carbon nano tube to obtain an oxidized carbon nano tube containing carboxyl, and further sulfonating to obtain a sulfonated carbon nano tube;
(3) reacting the sulfonated carbon nanotube with hydroxylated polyether ether ketone to generate sulfonated carbon nanotube grafted hydroxylated polyether ether ketone;
(4) mixing sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone and polyether-ether-ketone to form a mixed raw material, and performing hot press molding to prepare the sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material, wherein the mass fraction of polyether-ether-ketone in the mixed raw material is 2-5%.
Preferably, the mixed raw material in the step (4) is hot-pressed and molded at 378-382 ℃ under the condition of 3-5 MPa; and (3) dehydrating and condensing carboxyl in the oxidized carbon nano tube containing carboxyl in the step (2) and amino in sulfanilic acid to obtain the sulfonated carbon nano tube.
As a preferred embodiment, the method for preparing the oxidized carbon nanotube containing carboxyl comprises the following steps: adding the carbon nano tube into a mixed solution of concentrated sulfuric acid with the mass concentration of 98% and concentrated nitric acid with the mass concentration of 65% in a volume ratio of 3:1, performing ultrasonic dispersion at 45-55 ℃ for 100-140min,
the reaction at this time is:
in the formula: C-COOH: carbon oxide nanotube containing carboxyl group
And (3) carrying out suction filtration to obtain a filter cake, washing the filter cake to be neutral by using deionized water, and carrying out vacuum drying on the filter cake at 88-92 ℃ for 11-13h to obtain the dried carboxyl-containing oxidized carbon nanotube.
The preparation method of the sulfonated carbon nanotube comprises the following steps:
the reaction at this time is:
the specific preparation method of the sulfonated carbon nanotube comprises the following steps:
(1) placing the oxidized carbon nanotube containing carboxyl in DCC anhydrous ethanol solution mixed by DCC and anhydrous ethanol, and performing ultrasonic dispersion at 28-32 deg.C for 20-40min to obtain carbon nanotube solution;
(2) dissolving sulfanilic acid in deionized water to obtain sulfanilic acid solution;
(3) mixing the carbon nano tube solution and the sulfanilic acid solution, performing ultrasonic dispersion at 28-32 ℃ for 20-40min, performing magnetic stirring reaction at 48-52 ℃ for 5-7h, performing suction filtration to obtain a filter cake, washing the filter cake to be neutral by using absolute ethyl alcohol or deionized water, and performing vacuum drying on the filter cake at 88-92 ℃ for 12h to obtain a dried sulfonated carbon nano tube;
wherein, the amounts of the solutes in the carbon nanotube solution and the sulfanilic acid solution in the step (3) are equal.
The preferable preparation method of the hydroxylated polyether-ether-ketone comprises the following steps: reacting polyether-ether-ketone, sodium borohydride and DMSO at the temperature of 118-122 ℃ for 7-9h to obtain hydroxylated polyether-ether-ketone, performing suction filtration to obtain a filter cake, sequentially washing the filter cake with absolute ethyl alcohol, deionized water and hydrochloric acid, and drying the filter cake at the temperature of 78-82 ℃ for 10-14h to obtain dried hydroxylated polyether-ether-ketone. Preferably, the mass ratio of the polyether-ether-ketone to the sodium borohydride is (4-6): 1, and the mass-volume ratio of the polyether-ether-ketone to the DMSO is (0.03-0.05) g/mL.
The reaction equation is as follows:
as a preferred embodiment, the sulfonated carbon nanotube grafted hydroxylated polyetheretherketone can be prepared by the following steps:
(1) adding sulfonated carbon nano-tubes into DMF, and ultrasonically dispersing for 20-40min at 48-52 ℃ to form solution A;
(2) adding hydroxylated polyether ether ketone into DMF solution containing DCC and DMAP, and performing ultrasonic dispersion at 48-52 ℃ for 20-40min to form solution B;
(3) mixing the solution A and the solution B, performing ultrasonic dispersion at 48-52 ℃ for 25-35min, performing reflux reaction at 48-52 ℃ for 7-9h under an inert atmosphere to form a solution C, adding absolute ethanol into the solution C, treating for 25-35min under the condition of water bath stirring at 48-52 ℃, performing suction filtration on the obtained substance to obtain a primary filter cake, washing DCC and DMAP adsorbed on the primary filter cake with absolute ethanol to obtain a filter cake, and performing vacuum drying on the filter cake at 48-52 ℃ for 11-13h to obtain the sulfonated carbon nanotube grafted hydroxylated polyether ether ketone.
The reaction equation is as follows:
preferably, in the step (1), the mass-to-volume ratio of the sulfonated carbon nanotube to DMF is 0.004 g/mL; in the step (2), the mass ratio of the hydroxylated polyether ether ketone to the DCC to the DMAP is 6:8:1, and the mass-to-volume ratio of the hydroxylated polyether ether ketone to the N, N-dimethylformamide is 0.05 g/mL.
The preferable preparation method of the sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material comprises the following steps:
(1) adding the mixed raw materials into absolute ethyl alcohol, performing ultrasonic dispersion at normal temperature for 25-35min, performing vacuum drying at 48-52 ℃ for 18-22min, then continuing to perform ultrasonic dispersion at normal temperature for 25-35min, repeating the vacuum drying and ultrasonic dispersion for 3-5 times, and performing vacuum drying at 48-52 ℃ for 3-5h, wherein the mass-to-volume ratio of the sulfonated carbon nanotube grafted hydroxylated polyether ether ketone to the absolute ethyl alcohol is 0.001 g/mL;
(2) adding the mixed raw materials treated in the step (1) into a mold for compaction, and preheating the mold to 148-152 ℃ at low temperature;
(3) heating a flat vulcanizing machine to 378-382 ℃, placing the preheated mold between heating plates of the flat vulcanizing machine, closing the mold, heating the mold between the heating plates for 2h, controlling the pressure to be 3-5MPa, setting the exhaust frequency to be 3 times, and setting the exhaust distance to be 2 s;
(4) and controlling the pressure at 14-16MPa, and vulcanizing for 10min to obtain the sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material.
Of course, the flat vulcanizing machine is only one embodiment, and other hot press molding equipment such as a hot press, an extruder, an injection molding machine and the like can also obtain the sulfonated carbon nanotube grafted hydroxylated polyetheretherketone/polyetheretherketone composite material at 378-382 ℃ under 3-5 MPa.
As a general knowledge, chemicals are dried before use and, if necessary, ground, and the chemicals used in the present invention are not exceptional.
The method adopts the grafting reaction of the sulfonated carbon nano tube and the hydroxylated polyether-ether-ketone, so that the sulfonated carbon nano tube and the hydroxylated polyether-ether-ketone are connected through a chemical bond, and the dispersion of the carbon nano tube on the surface of the hydroxylated polyether-ether-ketone is promoted, so that the dispersion of the carbon nano tube in the composite material is promoted. The compatibility of the sulfonated carbon nano tube in the parent polyetheretherketone is increased. Meanwhile, the sulfonated carbon nanotube/hydroxylated polyether-ether-ketone and the original polyether-ether-ketone are molded by a hot press molding method, and the solution is mixed for molding, so that no holes are formed in the material, the structural stability of the material is improved, the chemical and physical properties of the polyether-ether-ketone can be greatly improved, the acid resistance, the alkali resistance and the friction resistance are enhanced, and the application range of the polyether-ether-ketone is expanded.
Drawings
FIG. 1 is an infrared spectrum of the modified carbon nanotube.
FIG. 2 is an infrared spectrum of modified polyetheretherketone.
Fig. 3 is a thermogravimetric plot of modified carbon nanotubes.
FIG. 4 is a thermogram of modified PEEK.
FIG. 5 is a scanning electron micrograph of the modified carbon nanotubes.
FIG. 6 is a scanning electron micrograph of modified polyetheretherketone.
Fig. 7 is a graph of the storage modulus of a material.
Fig. 8 is a loss factor graph of a material.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
Examples
A preparation method of sulfonated carbon nanotube grafted hydroxylated polyether ether ketone/polyether ether ketone composite material comprises the following steps:
(1) oxidation treatment of carbon nanotubes
1) Putting the carbon nano tube in a glass dish, and drying the carbon nano tube in a vacuum drying oven at 70 +/-2 ℃ for 12 hours;
2) weighing 3g +/-0.001 g of dried carbon nano tube, pouring the carbon nano tube into a 500mL three-neck flask, respectively weighing 180mL +/-1 mL of concentrated sulfuric acid and 60mL +/-1 mL of concentrated nitric acid, and pouring the concentrated nitric acid into the three-neck flask;
3) placing the three-neck flask on a dispersion ultrasonic instrument for ultrasonic dispersion, and setting the dispersion temperature to be 50 +/-2 ℃; dispersing and carrying out ultrasonic treatment for 2h,
the reaction at this time is:
in the formula: C-COOH: a carboxyl group-containing oxidized carbon nanotube;
4) after the oxidation reaction, closing the ultrasonic dispersion instrument, cooling the oxide in the three-neck flask to room temperature, simultaneously adding 1000mL of deionized water into a 2000mL beaker, then pouring the oxidized solution into the beaker to form a mixed solution, and standing for 24 hours;
5) performing suction filtration, namely performing suction filtration by using a Buchner funnel and microporous filter paper under the action of a circulating water pump, discarding supernatant liquid, and keeping a filter cake;
6) placing the filter cake into a beaker, washing with 300mL of deionized water while stirring for 5min, then performing suction filtration with a Buchner funnel and microporous filter paper to obtain a filter cake, and then washing with deionized water in the Buchner funnel until the oxidized carbon nano tube is washed to be neutral;
7) and (3) drying, namely putting the washed filter cake into a glass dish, putting the glass dish into a vacuum drying oven at 90 +/-2 ℃ for drying for 12h, taking out and storing to obtain the oxidized carbon nano tube.
(2) Preparation of sulfonated carbon nanotubes
1) Accurately weighing 0.3g +/-0.001 g of the oxidized carbon nano tube containing carboxyl after acidification, and pouring the carbon nano tube into a three-neck flask;
2) measuring 75mL +/-0.1 mL of absolute ethyl alcohol by using a measuring cylinder, pouring the absolute ethyl alcohol into a 100mL beaker, accurately weighing 0.5g +/-0.001 g of DCC, pouring the weighed N, N-dicyclohexyl carbon diamine into an absolute ethyl alcohol solution, putting the beaker on an ultrasonic instrument, setting the ultrasonic temperature to be 30 +/-2 ℃, and carrying out ultrasonic oscillation to accelerate the dissolution of the DCC;
3) pouring the dissolved DCC absolute ethyl alcohol solution into a three-neck flask, placing the three-neck flask in an ultrasonic instrument, setting the ultrasonic temperature to be 30 +/-2 ℃, and ultrasonically dispersing for 30min to promote the dispersion of the carbon nano tubes in the absolute ethyl alcohol;
4) accurately weighing 0.3g +/-0.001 g of sulfanilic acid, pouring sulfanilic acid into a 100mL beaker, weighing 75mL +/-0.1 mL of deionized water by using a measuring cylinder, pouring the deionized water into the beaker, placing the beaker on an ultrasonic instrument, setting the ultrasonic temperature to be 30 +/-2 ℃, and carrying out ultrasonic oscillation to accelerate the dissolution of sulfanilic acid;
5) pouring the dissolved water solution of the sulfanilic acid into a three-neck flask, continuously placing the three-neck flask on an ultrasonic instrument, setting the ultrasonic temperature to be 30 +/-2 ℃, and ultrasonically dispersing for 20 min;
6) fixing a three-neck flask on a water bath kettle, setting the temperature of the water bath kettle to be 50 +/-2 ℃, simultaneously adding magnetons, reacting for 6 hours at a certain rotating speed,
the reaction at this time is:
7) after the reaction is finished, cooling the reaction product to room temperature, then performing suction filtration by using microporous filter paper, and discarding filtrate to obtain a filter cake;
8) placing the filter cake in a glass dish, washing with a large amount of ethanol solution, performing suction filtration with microporous filter paper, and discarding filtrate to obtain a clean filter cake;
9) the filter cake was again placed in a glass dish, rinsed with copious amounts of deionized water, then filtered on a buchner funnel with microporous filter paper to obtain the filter cake again, and the filtrate was discarded. Continuing to rinse with deionized water until the pH of the solid is close to 7;
10) putting the sulfonated carbon nano tube into a clean glass dish, putting the glass dish into a vacuum drying oven, setting the drying temperature to be 90 +/-2 ℃, and continuously drying the glass dish in the drying oven for 12 hours to obtain the dried sulfonated carbon nano tube.
(3) Preparation of hydroxylated polyether ether ketone
1) Drying, namely weighing about 150g of polyether-ether-ketone, placing the polyether-ether-ketone in a glass dish, placing the glass dish in a vacuum drying oven, setting the drying temperature to be 80 +/-2 ℃, and drying for 12 h;
2) taking a certain amount of dried polyether-ether-ketone, placing the dried polyether-ether-ketone in a high-speed crusher for crushing, and then screening the crushed polyether-ether-ketone by using a 30-mesh sieve (the aperture is 0.6 mm);
3) weighing 100mL +/-1 mL of DMSO, placing the DMSO in a 500mL three-neck flask, weighing 4g +/-0.001 g of pulverized polyether-ether-ketone, pouring the polyether-ether-ketone into the three-neck flask, weighing 0.8g +/-0.001 g of sodium borohydride, and transferring the sodium borohydride into the three-neck flask;
4) the three-necked flask was placed in an oil bath (dimethylsilicone oil), and 1/2 of the three-necked flask was immersed in the oil bath. Setting the oil bath temperature to be 120 +/-2 ℃, stirring at a certain rotating speed, and reacting for 8 hours;
the reaction equation is as follows:
5) after the reaction is finished, cooling the temperature of the three-neck flask to room temperature, performing suction filtration by using microporous filter paper, and sequentially washing by using absolute ethyl alcohol, deionized water and a hydrochloric acid solution;
6) after the suction filtration is finished, removing filtrate, putting the obtained filter cake into a glass dish, putting the glass dish into a vacuum drying oven, setting the drying temperature to be 80 +/-2 ℃, and drying for 12 hours;
7) grinding, transferring the dried polyether-ether-ketone into a mortar, simply grinding the dried polyether-ether-ketone, and storing the ground hydroxylated polyether-ether-ketone in a plastic bag for later use.
(4) Preparation of sulfonated carbon nanotube grafted hydroxylated polyether ether ketone
1) Adding 0.2g +/-0.001 g of sulfonated carbon nano tube into a three-neck flask containing 50mL +/-1 mL of DMF (N, N-dimethylformamide), and performing ultrasonic dispersion at 50 +/-2 ℃ for 30min +/-2 min to form a suspension A;
2) adding 3g +/-0.001 g of hydroxylated polyether ether ketone into a mixture containing DCC and DMAP in a mass ratio of 8:1 in a 60mL +/-1 mL DMF solution beaker, placing the beaker on an ultrasonic instrument, setting the ultrasonic temperature at 50 +/-2 ℃, and ultrasonically dispersing for 30min to form a B suspension solution. Wherein the mass-volume ratio of DCC to DMF is 2/30 g/mL;
3) after the ultrasonic dispersion is finished, completely pouring the suspension solution B into the three-neck flask of the suspension solution A, continuously placing the three-neck flask into an ultrasonic instrument, setting the ultrasonic temperature to be 50 +/-2 ℃, and carrying out ultrasonic dispersion for 30 +/-2 min;
4) moving the three-neck flask to a magnetic heating stirring device, carrying out fixed stirring, setting the temperature of a water bath kettle to be 50 +/-2 ℃, starting the stirring device, adding a reflux device, simultaneously filling nitrogen, continuously filling the nitrogen for 30 +/-2 min, and carrying out reaction under the anaerobic condition for 8h to form a C suspension solution;
the reaction equation is as follows:
5) pouring the suspension solution C in the three-neck flask into a 1000mL beaker, simultaneously adding 300mL +/-10 mL of absolute ethyl alcohol into the beaker, putting the beaker on a water bath stirring device, and stirring to fully mix DMF and absolute ethyl alcohol;
6) performing suction filtration on the suspension on a Buchner funnel by using microporous filter paper, washing by using absolute ethyl alcohol, washing DCC and DMAP adsorbed on the suspension, then removing filtrate, and placing a filter cake in a glass dish;
7) and (3) putting the glass dish filled with the filter cake into a vacuum drying oven for drying, wherein the drying temperature is set to be 50 +/-2 ℃, and the drying time is 12 h.
(5) Shaping of composite materials
1) Weighing a certain content of sulfonated carbon nanotube grafted hydroxylated polyether ether ketone, simultaneously adding original polyether ether ketone to adjust the content of the carbon nanotube to 3%, pouring 3% of mixed raw materials into a beaker containing absolute ethyl alcohol, wherein the mass-volume ratio of the sulfonated carbon nanotube to the absolute ethyl alcohol is 0.001g/mL, then carrying out ultrasonic dispersion, and after 30min of dispersion, placing the mixture in a vacuum drying oven at 50 +/-2 ℃ for drying for 20 +/-2 min;
2) taking out the beaker, continuously placing on an ultrasonic instrument for ultrasonic treatment for 30min +/-2 min, and continuously placing in a vacuum drying oven for drying for 20min +/-2 min;
3) then taking out the beaker, continuing to carry out ultrasonic dispersion, repeating the process for 4 times, putting the beaker into a vacuum drying oven, and drying the mixed raw materials for 4 hours in the vacuum drying oven at 50 +/-2 ℃;
4) adding the dried mixed raw materials into a mould for cold pressing, compacting the raw materials, then putting the mould into a vacuum drying oven at 150 +/-2 ℃ for heating, and enabling the low-temperature preheating temperature of the mould to reach 150 +/-2 ℃;
5) heating a flat vulcanizing machine to 380 +/-2 ℃, putting the die preheated at low temperature between heating plates, closing the die, controlling the pressure to be 3-5MPa, and then heating the die on the heating plates for 2 hours;
6) setting the number of air exhausts to 3;
7) setting the exhaust distance to 2 s;
8) controlling the pressure at 15MPa, vulcanizing for 10min, and taking out the molding material.
Fig. 1 is an infrared spectrum of a modified carbon nanotube, and infrared curves of various carbon nanotubes during the modification process, wherein 1 is an infrared spectrum of a carbon nanotube, 2 is an infrared spectrum of an oxidized carbon nanotube containing a carboxyl group, and 3 is an infrared spectrum of a sulfonated carbon nanotube, the carboxyl group appears on the surface of the carbon nanotube through analysis of the two spectra 1 and 2, and the amide group and the corresponding sulfonic acid group appear on the surface of the oxidized carbon nanotube containing the carboxyl group through analysis of the two spectra 2 and 3, thereby proving that the carbon nanotube is successfully sulfonated.
FIG. 2 is an infrared spectrum of modified polyetheretherketone, and infrared curves of various polyetheretherketones during modification, wherein 1 is an infrared spectrum of polyetheretherketone, 2 is an infrared spectrum of hydroxylated polyetheretherketone, and 3 is an infrared spectrum of sulfonated carbon nanotube-grafted polyetheretherketone, and hydroxyl groups appear on polyetheretherketone by comparing 1 and 2, which proves that the hydroxylated modification is successful, and 2 and 3 compare to obtain the hydroxylated polyetheretherketone surface-grafted sulfonated carbon nanotube.
Fig. 3 is a thermogravimetric graph of the modified carbon nanotube, and a thermogravimetric graph of various carbon nanotubes in the modification process, wherein 1 is the carbon nanotube, 2 is the oxidized carbon nanotube containing carboxyl, and 3 is the sulfonated carbon nanotube, and the comparison of the three curves shows that the weight loss rate of the carbon nanotube is zero, the oxidized carbon nanotube containing carboxyl is more than 90%, and the sulfonated carbon nanotube shows that the weight loss rate is about 50%. And for the modified carbon nano tube, the weight loss rate is large only when the sulfanilic acid is grafted on the carbon nano tube.
FIG. 4 is a thermogravimetric plot of the modified PEEK, the thermogravimetric plot of PEEK during the modification process, wherein 1 is PEEK, 2 is hydroxylated PEEK, and 3 is PEEK grafted with sulfonated carbon nanotubes. Analysis 1 and 2 shows that the decomposition temperature of the polyetheretherketone is 550 ℃, and the decomposition temperature of the modified polyetheretherketone is reduced due to the change of the surface structure. Compared with the 2 and 3, the weight loss of the hydroxylated polyetheretherketone is fast at the beginning, while the weight loss of the sulfonated carbon nanotube grafted polyetheretherketone is slow, and the weight loss speed is basically the same when the temperature reaches about 480 ℃.
FIG. 5 is a scanning electron microscope image of the modified carbon nanotubes, wherein A is a carbon nanotube, B is an oxidized carbon nanotube containing carboxyl, C is a sulfonated carbon nanotube, and the carbon nanotubes in A have the same length, uniform thickness, larger tube gap and smoother surface. And in B, the thickness of the carbon nano tubes is not uniform, the winding degree of the carbon nano tubes is obviously reduced, the accumulation of the carbon nano tubes is serious, the tube gaps are obviously reduced, and the adhesion among the carbon nano tubes is serious. And the carbon nano tube in the C has uniform thickness, the tube end is slightly damaged, the dispersion is uniform, the roughness of the surface of the carbon nano tube can be seen, and the actual surface has organic matters.
Fig. 6 is a scanning electron microscope image of modified polyetheretherketone, wherein a is polyetheretherketone, B is hydroxylated polyetheretherketone, and C is sulfonated carbon nanotube-grafted polyetheretherketone, wherein a shows that the original polyetheretherketone has a smooth surface, while B has a relatively rough surface with pits in the surface, which proves that hydroxyl groups are generated during the modification process, and C shows that the carbon nanotubes on the polyetheretherketone surface are distributed uniformly and are in contact with polyetheretherketone.
Fig. 7 is a graph of the storage modulus of the prepared composite material and the original PEEK material, where 1 is the storage modulus of pure PEEK, and 2 is the storage modulus of the composite material of carbon nanotube grafted hydroxylated PEEK and pure PEEK, and it can be seen from the graph that the storage modulus of 2 is 20% higher than that of 1 at-120 ℃. And the mechanical property of the modified material is proved to be greatly improved at normal temperature by over ten percent.
Fig. 8 shows the loss factors, wherein 1 is the loss factor of pure polyetheretherketone, and 2 is the sulfonated carbon nanotube-grafted hydroxylated polyetheretherketone and original polyetheretherketone composite material, as can be seen from the figure, the glass transition temperature of the material is raised by 30 ℃ due to the addition of the carbon nanotubes, and the application temperature range of the material is further expanded.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A preparation method of sulfonated carbon nanotube grafted hydroxylated polyether ether ketone/polyether ether ketone composite material is characterized by comprising the following steps:
(1) performing surface modification on the polyether-ether-ketone to reduce carbonyl on the surface of the polyether-ether-ketone into hydroxyl to form hydroxylated polyether-ether-ketone;
(2) oxidizing the carbon nano tube to obtain an oxidized carbon nano tube containing carboxyl, and further sulfonating to obtain a sulfonated carbon nano tube;
(3) reacting the sulfonated carbon nanotube with hydroxylated polyether ether ketone to generate sulfonated carbon nanotube grafted hydroxylated polyether ether ketone;
(4) mixing sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone and polyether-ether-ketone to form a mixed raw material, and performing hot press molding to prepare the sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material, wherein the mass fraction of the sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone in the mixed raw material is 2-5%;
the preparation method of the oxidized carbon nanotube containing carboxyl comprises the following steps: adding the carbon nano tube into a mixed solution with the volume ratio of 98% concentrated sulfuric acid and 65% concentrated nitric acid being 3:1, performing ultrasonic dispersion at 45-55 ℃ for 140min, performing suction filtration to obtain a filter cake, cleaning the filter cake to be neutral by using deionized water, and performing vacuum drying on the filter cake at 88-92 ℃ for 12h to obtain a dried carboxyl-containing oxidized carbon nano tube;
the preparation method of the sulfonated carbon nanotube comprises the following steps:
(1) placing the oxidized carbon nanotube containing carboxyl in DCC anhydrous ethanol solution mixed by DCC and anhydrous ethanol, and performing ultrasonic dispersion at 28-32 deg.C for 20-40min to obtain carbon nanotube solution;
(2) dissolving sulfanilic acid in deionized water to obtain sulfanilic acid solution;
(3) mixing the carbon nano tube solution and the sulfanilic acid solution, performing ultrasonic dispersion at 28-32 ℃ for 20-40min, performing magnetic stirring reaction at 48-52 ℃ for 5-7h, performing suction filtration to obtain a filter cake, sequentially washing the filter cake to be neutral by using absolute ethyl alcohol and deionized water, and performing vacuum drying on the filter cake at 88-92 ℃ for 12h to obtain a dried sulfonated carbon nano tube;
wherein, the amounts of solute in the carbon nano tube solution and the sulfanilic acid solution in the step (3) are equal;
the sulfonated carbon nanotube grafted hydroxylated polyether ether ketone is prepared by the following steps:
(1) adding sulfonated carbon nano-tubes into DMF, and ultrasonically dispersing for 20-40min at 48-52 ℃ to form solution A;
(2) adding hydroxylated polyether ether ketone into DMF solution containing DCC and DMAP, and performing ultrasonic dispersion at 48-52 ℃ for 20-40min to form solution B;
(3) mixing the solution A and the solution B, performing ultrasonic dispersion at 48-52 ℃ for 25-35min, performing reflux reaction at 48-52 ℃ for 7-9h under an inert atmosphere to form a solution C, adding absolute ethanol into the solution C, treating for 25-35min under the water bath stirring condition at 48-52 ℃, performing suction filtration on the obtained substance to obtain a primary filter cake, washing DCC and DMAP adsorbed on the primary filter cake with absolute ethanol to obtain a filter cake, and performing vacuum drying on the filter cake at 48-52 ℃ for 11-13h to obtain sulfonated carbon nanotube grafted hydroxylated polyether ether ketone;
the preparation method of the sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material comprises the following steps:
(1) adding the mixed raw materials into absolute ethyl alcohol, performing ultrasonic dispersion at normal temperature for 25-35min, performing vacuum drying at 48-52 ℃ for 18-22min, then continuing performing ultrasonic dispersion at 40-50 ℃ for 25-35min, repeating the vacuum drying and ultrasonic dispersion for 3-5 times, and performing vacuum drying at 48-52 ℃ for 3-5h, wherein the mass-to-volume ratio of the sulfonated carbon nanotube grafted hydroxylated polyether ether ketone to the absolute ethyl alcohol is 0.001g:1 mL;
(2) adding the mixed raw materials treated in the step (1) into a mold for compaction, and preheating the mold to 148-152 ℃ at low temperature;
(3) heating a flat vulcanizing machine to 378-382 ℃, placing the preheated mold between heating plates of the flat vulcanizing machine, closing the mold, heating the mold between the heating plates for 2h, controlling the pressure to be 3-5MPa, setting the exhaust frequency to be 3 times, and setting the exhaust distance to be 2 s;
(4) and controlling the pressure at 14-16MPa, and carrying out hot pressing for 10min to obtain the sulfonated carbon nanotube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material.
2. The method for preparing sulfonated carbon nanotube-grafted hydroxylated polyetheretherketone/polyetheretherketone composite material according to claim 1, wherein: the preparation method of the hydroxylated polyether-ether-ketone comprises the following steps: reacting polyether-ether-ketone, sodium borohydride and DMSO at the temperature of 118-122 ℃ for 7-9h, performing suction filtration to obtain a filter cake, washing the filter cake with absolute ethyl alcohol, deionized water and hydrochloric acid in sequence, and drying the filter cake at the temperature of 78-82 ℃ for 10-14h to obtain the dried hydroxylated polyether-ether-ketone.
3. The method for preparing sulfonated carbon nanotube-grafted hydroxylated polyetheretherketone/polyetheretherketone composite material according to claim 2, wherein: the mass ratio of the polyether-ether-ketone to the sodium borohydride is (4-6): 1, and the mass-volume ratio of the polyether-ether-ketone to the DMSO is (0.03-0.05) g:1 mL.
4. The method for preparing sulfonated carbon nanotube-grafted hydroxylated polyetheretherketone/polyetheretherketone composite material according to claim 1, wherein: in the step (1) of grafting the sulfonated carbon nanotube with the hydroxylated polyether-ether-ketone, the mass-volume ratio of the sulfonated carbon nanotube to DMF is 0.004g to 1 mL; in the step (2), the mass ratio of the hydroxylated polyether ether ketone to the DCC to the DMAP is 6:8:1, and the mass-volume ratio of the hydroxylated polyether ether ketone to the DMF is 0.05 g to 1 mL.
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