CN112063151B

CN112063151B - Multi-walled carbon nanotube and polyaryletherketone compound thermosetting material containing furan benzene side group and preparation method thereof

Info

Publication number: CN112063151B
Application number: CN202010907772.9A
Authority: CN
Inventors: 刘梦竹; 王永鹏; 张清文
Original assignee: Jilin Institute of Chemical Technology
Current assignee: Jilin Institute of Chemical Technology
Priority date: 2020-09-02
Filing date: 2020-09-02
Publication date: 2022-12-02
Anticipated expiration: 2040-09-02
Also published as: CN112063151A

Abstract

The invention relates to a multi-walled carbon nanotube and polyaryletherketone containing a furan-benzene side group composite thermosetting material, which is prepared by blending the multi-walled carbon nanotube and the polyaryletherketone containing the furan-benzene side group, wherein the polyaryletherketone containing the furan-benzene side group is a polymer solution with the concentration of 0.08-0.1 g/mL, and the mass ratio of the multi-walled carbon nanotube to the polyaryletherketone containing the furan-benzene side group is 1:20 to 100; the preparation method comprises the following steps: preparing polyaryletherketone polymer containing aminophenyl side group, (2) preparing polyaryletherketone material containing furan phenyl side group, and (3) preparing composite thermosetting material. The composite material is a typical thermosetting material which is treated at 150-200 ℃ and then cooled to room temperature for curing, and can improve the strength and the hardness of polyaryletherketone and expand the application field of the polyaryletherketone; and the material can be re-dissolved in an organic solvent after being heated to 200 ℃, so that reprocessing and repairing can be realized, and the processability of the thermosetting material can be improved.

Description

Multi-walled carbon nanotube and polyaryletherketone compound thermosetting material containing furan benzene side group and preparation method thereof

Technical Field

The invention belongs to the technical field of polymer material preparation, and particularly relates to a multi-walled carbon nanotube and polyaryletherketone composite thermosetting material containing a furan benzene side group and a preparation method thereof.

Background

Materials, information and energy have become three major pillars of the future world, and the materials provide support for information and energy, so that more novel materials with functionality are needed. The thermosetting material has wide application range due to excellent mechanical property, solvent resistance, wear resistance and bearing capacity. Because the thermosetting material has a stable cross-linking structure, the thermosetting material is not melted and dissolved after being cured and cross-linked, is difficult to recycle and reprocess, is difficult to maintain, and causes a serious environmental pollution problem due to the obsolete thermosetting material. If dynamic covalent bonds can be incorporated into a thermoset, the processability of the thermoset can be improved, making it both recyclable and repairable.

The polyaryletherketone material is a special engineering plastic with excellent comprehensive performance, has excellent mechanical performance, good high temperature resistance, excellent electrical performance and chemical corrosion resistance, and has wide application in the fields of aerospace, national defense equipment, automobile manufacturing and the like. The strength and hardness of the polyaryletherketone can be further improved by introducing a cross-linking structure, and the application field of the polyaryletherketone is expanded. However, after the cross-linked structure is introduced, the material is difficult to recover and reprocess due to the infusibility, so that not only is maintenance difficult, but also the damaged thermosetting material cannot be repaired or reprocessed, thereby causing serious environmental pollution problems. Therefore, the processability of the thermosetting polyaryletherketone material is improved, and the thermosetting polyaryletherketone material has recyclability and repairability, and has very important significance.

Disclosure of Invention

The invention aims to provide a multi-walled carbon nanotube and polyaryletherketone ketone composite thermosetting material containing furan benzene side groups and a preparation method thereof.

The technical scheme of the invention is as follows: a multi-walled carbon nanotube and polyaryletherketone ketone compound thermosetting material containing furan phenyl side groups are characterized in that: the composite thermosetting material is formed by blending a multiwalled carbon nanotube and polyaryletherketone containing a furan-benzene side group, wherein the polyaryletherketone containing the furan-benzene side group is a polymer solution with the concentration of 0.08-0.1 g/mL, and the mass ratio of the multiwalled carbon nanotube to the polyaryletherketone containing the furan-benzene side group is 1:20 to 100;

the polyaryletherketone containing the furan-benzene side group is generated by reacting polyaryletherketone containing the aminobenzene side group with a furancarboxylic acid monomer, and the structural formula of the polyaryletherketone containing the furan-benzene side group is shown as follows:

wherein the molar content of the furan is 20-60%

n＝15～26；x＝0.2～0.6，x+y＝1；

The polyaryletherketone containing the aminophenyl side group consists of a polyaryletherketone main chain and a side chain containing the aminophenyl side group, wherein the molar content of the side chain containing the aminophenyl side group is 20-60%, and the structural formula is shown as the following figure:

wherein m =14 to 24; a = 0.2-0.6, a + b =1.

The preparation method of the multi-walled carbon nanotube and polyaryletherketone ketone composite thermosetting material containing furan phenyl side groups comprises the following steps:

(1) Preparation of polyaryletherketone polymer containing aminophenyl lateral group

1.1 Taking a certain amount of 2- (4 ' -aminobenzene) -hydroquinone monomer, a certain amount of 4,4' -difluorobenzophenone monomer with the molar amount equal to the sum of the hexafluorobisphenol A diphenol monomer and the diphenol, and anhydrous potassium carbonate, dimethyl sulfoxide and toluene (azeotropic dehydrating agent) with the molar amount 1.05-1.10 times that of 4,4' -difluorobenzophenone monomer; the sum of diphenols is: the sum of 2- (4' -aminobenzene) -hydroquinone monomer and hexafluorobisphenol a-type diphenol monomer; the dosage of the dimethyl sulfoxide is 3-6 times of the sum of the mass of three reaction monomers, namely a 2- (4 '-aminobenzene) -hydroquinone monomer, a hexafluorobisphenol A type diphenol monomer and a 4,4' -difluorobenzophenone monomer, and the dosage of the toluene is 20-30% of the volume of the dimethyl sulfoxide;

1.2 Putting the raw materials selected in the step 1) into a three-neck flask provided with a nitrogen through hole, mechanical stirring and a water carrying device;

1.3 Introducing nitrogen into a three-neck flask, starting stirring, heating to 120-140 ℃, refluxing an azeotropic dehydrating agent toluene, continuously stirring and reacting for 1-3 hours at constant temperature under the atmosphere of nitrogen, further removing the azeotropic dehydrating agent toluene, heating to 150-170 ℃, continuously reacting for 7-10 hours at constant temperature, increasing the molecular weight of the polymer and making the polymer uniform, then cooling to room temperature to obtain a polyaryletherketone polymer solution containing the aminophenyl side group, pouring the polymer solution into deionized water with the volume of 50-60 times of that of dimethyl sulfoxide, making the polymer precipitate to be an off-white thin strip solid, and crushing, washing and drying to obtain the polyaryletherketone solid polymer containing the aminophenyl side group;

(2) Preparation of polyaryletherketone material containing furan benzene side group

Putting the polyaryletherketone solid polymer containing the aminophenyl side group obtained in the step 1.3) and furancarboxylic acid into a container with a stirrer, adding a dehydrating agent N, N-dicyclohexyldiimine and 4-dimethylaminopyridine, then vacuumizing, then discharging high-purity nitrogen, vacuumizing again, discharging high-purity nitrogen, removing oxygen and water vapor, repeating for 3-5 times, then injecting tetrahydrofuran, wherein the tetrahydrofuran is added by 5ml of tetrahydrofuran in each 1g of polyaryletherketone solid polymer containing the aminophenyl side group, dissolving, sealing, starting stirring, stirring at room temperature for 48-60 hours, carrying out amidation reaction, then filtering by using diatomite, distilling under reduced pressure to remove an organic solvent, washing by using acetone for 3-5 times, further removing the organic solvent and impurities, vacuumizing, and drying at 80 ℃ to obtain a polyaryletherketone material containing the furan phenyl polyaryletherketone side group;

wherein, the dosage of the furoic acid is as follows: 1.1 times of the molar weight of amino in the polyaryletherketone containing the aminophenyl side group;

the dosage of N, N-dicyclohexyl Diimine (DCC) is 1.5 times of the molar weight of amino in the polyaryletherketone containing the aminophenyl side group; the amount of 4-Dimethylaminopyridine (DMAP) used was: the molar weight of amino in the polyaryletherketone containing the aminophenyl side group is 0.15 time;

(3) Preparation of composite thermosetting material

3.1 Preparing a polyaryletherketone polymer solution containing furan benzene side groups: dissolving polyaryletherketone containing furan phenyl side groups by using an organic solvent to prepare 0.08-0.1 g/mL polyaryletherketone polymer solution containing furan phenyl side groups, wherein the organic solvent is one of dimethyl sulfoxide, N-dimethylacetamide or N-methylpyrrolidone;

3.2 Preparing a multi-walled carbon nanotube solution: the mass ratio of the multi-walled carbon nano-tube to the polyaryletherketone containing the furan benzene side group is 1: 20-100, adding the multi-walled carbon nano-tubes into an organic solvent according to a proportion, preparing a multi-walled carbon nano-tube solution with the concentration of 0.005-0.01 g/mL, stirring for 1-3 hours, and performing ultrasonic treatment for 2-4 hours to uniformly disperse the multi-walled carbon nano-tubes (MWCNTs) in the organic solvent; the organic solvent is one of dimethyl sulfoxide, N-dimethylacetamide and N-methylpyrrolidone;

3.3 Preparation of composite materials: adding the multi-walled carbon nanotube solution obtained in the step 3.2) into the polyaryletherketone polymer solution containing the furan-benzene side group obtained in the step 1), continuing performing ultrasonic treatment on the obtained mixed solution for 1-3 hours to prepare a composite material solution, discharging the composite material solution into deionized water to precipitate the composite material solution, drying at 100 ℃ to obtain a black powdery solid composite material, and storing;

3.4 Curing): using the composite material solution or the powdery solid composite material obtained in the step 3.3), treating at 150-200 ℃ for 1-2 hours, and then cooling to room temperature to obtain the multi-walled carbon nanotube and polyaryletherketone composite thermosetting material containing furan phenyl side groups.

The composite material solution or powdery solid composite material is used as a raw material to prepare a product in a corresponding application field, the product is treated at 150-200 ℃, and then cooled to room temperature for solidification, the product has the performance of a thermosetting material, and is heated to 200 ℃ in an organic solvent for 12 hours to be redissolved, so that the reprocessing can be realized. After being heated to 200 ℃ in a mould and treated for 2 hours, the temperature is reduced to room temperature, and the reparation can be realized.

The multi-walled carbon nanotube and the polyaryletherketone compound thermosetting material containing the furan benzene side group can form a cross-linked network structure through Dials-Alder reaction at the temperature of below 150 ℃, are insoluble and infusible and are typical thermosetting materials; the multi-walled carbon nano-tube and the polyaryletherketone body containing the furan benzene side group can be formed by ring opening through a Dials-Alder reverse reaction at the temperature of more than 150 ℃, can be dissolved and melted for processing, and can be subjected to ring forming and solidification after being cooled to the temperature of less than 150 ℃, so that the multi-walled carbon nano-tube and polyaryletherketone body becomes a recyclable or repairable thermosetting material.

The invention selects an amidation method to successfully introduce the furan monomer into the polyaryletherketone, which not only can not influence the performance of the polyaryletherketone, but also can generate the polyaryletherketone containing the furan phenyl side group, which is a novel high polymer material with stable performance. By using the polyaryletherketone containing the furan-benzene side group and the multi-walled carbon nano tube for solution blending, the multi-walled carbon nano tube can be well dispersed in the polyaryletherketone containing the furan-benzene side group, and then the conjugated double bond of the furan group in the polymer is used as a diene body by high-temperature treatment, and the conjugated double bond and the multi-walled carbon nano tube are subjected to Diels-Alder reaction to obtain the repairable and recyclable multi-walled carbon nano tube and polyaryletherketone containing the furan-benzene side group composite thermosetting material with excellent mechanical properties.

The invention can further improve the strength and the hardness of the polyaryletherketone by introducing a cross-linking structure, and expand the application field of the polyaryletherketone. The multi-wall carbon nanotube has excellent performance, contains a large amount of conjugated double bonds in the structure, can be used as a diene or a dienophile to perform Diels-Alder reaction with a polymer matrix, and endows the material with good repairability and recoverability. Therefore, the invention takes the introduction of furan groups with controllable content into the side chain of the polyaryletherketone as the starting point to prepare the polyaryletherketone containing the furan-benzene side group with different furan contents, and takes the conjugated double bond of the furan groups in the polymer as a diene and the carbon nano tube as a dienophile to carry out Diels-Alder reaction on the two, thus preparing the carbon nano tube and the polyaryletherketone containing the furan-benzene side group composite thermosetting material which is used in the field of repairable and recyclable thermosetting materials.

Mechanical property experiment results show that after heat treatment, the mechanical property of the multi-walled carbon nanotube and polyaryletherketone containing furan phenyl side groups composite thermosetting material film is obviously improved, the tensile strength of the multi-walled carbon nanotube and polyaryletherketone containing furan phenyl side groups is continuously enhanced along with the continuous increase of the heat treatment temperature, the elongation at break of the multi-walled carbon nanotube is continuously reduced, the DA reaction is more completely carried out along with the increase of the temperature, the crosslinking density of the composite material is gradually increased, and therefore the tensile strength of the composite material is gradually increased along with the increase of the treatment temperature, and the elongation at break of the composite material is gradually reduced. After 200 ℃ treatment, the material can be completely crosslinked.

Drawings

FIG. 1: the structural formula of the polyaryletherketone containing the aminophenyl side group and containing 20 mol% of amino groups is shown in the specification;

FIG. 2: amino group-containing mols according to the inventionPolyaryletherketone containing amino benzene side group with content of 20% ¹ H-NMR spectrum;

FIG. 3: the structural formula of the polyaryletherketone containing the aminophenyl side group and the amino molar content of 40 percent is shown in the specification;

FIG. 4 is a schematic view of: the polyaryletherketone containing aminophenyl lateral group and containing 40% of amino mol content ¹ H-NMR spectrum;

FIG. 5 is a schematic view of: the structural formula of the polyaryletherketone containing the aminophenyl side group and containing the amino molar content of 60 percent is shown in the specification;

FIG. 6: the polyaryletherketone containing aminophenyl lateral group and containing 60% of amino mol content ¹ H-NMR spectrum;

FIG. 7: the structural formula of the polyaryletherketone containing the furan benzene side group with the molar furan content of 20 percent is shown in the specification;

FIG. 8: the polyaryletherketone containing furan benzene side group with the molar content of furan of 20 percent ¹ H-NMR spectrum;

FIG. 9: the structural formula of the polyaryletherketone containing furan benzene side groups with the molar content of furan of 40 percent is disclosed;

FIG. 10: the polyaryletherketone containing furan benzene side group with the molar content of furan of 40 percent ¹ H-NMR spectrum;

FIG. 11: the DSC curve of the polyaryletherketone containing the aminophenyl lateral group;

FIG. 12: the DSC curve of the polyaryletherketone containing the furan phenyl side group is shown in the specification;

FIG. 13: the invention processes the DMA curve of multi-walled carbon nano-tube and the polyaryletherketone composite material containing the furan benzene side group with the molar content of 20 percent at 100 ℃ for 1 hour;

FIG. 14 is a schematic view of: the invention processes the DMA curve of multi-walled carbon nano-tube and the polyaryletherketone composite material containing the furan benzene side group with the molar content of 20 percent at 150 ℃ for 1 hour;

FIG. 15: the invention processes the DMA curve of multi-walled carbon nano-tube and the polyaryletherketone composite material containing the furan benzene side group with the molar content of 20 percent at 170 ℃ for 1 hour;

FIG. 16: the invention processes the DMA curve of multi-walled carbon nano-tube and the polyaryletherketone composite material containing the furan benzene side group with the molar content of 20 percent at 200 ℃ for 1 hour;

FIG. 17: the invention processes the DMA curve of multi-walled carbon nano-tube and the polyaryletherketone composite material containing furan phenyl side group with the molar content of 40 percent at 100 ℃ for 1 hour;

FIG. 18: the invention processes the DMA curve of multi-walled carbon nano-tube and the polyaryletherketone composite material containing the furan benzene side group with the molar content of 40 percent at 150 ℃ for 1 hour;

FIG. 19: the invention processes the DMA curve of multi-walled carbon nano-tube and the polyaryletherketone composite material containing the furan-benzene side group with the molar content of 40 percent for 1 hour at 170 ℃;

FIG. 20: the invention processes the DMA curve of multi-walled carbon nano-tube and the polyaryletherketone composite material containing the furan benzene side group with the molar content of 40 percent at 200 ℃ for 1 hour;

FIG. 21: the tensile curve of the multi-walled carbon nanotube and the polyaryletherketone composite material containing the furan benzene side group with the molar content of 20 percent is shown;

FIG. 22: the tensile curve of the multi-walled carbon nano-tube and the polyaryletherketone composite material containing the furan phenyl side group with the molar content of 40 percent;

FIG. 23: SEM photograph of the multi-walled carbon nanotube and the polyaryletherketone composite material containing the furan benzene side group;

FIG. 24: the TGA curve of the multi-walled carbon nanotube and the polyaryletherketone composite material containing the furan benzene side group and containing 20 mol% of furan is provided;

FIG. 25 is a schematic view of: the TGA curve of the multi-walled carbon nano-tube and the polyaryletherketone composite material containing the furan phenyl side group with the molar content of 40 percent;

FIG. 26: the reaction principle of the multi-walled carbon nano-tube and the polyaryletherketone composite material containing the furan benzene side group is shown in the figure.

Detailed Description

The multi-walled carbon nanotube and polyaryletherketone containing the furan-benzene side group are compounded into a thermosetting material, and the compound thermosetting material is formed by blending the multi-walled carbon nanotube and the polyaryletherketone containing the furan-benzene side group, wherein the polyaryletherketone containing the furan-benzene side group is a polymer solution with the concentration of 0.08-0.1 g/mL, and the mass ratio of the multi-walled carbon nanotube to the polyaryletherketone containing the furan-benzene side group is 1:20 to 100;

wherein, the molar content of the furan is 20 to 60 percent

n＝15～26；x＝0.2～0.6，x+y＝1；

wherein m =14 to 24; a = 0.2-0.6, a + b =1.

The preparation method of the multi-walled carbon nanotube and polyaryletherketone ketone composite thermosetting material containing furan benzene side groups comprises the following steps:

(1) Preparation of polyaryletherketone polymer containing aminophenyl side group

1.1 A certain amount of 2- (4 ' -aminobenzene) -hydroquinone monomer, a certain amount of hexafluorobisphenol A diphenol monomer and 4,4' -difluorobenzophenone monomer with the same mol of the sum of the diphenol, and 1.05 to 1.10 times of anhydrous potassium carbonate, dimethyl sulfoxide and toluene (azeotropic dehydrating agent) with the mol of 4,4' -difluorobenzophenone monomer are taken; the sum of diphenols is: the sum of 2- (4' -aminobenzene) -hydroquinone monomer and hexafluorobisphenol a-type diphenol monomer; the dosage of the dimethyl sulfoxide is 3-6 times of the sum of the mass of three reaction monomers, namely a 2- (4 '-aminobenzene) -hydroquinone monomer, a hexafluorobisphenol A monomer and a 4,4' -difluorobenzophenone monomer, and the dosage of the toluene is 20-30% of the volume of the dimethyl sulfoxide;

Putting the polyaryletherketone solid polymer containing the aminophenyl side group obtained in the step 1.3) and furancarboxylic acid into a container with a stirrer, adding a dehydrating agent N, N-dicyclohexyldiimine and 4-dimethylaminopyridine, vacuumizing, then discharging high-purity nitrogen after vacuumizing, further vacuumizing, discharging high-purity nitrogen, removing oxygen and water vapor, repeating for 3-5 times, then injecting tetrahydrofuran, wherein the tetrahydrofuran is added by 5ml of tetrahydrofuran in each 1g of the polyaryletherketone solid polymer containing the aminophenyl side group, dissolving, sealing, starting stirring, stirring at room temperature for 48-60 hours, carrying out amidation reaction, then filtering by using diatomite, distilling under reduced pressure to remove an organic solvent, washing by using acetone for 3-5 times, further removing the organic solvent and impurities, and drying at the vacuum temperature of 80 ℃ to obtain a polyaryletherketone material containing the furan phenyl side group;

(3) Preparation of composite thermosetting material

3.4 Curing): and (4) using the composite material solution or the powdery solid composite material obtained in the step 3.3), continuously treating at 150-200 ℃ for 1-2 hours, and then cooling to room temperature to obtain the multi-walled carbon nanotube and polyaryletherketone containing furan phenyl side groups composite thermosetting material.

Taking the film product as an example, the composite material solution of the present invention was filtered using a copper mesh in a vacuum oven preheated at 40 ℃ and poured onto a glass plate having a pre-leveled dimension of 10cm × 10 cm. Firstly keeping the temperature at the normal pressure of 60 ℃ for 24 hours, removing the solvent volatilized from the oven every 12 hours, raising the temperature after the solvent is completely volatilized, keeping the temperature at the normal pressure of 80 ℃, 100 ℃ and 120 ℃ for 1 to 3 hours respectively, naturally cooling to 60 ℃, vacuumizing at the temperature of 60 ℃, 80 ℃, 100 ℃ and 120 ℃ and then drying for 2 to 4 hours respectively, and soaking the glass plate cooled to the room temperature in deionized water after the solvent is completely removed to obtain the composite material film with the addition of the multi-walled carbon nanotube (MWCNT) of 1 weight percent. Then processing for 1-2 h at 170-200 ℃ to obtain the multi-walled carbon nanotube (MWCNT) and the polyaryletherketone containing the furan benzene side group composite thermosetting film material.

FIG. 1 shows a structural diagram of an amino-phenyl group-containing polyaryletherketone (example 1) of the present invention having a molar amino group content of 20%, from which the structure of the polymer can be seen.

FIG. 2 shows the hydrogen nuclear magnetic spectrum of the polyaryletherketone containing amino-benzene side groups (example 1) with the amino group molar content of 20% according to the present invention, and it can be seen that the correct assignment of each hydrogen in the polymer structure is obtained.

FIG. 3 shows a structural diagram of an amino-phenyl group-containing polyaryletherketone (example 3) of the present invention having a 40% amino molar content, from which the structure of the polymer can be seen.

FIG. 4 shows the hydrogen nuclear magnetic spectrum of the polyaryletherketone containing amino-phenyl side groups (example 3) with an amino molar content of 40% according to the invention, from which it can be seen that each hydrogen in the polymer structure is correctly assigned.

FIG. 5 shows a structural diagram of an aminophenyl group-containing polyaryletherketone having a molar amino group content of 60% (example 5) according to the invention, from which the structure of the polymer can be seen.

FIG. 6 shows the hydrogen nuclear magnetic spectrum of the polyaryletherketone containing amino-benzene side group (example 5) with 60 mol% amino group, from which it can be seen that each hydrogen in the polymer structure is correctly assigned.

FIG. 7 shows a structural diagram of 20 mole percent furan-containing polyaryletherketone having pendant furan benzene groups (example 1) according to the present invention, from which the structure of the polymer can be seen.

FIG. 8 shows the hydrogen nuclear magnetic spectrum of 20 mole percent furan-containing polyaryletherketone (example 1) containing pendant furan phenyl groups according to the present invention, from which it can be seen that the correct assignment of each hydrogen in the polymer structure is obtained.

FIG. 9 shows a structural diagram of a polyaryletherketone containing furan benzene pendant groups with a mole fraction of 40% furan (example 3) according to the invention, from which the structure of the polymer can be seen.

FIG. 10 shows the hydrogen nuclear magnetic spectrum of the polyaryletherketone containing furan benzene side groups (example 3) with a furan mole fraction of 40% respectively, from which it can be seen that each hydrogen in the polymer structure has the correct assignment.

FIG. 11 shows DSC curves of the amino phenyl group-containing polyaryletherketones of the present invention (examples 1,3, 5) with amino mole fractions of 20%, 40% and 60%, respectively, from which it can be seen that the Tg's of the amino phenyl group-containing polyaryletherketones with amino mole fractions of 20%, 40% and 60%, respectively, are 166 deg.C, 178 deg.C and 184 deg.C, respectively.

FIG. 12 shows DSC curves of 20%, 40% and 60% furan-phenyl group-containing polyaryletherketones according to the present invention (examples 1,3 and 5), respectively, and it can be seen that Tg's of the 20% and 40% furan-phenyl group-containing polyaryletherketones according to the present invention are 191 degrees Celsius, 210 degrees Celsius and 226 degrees Celsius, respectively.

FIG. 13 shows the DMA curves of the multi-walled carbon nanotubes of the present invention and the polyaryletherketone containing a furan-phenyl pendant group with a molar furan content of 20% (example 1), from which the storage modulus, loss modulus and loss factor Tan delta of the multi-walled carbon nanotubes of the present invention and the polyaryletherketone containing a furan-phenyl pendant group with a molar furan content of 20% can be seen.

FIG. 14 shows the DMA curves of the multiwalled carbon nanotube of the invention treated at 150 ℃ for 1 hour and the polyaryletherketone composite containing the furan phenyl pendant group with a molar furan content of 20% (example 1), and it can be seen from the DMA curves that the multiwalled carbon nanotube of the invention treated at 150 ℃ for 1 hour and the polyaryletherketone composite containing the furan phenyl pendant group with a molar furan content of 20% have the storage modulus, loss modulus and loss factor Tan delta.

FIG. 15 shows the DMA curves of the multiwalled carbon nanotubes treated at 170 ℃ for 1 hour and the polyaryletherketone composite containing the furan-phenyl pendant group with a molar furan content of 20% (example 1) of the present invention, and it can be seen from the DMA curves that the storage modulus, loss modulus and loss factor Tan delta of the multiwalled carbon nanotubes treated at 170 ℃ for 1 hour and the polyaryletherketone composite containing the furan-phenyl pendant group with a molar furan content of 20% of the present invention are.

FIG. 16 shows the DMA curves of the multiwalled carbon nanotube of the invention treated at 200 ℃ for 1 hour and the polyaryletherketone composite containing the furan phenyl pendant group with a molar furan content of 20% (example 1), and it can be seen from the DMA curves that the multiwalled carbon nanotube of the invention treated at 200 ℃ for 1 hour and the polyaryletherketone composite containing the furan phenyl pendant group with a molar furan content of 20% have the storage modulus, loss modulus and loss factor Tan delta.

FIG. 17 shows the DMA curves of the multi-walled carbon nanotubes of the present invention and the polyaryletherketone ketone containing the furan phenyl pendant group with a molar furan content of 40% (example 3), from which the storage modulus, loss modulus and loss factor Tan delta of the multi-walled carbon nanotubes of the present invention and the polyaryletherketone containing the furan phenyl pendant group with a molar furan content of 40% can be seen.

FIG. 18 shows the DMA curves of the multiwalled carbon nanotubes treated at 150 ℃ for 1 hour and the polyaryletherketone composite containing the furan phenyl pendant group with a molar furan content of 40% (example 3) of the present invention, and it can be seen from the DMA curves that the storage modulus, loss modulus and loss factor Tan delta of the multiwalled carbon nanotubes treated at 150 ℃ for 1 hour and the polyaryletherketone composite containing the furan phenyl pendant group with a molar furan content of 40% of the present invention are.

FIG. 19 shows the DMA curves of the multiwalled carbon nanotubes treated at 170 ℃ for 1 hour and the polyaryletherketone composite containing the furan-phenyl pendant group with a molar furan content of 40% (example 3) of the present invention, and it can be seen from the DMA curves that the storage modulus, loss modulus and loss factor Tan delta of the multiwalled carbon nanotubes treated at 170 ℃ for 1 hour and the polyaryletherketone composite containing the furan-phenyl pendant group with a molar furan content of 40% of the present invention are.

FIG. 20 shows the DMA curves of the multiwalled carbon nanotubes treated at 200 ℃ for 1 hour and the polyaryletherketone composite containing the furan phenyl pendant group with a molar furan content of 40% (example 3) of the present invention, and it can be seen from the DMA curves that the storage modulus, loss modulus and loss factor Tan delta of the multiwalled carbon nanotubes treated at 200 ℃ for 1 hour and the polyaryletherketone composite containing the furan phenyl pendant group with a molar furan content of 40% of the present invention are.

FIG. 21 shows the tensile curve of the multi-walled carbon nanotube of the present invention and the polyaryletherketone containing the furan-phenyl pendant group with a molar furan content of 20% (example 1), from which the Young's modulus, tensile strength and elongation at break of the multi-walled carbon nanotube of the present invention and the polyaryletherketone containing the furan-phenyl pendant group with a molar furan content of 20% can be seen.

FIG. 22 shows the tensile curve of the multi-walled carbon nanotube of the present invention and the polyaryletherketone ketone containing the furan phenyl pendant group with a molar furan content of 40% (example 3), from which the Young's modulus, tensile strength and elongation at break of the multi-walled carbon nanotube of the present invention and the polyaryletherketone containing the furan phenyl pendant group with a molar furan content of 40% can be seen.

FIG. 23 shows scanning electron micrographs of a multi-walled carbon nanotube and a polyaryletherketone composite material containing a furan-phenyl side group with a molar furan content of 20% and a multi-walled carbon nanotube and a polyaryletherketone composite material containing a furan-phenyl side group with a molar furan content of 40% (example 1,3), respectively. It can be seen from the figure that the multi-walled carbon nanotubes and the polyaryletherketone containing the furan benzene side group with the molar content of 20 percent (figure 12) and the multi-walled carbon nanotubes and the polyaryletherketone containing the furan benzene side group with the molar content of 40 percent (figure 12) are uniformly dispersed.

FIG. 24 shows the TGA curve of the multi-walled carbon nanotube of the present invention and the polyaryletherketone containing 20% furan-phenyl pendant group (example 1), from which it can be seen that the multi-walled carbon nanotube and the polyaryletherketone containing 20% furan-phenyl pendant group have good thermal stability after being treated at 150 deg.C, 170 deg.C and 200 deg.C.

FIG. 25 shows the TGA curve of the multi-walled carbon nanotube of the present invention and the polyaryletherketone ketone containing the furan phenyl pendant group with a molar furan content of 40% (example 3), and it can be seen that the multi-walled carbon nanotube and the polyaryletherketone ketone containing the furan phenyl pendant group with a molar furan content of 40% have good thermal stability after being treated at 150 ℃, 170 ℃ and 200 ℃.

FIG. 26: the reaction schematic diagram of the multi-walled carbon nano-tube and the polyaryletherketone composite material containing the furan benzene side group is provided. When the temperature is lower than 150 ℃, the composite thermosetting material is formed, and when the temperature is higher than 150 ℃, the soluble and meltable composite material is formed.

Example 1

According to the weight ratio of 0.2:0.8:1.0:1.2 batch ratios 1.0061g (0.005 mol) 2- (4 '-aminobenzene) -hydroquinone, 6.7246g (0.02 mol) hexafluorobisphenol A,5.4550g (0.025 mol) 4,4' -difluorobenzophenone, 4.1463g (0.03 mol) potassium carbonate (salt former) were weighed into a 100mL round bottom three neck flask equipped with mechanical stirring paddle, nitrogen vent, thermometer, water trap and spherical condenser, while adding 45mL dimethyl sulfoxide as solvent and 15mL toluene as azeotropic water trap. Introducing nitrogen, starting stirring, heating to toluene reflux, carrying water at the temperature of about 120 ℃, and slowly discharging the toluene after carrying water for two hours. And continuously heating the reaction system to 150 ℃ for polymerization reaction, discharging the obtained polymer solution into deionized water after 10-hour reaction, crushing the precipitated polymer, and boiling and washing the crushed polymer for 3 times by using distilled water and absolute ethyl alcohol respectively under the protection of nitrogen. To remove the excess solvent, inorganic salts, unreacted monomers and oligomers with lower molecular weight from the polymer. And (3) putting the light purple polymer obtained by washing and filtering into a vacuum oven, and carrying out vacuum-pumping drying at 60 ℃ for 24 hours to obtain the polyaryletherketone containing the aminophenyl side group and having the amino molar content of 20%, wherein the molecular formula is as follows:

wherein m =16 to 24; a =0.2, a + b =1.

5.0584g (10 mmol) of the polyaryletherketone containing the amino-benzene side group obtained above and 0.2466g (2.2 mmol) of furancarboxylic acid (1.1 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) are put into a container with a stirrer, 0.62g of N, N-Dicyclohexyldiimine (DCC) (1.5 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) and 0.36g of 4-Dimethylaminopyridine (DMAP) (0.15 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) are added, then the container is vacuumized until the vacuum degree reaches 0.1MPa, high-purity nitrogen is discharged and then vacuumized until the vacuum degree reaches 0.1MPa, high-purity nitrogen is discharged and is repeatedly used for 4 times, finally 200mL of tetrahydrofuran is injected for dissolving, then the container is sealed, stirring is started, and the room temperature reaction is carried out for 48 hours; filtering with diatomite, removing solvent under reduced pressure, washing with acetone for 4 times, filtering, and vacuum-pumping and oven-drying at 80 deg.C to obtain 5.0g polyaryletherketone material containing furan benzene side group with molar content of 20%.

The molecular formula is as follows:

wherein n = 17-26; x =0.2, x+y=1.

The MWCNT/polyaryletherketone composite material film with the furan-benzene side groups is prepared by adopting a solution blending and sol-gel method and taking a multi-walled carbon nanotube as a disperse phase and polyaryletherketone containing the furan-benzene side groups as matrix resin, wherein the addition amount of the MWCNT is 1wt%, and the specific preparation method of the composite material is as follows:

0.99g of polyaryletherketone containing furan benzene side groups and having a furan molar content of 20% and fully dried in a vacuum oven is weighed and added into a 50ml conical flask, 10ml of DMAc is added, stirring is started to completely dissolve the polymer, 0.01g of multi-walled carbon nanotubes (MWCNT) are weighed and dissolved into 2ml of DMAc, stirring is carried out for 2 hours, and ultrasound is carried out for 3 hours. And adding the uniformly dispersed multi-walled carbon nanotube (MWCNT) solution into the polymer solution, and continuing to perform ultrasonic treatment on the mixed solution for 2 hours to prepare a composite material solution with uniformly dispersed multi-walled carbon nanotubes. The mixed solution filtered using a copper mesh was then poured uniformly onto a previously leveled glass plate of 10cm by 10cm size in a vacuum oven preheated at 40 ℃. Firstly keeping the temperature at the normal pressure of 60 ℃ for 24 hours, removing the solvent volatilized from the oven every 12 hours, raising the temperature after the solvent is completely volatilized, keeping the temperature at the normal pressure of 80 ℃, 100 ℃ and 120 ℃ for 2 hours respectively, naturally cooling to 60 ℃, vacuumizing at the temperature of 60 ℃, 80 ℃, 100 ℃ and 120 ℃ and then drying for 2 hours respectively, and soaking the glass plate cooled to the room temperature in deionized water after the solvent is completely removed to obtain the composite material film with the MWCNT addition of 1 wt%.

Placing the multi-walled carbon nanotube and the polyaryletherketone composite material containing the furan benzene side group in a tube furnace, respectively carrying out heat treatment for 1 hour at the conditions of 150 ℃, 170 ℃ and 200 ℃ under the protection of nitrogen, and carrying out crosslinking and curing under the condition of high-temperature heating to obtain the repairable and recyclable multi-walled carbon nanotube/polyaryletherketone thermosetting composite material. Can be heated to 200 ℃ in N-methyl pyrrolidone for 12 hours for processing, and re-dissolution and film spreading are carried out to realize reprocessing. The repairing can be realized by heating to 200 ℃ in a mould, treating for 2 hours and then cooling to room temperature.

Example 2

According to the weight ratio of 0.2:0.8:1.0: 1.0061g (0.005 mol) 2- (4 '-aminobenzene) -hydroquinone, 6.7246g (0.02 mol) hexafluorobisphenol A,5.4550g (0.025 mol) 4,4' -difluorobenzophenone, 4.1463g (0.03 mol) potassium carbonate (salt former) were weighed into a 100mL round bottom three-neck flask equipped with mechanical stirring paddle, nitrogen vent, thermometer, water-carrying device and spherical condenser, along with 45mL dimethyl sulfoxide as solvent and 15mL toluene as azeotropic water-carrying device at a charge ratio of 1.2. Introducing nitrogen, starting stirring, heating to toluene reflux, carrying out water temperature of about 140 ℃, and slowly discharging the toluene after carrying water for two hours. And continuously heating the reaction system to 170 ℃ for polymerization reaction, discharging the obtained polymer solution into deionized water after 7-hour reaction, crushing the precipitated polymer, and boiling and washing the crushed polymer for 3 times by using distilled water and absolute ethyl alcohol respectively under the protection of nitrogen. So as to remove redundant solvent, inorganic salt, unreacted monomer and oligomer with lower molecular weight in the polymer. And (3) placing the light purple polymer obtained by washing and suction filtration into a vacuum oven, and carrying out vacuum-pumping drying at 60 ℃ for 24 hours to obtain the polyaryletherketone containing the amino benzene side group, wherein the amino benzene side group has the amino molar content of 20%, and the molecular formula is as follows:

wherein m =16 to 24; a =0.2,a + b =1.

5.0584g (10 mmol) of the polyaryletherketone containing the amino-benzene side group obtained above and 0.2466g (2.2 mmol) of furancarboxylic acid (1.1 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) are put into a container with a stirrer, 0.62g of N, N-Dicyclohexyldiimine (DCC) (1.5 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) and 0.36g of 4-Dimethylaminopyridine (DMAP) (0.15 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) are added, then the container is vacuumized until the vacuum degree reaches 0.1MPa, high-purity nitrogen is discharged and then vacuumized until the vacuum degree reaches 0.1MPa, high-purity nitrogen is discharged and is repeatedly used for 4 times, finally 200mL of tetrahydrofuran is injected for dissolving, then the container is sealed, stirring is started, and the room temperature reaction is carried out for 60 hours; filtering with diatomite, removing solvent under reduced pressure, washing with acetone for 4 times, filtering, and vacuum-pumping and oven-drying at 80 deg.C to obtain 5.0g polyaryletherketone material containing furan benzene side group with molar content of 20%.

The molecular formula is as follows:

wherein n = 17-26; x =0.2, x+y=1.

A MWCNT/polyaryletherketone with a furan-benzene side group composite material film is prepared by adopting a solution blending and sol-gel method and taking a multiwalled carbon nanotube as a disperse phase and polyaryletherketone with the furan-benzene side group as matrix resin, wherein the addition amount of the MWCNT is 1wt%, and the specific preparation method of the composite material is as follows:

weighing 0.99g of polyaryletherketone containing furan phenyl side group with the molar content of 20% and fully dried in a vacuum oven, adding into a 50ml conical flask, adding 10ml of DMAc, starting stirring to completely dissolve the polymer, weighing 0.01g of multi-walled carbon nanotube (MWCNT), dissolving in 2ml of DMAc, stirring for 2 hours, and performing ultrasonic treatment for 3 hours. And adding the uniformly dispersed multi-walled carbon nanotube (MWCNT) solution into the polymer solution, and continuing to perform ultrasonic treatment on the mixed solution for 2 hours to prepare a composite material solution with uniformly dispersed multi-walled carbon nanotubes. The mixed solution filtered using a copper mesh was then poured uniformly onto pre-leveled glass plates of 10cm by 10cm size in a vacuum oven preheated at 40 ℃. Firstly keeping the temperature at 60 ℃ under normal pressure for 24 hours, removing the solvent volatilized out in an oven every 12 hours, raising the temperature after the solvent is completely volatilized, keeping the temperature at 80 ℃, 100 ℃ and 120 ℃ under normal pressure for 2 hours respectively, naturally cooling to 60 ℃, vacuumizing at 60 ℃, 80 ℃, 100 ℃ and 120 ℃ and then drying for 4 hours respectively, and soaking the glass plate cooled to room temperature in deionized water after the solvent is completely removed to obtain the composite material film with the MWCNT addition of 1 wt%.

Placing the multi-walled carbon nanotube and the polyaryletherketone composite material containing the furan benzene side group in a tube furnace, respectively carrying out heat treatment for 1 hour at the conditions of 150 ℃, 170 ℃ and 200 ℃ under the protection of nitrogen, and carrying out crosslinking and curing under the condition of high-temperature heating to obtain the repairable and recyclable multi-walled carbon nanotube/polyaryletherketone thermosetting composite material. Can be heated to 200 ℃ in N-methyl pyrrolidone for 12 hours for processing, and re-dissolution and film spreading are carried out to realize reprocessing. The repairing can be realized by heating the mixture in a mold to 200 ℃, treating the mixture for 2 hours and then cooling the mixture to room temperature.

Example 3

According to the weight ratio of 0.4:0.6:1.0:1.2 batch ratios 2.0122g (0.01 mol) 2- (4 '-aminobenzene) -hydroquinone, 5.0435 g (0.015 mol) hexafluorobisphenol A,5.4550g (0.025 mol) 4,4' -difluorobenzophenone, 4.1463g (0.03 mol) potassium carbonate (salt former) were weighed into a 100mL round bottom three-neck flask equipped with mechanical stirring paddle, nitrogen vent, thermometer, water-carrying device and spherical condenser, while adding 45mL dimethyl sulfoxide as solvent and 15mL toluene as azeotropic water-carrying agent. Introducing nitrogen, starting stirring, heating to toluene reflux, carrying out water temperature of about 120 ℃, and slowly discharging the toluene after carrying water for two hours. And continuously heating the reaction system to 150 ℃ for polymerization reaction, discharging the obtained polymer solution into deionized water after 10-hour reaction, crushing the precipitated polymer, and boiling and washing the crushed polymer for 3 times by using distilled water and absolute ethyl alcohol respectively under the protection of nitrogen. So as to remove redundant solvent, inorganic salt, unreacted monomer and oligomer with lower molecular weight in the polymer. And (3) putting the light purple polymer obtained by washing and suction filtration into a vacuum oven, and carrying out vacuum-pumping drying at 60 ℃ for 24 hours to obtain the polyaryletherketone containing the aminophenyl side group and having the amino molar content of 40%, wherein the molecular formula is as follows:

wherein m =14 to 22; a =0.4,a + b =1.

4.9726g (10 mmol) of the polyaryletherketone containing the amino-benzene side group obtained above and 0.4932g (4.4 mmol) of furancarboxylic acid (1.1 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) are put into a container with a stirrer, then 1.24g of N, N-Dicyclohexyldiimine (DCC) (1.5 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) and 0.72g of 4-Dimethylaminopyridine (DMAP) (0.15 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) are added, then the container is vacuumized until the vacuum degree reaches 0.1MPa, high-purity nitrogen is discharged and then vacuumized until the vacuum degree reaches 0.1MPa, high-purity nitrogen is discharged and is repeatedly used for 4 times, finally 400mL of tetrahydrofuran is injected for dissolving, then the container is sealed, stirring is started, and the room temperature reaction is carried out for 48 hours; filtering with diatomite, removing solvent under reduced pressure, washing with acetone for 4 times, filtering, and vacuum-pumping and oven-drying at 80 deg.C to obtain 5.2g polyaryletherketone material containing furan benzene side group with furan molar content of 40%.

The molecular formula is as follows:

wherein n =15 to 23; x =0.4, x + y =1.

Weighing 0.99g of polyaryletherketone containing furan benzene side groups and containing 40% of furan molar content, which is fully dried in a vacuum oven, into a 50ml conical flask, adding 10ml of DMAc, starting stirring to completely dissolve the polymer, weighing 0.01g of multi-walled carbon nanotubes (MWCNT), dissolving in 2ml of DMAc, stirring for 2 hours, and performing ultrasonic treatment for 3 hours. The homogeneously dispersed multi-walled carbon nanotube (MWCNT) solution was added to the polymer solution, the mixed solution was sonicated for 2 hours and then the mixed solution filtered using a copper mesh was poured uniformly onto a pre-leveled glass plate of 10cm x 10cm size in a vacuum oven preheated at 40 ℃. Firstly keeping the temperature at 60 ℃ under normal pressure for 24 hours, removing the solvent volatilized out from the oven every 12 hours, raising the temperature after the solvent is completely volatilized, keeping the temperature at 80 ℃, 100 ℃ and 120 ℃ under normal pressure for 2 hours respectively, naturally cooling to 60 ℃, vacuumizing at 60 ℃, 80 ℃, 100 ℃ and 120 ℃ and then drying for 2 hours respectively, and soaking the glass plate cooled to room temperature in deionized water after the solvent is completely removed to obtain the composite material film with the MWCNT addition of 1 wt%.

Placing the multi-walled carbon nanotube and the polyaryletherketone ketone composite material containing the furan-benzene side group in a tube furnace, respectively carrying out heat treatment for 1 hour at the conditions of 150 ℃, 170 ℃ and 200 ℃ under the protection of nitrogen, and carrying out crosslinking and curing under the condition of high-temperature heating to obtain the repairable and recyclable multi-walled carbon nanotube and polyaryletherketone composite thermosetting material containing the furan-benzene side group. Can be heated to 200 ℃ in N-methyl pyrrolidone for 12 hours for processing, and re-dissolution and film spreading are carried out to realize reprocessing. The repairing can be realized by heating the mixture in a mould to 200 ℃ for 2 hours and then cooling the mixture to room temperature.

Example 4

According to the weight ratio of 0.4:0.6:1.0:1.2 batch ratios 2.0122g (0.01 mol) 2- (4 '-aminobenzene) -hydroquinone, 5.0435 g (0.015 mol) hexafluorobisphenol A,5.4550g (0.025 mol) 4,4' -difluorobenzophenone, 4.1463g (0.03 mol) potassium carbonate (salt former) were weighed into a 100mL round bottom three-neck flask equipped with mechanical stirring paddle, nitrogen vent, thermometer, water-carrying device and spherical condenser, while adding 45mL dimethyl sulfoxide as solvent and 15mL toluene as azeotropic water-carrying agent. Introducing nitrogen, starting stirring, heating to toluene reflux, carrying out water temperature of about 140 ℃, and slowly discharging the toluene after carrying water for two hours. And continuously heating the reaction system to 170 ℃ for polymerization reaction, discharging the obtained polymer solution into deionized water after 7-hour reaction, crushing the precipitated polymer, and boiling and washing the crushed polymer for 3 times by using distilled water and absolute ethyl alcohol respectively under the protection of nitrogen. To remove the excess solvent, inorganic salts, unreacted monomers and oligomers with lower molecular weight from the polymer. And (3) placing the light purple polymer obtained by washing and suction filtration into a vacuum oven, and carrying out vacuum-pumping drying at 60 ℃ for 24 hours to obtain the polyaryletherketone containing the amino-benzene side group and having the amino molar content of 40%, wherein the molecular formula is as follows:

wherein m =14 to 22; a =0.4,a + b =1.

4.9726g (10 mmol) of the polyaryletherketone containing the amino-benzene side group obtained above and 0.4932g (4.4 mmol) of furancarboxylic acid (1.1 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) are put into a container with a stirrer, then 1.24g of N, N-Dicyclohexyldiimine (DCC) (1.5 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) and 0.72g of 4-Dimethylaminopyridine (DMAP) (0.15 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) are added, then the container is vacuumized until the vacuum degree reaches 0.1MPa, high-purity nitrogen is added and the container is repeatedly used for 4 times, finally 400mL of tetrahydrofuran is injected and dissolved, then the container is sealed, the stirring is started and the room temperature reaction is carried out for 60 hours; filtering with diatomite, removing solvent under reduced pressure, washing with acetone for 4 times, filtering, and vacuum-pumping and oven-drying at 80 deg.C to obtain 5.2g polyaryletherketone material containing furan benzene side group with furan molar content of 40%.

The molecular formula is as follows:

wherein n =15 to 23; x =0.4, x + y =1.

Weighing 0.99g of polyaryletherketone containing furan phenyl side group with the molar content of 40 percent and fully dried in a vacuum oven, adding the polyaryletherketone into a 50ml conical flask, adding 10ml of DMAc, starting stirring to completely dissolve the polymer, weighing 0.01g of multi-walled carbon nano-tube (MWCNT), dissolving the multi-walled carbon nano-tube in 2ml of DMAc, stirring for 2 hours, and carrying out ultrasound for 3 hours. The homogeneously dispersed multi-walled carbon nanotube (MWCNT) solution was added to the polymer solution, the mixed solution was sonicated for 2 hours and then the mixed solution filtered using a copper mesh was poured uniformly onto a pre-leveled glass plate of 10cm x 10cm size in a vacuum oven preheated at 40 ℃. Firstly keeping the temperature at the normal pressure of 60 ℃ for 24 hours, removing the solvent volatilized from the oven every 12 hours, raising the temperature after the solvent is completely volatilized, keeping the temperature at the normal pressure of 80 ℃, 100 ℃ and 120 ℃ for 2 hours respectively, naturally cooling to 60 ℃, vacuumizing at the temperature of 60 ℃, 80 ℃, 100 ℃ and 120 ℃ and then drying for 4 hours respectively, and soaking the glass plate cooled to the room temperature in deionized water after the solvent is completely removed to obtain the composite material film with the MWCNT addition of 1 wt%.

Placing the multi-walled carbon nanotube and the polyaryletherketone ketone composite material containing the furan-benzene side group in a tube furnace, respectively carrying out heat treatment for 1 hour at the conditions of 150 ℃, 170 ℃ and 200 ℃ under the protection of nitrogen, and carrying out crosslinking and curing under the condition of high-temperature heating to obtain the repairable and recyclable multi-walled carbon nanotube and polyaryletherketone composite thermosetting material containing the furan-benzene side group. Can be heated to 200 ℃ in N-methylpyrrolidone for 12 hours for re-dissolving and film-spreading to realize reprocessing. The repairing can be realized by heating the mixture in a mould to 200 ℃ for 2 hours and then cooling the mixture to room temperature.

Example 5

According to the weight ratio of 0.6:0.4:1.0:1.2 batch ratios 3.0183g (0.015 mol) 2- (4 '-aminobenzene) -hydroquinone, 3.3623g (0.01 mol) hexafluorobisphenol A,5.4550g (0.025 mol) 4,4' -difluorobenzophenone, 4.1463g (0.03 mol) potassium carbonate (salt former) were weighed into a 100mL round bottom three-neck flask equipped with a mechanical stirring paddle, nitrogen vent, thermometer, water-carrying device and spherical condenser, while 45mL dimethyl sulfoxide was added as solvent and 15mL toluene was added as azeotropic water-carrying device. Introducing nitrogen, starting stirring, heating to toluene reflux, carrying out water temperature of about 120 ℃, and slowly discharging the toluene after carrying water for two hours. And continuously heating the reaction system to 150 ℃ for polymerization reaction, discharging the obtained polymer solution into deionized water after 10-hour reaction, crushing the precipitated polymer, and boiling and washing the crushed polymer for 3 times by using distilled water and absolute ethyl alcohol respectively under the protection of nitrogen. To remove the excess solvent, inorganic salts, unreacted monomers and oligomers with lower molecular weight from the polymer. And (3) placing the light purple polymer obtained by washing and suction filtration into a vacuum oven, and carrying out vacuum-pumping drying at 60 ℃ for 24 hours to obtain the polyaryletherketone containing the aminophenyl side group and having the amino molar content of 60%, wherein the molecular formula is as follows:

wherein m =14 to 23; a =0.6,a + b =1.

4.8866g (10 mmol) of the polyaryletherketone containing the amino-benzene side group obtained above and 0.7398g (6.6 mmol) of furancarboxylic acid (1.1 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) are put into a container with a stirrer, then 1.86g of N, N-Dicyclohexyldiimine (DCC) (1.5 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) and 1.08g of 4-Dimethylaminopyridine (DMAP) (0.15 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) are added, then the container is vacuumized until the vacuum degree reaches 0.1MPa, high-purity nitrogen is discharged and then vacuumized until the vacuum degree reaches 0.1MPa, high-purity nitrogen is discharged and is repeatedly used for 4 times, finally 600mL of tetrahydrofuran is injected for dissolving, then the container is sealed, stirring is started, and the room temperature reaction is carried out for 48 hours; filtering with diatomite, removing solvent under reduced pressure, washing with acetone for 4 times, filtering, and vacuum-pumping and oven-drying at 80 deg.C to obtain 5.3g polyaryletherketone material containing furan benzene side group with furan molar content of 60%.

The molecular formula is as follows:

wherein n =16 to 25; x =0.6,x + y =1.

Weighing 0.99g of the polyaryletherketone containing the furan benzene side group with the molar content of 60 percent, which is fully dried in a vacuum oven, adding the polyaryletherketone into a 50ml conical flask, adding 10ml of DMAc, starting stirring to completely dissolve the polymer, weighing 0.01g of multi-walled carbon nanotubes (MWCNT) and dissolving the multi-walled carbon nanotubes (MWCNT) into 2ml of DMAc, stirring for 2 hours, and carrying out ultrasonic treatment for 2-4 hours. The homogeneously dispersed multi-walled carbon nanotube (MWCNT) solution was added to the polymer solution, the mixed solution was sonicated for 2 hours and then the mixed solution filtered using a copper mesh was poured uniformly onto a pre-leveled glass plate of 10cm x 10cm size in a vacuum oven preheated at 40 ℃. Firstly keeping the temperature at 60 ℃ under normal pressure for 24 hours, removing the solvent volatilized out from the oven every 12 hours, raising the temperature after the solvent is completely volatilized, keeping the temperature at 80 ℃, 100 ℃ and 120 ℃ under normal pressure for 2 hours respectively, naturally cooling to 60 ℃, vacuumizing at 60 ℃, 80 ℃, 100 ℃ and 120 ℃ and then drying for 2 hours respectively, and soaking a glass plate cooled to room temperature in deionized water after the solvent is completely removed to obtain the composite material film with the addition of the multi-walled carbon nanotube (MWCNT) of 1 wt%.

Example 6

According to the weight ratio of 0.6:0.4:1.0: 3.0183g (0.015 mol) 2- (4 '-aminobenzene) -hydroquinone, 3.3623g (0.01 mol) hexafluorobisphenol A,5.4550g (0.025 mol) 4,4' -difluorobenzophenone, 4.1463g (0.03 mol) potassium carbonate (salt former) were weighed into a 100mL round bottom three-neck flask equipped with mechanical stirring paddle, nitrogen vent, thermometer, water-carrying device and spherical condenser, along with 45mL dimethyl sulfoxide as solvent and 15mL toluene as azeotropic water-carrying device at a charge ratio of 1.2. Introducing nitrogen, starting stirring, heating to toluene reflux, carrying out water temperature of about 140 ℃, and slowly discharging the toluene after carrying water for two hours. And continuously heating the reaction system to 170 ℃ for polymerization reaction, discharging the obtained polymer solution into deionized water after 7-hour reaction, crushing the precipitated polymer, and boiling and washing the crushed polymer for 3 times by using distilled water and absolute ethyl alcohol respectively under the protection of nitrogen. To remove the excess solvent, inorganic salts, unreacted monomers and oligomers with lower molecular weight from the polymer. And (3) placing the light purple polymer obtained by washing and suction filtration into a vacuum oven, and carrying out vacuum-pumping drying at 60 ℃ for 24 hours to obtain the polyaryletherketone containing the aminophenyl side group and having the amino molar content of 60%, wherein the molecular formula is as follows:

wherein m =14 to 23; a =0.6,a + b =1.

4.8866g (10 mmol) of the polyaryletherketone containing the amino-benzene side group obtained above and 0.7398g (6.6 mmol) of furancarboxylic acid (1.1 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) are put into a container with a stirrer, then 1.86g of N, N-Dicyclohexyldiimine (DCC) (1.5 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) and 1.08g of 4-Dimethylaminopyridine (DMAP) (0.15 times of the molar weight of the amino group in the polyaryletherketone containing the amino-benzene side group) are added, then the container is vacuumized until the vacuum degree reaches 0.1MPa, high-purity nitrogen is discharged and then vacuumized until the vacuum degree reaches 0.1MPa, high-purity nitrogen is discharged and is repeatedly used for 4 times, finally 600mL of tetrahydrofuran is injected for dissolving, then the container is sealed, stirring is started, and the room temperature reaction is carried out for 60 hours; filtering with diatomite, removing solvent under reduced pressure, washing with acetone for 4 times, filtering, vacuumizing, and oven drying at 80 deg.C to obtain 5.3g polyaryletherketone material containing furan phenyl side group with molar content of 60%.

The molecular formula is as follows:

wherein n =16 to 25; x =0.6,x + y =1.

Weighing 0.99g of the polyaryletherketone containing the furan benzene side group with the molar content of 60 percent, which is fully dried in a vacuum oven, adding the polyaryletherketone into a 50ml conical flask, adding 10ml of DMAc, starting stirring to completely dissolve the polymer, weighing 0.01g of multi-walled carbon nanotubes (MWCNT) and dissolving the multi-walled carbon nanotubes (MWCNT) into 2ml of DMAc, stirring for 2 hours, and carrying out ultrasonic treatment for 2-4 hours. The homogeneously dispersed multi-walled carbon nanotube (MWCNT) solution was added to the polymer solution, the mixed solution was sonicated for 2 hours and then the mixed solution filtered using a copper mesh was poured uniformly onto a pre-leveled glass plate of 10cm x 10cm size in a vacuum oven preheated at 40 ℃. Firstly keeping the temperature at the normal pressure of 60 ℃ for 24 hours, removing the solvent volatilized from the oven every 12 hours, raising the temperature after the solvent is completely volatilized, keeping the temperature at the normal pressure of 80 ℃, 100 ℃ and 120 ℃ for 2 hours respectively, naturally cooling to 60 ℃, vacuumizing at the temperature of 60 ℃, 80 ℃, 100 ℃ and 120 ℃ and then drying for 4 hours respectively, and soaking the glass plate cooled to room temperature in deionized water after the solvent is completely removed to obtain the composite material film with the addition of the multiwalled carbon nanotube (MWCNT) of 1 wt%.

Placing the multi-walled carbon nanotube and the polyaryletherketone ketone composite material containing the furan-benzene side group in a tube furnace, respectively carrying out heat treatment for 1 hour at the conditions of 150 ℃, 170 ℃ and 200 ℃ under the protection of nitrogen, and carrying out crosslinking and curing under the condition of high-temperature heating to obtain the repairable and recyclable multi-walled carbon nanotube and polyaryletherketone composite thermosetting material containing the furan-benzene side group. Can be heated to 200 ℃ in N-methyl pyrrolidone for 12 hours for processing, and re-dissolution and film spreading are carried out to realize reprocessing. The repairing can be realized by heating to 200 ℃ in a mould, treating for 2 hours, and then cooling to room temperature.

Performance testing

The films obtained in example 1, example 3 and example 5 were punched out to form two dumbbell-shaped tensile bars (75 mm long, 10mm wide and 5mm wide, 0.1mm thick for tensile testing) and rectangular DMA bars (50 mm long, 5mm wide and 0.1mm thick for dynamic thermomechanical testing).

Table 1: mechanical property of multi-wall carbon nano tube and polyaryletherketone (MWCNT/PAEK-Fu) composite material containing furan benzene side group

Note: table 1 (MWCNT/PAEK-Fu-20/weichuli) shows a composite film in which MWCNT added in an amount of 1wt% in example 1 has not been subjected to high-temperature treatment; 2 (MWCNT/PAEK-Fu-20/150) is a sample obtained by subjecting the composite film of example 1 in which MWCNT is added in an amount of 1wt% to a heat treatment at 150 ℃ for 1 hour; 3 (MWCNT/PAEK-Fu-20/170) is a sample obtained by subjecting the composite film of example 1 in which MWCNT is added in an amount of 1wt% to a heat treatment at 170 ℃ for 1 hour; 4 (MWCNT/PAEK-Fu-20/200) is a sample obtained by subjecting the composite film of example 1 in which MWCNT is added in an amount of 1wt% to a heat treatment at 200 ℃ for 1 hour. Table 5 (MWCNT/PAEK-Fu-40/weichuli) is a composite film in which MWCNT not subjected to high temperature treatment in example 3 is added in an amount of 1 wt%; 6 (MWCNT/PAEK-Fu-40/150) is a sample obtained by subjecting the composite film of example 3, in which MWCNT was added in an amount of 1wt%, to a heat treatment at 150 ℃ for 1 hour; 7 (MWCNT/PAEK-Fu-40/170) is a sample obtained by subjecting the composite film of example 3, in which MWCNT was added in an amount of 1wt%, to a heat treatment at 170 ℃ for 1 hour; the sample 8 (MWCNT/PAEK-Fu-40/200) was obtained by subjecting the composite film of example 3, in which the MWCNT content was 1wt%, to a heat treatment at 200 ℃ for 0.5 to 1 hour.

As shown in Table 1, after the MWCNT/PAEK-Fu-20 is subjected to heat treatment, the mechanical property is obviously improved, the tensile strength is continuously enhanced along with the continuous increase of the heat treatment temperature, and the tensile strength is improved from 61.7MPa without heat treatment to 75.3 MPa after the heat treatment at 200 ℃; the elongation at break is reduced continuously from 7.2% without heat treatment to 5.2% after heat treatment at 200 ℃. Because the DA reaction proceeds more completely with increasing temperature, the crosslink density of the composite gradually increases, resulting in a gradually increasing tensile strength and a gradually decreasing elongation at break of the composite with increasing processing temperature. The material was almost completely crosslinked by treatment at 200 ℃. The tensile strength of the MWCNT/PAEK-Fu-40 is continuously enhanced along with the increase of the heat treatment temperature, and is improved from 63.1MPa without heat treatment to 84MPa after heat treatment at 200 ℃; the elongation at break shows a tendency to increase first and then decrease. This is because PAEK-Fu-40 has a smaller molecular weight, and as the temperature increases, the DA reaction proceeds more completely, the crosslinking density of the composite material gradually increases, the mechanical strength increases, and when the treatment temperature reaches 200 ℃, the material becomes brittle after further crosslinking, and the elongation at break begins to decrease.

The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention should be covered within the scope of the present invention.

Claims

1. A multi-walled carbon nanotube and polyaryletherketone ketone compound thermosetting material containing furan benzene side groups is characterized in that: the composite thermosetting material is formed by blending a multiwalled carbon nanotube and polyaryletherketone containing a furan-benzene side group, wherein the polyaryletherketone containing the furan-benzene side group is a polymer solution with the concentration of 0.08-0.1 g/mL, and the mass ratio of the multiwalled carbon nanotube to the polyaryletherketone containing the furan-benzene side group is 1:20 to 100;

the polyaryletherketone containing the furan-benzene side group is generated by reacting polyaryletherketone containing the amino-benzene side group with a furanformic acid monomer, and the structural formula of the polyaryletherketone containing the furan-benzene side group is as follows:

wherein, the molar content of the furan is 20 to 60 percent

n＝16～23；x＝0.2～0.6，x+y＝1；

The polyaryletherketone containing the aminophenyl side group consists of a polyaryletherketone main chain and a polyaryletherketone side chain containing the aminophenyl side group, wherein the molar content of the side chain containing the aminophenyl side group is 20-60%, and the structural formula is as follows:

wherein m =16 to 23; a = 0.2-0.6, a + b =1.

2. The method for preparing the multi-walled carbon nanotube and polyaryletherketone ketone composite thermosetting material containing furan benzene side groups as claimed in claim 1 comprises the following steps: the method comprises the following steps:

1.1 Taking a certain amount of 2- (4 ' -aminobenzene) -hydroquinone monomer, a certain amount of hexafluorobisphenol A diphenol monomer and 4,4' -difluorobenzophenone monomer with the total mole of diphenol being equal to the mole of the diphenol, and anhydrous potassium carbonate, dimethyl sulfoxide and toluene azeotropic dehydrating agent with the mole amount being 1.05-1.10 times of 4,4' -difluorobenzophenone monomer; the sum of diphenols is: the sum of 2- (4' -aminobenzene) -hydroquinone monomer and hexafluorobisphenol a-type diphenol monomer; the dosage of the dimethyl sulfoxide is 3-6 times of the sum of the mass of three reaction monomers, namely a 2- (4 '-aminobenzene) -hydroquinone monomer, a hexafluorobisphenol A type diphenol monomer and a 4,4' -difluorobenzophenone monomer, and the dosage of the toluene is 20-30% of the volume of the dimethyl sulfoxide;

1.2 Putting the raw materials selected in the step 1.1) into a three-neck flask provided with a nitrogen through hole, mechanical stirring and a water carrying device;

1.3 Introducing nitrogen into a three-neck flask, starting stirring, heating to 120-140 ℃, refluxing an azeotropic dehydrating agent toluene, continuously stirring and reacting for 1-3 hours at constant temperature under the atmosphere of nitrogen, further removing the azeotropic dehydrating agent toluene, heating to 150-170 ℃, continuously reacting for 7-10 hours at constant temperature, increasing the molecular weight of the polymer and making the polymer uniform, then cooling to room temperature to obtain a polyaryletherketone polymer solution containing the aminophenyl side group, pouring the polymer solution into deionized water with the volume of 50-60 times of that of dimethyl sulfoxide to make the polymer precipitate to be an off-white thin strip solid, and crushing, washing and drying to obtain the polyaryletherketone solid polymer containing the aminophenyl side group;

Putting the polyaryletherketone solid polymer containing the aminophenyl side group obtained in the step 1.3) and furancarboxylic acid into a container with a stirrer, adding a dehydrating agent N, N-dicyclohexyl diimine and 4-dimethylaminopyridine, vacuumizing, then, discharging high-purity nitrogen after vacuumizing, vacuumizing again, discharging high-purity nitrogen, removing oxygen and water vapor, repeating for 3-5 times, then, injecting tetrahydrofuran, wherein the tetrahydrofuran is used by adding 5ml of tetrahydrofuran into each 1g of polyaryletherketone solid polymer containing the aminophenyl side group, dissolving, sealing, starting stirring, stirring at room temperature for 48-60 hours, carrying out amidation reaction, then, filtering by using diatomite, distilling under reduced pressure to remove the organic solvent, washing by using acetone for 3-5 times, further removing the organic solvent and impurities, and drying at the vacuum temperature of 80 ℃ to obtain the polyaryletherketone material containing the furan phenyl side group;

(3) Preparation of composite thermosetting material

3.1 Preparing a polyaryletherketone polymer solution containing furan benzene side groups: dissolving polyaryletherketone containing furan-phenyl side groups by using an organic solvent to prepare a polyaryletherketone polymer solution containing furan-phenyl side groups with the concentration of 0.08-0.1 g/mL, wherein the organic solvent is one of dimethyl sulfoxide, N-dimethylacetamide or N-methylpyrrolidone;

3.2 Preparing a multi-walled carbon nanotube solution: the mass ratio of the multi-walled carbon nano-tube to the polyaryletherketone containing the furan phenyl side group is 1: 20-100, adding the multi-walled carbon nanotubes into an organic solvent according to a proportion, preparing a multi-walled carbon nanotube solution with the concentration of 0.005-0.01 g/mL, stirring for 1-3 hours, and performing ultrasonic treatment for 2-4 hours to uniformly disperse the multi-walled carbon nanotubes (MWCNT) in the organic solvent; the organic solvent is one of dimethyl sulfoxide, N-dimethylacetamide and N-methylpyrrolidone;

3.3 Preparation of composite materials: adding the multi-walled carbon nanotube solution obtained in the step 3.2) into the polyaryletherketone polymer solution containing the furan phenyl side group obtained in the step 3.1), continuing performing ultrasonic treatment on the obtained mixed solution for 1-3 hours to prepare a composite material solution, discharging the composite material solution into deionized water to precipitate the composite material solution, drying at 100 ℃ to obtain a black powdery solid composite material, and storing;

3.4 Curing): using the composite material solution or the powdery solid composite material obtained in the step 3.3), treating at 150-200 ℃ for 1-2 hours, and cooling to room temperature to obtain the multi-walled carbon nanotube and polyaryletherketone composite thermosetting material containing furan phenyl side groups.