A high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer and its preparation method and application

Abstract

The present invention relates to the field of polymer material technology, and in particular to a high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer, and a preparation method and application thereof. The high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer of the present invention can undergo a cross-linking reaction at 320-350°C to form a certain cross-linked network, thereby improving the high-temperature modulus of the polyetheretherketone resin. At the same time, the cross-linked polymer still retains a certain degree of crystallinity and thermal enthalpy, so that it still has properties such as high strength, solvent resistance and thermal stability similar to those of semi-crystalline polymers such as PEEK. In addition, the cross-linkable crystalline high-temperature resistant biphenyl polyaryletherketone has a low polymerization reaction temperature and reaction conditions compared to the existing polyetheretherketone polymerization reaction temperature, and the post-processing is simple, which can reduce costs and broaden applications.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer, a preparation method thereof, and applications thereof. Background Art

[0002] In recent decades, with the rapid development of aerospace, electronics, defense, and civil construction, the requirements for high-temperature modulus and strength of materials have gradually increased. Polyetheretherketone (PEEK) is a typical fully aromatic, semi-crystalline polymer material with excellent heat resistance, solvent resistance, and mechanical properties. However, the glass transition temperature of PEEK is only around 140°C, resulting in a significant decrease in mechanical properties at higher temperatures, limiting its application in high-temperature and harsh environments.

[0003] Cross-linking is an effective method to improve the high-temperature modulus and strength of polymers. The patent with publication number CN105461918A uses the cross-linking properties of allyl groups to prepare a polyarylethernitrile that can be cross-linked by ultraviolet radiation and further improves the heat resistance level, solvent resistance and mechanical properties of the material through ultraviolet radiation cross-linking and curing technology; in the patent with publication number CN108559264A, allyl groups are introduced as cross-linking groups in polyarylethersulfone, and its glass transition temperature is increased by thermal cross-linking, thereby increasing its breakdown field strength as a dielectric material and its energy storage density at high temperature. In the patent with publication number CN103755951A, allyl groups are introduced into polyaryletherketone to prepare sulfonated polyaryletherketone proton exchange membrane, which has good vanadium ion permeation resistance and high proton conductivity, and has good chemical stability. However, compared with semi-crystalline polymers, the amorphous polymers prepared by the above patents have shortcomings in corrosion resistance, high-temperature modulus attenuation and strength. Summary of the Invention

[0004] The present invention aims to provide a high-temperature-resistant, cross-linkable, semi-crystalline poly(aryletherketone) polymer, its preparation method, and its application. This high-temperature-resistant, cross-linkable, semi-crystalline poly(aryletherketone) polymer undergoes a cross-linking reaction at 320-350°C, forming a cross-linked network that improves the high-temperature modulus of the poly(aryletherketone) resin. Furthermore, the cross-linked polymer retains a certain degree of crystallinity and thermal enthalpy, enabling it to maintain properties similar to those of semi-crystalline polymers such as PEEK, such as high strength, solvent resistance, and thermal stability.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer having a structure shown in Formula 1:

[0007]

[0008] In formula 1, R is

[0009] n is the degree of polymerization and is 0.1 to 0.9.

[0010] The present invention provides a method for preparing the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer described in the above technical solution, comprising the following steps:

[0011] 2,2'-allyl bisphenol A, 4,4'-difluorobenzophenone, a water-carrying agent, a catalyst and an organic solvent are first mixed, and a first water-carrying reaction and a polymerization reaction are sequentially performed to obtain an intermediate product system;

[0012] The intermediate product system and HRH are mixed for a second time, and a second water-carrying reaction and a nucleophilic polycondensation reaction are sequentially performed to obtain the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer;

[0013] The R in the HRH is

[0014] Preferably, the water-carrying agent includes one or more of benzene, toluene, xylene and cyclohexane;

[0015] The catalyst includes one or more of sodium carbonate, potassium carbonate, cesium carbonate, calcium hydride and potassium fluoride;

[0016] The organic solvent includes sulfolane and / or diphenyl sulfone.

[0017] Preferably, the molar ratio of 2,2'-allyl bisphenol A to 4,4'-difluorobenzophenone is (0.1-0.5):1;

[0018] The molar ratio of the HRH to 4,4'-difluorobenzophenone is (0.1-0.5):1.

[0019] Preferably, the molar ratio of the catalyst to HRH is (0.9-2): (0.1-0.5).

[0020] Preferably, the usage ratio of the water-carrying agent and the organic solvent is (10-50) mL:100 g.

[0021] Preferably, the solid content of the mixed solution obtained by the first mixing is 15-25%.

[0022] Preferably, the temperature of the first water-containing reaction is 130-150° C. and the time is 2-4 hours;

[0023] The polymerization reaction temperature is 160-210° C., and the reaction time is 2-6 hours.

[0024] Preferably, the temperature of the second water-containing reaction is 130-150° C. and the time is 2-4 hours;

[0025] The temperature of the nucleophilic polycondensation reaction is 160-210° C., and the time is 2-6 hours.

[0026] The present invention also provides the use of the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer described in the above technical solution or the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer prepared by the preparation method described in the above technical solution in high-temperature resistant electronic devices, aerospace structural parts and radar casings.

[0027] The present invention provides a high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer having a structure shown in Formula 1:

[0028]

[0029] In formula 1, R is

[0030] n is the degree of polymerization and is 0.1 to 0.9.

[0031] The high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer of the present invention can be cross-linked at 320-350°C, and still retains a certain degree of crystallinity and thermal enthalpy after cross-linking. Compared with commercial polyetheretherketone, the glass transition temperature of the cross-linked polymer is increased to 165-175°C. More importantly, it still maintains a high modulus above the melting point of the polymer, which broadens the scope of use of polyetheretherketone in high-temperature areas. At the same time, the cross-linked polymer still maintains the high strength, solvent resistance, and thermal stability of polyetheretherketone. In addition, the cross-linkable crystalline high-temperature resistant biphenyl polyaryletherketone has a low polymerization reaction temperature and reaction conditions compared to the existing polyetheretherketone polymerization reaction temperature, and the post-processing is simple, which can reduce costs and broaden applications;

[0032] The present invention also provides a preparation method of the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer described in the above technical solution, comprising the following steps: first mixing 2,2'-allylbisphenol A, 4,4'-difluorobenzophenone, a first water-carrying agent, a first catalyst and a first organic solvent, sequentially performing a first water-carrying reaction and a polymerization reaction to obtain an intermediate product system; second mixing the intermediate product system, HRH, a second water-carrying agent, a second catalyst and a second organic solvent, sequentially performing a second water-carrying reaction and a nucleophilic condensation reaction to obtain the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer; R in the HRH is The present invention achieves a cross-linked polyaryletherketone material with enhanced heat resistance and a higher operating temperature by thermally cross-linking the propylene structures (cross-linking points) within the polyaryletherketone segments. This improved heat resistance while maintaining crystalline properties is the main innovation and technical feature of the present invention.

[0033] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0034] 1) While retaining the solvent resistance and melt processability of polyaryletherketone materials, the dimensional stability, heat resistance and strength of the materials are further improved through thermal cross-linking and curing, thereby broadening their application range;

[0035] 2) After cross-linking and annealing, the cross-linked polyaryletherketone still retains crystalline properties, which ensures that the polymer still retains certain processability and toughness;

[0036] 3) The performance of cross-linked polyaryletherketone materials can be regulated by the content of cross-linking point structure in the polymer structure and the thermal cross-linking time. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is an infrared spectrum of the high-temperature resistant, cross-linkable, semi-crystalline polyaryletherketone polymer powder described in Example 1;

[0038] Figure 2 This is an infrared spectrum of the high-temperature resistant, cross-linkable, semi-crystalline polyaryletherketone polymer powder after curing described in Example 1;

[0039] Figure 3 This is the DSC curve of the high temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder described in Example 4;

[0040] Figure 4 This is the DSC curve of the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder after curing and annealing as described in Example 4;

[0041] Figure 5 This is the high temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder described in Example 7 and the DMA curve after curing;

[0042] Figure 6 This is the TGA curve of the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder described in Example 7 after heat treatment. DETAILED DESCRIPTION

[0043] The present invention provides a high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer having a structure shown in Formula 1:

[0044]

[0045] In formula 1, R is

[0046] n is the degree of polymerization and is 0.1 to 0.9.

[0047] The present invention provides a method for preparing the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer described in the above technical solution, comprising the following steps:

[0048] 2,2'-allyl bisphenol A, 4,4'-difluorobenzophenone, a water-carrying agent, a catalyst and an organic solvent are first mixed, and a first water-carrying reaction and a polymerization reaction are sequentially performed to obtain an intermediate product system;

[0049] The intermediate product system and HRH are mixed for a second time, and a second water-carrying reaction and a nucleophilic polycondensation reaction are sequentially performed to obtain the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer;

[0050] The R in the HRH is

[0051] In the present invention, unless otherwise specified, all preparation raw materials are commercially available products well known to those skilled in the art.

[0052] The present invention performs a first mixing of 2,2'-allyl bisphenol A, 4,4'-difluorobenzophenone, a water-carrying agent, a catalyst and an organic solvent, and sequentially performs a first water-carrying reaction and a polymerization reaction to obtain an intermediate product system.

[0053] In the present invention, the water-carrying agent preferably includes one or more of benzene, toluene, xylene and cyclohexane. When the water-carrying agent is two or more of the above-mentioned specific selections, the present invention has no special restrictions on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio.

[0054] In the present invention, the catalyst preferably includes one or more of sodium carbonate, potassium carbonate, cesium carbonate, calcium hydride and potassium fluoride. When the catalyst is two or more of the above-mentioned specific selections, the present invention has no special restrictions on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio.

[0055] In the present invention, the organic solvent preferably includes sulfolane and / or diphenyl sulfone. When the first organic solvent is sulfolane and diphenyl sulfone, the present invention has no special limitation on the ratio of the sulfolane and diphenyl sulfone, and they can be mixed in any ratio.

[0056] In the present invention, the molar ratio of the 2,2'-allyl bisphenol A to 4,4'-difluorobenzophenone is preferably (0.1-0.5):1, more preferably (0.2-0.4):1, and most preferably (0.25-0.35):1; the usage ratio of the water-carrying agent to the organic solvent is preferably (10-50) mL:100 g, more preferably (20-40) mL:100 g, and most preferably (25-35) mL:100 g; the molar ratio of the 2,2'-allyl bisphenol A to the catalyst is preferably (1-1.5):1, more preferably (1.1-1.4):1, and most preferably (1.2-1.3):1.

[0057] The present invention does not have any special limitation on the first mixing process, and the process well known to those skilled in the art can be used.

[0058] In the present invention, the solid content of the mixed solution obtained by the first mixing is preferably 15-25%, more preferably 18-22%, and most preferably 19-21%.

[0059] In the present invention, the first water-containing reaction is preferably carried out under reflux conditions, and the temperature of the first water-containing reaction is preferably 130-150°C, more preferably 135-145°C, and most preferably 138-142°C; the time is preferably 2-4 hours, more preferably 2.5-3.5 hours, and most preferably 2.8-3.2 hours. The temperature of the first water-containing reaction is preferably increased under stirring conditions. The present invention does not have any special restrictions on the stirring process, and the process well known to those skilled in the art can be used.

[0060] In the present invention, the polymerization reaction temperature is preferably 160-210° C., more preferably 165-180° C., most preferably 168-172° C.; the polymerization time is preferably 2-6 h, more preferably 4.5-5.5 h, most preferably 4.8-5.2 h.

[0061] After the polymerization reaction is completed, the present invention further preferably includes cooling. The present invention has no special limitation on the cooling process. The temperature of the reaction system can be reduced to below 100° C. using a process well known to those skilled in the art.

[0062] In the present invention, the intermediate product system includes polyaryletherketone containing acryl side groups.

[0063] After obtaining the intermediate product system, the present invention performs a second mixing of the intermediate product system and HRH, and sequentially performs a second water-carrying reaction and a nucleophilic polycondensation reaction to obtain the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer.

[0064] In the present invention, the HRH includes hydroquinone, biphenol or 4,4'-dihydroxybenzophenone.

[0065] In the present invention, the molar ratio of HRH to 4,4'-difluorobenzophenone is preferably (0.1-0.5):1, more preferably (0.2-0.4):1, and most preferably (0.25-0.35):1.

[0066] In the present invention, the temperature of the second water-containing reaction is preferably 130-150°C, more preferably 135-145°C, and most preferably 138-142°C; the time is preferably 2-4h, more preferably 2.5-3.5h, and most preferably 2.8-3.2h.

[0067] In the present invention, the temperature of the nucleophilic condensation reaction is preferably 160-210°C, and the time is preferably 2-6 hours; more preferably, it is a programmed temperature reaction, and the programmed temperature reaction is preferably heated to 160°C for 4 hours, 180°C for 3 hours, 200°C for 2 hours, and 210°C for 2 hours.

[0068] After the nucleophilic polycondensation reaction is completed, the present invention preferably further comprises crushing the obtained strip-shaped crude product in the product system, boiling and washing it with ethanol and distilled water for 3 to 5 times respectively to remove organic solvents, small organic molecules and inorganic salts, and then drying it at 120° C. for 12 hours.

[0069] In the present invention, the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer can preferably undergo a cross-linking reaction under the following cross-linking conditions. In the present invention, the cross-linking reaction is preferably carried out under vacuum conditions. The temperature of the cross-linking reaction is preferably 320-370°C, more preferably 325-365°C, and most preferably 325-360°C; the time of the cross-linking reaction is preferably 1-8h, more preferably 1.5-7.5h, and most preferably 2-6h.

[0070] The present invention also provides for the use of the high-temperature-resistant, cross-linkable, semi-crystalline poly(aryletherketone) polymer described in the above technical solution, or the high-temperature-resistant, cross-linkable, semi-crystalline poly(aryletherketone) polymer prepared by the preparation method described in the above technical solution, in high-temperature-resistant electronic devices, aerospace structural parts, and radar casings. The present invention does not impose any particular limitations on the method of such application; methods well known to those skilled in the art may be employed.

[0071] The high temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer provided by the present invention, its preparation method and application are described in detail below with reference to the examples, but they should not be construed as limiting the scope of protection of the present invention.

[0072] Example 1

[0073] 15.27 g (0.07 mol) of 4,4'-difluorobenzophenone, 6.48 g (0.021 mol) of 2,2'-allyl bisphenol A, 72 mL of sulfolane, 3.48 g of anhydrous potassium carbonate and 30 mL of toluene were added to a 500 mL three-necked flask equipped with a mechanical stirrer, a thermometer and nitrogen protection, and the temperature was raised to 140 ° C with stirring. The toluene was refluxed with water for 2 h, and the temperature was raised to 160 ° C for 4 h. The system was cooled to below 100 ° C, 9.12 g (0.049 mol) of biphenyl diphenol was added, and the temperature was raised to 14 At 0°C, toluene and water were refluxed for 2 hours, and the toluene in the reaction system was gradually removed. The temperature was raised to 160°C for 4 hours, 180°C for 3 hours, 200°C for 2 hours, and 210°C for 2 hours. The polymer solution was dispersed in water, and the obtained strip-shaped crude product was crushed and washed with ethanol and distilled water for 5 times to remove the organic solvent cyclopentane sulfone, a small amount of organic small molecules and inorganic salts. The obtained product was dried at 120°C for 12 hours to obtain a white powder sample of high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder (yield 97%).

[0074] Example 2

[0075] Refer to Example 1, except that the biphenol in Example 1 is replaced by hydroquinone to obtain a white high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder containing 30% of a cross-linking group (2,2'-allylbisphenol A) (i.e., the molar ratio of 2,2'-allylbisphenol A to hydroquinone is 3:7, and the yield is 95%).

[0076] Example 3

[0077] Refer to Example 1, except that the biphenol in Example 1 is replaced by 4,4'-dihydroxybenzophenone to obtain a white high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder containing a cross-linking group (2,2'-allyl bisphenol A) with a content of 30% (ie, the molar ratio of 2,2'-allyl bisphenol A to 4,4'-dihydroxybenzophenone is 3:7, and the yield is 95%).

[0078] Example 4

[0079] Refer to Example 1, except that the amount of 2,2'-allyl bisphenol A used is 2.16 g (0.007 mol, the molar percentage of 2,2'-allyl bisphenol A in 4,4'-difluorobenzophenone is 10%), to obtain a high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder (yield 93%).

[0080] Example 5

[0081] Refer to Example 1, except that the amount of 2,2'-allyl bisphenol A used is 3.24 g (0.0105 mol, the molar percentage of 2,2'-allyl bisphenol A in 4,4'-difluorobenzophenone is 15%), to obtain a high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder (yield 95%).

[0082] Example 6

[0083] Refer to Example 1, except that the amount of 2,2'-allyl bisphenol A used is 4.32 g (0.014 mol, the molar percentage of 2,2'-allyl bisphenol A in 4,4'-difluorobenzophenone is 20%), to obtain a high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder (yield 92%).

[0084] Example 7

[0085] Refer to Example 1, except that the amount of 2,2'-allyl bisphenol A used is 5.397 g (0.0175 mol, the molar percentage of 2,2'-allyl bisphenol A in 4,4'-difluorobenzophenone is 25%), to obtain a high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder (yield is 92%).

[0086] Example 8

[0087] Refer to Example 1, except that the amount of 2,2'-allyl bisphenol A used is 6.477 g (0.021 mol, the molar percentage of 2,2'-allyl bisphenol A in 4,4'-difluorobenzophenone is 30%), to obtain a high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder (yield 93%).

[0088] Example 9

[0089] Refer to Example 1, except that the amount of 2,2'-allyl bisphenol A used is 7.556 g (0.0245 mol, the molar percentage of 2,2'-allyl bisphenol A in 4,4'-difluorobenzophenone is 35%), to obtain a high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder (yield 94%).

[0090] Example 10

[0091] Refer to Example 1, except that the amount of 2,2'-allyl bisphenol A used is 8.635 g (0.028 mol, the molar percentage of 2,2'-allyl bisphenol A in 4,4'-difluorobenzophenone is 40%), to obtain a high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder (yield 95%).

[0092] Test Case

[0093] The high temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder described in Example 1 was subjected to infrared spectrum test. The test results are as follows: Figure 1 Shown: 1649cm -1 The peaks at 1588 cm correspond to the carbonyl (C=O) and propenyl absorption peaks; -1 , 1482cm -1 It is the absorption peak of the vibration of C=C skeleton on the benzene ring of the polymer molecule; 1222cm -1 is the Ar-O-Ar (Ar is an aromatic group) stretching vibration absorption peak; 960cm -1 The absorption peaks can be attributed to the symmetric and asymmetric stretching vibration peaks of the propylene group, proving that the target polymer was successfully synthesized.

[0094] The high temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder described in Example 1 was maintained at 350°C for 1 hour and subjected to infrared spectrum test. The test results are as follows: Figure 2 shown; contrast Figure 1 It can be found that the cross-linked crystalline high-temperature resistant polyaryletherketone is 1649cm after cross-linking. -1 and 960cm -1 The absorption peak of the propylene side group at the position decreased significantly, and the cross-linking consumed the propylene group, indicating that the polymer underwent a cross-linking reaction.

[0095] The high temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder described in Example 4 was subjected to DSC test. The test results are as follows: Figure 3 As shown, the glass transition temperature (T g ) is 150℃, melting point (T m ) is 312℃, and the melting enthalpy (△H) is 30J / g. A cross-linking peak appears, and the cross-linking peak temperature (T p ) is 429°C, indicating its cross-linkable characteristics.

[0096] The high temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder described in Example 4 was maintained at 350°C for 1 hour and then annealed at 200°C for 2 hours. The DSC test was performed. The test results are as follows. Figure 4 As shown, the glass transition temperature (T g ) increased to 165℃, indicating that the polymer was cross-linked and its operating temperature was increased. m ) is 283 °C and the melting enthalpy (△H) is 11 J / g, indicating that the polymer still retains a certain degree of crystallinity after cross-linking.

[0097] The high temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer film described in Example 7 was maintained at 350°C for 1 hour under vacuum and then subjected to DMA test. At the same time, the pure polyetheretherketone film was subjected to DMA test. The test results are as follows. Figure 5 As shown by Figure 5 It can be seen that the glass transition temperature of the cured cross-linked crystalline high-temperature resistant polyaryletherketone is significantly higher than that of pure polyetheretherketone, increasing by 30°C. At the same time, it was observed that the storage modulus dropped rapidly when the polyetheretherketone reached the melting point (around 340°C). However, the cured cross-linked crystalline high-temperature resistant polyaryletherketone can still maintain a high storage modulus at 400°C, at which point the polyetheretherketone has completely melted and cannot be used.

[0098] The high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer film described in Example 7 was subjected to a tensile performance test. The test process was a tensile test speed of 5 mm / min at room temperature. The test result showed that the tensile strength was 90 MPa.

[0099] The high temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder described in Example 7 was heat treated (at 350° C. for 1 hour) and then subjected to TGA test. The test results are as follows: Figure 6 As shown by Figure 6 It can be seen that the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer powder has good high-temperature resistance similar to that of polyetheretherketone.

[0100] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A high temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer, characterized in that: It has the structure shown in formula 1: Formula 1; In formula 1, R is or ; n is the degree of polymerization and n is 0.1 to 0.9; The method for preparing the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer comprises the following steps: 2,2'-allyl bisphenol A, 4,4'-difluorobenzophenone, a water-carrying agent, a catalyst and an organic solvent are first mixed, and a first water-carrying reaction and a polymerization reaction are sequentially performed to obtain an intermediate product system; The intermediate product system and HRH are mixed for a second time, and a second water-carrying reaction and a nucleophilic polycondensation reaction are sequentially performed to obtain the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer; The R in the HRH is or ; The catalyst includes potassium carbonate.

2. The method for preparing the high temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer according to claim 1, characterized in that: The following steps are involved: 2,2'-allyl bisphenol A, 4,4'-difluorobenzophenone, a water-carrying agent, a catalyst and an organic solvent are first mixed, and a first water-carrying reaction and a polymerization reaction are sequentially performed to obtain an intermediate product system; The intermediate product system and HRH are mixed for a second time, and a second water-carrying reaction and a nucleophilic polycondensation reaction are sequentially performed to obtain the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer; The R in the HRH is or .

3. The preparation method according to claim 2, wherein The water-carrying agent includes one or more of benzene, toluene, xylene and cyclohexane; The organic solvent includes sulfolane and / or diphenyl sulfone.

4. The preparation method according to claim 2, wherein The molar ratio of 2,2'-allyl bisphenol A to 4,4'-difluorobenzophenone is (0.1-0.5):1; The molar ratio of HRH to 4,4'-difluorobenzophenone is (0.1-0.5):

1.

5. The preparation method according to any one of claims 2 to 4, wherein The molar ratio of the catalyst to HRH is (0.9-2): (0.1-0.5).

6. The preparation method according to any one of claims 2 to 4, wherein The dosage ratio of the water-carrying agent and the organic solvent is (10-50) mL:100 g.

7. The preparation method according to claim 2, wherein The solid content of the mixed solution obtained by the first mixing is 15-25%.

8. The preparation method according to claim 2, wherein The temperature of the first water-containing reaction is 130-150°C and the time is 2-4 hours; The polymerization reaction temperature is 160-210° C., and the reaction time is 2-6 hours.

9. The preparation method according to claim 2, wherein The temperature of the second water-containing reaction is 130-150° C., and the time is 2-4 hours.

10. Use of the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone polymer according to claim 1 or the high-temperature resistant cross-linkable semi-crystalline polyaryletherketone prepared by the preparation method according to any one of claims 2 to 9 in high-temperature resistant electronic devices, aerospace structural parts and radar casings.

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