Modified boron nitride, preparation method, application, polyaryletherketone composite material and preparation method thereof

Abstract

The application belongs to the technical field of polymer composites, and particularly relates to modified boron nitride, a preparation method and application thereof, a polyaryletherketone composite material and a preparation method thereof. The modified boron nitride provided by the application has good thermal stability and no obvious thermal decomposition before 460 DEG C. The modified boron nitride provided by the application is surface-functionalized and has fluorine-containing groups grafted on the surface, so that the boron nitride can participate in the preparation process of the polyaryletherketone, and the boron nitride covalently modifies the polyaryletherketone. The modified boron nitride provided by the application has good thermal stability, can be used for modifying resin, especially polyaryletherketone resin, can significantly improve the thermal conductivity and mechanical properties of the resin, and plays an extremely key role in preparing high-thermal-conductivity polyaryletherketone composite materials. The polyaryletherketone composite material provided by the application is modified by the modified boron nitride in the above scheme, so that the polyaryletherketone composite material has good thermal conductivity and mechanical properties.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer composite materials, and particularly relates to modified boron nitride, a preparation method and application thereof, and a polyaryletherketone composite material and a preparation method. BACKGROUND

[0002] Polyaryletherketone (PAEK) is a kind of special engineering plastic with excellent performance, which has excellent extreme environment resistance and can adapt to various severe application conditions, from civil high-tech fields to aerospace and military fields. With the rapid development of science and technology and the continuous expansion of exploration fields, the performance requirements of polyaryletherketone materials are also increasing, especially in terms of high temperature resistance. The low intrinsic thermal conductivity of polyaryletherketone leads to a large amount of heat accumulation in the material, which affects the service life and operation reliability. In order to prepare high-thermal-conductivity polyaryletherketone composite materials, people began to use thermal conductive fillers to fill polyaryletherketone to modify its high thermal conductivity.

[0003] Boron nitride (BN) and boron nitride nanosheet (BNNS) have excellent thermal conductivity, mechanical properties, thermal stability and insulation performance due to their unique two-dimensional sheet structure, and are known as "white graphite", and are considered as an ideal filler for preparing high-thermal-conductivity insulation composite materials. However, the chemical inertness of the surface of boron nitride limits its chemical connection with resin materials, and it is difficult for the two to form strong interfacial bonding force, which affects the filling and reinforcing efficiency.

[0004] In order to solve the above problems, people use covalent bond modification and non-covalent bond modification methods to improve the interfacial bonding force between boron nitride and polyaryletherketone resin. Common methods include mixed acid etching, mixed alkali ball milling, hydrothermal synthesis and alkali etching. However, the functional group activity of boron nitride treated by the above methods is low, and it is difficult to form chemical bonds with polyaryletherketone. Its thermal stability cannot support the processing temperature of polyaryletherketone above 300 DEG C. SUMMARY

[0005] The purpose of the present application is to provide a modified boron nitride and its preparation method and application, and a polyaryletherketone composite material and its preparation method. The modified boron nitride provided by the present application can covalently bond with the polyaryletherketone composite material, and can support the processing temperature of polyaryletherketone above 300 DEG C.

[0006] In order to achieve the above purpose, the present application provides the following technical scheme:

[0007] The present application provides a modified boron nitride, which comprises boron nitride and a fluorine-containing group grafted to the boron nitride through an oxygen atom, wherein the oxygen atom is connected to a bare boron atom of the boron nitride; and the fluorine-containing group comprises one or more of 1,4-bis(4-fluorobenzoyl)phenyl and 4,4'-difluorobenzophenone group.

[0008] Preferably, the boron nitride is boron nitride nanoplatelets; and the grafting amount of fluorine-containing groups in the modified boron nitride is 0.5-20wt%.

[0009] The application also provides a preparation method of the modified boron nitride as described above, comprising the following steps:

[0010] The boron nitride, the fluorine-containing compound, the catalyst and the aprotic solvent are mixed to perform grafting reaction to obtain the modified boron nitride; the fluorine-containing compound includes one or more of 1,4-bis(4-fluorobenzoyl)benzene and 4,4'-difluorobenzophenone.

[0011] Preferably, the mass ratio of the boron nitride to the fluorine-containing compound is 1:0.1-10; and the mass ratio of the boron nitride to the catalyst is 1:0.1-20.

[0012] The application also provides an application of the modified boron nitride as described above or the modified boron nitride obtained by the preparation method as described above in resin modification.

[0013] The application also provides a polyaryletherketone composite material, which comprises a polyaryletherketone matrix and modified boron nitride covalently bonded to the polyaryletherketone matrix; the modified boron nitride is the modified boron nitride as described above or the modified boron nitride obtained by the preparation method as described above.

[0014] Preferably, the mass ratio of the polyaryletherketone matrix to the modified boron nitride is 100:1-40.

[0015] The application also provides a preparation method of the polyaryletherketone composite material as described above, comprising the following steps:

[0016] The fluorine-containing compound, the aromatic compound, the modified boron nitride, the catalyst, the water-carrying agent and the aprotic solvent are mixed to perform covalent in-situ polymerization reaction to obtain the polyaryletherketone composite material; the fluorine-containing compound includes one or more of 1,4-bis(4-fluorobenzoyl)benzene and 4,4'-difluorobenzophenone; the aromatic compound includes one of hydroquinone and 4,4'-dihydroxybenzophenone; and the modified boron nitride is the modified boron nitride as described above or the modified boron nitride obtained by the preparation method as described above.

[0017] Preferably, the molar ratio of the fluorine-containing compound to the aromatic compound is 1-1.2:1; the addition amount of the modified boron nitride is 0.5-40wt% of the modified boron nitride in the polyaryletherketone composite material; the molar ratio of the catalyst to the aromatic compound is 1-1.2:1; and the volume ratio of the water-carrying agent to the aprotic solvent is 0.3-0.5:1.

[0018] Preferably, the covalent bond in-situ polymerization reaction comprises a first stage, a second stage, a third stage and a fourth stage; the first stage has a temperature of 160-195 DEG C and a holding reaction time of 1-3 h; the second stage has a temperature of 200-260 DEG C and a holding reaction time of 1-5 h; the third stage has a temperature of 260-280 DEG C and a holding reaction time of 0.5-1.5 h; and the fourth stage has a temperature of 300-315 DEG C and a holding reaction time of 0.5-1.5 h.

[0019] The application provides a modified boron nitride.

[0020] The application also provides a preparation method of the modified boron nitride.

[0021] The application also provides an application of the modified boron nitride in resin modification.

[0022] The application also provides a polyaryletherketone composite material.

[0023] The application also provides a preparation method of the polyaryletherketone composite material. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the application or the prior art, the following will briefly introduce the drawings needed in the embodiments. Obviously, the drawings in the following description are only some embodiments of the application, and for those skilled in the art, other drawings can also be obtained from these drawings without creative labor.

[0025] Figure 1 XPS spectra of boron nitride and modified boron nitride in Example 3;

[0026] Figure 2 TGA graph of boron nitride and modified boron nitride in Example 3;

[0027] Figure 3 Infrared spectrum of modified boron nitride in Example 3;

[0028] Figure 4 Synthesis principle diagram of modified boron nitride provided by the present application;

[0029] Figure 5 TEM diagram of polyaryletherketone composite material of Example 7;

[0030] Figure 6 Interface thermal resistance diagram of polyaryletherketone composite material of Example 7;

[0031] Figure 7 Thermogravimetric analysis diagram of polyaryletherketone composite material of Example 5. DETAILED DESCRIPTION

[0032] The present application provides a modified boron nitride, comprising boron nitride and fluorine-containing groups grafted to the boron nitride through oxygen atoms, the oxygen atoms being connected to exposed boron atoms of the boron nitride; the fluorine-containing groups comprising one or more of 1,4-bis(4-fluorobenzoyl)phenyl and 4,4'-difluorobenzophenone groups.

[0033] In the present application, the boron nitride is preferably boron nitride nanosheet.

[0034] In the present application, the grafting amount of the boron nitride is preferably 0.5-20wt%, and can be specifically 0.5wt%, 1wt%, 2wt%, 5wt%, 6wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt% or 20wt%.

[0035] The present application also provides a preparation method of the modified boron nitride described in the above scheme, comprising the following steps:

[0036] The boron nitride, fluorine-containing compound, catalyst and aprotic solvent are mixed to carry out grafting reaction to obtain the modified boron nitride; the fluorine-containing compound comprises one or more of 1,4-bis(4-fluorobenzoyl)phenyl and 4,4'-difluorobenzophenone.

[0037] The present application mixes the boron nitride, fluorine-containing compound, catalyst and aprotic solvent. In the present application, the mass ratio of the boron nitride and fluorine-containing compound is preferably 1:0.1-10, and can be specifically 1:0.1, 1:0.2, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.7, 1:2, 1:3, 1:5, 1:7 or 1:10.

[0038] In the present application, the catalyst is preferably a base compound; the base compound is preferably an alkali hydroxide; the alkali hydroxide preferably includes one or several of sodium hydroxide and potassium hydroxide.

[0039] In the present application, the mass ratio of the boron nitride and the catalyst is preferably 1:0.1-20, and can be 1:0.1, 1:0.5, 1:1, 1:2, 1:5, 1:8, 1:10, 1:12, 1:15, 1:18 or 1:20.

[0040] In the present application, the aprotic solvent preferably includes one or several of sulfolane, N,N-dimethylacetamide and N-methylpyrrolidone. The present application provides a reaction environment through the aprotic solvent.

[0041] In the present application, the mass-volume ratio of the boron nitride and the aprotic solvent is preferably 1g:(10-50)mL, and can be 1g:10mL, 1g:15mL, 1g:20mL, 1g:25mL, 1g:30mL, 1g:40mL or 1g:50mL.

[0042] After mixing, the present application carries out a grafting reaction to obtain modified boron nitride. In the present application, the grafting reaction is preferably carried out in an inert atmosphere; the inert atmosphere is preferably dry nitrogen.

[0043] In the present application, the temperature of the grafting reaction is preferably 120-200℃, and can be 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃ or 200℃, and the holding reaction time is preferably 2-10h, and can be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h.

[0044] In the present application, the grafting reaction more preferably includes a first reaction stage and a second reaction stage; the temperature of the first reaction stage is preferably 120-140℃, and can be 120℃, 125℃, 130℃, 135℃ or 140℃, and the holding reaction time is preferably 1-5h, and can be 1h, 2h, 3h, 4h or 5h; the temperature of the second reaction stage is preferably 150-200℃, and can be 150℃, 160℃, 170℃, 180℃, 190℃ or 200℃, and the holding reaction time is preferably 2-10h, and can be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h. In the present application, the fluorine-containing group is grafted to the surface of the boron nitride during the grafting reaction, and the low-activity hydroxyl group is converted into a F group with higher reactivity to participate in the grafting of the polyaryletherketone.

[0045] In the present application, the grafting reaction preferably further comprises: after discharging the product obtained by the grafting reaction into water, sequentially performing alcohol washing and water washing; the water is preferably deionized water; the alcohol used for the alcohol washing is preferably ethanol; and the water used for the water washing is preferably deionized water.

[0046] For example, taking sodium hydroxide and 4,4'-difluorobenzophenone as an example, the mechanism for preparing the modified boron nitride according to the present application is as shown in the following formula (I): Figure 4 First, under the action of sodium hydroxide, hydroxyl groups are grafted on the surface of the boron nitride, so that the hydroxyl groups are connected to the exposed boron atoms of the boron nitride, and then 4,4'-difluorobenzophenone groups are grafted therefrom to obtain 4,4'-difluorobenzophenone-modified modified boron nitride.

[0047] The present application also provides an application of the modified boron nitride described in the above scheme or the modified boron nitride obtained by the preparation method described in the above scheme in resin modification.

[0048] The modified boron nitride provided by the present application has good thermal stability and can be used for resin modification, especially polyaryletherketone resin modification, and can significantly improve the thermal conductivity and mechanical properties of the resin, and plays an extremely key role in preparing high-thermal-conductivity polyaryletherketone composite materials.

[0049] The present application also provides a polyaryletherketone composite material, which comprises a polyaryletherketone matrix and modified boron nitride covalently modified on the polyaryletherketone matrix; the modified boron nitride is the modified boron nitride described in the above scheme or the modified boron nitride obtained by the preparation method described in the above scheme.

[0050] In the present application, the melt index of the polyaryletherketone matrix is preferably 20-100 g / 10 min, and can be specifically 20 g / 10 min, 30 g / 10 min, 40 g / 10 min, 50 g / 10 min, 60 g / 10 min, 70 g / 10 min, 80 g / 10 min, 90 g / 10 min or 100 g / 10 min.

[0051] In the present application, the mass ratio of the polyaryletherketone matrix to the modified boron nitride is preferably 100:1-40, and can be specifically 100:1, 100:3, 100:5, 100:8, 100:10, 100:13, 100:15, 100:18, 100:20, 100:22, 100:25, 100:27, 100:30, 100:33, 100:36 or 100:40.

[0052] The present application also provides a preparation method of the polyaryletherketone composite material described in the above scheme, comprising the following steps:

[0053] The fluorine-containing compound, the aromatic compound, the modified boron nitride, the catalyst, the water-carrying agent and the aprotic solvent are mixed to carry out in-situ covalent bond polymerization to obtain the polyaryletherketone composite material; the fluorine-containing compound includes one or more of 1,4-bis(4-fluorobenzoyl)benzene and 4,4'-difluorobenzophenone; the aromatic compound includes one of hydroquinone and 4,4'-dihydroxybenzophenone; the modified boron nitride is the modified boron nitride in the above scheme or the modified boron nitride obtained by the preparation method in the above scheme.

[0054] The fluorine-containing compound, the aromatic compound, the modified boron nitride, the catalyst, the water-carrying agent and the aprotic solvent are mixed in the present application. In the present application, the molar ratio of the fluorine-containing compound and the aromatic compound is preferably 1-1.2:1, and can be 1:1, 1.05:1, 1.1:1, 1.15:1 or 1.2:1.

[0055] In the present application, the addition amount of the modified boron nitride is preferably 0.5-40% of the mass content of the modified boron nitride in the polyaryletherketone composite material, and can be 0.5%, 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40%.

[0056] In the present application, the catalyst is preferably an alkali compound; the alkali compound is preferably an alkali metal carbonate; and the alkali metal carbonate preferably includes one or more of sodium carbonate and potassium carbonate.

[0057] In the present application, the molar ratio of the catalyst and the aromatic compound is preferably 1-1.2:1, and can be 1:1, 1.05:1, 1.1:1, 1.15:1 or 1.2:1.

[0058] In the present application, the water-carrying agent preferably includes xylene.

[0059] In the present application, the volume ratio of the water-carrying agent and the aprotic solvent is preferably 0.3-0.5:1, and can be 0.3:1, 0.33:1, 0.35:1, 0.38:1, 0.4:1, 0.42:1, 0.45:1, 0.48:1 or 0.5:1.

[0060] In the present application, the aprotic solvent preferably includes diphenyl sulfone.

[0061] In the present application, the mass-volume ratio of the fluorine-containing compound and the aprotic solvent is preferably 1g:(1-10)mL, and can be 1g:1mL, 1g:3mL, 1g:5mL, 1g:8mL or 1g:10mL.

[0062] After mixing, the present application carries out a covalent bond in-situ polymerization reaction to obtain a polyaryletherketone composite material. In the present application, the covalent bond in-situ polymerization reaction is preferably carried out in an inert atmosphere; the inert atmosphere is preferably dry nitrogen; and the covalent bond in-situ polymerization reaction preferably comprises a first stage, a second stage, a third stage and a fourth stage.

[0063] In the present application, the temperature of the first stage is preferably 160-195℃, and can be specifically 160℃, 165℃, 170℃, 175℃, 180℃, 185℃, 190℃ or 195℃, and the holding reaction time is preferably 1-3h, and can be specifically 1h, 1.5h, 2h, 2.5h or 3h.

[0064] In the present application, the temperature of the second stage is preferably 200-260℃, and can be specifically 200℃, 210℃, 220℃, 230℃, 240℃, 250℃ or 260℃, and the holding reaction time is preferably 1-5h, and can be specifically 1h, 2h, 3h, 4h or 5h.

[0065] In the present application, the temperature of the third stage is preferably 260-280℃, and can be specifically 260℃, 265℃, 270℃, 275℃ or 280℃, and the holding reaction time is preferably 0.5-1.5h, and can be specifically 0.5h, 0.8h, 1h, 1.3h or 1.5h.

[0066] In the present application, the temperature of the fourth stage is preferably 300-315℃, and can be specifically 300℃, 303℃, 305℃, 308℃, 310℃, 312℃ or 315℃, and the holding reaction time is preferably 0.5-1.5h, and can be specifically 0.5h, 0.8h, 1h, 1.2h or 1.5h.

[0067] In the present application, in the first stage, the water-carrying agent functions to carry out water generated in the reaction system; in the second stage, the water-carrying agent is removed and a polymerization reaction is carried out by increasing the temperature; in the third stage, the oligomers continue to carry out a polymerization reaction, which is a stage of significant increase in molecular weight; and in the fourth stage, the degree of polymerization of the polymer gradually stabilizes, the molecular weight is uniform, and a polyaryletherketone composite material is obtained.

[0068] In order to further illustrate the present application, the schemes of the present application are described in detail below in combination with the drawings and examples, but they should not be understood as limiting the protection scope of the present application.

[0069] In the specific embodiments of the present application, the raw materials used are all commercially available goods unless otherwise specified.

[0070] Example 1

[0071] 10 g of boron nitride nanosheets, 1 g of sodium hydroxide and 10 g of 4,4'-difluorobenzophenone were added to 100 mL of sulfolane, stirred at 140°C for 2 h in a dry nitrogen environment, then heated to 150°C for 2 h, discharged into deionized water, washed with ethanol and deionized water, to obtain modified boron nitride nanosheets (denoted as BNNS-FOH-1).

[0072] Example 2

[0073] 10 g of boron nitride nanosheets, 2 g of sodium hydroxide and 10 g of 4,4'-difluorobenzophenone were added to 100 mL of sulfolane, stirred at 140°C for 2 h in a dry nitrogen environment, then heated to 150°C for 2 h, discharged into deionized water, washed with ethanol and deionized water, to obtain modified boron nitride nanosheets (denoted as BNNS-FOH-2).

[0074] Example 3

[0075] 10 g of boron nitride nanosheets, 5 g of sodium hydroxide and 10 g of 4,4'-difluorobenzophenone were added to 100 mL of sulfolane, stirred at 140°C for 2 h in a dry nitrogen environment, then heated to 150°C for 2 h, discharged into deionized water, washed with ethanol and deionized water, to obtain modified boron nitride nanosheets (denoted as BNNS-FOH-5).

[0076] Example 4

[0077] The preparation method of this example is the same as that of Example 1, except that the addition amount of 4,4'-difluorobenzophenone is 20 g.

[0078] Example 5 Modified boron nitride theoretical mass of 10wt% polyaryletherketone composite material

[0079] 0.25 mol of 4,4'-difluorobenzophenone (54.82 g), 0.25 mol of hydroquinone (27.53 g), 0.25 mol of mixed alkali composed of sodium carbonate and potassium carbonate (30.21 g of sodium carbonate and 2.07 g of potassium carbonate), modified boron nitride nanosheets (8.04 g), 100 mL of xylene were added to 300 mL of melted diphenyl sulfone, stirred at 170°C for 2 h in a dry nitrogen gas environment, then heated to 210°C for 3 h, removed the water-carrying agent, heated to 280°C, stirred for 1 h, heated to 310°C, stirred for 1 h, to obtain a polyaryletherketone composite material (modified boron nitride theoretical mass of 10wt%, denoted as BNNS-FOH-PEEK-10).

[0080] Example 6 Modified boron nitride theoretical mass of 20wt% polyaryletherketone composite material

[0081] 0.25 mol of 4,4'-difluorobenzophenone (54.82 g), 0.25 mol of hydroquinone (27.53 g), 0.25 mol of a mixed alkali consisting of sodium carbonate and potassium carbonate (30.21 g of sodium carbonate and 2.07 g of potassium carbonate), 100 mL of modified boron nitride nanosheets (18.09 g), and 100 mL of xylene were added to 300 mL of molten diphenyl sulfone. The mixture was stirred at 170 °C for 2 h to remove water under a dry nitrogen atmosphere. Then the temperature was raised to 210 °C and stirred for 3 h to remove the water-removing agent. The temperature was then raised to 280 °C and stirred for 1 h. Finally, the temperature was raised to 310 °C and stirred for 1 h to obtain a polyaryletherketone composite material (theoretical mass of modified boron nitride is 20 wt%, denoted as BNNS-FOH-PEEK-20).

[0082] Example 7: Polyaryletherketone composite material with a theoretical boron nitride content of 30 wt%.

[0083] 0.25 mol of 4,4'-difluorobenzophenone (54.82 g), 0.25 mol of hydroquinone (27.53 g), 0.25 mol of a mixed alkali consisting of sodium carbonate and potassium carbonate (30.21 g of sodium carbonate and 2.07 g of potassium carbonate), 100 mL of modified boron nitride nanosheets (31.01 g), and 100 mL of xylene were added to 300 mL of molten diphenyl sulfone. The mixture was stirred at 170 °C for 2 h to remove water under a dry nitrogen atmosphere. Then the temperature was raised to 210 °C and stirred for 3 h to remove the water-removing agent. The temperature was then raised to 280 °C and stirred for 1 h. Finally, the temperature was raised to 310 °C and stirred for 1 h to obtain a polyaryletherketone composite material (theoretical mass of modified boron nitride is 30 wt%, denoted as BNNS-FOH-PEEK-30).

[0084] Structural characterization and performance testing

[0085] XPS analysis was performed on the boron nitride nanosheets used in Example 3, and the results are as follows: Figure 1 As shown. According to Figure 1 It can be seen that the surface of the boron nitride nanosheets does not contain fluorine (F) element.

[0086] XPS analysis was performed on the modified boron nitride prepared in Example 3, and the results are as follows: Figure 1 As shown. According to Figure 1 It can be seen that the modified boron nitride prepared in this embodiment contains F element on its surface. The presence of F element proves that one end of 4,4'-difluorobenzophenone has been successfully grafted onto the surface of boron nitride nanosheets. This indicates that the present invention has successfully prepared modified boron nitride grafted with 4,4'-difluorobenzophenone.

[0087] The modified boron nitride prepared in Example 3 was analyzed by TGA, and the results are as follows: Figure 2 As shown. According to Figure 2It can be seen that the modified boron nitride prepared by the application has high thermal stability, which can reach 460℃. And by comparing the thermogravimetric curves before and after grafting, it can be calculated that the amount of 4,4'-difluorobenzophenone grafted on the surface of the modified boron nitride is 2wt%.

[0088] The modified boron nitride prepared in Example 3 was subjected to infrared analysis, and the results are shown in Figure 3 Figure 3 It can be seen that the modified boron nitride is successfully prepared by the application.

[0089] The polyaryletherketone composite material prepared in Example 7 was subjected to SEM test, and the results are shown in Figure 5 Figure 5 It can be seen that the boron nitride is uniformly dispersed in the polyaryletherketone composite material and has good interface.

[0090] The polyaryletherketone composite material prepared in Example 7 was subjected to mechanical property test, and the test standard was GB / T1040.1 and GB / T 9431. The polyaryletherketone composite material prepared by the ungrafted boron nitride nanosheet was used as a control, and the test results are shown in Table 1.

[0091] Table 1 Mechanical properties of polyaryletherketone composite material

[0092] Polyaryletherketone composite Tensile strength (MPa) Elongation at break (%) Control 73 1.9 Example 6 81 2.7

[0093] According to Table 1, it can be seen that the tensile strength and elongation at break of the polyaryletherketone composite material modified by the modified boron nitride prepared by the application are significantly improved.

[0094] The polyaryletherketone composite material prepared in Example 7 was subjected to thermal conductivity test, and the test standard was ASTM 1461. The polyaryletherketone composite material prepared by the ungrafted boron nitride nanosheet was used as a control, and the test results are shown in Table 2.

[0095] Table 2 Thermal conductivity of polyaryletherketone composite material

[0096]

[0097] According to Table 2, it can be seen that the thermal conductivity of the polyaryletherketone composite material modified by the modified boron nitride prepared by the application is significantly improved, which is increased by nearly 12%.

[0098] The polyaryletherketone composite material prepared in Example 7 was subjected to interface thermal resistance fitting, and the fitting model was the general Foygel model, and the results are shown in Figure 6

[0099] According to Figure 6 ​​​It can be seen that the interfacial thermal resistance of the polyaryletherketone composite material prepared by the modified boron nitride is reduced by nearly 49%.

[0100] The polyaryletherketone composite material of Example 5 was subjected to TGA detection, and the results are shown in Figure 7 Figure 7 It can be seen that the polyaryletherketone composite material prepared by the application has high thermal stability, which can reach 530℃, and can meet the processing requirements of polyaryletherketone.

[0101] From the above examples, it can be seen that the polyaryletherketone composite material provided by the application has good mechanical properties and thermal conductivity.

[0102] Although the above examples have made a detailed description of the application, it is only a part of the embodiments of the application, not all the embodiments, and other embodiments can be obtained according to the embodiments without creativity, which belong to the protection scope of the application.​

Claims

1. A polyaryletherketone composite material, characterized by, The modified boron nitride includes boron nitride and fluorine-containing groups grafted to the boron nitride through oxygen atoms connected to exposed boron atoms of the boron nitride; The modified boron nitride includes boron nitride and fluorine-containing groups grafted to the boron nitride through oxygen atoms connected to exposed boron atoms of the boron nitride; The fluorine-containing groups include one or more of 1,4-bis(4-fluorobenzoyl)phenyl and 4,4'-difluorobenzophenone; The boron nitride is boron nitride nanosheets; the grafting amount of the fluorine-containing groups in the modified boron nitride is 0.5-20wt%; The mass ratio of the polyaryletherketone matrix to the modified boron nitride is 100:1-40; The preparation method of the polyaryletherketone composite material includes the following steps: Mixing fluorine-containing compounds, aromatic compounds, modified boron nitride, catalysts, water-carrying agents and aprotic solvents to perform covalent in-situ polymerization to obtain a polyaryletherketone composite material; The fluorine-containing compounds include one or more of 1,4-bis(4-fluorobenzoyl)phenyl and 4,4'-difluorobenzophenone; The aromatic compounds include one of hydroquinone and 4,4'-dihydroxybenzophenone; The covalent in-situ polymerization includes a first stage, a second stage, a third stage and a fourth stage; The temperature of the first stage is 160-195℃, and the holding reaction time is 1-3h; The temperature of the second stage is 200-260℃, and the holding reaction time is 1-5h; The temperature of the third stage is 260-280℃, and the holding reaction time is 0.5-1.5h; The temperature of the fourth stage is 300-315℃, and the holding reaction time is 0.5-1.5h.

2. The polyaryletherketone composite according to claim 1, characterized in that The preparation of the modified boron nitride includes the following steps: Mixing boron nitride, fluorine-containing compounds, catalysts and aprotic solvents to perform grafting reaction to obtain modified boron nitride; the fluorine-containing compounds include one or more of 1,4-bis(4-fluorobenzoyl)phenyl and 4,4'-difluorobenzophenone.

3. The polyaryletherketone composite according to claim 2, characterized in that The mass ratio of the boron nitride to the fluorine-containing compounds is 1:0.1-10; the mass ratio of the boron nitride to the catalysts is 1:0.1-20.

4. The method of making the polyaryletherketone composite of claim 1, wherein, The preparation method of the polyaryletherketone composite material includes the following steps: Mixing fluorine-containing compounds, aromatic compounds, modified boron nitride, catalysts, water-carrying agents and aprotic solvents to perform covalent in-situ polymerization to obtain a polyaryletherketone composite material; The fluorine-containing compounds include one or more of 1,4-bis(4-fluorobenzoyl)phenyl and 4,4'-difluorobenzophenone; The aromatic compounds include one of hydroquinone and 4,4'-dihydroxybenzophenone; The covalent in-situ polymerization includes a first stage, a second stage, a third stage and a fourth stage; The temperature of the first stage is 160-195℃, and the holding reaction time is 1-3h; The temperature of the second stage is 200-260℃, and the holding reaction time is 1-5h; The temperature of the third stage is 260-280℃, and the holding reaction time is 0.5-1.5h; The temperature of the fourth stage is 300-315℃, and the holding reaction time is 0.5-1.5h.

5. The preparation method according to claim 4, characterized in that, The molar ratio of the fluorine-containing compounds to the aromatic compounds is 1-1.2:1; The addition amount of the modified boron nitride is 0.5-40% of the mass content of the modified boron nitride in the polyaryletherketone composite material; the molar ratio of the catalyst and the aromatic compound is 1-1.2:1; and the volume ratio of the water-carrying agent and the aprotic solvent is 0.3-0.5:1.

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