CN113698590B - Melt-processable end-capped fluorine-containing polyarylether resin as well as preparation method and application thereof - Google Patents

Abstract

The invention provides a melt-processable end-capped fluorine-containing polyarylether resin and a preparation method and application thereof, belonging to the technical field of high polymer materials. The invention adopts the stable aromatic monomer containing the monofluorine group as the end capping agent, utilizes the structure that the end capping agent contains two or single fluorine groups, fully eliminates the active phenolic hydroxyl end group, reduces the condition that lateral fluorine groups and active end groups generate branching crosslinking in the high-temperature melting processing process of decafluorobiphenyl, improves the problem that the melt fluidity and stability are influenced by the generation of the branching crosslinking structure in the melting processing process, realizes the melting processing of the fluorine-containing polyarylether polymer, and provides a new idea for obtaining the body type material with high thermal stability.

Description

A kind of melt processable end-capped fluorine-containing polyarylene ether resin and its preparation method and application

technical field

The invention relates to the technical field of polymer materials, in particular to a melt-processable end-capped fluorine-containing polyarylene ether resin and a preparation method and application thereof.

Background technique

There are a large number of C-F bonds and aromatic ring structures in fluorinated polyarylene ethers, which make them usually have good solubility, thermal stability, optical properties, low surface energy, low friction coefficient, low dielectric constant and chemical resistance, etc. Due to its excellent performance, the polyarylene ether materials containing decafluorobifluorine have been widely used in the fields of high-performance coatings, fuel cells, composite materials and optical materials. Fluorine content is often used in polymer materials.

For traditional thermoplastic resins, melt processing is one of the important means of shaping and processing body materials. However, the polymer prepared by using decafluorobiphenyl monomer has reactive activity because all ten fluorine atoms of the monomer are reactive, so it is very easy to react with the active end groups remaining in the polymerization reaction during the polymerization reaction and high temperature processing, resulting in branching, Structures such as crosslinking affect the fluidity and stability of the melt, and are not conducive to melt processing to construct bulk materials. Therefore, the existing linear decafluorobiphenyl-containing polymers are usually prepared by solution casting for application as film-forming materials, such as Chinese patents CN111530511A, CN111662446A, CN111363140A and CN110756060A. However, the solution casting method can only prepare membrane materials, and it is difficult to process them into bulk materials such as pipes, rods and sheets, which limits the application of fluoropolymers in other fields to a certain extent.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a melt-processable end-capped fluorine-containing polyarylether resin and a preparation method and application thereof. Scope of application.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

The invention provides a preparation method of end-capped fluorine-containing polyarylene ether resin, comprising the following steps:

Mixing the bisphenol monomer, the salt-forming agent, the dehydrating agent and the aprotic polar organic solvent to carry out a salt-forming reaction to obtain the first product;

Mixing the first product with decafluorobiphenyl, carrying out a polymerization reaction, adding an end-capping agent to the obtained product, and capping to obtain an end-capped fluorine-containing polyarylene ether resin;

The capping agent includes 4,4'-difluorodiphenylsulfone, 4,4'difluorobenzophenone, 3,3'difluorobenzophenone, 4-fluorophenylphenylsulfone, or 4-fluoro Benzophenone.

Preferably, the bisphenol monomer includes one or more of bisphenol A, bisphenol AF and bisphenol fluorene.

Preferably, the molar ratio of the decafluorobiphenyl to the bisphenol monomer is (0.95-1.05):1.

Preferably, the salt-forming agent comprises one or more of cesium carbonate, potassium carbonate and sodium carbonate; the molar ratio of the salt-forming agent to the bisphenol monomer is (1.001-1.35):1.

Preferably, the dehydrating agent includes one or more of toluene, xylene and cyclohexane; the aprotic polar organic solvent includes dimethylformamide, dimethylacetamide, sulfolane or N-methylformamide pyrrolidone; the volume of the dehydrating agent is 30-50% of the volume of the aprotic polar organic solvent.

Preferably, the total solid content of the bisphenol monomer and decafluorobiphenyl in the aprotic polar organic solvent is 10-25 wt%.

Preferably, the molar ratio of the capping agent to the bisphenol monomer is (0.01-0.05):1.

The present invention provides the end-capped fluorine-containing polyarylether resin prepared by the preparation method described in the above technical solution, which has the structure shown in formula I:

In formula I, n is the degree of polymerization, n=2×10 ⁴ to 1×10 ⁵ ; R is the group corresponding to the removal of the phenolic hydroxyl groups at both ends of the bisphenol monomer, and R ₁ includes

preferably, including

n＝6×10⁴、

n=6×10 ⁴ ,

n＝7×10⁴或

n=7× ¹⁰⁴ or

n＝8×10⁴。

n=8×10 ⁴ .

The present invention provides the application of the end-capped fluorine-containing polyarylene ether resin in the preparation of a thermally stable bulk material according to the above technical solution.

The present invention provides a method for preparing an end-capped fluorine-containing polyarylene ether resin. a product; the first product is mixed with decafluorobiphenyl to carry out a polymerization reaction, and an end-capping agent is added to the obtained product to perform end-capping to obtain an end-capped fluorine-containing polyarylene ether resin; the end-capping agent includes ten Fluorobiphenyl, 4,4'-difluorodiphenylsulfone, 4,4'difluorobenzophenone, 3,3'difluorobenzophenone, 4-fluorophenylphenylsulfone, or 4-fluorodiphenyl ketone. The invention adopts a stable aromatic monomer containing a single fluorine group as the end-capping agent, and utilizes the structure of the end-capping agent containing two or single fluorine groups to fully eliminate the unreacted active phenolic hydroxyl end of the bisphenol monomer at the polymer end It can reduce the branching and cross-linking of the lateral fluorine group and the active end group of decafluorobiphenyl during high-temperature melt processing, and improve the melt fluidity and stability of the melt due to the branched cross-linking structure during melt processing. To solve the problem of properties, realize the melt processing of fluorine-containing polyarylene ether polymers, which provides a new idea for obtaining bulk materials with high thermal stability.

The end-capping agent used in the present invention has a similar functional group structure as the bisphenol monomer, and the fluorine group has high reactivity, which can not only avoid the introduction of other groups into the polymer to have a great influence on the performance of the polymer, but also ensure the polymer's performance. The linear structure is not changed, so as to ensure that the melt has a certain fluidity, which is beneficial to extrusion melt processing.

The method of carrying out end-capping treatment in the later stage of the polymerization reaction of the present invention obtains a linear material of fluorine-containing polyarylene ether resin with high fluorine content, and can reduce the molecular weight of the polymer by changing the feeding ratio of bisphenol monomer and decafluorobiphenyl to improve the The melt fluidity is improved, and the fluorine-containing polyarylene ether resin that can be used for melt processing is prepared. The method of the present invention has a good end-capping effect, and the end-capped resin product can obtain the end-capped polyarylene ether resin of the body shape material by the melt processing method.

The method of the invention breaks the limitation that the traditional fluorine-containing polymer can only obtain the membrane material through the solution casting method, not only can save the use of the solvent in the solution casting method, reduce the pollution and harm of the organic solvent to the environment, but also can obtain different shapes The body type materials are used in various fields, giving full play to the advantages of fluorine materials in wear reduction and wear resistance.

Description of drawings

Fig. 1 is the nuclear magnetic H ¹ diagram of the end-capped fluorine-containing polyarylene ether prepared in Example 1;

Fig. 2 is the NMR F ¹⁹ diagram of the end-capped fluorine-containing polyarylene ether prepared in Example 1;

Fig. 3 is the nuclear magnetic H ¹ map of the end-capped fluorine-containing polyarylene ether prepared in Example 3;

Fig. 4 is the nuclear magnetic F ¹⁹ image of the end-capped fluorine-containing polyarylene ether prepared in Example 3;

Fig. 5 is the melt extrusion spline diagram of the end-capped fluorine-containing polyarylene ether prepared in Example 1;

Fig. 6 is the physical drawing of the spline required for the mechanical property and friction property test of the end-capped fluorine-containing polyarylene ether prepared in Example 1;

Detailed ways

The invention provides a preparation method of end-capped fluorine-containing polyarylene ether resin, comprising the following steps:

Mixing the bisphenol monomer, the salt-forming agent, the dehydrating agent and the aprotic polar organic solvent to carry out a salt-forming reaction to obtain the first product;

Mixing the first product with decafluorobiphenyl, carrying out a polymerization reaction, adding an end-capping agent to the obtained product, and capping to obtain an end-capped fluorine-containing polyarylene ether resin;

The capping agent includes 4,4'-difluorodiphenylsulfone, 4,4'difluorobenzophenone, 3,3'difluorobenzophenone, 4-fluorophenylphenylsulfone, or 4-fluoro Benzophenone.

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

In the present invention, the bisphenol monomer, the salt-forming agent, the dehydrating agent and the aprotic polar organic solvent are mixed, and the salt-forming reaction is carried out to obtain the first product. In the present invention, the bisphenol monomer preferably includes one or more of bisphenol A, bisphenol AF and bisphenol fluorene; when the bisphenol monomer is several of the above, the The ratio of different types of bisphenol monomers is not particularly limited, and any ratio can be used.

In the present invention, the salt-forming agent preferably includes one or more of cesium carbonate, potassium carbonate and sodium carbonate; when the salt-forming agent is several of the above, the present invention is suitable for different types of salt-forming agents. There is no special restriction on the ratio of , and any ratio can be used. In the present invention, the molar ratio of the salt-forming agent to the bisphenol monomer is preferably (1.001-1.35):1, more preferably (1.1-1.25):1.

In the present invention, the dehydrating agent preferably includes one or more of toluene, xylene and cyclohexane; when the salt-forming agent is several of the above, the There is no special restriction on the ratio, and any ratio can be used.

In the present invention, the aprotic polar organic solvent preferably includes dimethylformamide, dimethylacetamide, sulfolane or N-methylpyrrolidone; the volume of the dehydrating agent is preferably the same as that of the aprotic polar organic solvent 30 to 50% of the solvent volume, more preferably 35 to 45%.

In the present invention, the process of mixing the bisphenol monomer, the salt-forming agent, the dehydrating agent and the aprotic polar organic solvent is preferably performed under stirring conditions, and the stirring time is preferably 0.5-1 h. The present invention does not have a special limitation on the stirring speed, and the stirring speed is well known in the art.

In the present invention, the salt-forming reaction is preferably carried out in an argon atmosphere; the temperature of the salt-forming reaction is preferably 110-140°C, more preferably 120-130°C; the time is preferably 2-4h, more preferably 2.5～3.5h. The present invention has no particular limitation on the rate of temperature increase to the temperature of the salt-forming reaction, and the temperature may be increased according to a rate well known in the art. During the salt-forming reaction, the water produced by the salt-forming of the bisphenol monomer and the salt-forming agent is subjected to azeotropic dehydration with the dehydrating agent, and the dehydrating agent is removed by a water separator; after the salt-forming reaction is completed, the present invention preferably raises the temperature To above the boiling point of the dehydrating agent, discharge the dehydrating agent.

After discharging the dehydrating agent, the present invention preferably cools the obtained reaction feed liquid to room temperature to obtain the first product.

After the first product is obtained, in the present invention, the first product is mixed with decafluorobiphenyl to carry out a polymerization reaction, and an end capping agent is added to the obtained product to perform end capping to obtain an end capped fluorine-containing polyarylene ether resin. In the present invention, the molar ratio of the decafluorobiphenyl to the bisphenol monomer is preferably (0.95-1.05):1, more preferably (1.02-1.03):1. In the present invention, the total solid content of the bisphenol monomer and decafluorobiphenyl in the aprotic polar organic solvent is preferably 10-25 wt %, more preferably 15-20 wt %.

In the present invention, the end-capping agent includes 4,4'-difluorodiphenylsulfone, 4,4'difluorobenzophenone, 3,3'difluorobenzophenone, 4-fluorophenylbenzene Sulfone or 4-fluorobenzophenone; preferably 4,4'-difluorodiphenylsulfone, 4-fluorophenylphenylsulfone or 4-fluorobenzophenone.

In the present invention, the structural formula of the end-capping agent is specifically:

(4,4’-二氟二苯砜)、

(4,4’二氟二苯甲酮)、

(3,3’二氟二苯甲酮)、

(4-氟苯基苯砜)或

(4-氟二苯甲酮)。

(4,4'-difluorodiphenylsulfone),

(4,4'difluorobenzophenone),

(3,3'difluorobenzophenone),

(4-Fluorophenylphenylsulfone) or

(4-Fluorobenzophenone).

In the present invention, the molar ratio of the capping agent to the bisphenol monomer is preferably (0.01-0.05):1, more preferably (0.02-0.03):1.

In the present invention, decafluorobiphenyl is preferably added to the first product, and the mixture is stirred and mixed evenly. The present invention does not have a special limitation on the stirring process, and it can be carried out according to a well-known process in the art.

In the present invention, the polymerization reaction is preferably carried out under an argon atmosphere.

In the present invention, the process of the polymerization reaction preferably includes: firstly raising the temperature to 30-40°C, performing the first polymerization reaction for 6-12 hours, and secondly raising the temperature to 50-70°C, performing the second polymerization reaction for 6-12 hours, The third temperature is raised to 80-100° C., and the third polymerization reaction is carried out for 6-12 hours. The present invention does not specifically limit the heating rates of the first, second, and third temperature rises, and the temperature rises at rates well known in the art.

After the polymerization reaction is completed, the present invention adds an end-capping agent to the obtained material, performs the first end-capping at 80-100° C. for 1-2 hours, and then ramps the temperature to 120-130° C. and performs the second end-capping for 1-2 hours. Then, the temperature is gradually increased to 140-160° C., and the third end capping is performed for 1-2 h. The present invention does not have a special limitation on the heating rate of the gradient heating, and the temperature may be increased according to the gradient rate well known in the art.

After the end capping is completed, in the present invention, the obtained polymer mucus is preferably placed in deionized water for precipitation, and the obtained precipitation is sequentially pulverized, filtered, washed and dried to obtain an end capped fluorine-containing polyarylene ether resin. In the present invention, the washing preferably adopts a low-boiling organic solvent and deionized water to boil and wash in sequence; the low-boiling polar solvent is preferably methanol and/or ethanol; when the low-boiling organic solvent is methanol and ethanol, The present invention has no special limitation on the ratio of methanol and ethanol, and any ratio can be used.

The present invention has no special limitation on the number of times of washing, as long as the solvent and by-product salt can be completely removed; the present invention has no special limitation on the processes of pulverization, filtration and drying, and can be carried out according to well-known processes in the art. .

The present invention provides the end-capped fluorine-containing polyarylether resin prepared by the preparation method described in the above technical solution, which has the structure shown in formula I:

In formula I, n is the degree of polymerization, n=2×10 ⁴ to 1×10 ⁵ ; R is the group corresponding to the removal of the phenolic hydroxyl groups at both ends of the bisphenol monomer, and R ₁ includes

preferably, including

n＝6×10⁴、

n=6×10 ⁴ ,

n＝7×10⁴或

n=7× ¹⁰⁴ or

n＝8×10⁴。

n=8×10 ⁴ .

The present invention provides the application of the end-capped fluorine-containing polyarylene ether resin in the preparation of a thermally stable bulk material according to the above technical solution. The application method is not particularly limited in the present invention, and the end-capped fluorine-containing polyarylene ether resin can be made into a body-shaped material according to a method well known in the art.

The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some, but not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

420 mL of N,N-dimethylacetamide, 200 mL of toluene, 0.1 mol of bisphenol AF and 0.12 mol of anhydrous potassium carbonate were placed in a 1000 mL three-necked flask. Boiling dehydration and refluxing for 2.5h, the temperature was raised to 152°C, the dehydrating agent was discharged, and after the temperature of the reaction system was lowered to room temperature, 0.104mol decafluorobiphenyl was added to the reaction system, and the total solid content of bisphenol AF and decafluorobiphenyl was 15wt %, stir evenly, then heat up to 40°C, react for 12h, heat up to 60°C, react for 12h, heat up to 80°C, react for 12h, then add 0.002mol 4,4'-difluorodiphenylsulfone to the obtained material, at 80°C React for 2 hours, heat up to 120 °C, react for 2 hours, heat up to 160 °C, react for 2 hours, and separate the obtained polymer mucilage in deionized water. The end-capped fluorine-containing polyarylene ether resin is obtained, and the structural formula is:

n＝6×10⁴。

n=6×10 ⁴ .

The melt index, reduced viscosity and glass transition temperature of the end-capped fluorine-containing polyarylene ether resin prepared in Example 1 were tested, wherein the melt index test standard was 260° C. and the pressure was 5Kg; the concentration of the polymer in the reduced viscosity test was 0.5g/dL; DSC test temperature range is 80～400℃, under N ₂ atmosphere; the results show that: end-capped fluorine-containing polyaryletherketone resin melt index MI=7.0g/10min (260.0℃, 5KG, 5 minutes) ; MI=6.6 g/10min (260.0°C, 5KG, 30 minutes); Reduced viscosity in NMP η _sp /c=0.25 [dL/g] (25°C); Tg: 174°C.

Example 2

500 mL of dimethylacetamide, 250 mL of toluene, 0.12 mol of bisphenol AF and 0.144 mol of anhydrous potassium carbonate were placed in a 1000 mL three-necked flask, under argon atmosphere, mechanically stirred for 1 h, then heated to 132 ° C, azeotropic dehydration and reflux After 2.5h, the temperature was raised to 147°C, the dehydrating agent was discharged, and the temperature of the reaction system was lowered to room temperature, and 0.1236mol of decafluorobiphenyl was added to the reaction system. After uniform, the temperature was raised to 40°C, reacted for 12h, heated to 60°C, reacted for 12h, heated to 80°C, reacted for 12h, then added 0.006mol 4-fluorobenzophenone to the obtained material, reacted at 80°C for 2h, and heated to 120°C ℃, reacted for 2h, heated to 160℃, reacted for 2h, precipitated the obtained polymer mucilage in deionized water, pulverized the obtained precipitate, boiled and washed with methanol and deionized water in turn, and dried to obtain the end-capped fluoropolymer. Aromatic ether resin, the structural formula is:

n＝7×10⁴。

n=7×10 ⁴ .

According to the method described in Example 1, the end-capped fluorine-containing polyaryl ether ketone resin prepared in Example 2 was tested. , 5KG, 5 minutes); MI=6.0g/10min (280.0°C, 5KG, 30 minutes); Reduced viscosity in NMP η _sp /c=0.28 [dL/g] (25°C); Tg: 188°C .

Example 3

Put 120 mL of dimethylacetamide, 50 mL of toluene, 0.05 mol of bisphenol A and 0.06 mol of anhydrous potassium carbonate into a 250 mL three-necked flask, and under argon atmosphere, mechanically stir for 0.5 h, then heat up to 130 °C, and azeotropically dehydrate Reflux for 2h, heat up to 146°C, discharge the dehydrating agent, and after the temperature of the reaction system is lowered to room temperature, 0.051mol of decafluorobiphenyl is added to the reaction system, and the total solid content of bisphenol A and decafluorobiphenyl is 20wt%, After stirring evenly, the temperature was raised to 40°C, reacted for 12h, heated to 60°C, reacted for 12h, heated to 80°C, reacted for 12h, then added 0.0025mol 4,4'difluorobenzophenone to the obtained material, and reacted at 80°C for 2h , heated to 120 °C, reacted for 2 h, heated to 160 °C, reacted for 2 h, the obtained polymer mucus was precipitated in deionized water, the obtained precipitate was pulverized, boiled and washed with methanol and deionized water in turn, and dried to obtain a sealant. Terminal fluorine-containing polyarylene ether resin, the structural formula is:

n＝8×10⁴。

n=8×10 ⁴ .

According to the method described in Example 1, the end-capped fluorine-containing polyaryletherketone resin prepared in Example 3 was tested. , 5KG, 5 minutes); MI=8.9g/10min (280.0°C, 5KG, 30 minutes); Reduced viscosity in NMP η _sp /c=0.38 [dL/g] (25°C); Tg: 168°C .

Comparative Example 1

Put 410 mL of dimethylacetamide, 150 mL of toluene, 0.1 mol of bisphenol AF and 0.12 mol of anhydrous potassium carbonate into a 1000 mL three-necked flask, under argon atmosphere, mechanically stir for 1 h, then heat up to 130 ° C, azeotropic dehydration and reflux After 1.5h, the temperature was raised to 138°C, the dehydrating agent was discharged, and the temperature of the reaction system was lowered to room temperature. After uniform, the temperature was raised to 80°C, and the reaction was carried out for 24 hours. The obtained polymer mucilage was precipitated in deionized water. The obtained precipitate was pulverized, boiled and washed with methanol and deionized water in turn, and dried to obtain uncapped fluorine-containing polyarylene ether. Ketone resin, the structural formula is

n≈8×10⁴。

n≈8×10 ⁴ .

According to the method described in Example 1, the fluorinated polyaryletherketone resin prepared in Comparative Example 1 was tested, and the results showed that: the fluorinated polyaryletherketone resin prepared in Comparative Example 1 could not be measured for melt index; Thick viscosity η _sp /c = 0.36 [dL/g] (25°C); Tg: 185°C.

Characterization and Performance Testing

1) Carry out NMR characterization on the end-capped fluorine-containing polyarylether resin prepared in Example 1, and the obtained results are shown in Figures 1-2; it can be seen from Figures 1-2 that the ¹ H-NMR spectrum in Figure 1 can be seen at 7.91 ppm and 7.19ppm of two groups of absorptions come from two types of hydrogen atoms "1" and "2" on the benzene ring, in the ¹⁹ F-NMR spectrum 2, "1" belongs to the hexafluoroisopropyl group in bisphenol AF, "2" and "3" belong to the ortho and meta fluorine atoms on the decafluorobiphenyl respectively. It is confirmed by the nuclear magnetic spectrum that the present invention has successfully prepared a linear end-capped fluorine-containing polymer. The end-capped fluorine-containing polyarylene ether resin prepared in Example 2 has the same nuclear magnetic spectrum as in Example 1.

2) Carry out nuclear magnetic characterization on the fluorine-containing polyarylene ether resin prepared in Example 3, and the obtained results are shown in Figures 3-4; it can be seen in Figure 3 of the ¹ H-NMR spectrum that the two groups of absorptions at 6.97 ppm and 7.23 ppm come from Two types of hydrogen atoms "1" and "2" on the benzene ring, the absorption peak at 1.70ppm is from the hydrogen atom on the isopropyl group, it can be seen in the ¹⁹ F-NMR spectrum Figure 4, "1" and " 2” belong to the ortho and meta fluorine atoms on decafluorobiphenyl, respectively. It is proved by the nuclear magnetic spectrum that the linear end-capped fluorine-containing polymer is successfully synthesized in Example 3.

3) Fig. 5 is a real picture of a melt-extruded spline for melt-injection processing of the capped fluorinated polyarylene ether prepared in Example 1 at 260°C; Figure 5 and Figure 6 show that the surface of the melt extruded spline is smooth and the color is light yellow, which can prove that its melt It has good flow and stability, and can get a complete test strip, which proves that it can be melt processed.

6) The mechanical properties, friction properties and surface energy of the end-capped fluorinated polyarylene ether resins prepared in Examples 1-3 were tested, wherein the mechanical properties were tested by the GB/T 9341-2008 standard; the friction properties were tested by ring-block Type friction and wear testing machine was used to test, the dual surface was 45# steel ring, the pressure was 30N, the speed was 200rpm, and the sliding time was 2h; the results obtained are shown in Table 1.

Table 1 Mechanical properties, friction properties and surface energy data of the end-capped fluorine-containing polyarylene ether resins prepared in Examples 1-3

Comparing Examples 1 to 3, it is found that the molecular weights of the end-capped fluoropolymers prepared in Examples 1 and 2 are slightly higher, so various properties are also slightly improved.

The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (9)

1. a preparation method of end-capped fluorine-containing polyarylene ether resin, is characterized in that, comprises the following steps: The bisphenol monomer, the salt-forming agent, the dehydrating agent and the aprotic polar organic solvent are mixed, and a salt-forming reaction is carried out to obtain a first product; the bisphenol monomer comprises bisphenol A, bisphenol AF and bisphenol fluorene one or more of; Mixing the first product with decafluorobiphenyl, carrying out a polymerization reaction, adding an end-capping agent to the obtained product, and capping to obtain an end-capped fluorine-containing polyarylene ether resin; The capping agent includes 4,4'-difluorodiphenylsulfone, 4,4'difluorobenzophenone, 3,3'difluorobenzophenone, 4-fluorophenylphenylsulfone, or 4-fluoro Benzophenone; The end-capped fluorine-containing polyarylene ether resin has the structure shown in formula I:

In formula I, n is the degree of polymerization, n=2×10 ⁴ to 1×10 ⁵ ; R is the group corresponding to the removal of the phenolic hydroxyl groups at both ends of the bisphenol monomer, and R ₁ includes

2 . The preparation method according to claim 1 , wherein the molar ratio of the decafluorobiphenyl to the bisphenol monomer is (0.95-1.05):1. 3 . 3. preparation method according to claim 1, is characterized in that, described salt-forming agent comprises one or more in cesium carbonate, potassium carbonate and sodium carbonate; Described salt-forming agent and described bisphenol monomer The molar ratio is (1.001～1.35):1. 4. preparation method according to claim 1 is characterized in that, described dehydrating agent comprises one or more in toluene, xylene and cyclohexane; Described aprotic polar organic solvent comprises dimethylformaldehyde amide, dimethylacetamide, sulfolane or N-methylpyrrolidone; the volume of the dehydrating agent is 30-50% of the volume of the aprotic polar organic solvent. 5 . The preparation method according to claim 1 , wherein the total solid content of the bisphenol monomer and decafluorobiphenyl in the aprotic polar organic solvent is 10-25 wt %. 6 . 6 . The preparation method according to claim 1 , wherein the molar ratio of the capping agent to the bisphenol monomer is (0.01-0.05):1. 7 . 7. The end-capped fluorine-containing polyarylene ether resin prepared by the preparation method according to any one of claims 1 to 6 is characterized in that, having the structure shown in formula I:

In formula I, n is the degree of polymerization, n=2×10 ⁴ to 1×10 ⁵ ; R is the group corresponding to the removal of the phenolic hydroxyl groups at both ends of the bisphenol monomer, and R ₁ includes

8. The end-capped fluorine-containing polyarylene ether resin according to claim 7, characterized in that it comprises

9. The application of the end-capped fluorine-containing polyarylene ether resin according to claim 7 or 8 in the preparation of thermally stable bulk materials.

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