Process for preparing a heteronaphthalene-coupled phenyl ether resin and a heteronaphthalene-coupled phenyl ether resin

Abstract

The present application relates to a kind of preparation method of hetero naphthalene diphenyl polyarylether resin and hetero naphthalene diphenyl polyarylether resin, by flexible monomer partial replacement phthalazinone biphenyl bisphenol molecular structure, retain rigid structure such as hetero naphthalene diphenyl structure, benzene ring, sulfone group and carbonyl in target polymer molecular chain, while introducing flexible structure.Preparation method includes, with phthalazinone biphenyl bisphenol, carboxylic acid salt, halogenated diphenyl sulfone and halogenated diphenone as polymer monomer, anhydrous carbonate as catalyst, tetrahydrothiophene oxide as reaction solvent, aromatic hydrocarbon as water-carrying agent, construct polymerization reaction system, the solid content of polymerization reaction system is 50%, by high-temperature solution nucleophilic substitution polycondensation reaction and acidification settlement, repeated washing and dissolution-precipitation refining process, can obtain polymer with good solubility, and retain the high-temperature resistance of hetero naphthalene diphenyl polyarylether resin, obtain hetero naphthalene diphenyl polyarylether resin with high toughness, solubility and high-temperature resistance.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a method for preparing a naphthalene-biphenyl polyarylene ether resin and the naphthalene-biphenyl polyarylene ether resin itself. Background Technology

[0002] High-performance thermoplastic resins possess excellent heat resistance, superior mechanical properties, reprocessability, and strong environmental adaptability, making them valuable for applications in aerospace, electronics, advanced composite materials, and deployable space structures. However, traditional high-performance thermoplastic resins often suffer from high melt viscosity and processing difficulties, while composite material manufacturing processes such as solution impregnation and solution film formation require resins with good solubility. Therefore, it is often difficult to simultaneously achieve high performance resins that are heat-resistant, soluble, and tough.

[0003] Poly(phenylene ether sulfone ketone) (PPESK) is a class of high-performance thermoplastic resins containing a diazonylene biphenyl bisphenol (DHPZ) structure. The twisted, non-coplanar poly(phenylene ether sulfone) structure in this class of resins disrupts the regularity of the molecular chain, resulting in good solubility; the aromatic rings, sulfone groups, and carbonyl groups in the main chain endow it with excellent heat resistance and mechanical properties. Therefore, PPESK resins have become an important representative of high-temperature resistant, soluble thermoplastic engineering plastics.

[0004] However, PPESK molecules have a high content of rigid structures and insufficient chain flexibility. This limits the resin's ability to move chain segments and adjust conformation under external forces, making it prone to intrinsic brittleness. Consequently, it struggles to meet the toughness requirements of applications involving repeated large deformation folding / unfolding, elastic support rods, and high-toughness composite matrices. Existing toughening methods include dynamic covalent networks, hyperbranched structures, flexible segment copolymerization, and the introduction of flexible side chains. Among these, dynamic covalent networks and hyperbranched structures often rely on cross-linking networks, potentially reducing the solubility and reprocessability of thermoplastic resins, while conventional flexible segment modification may significantly sacrifice heat resistance.

[0005] Therefore, there is an urgent need to propose a method for preparing naphthalene-biphenyl polyarylene ether resin and a naphthalene-biphenyl polyarylene ether resin that, while retaining the high temperature resistance and solubility of PPESK resins, improves the flexibility of the resin molecular chain, the ability of chain segment movement, and the energy dissipation ability before fracture, thereby achieving a synergistic improvement in the resin's strength, toughness, heat resistance, and solubility. Summary of the Invention

[0006] To address the above problems, this invention proposes a novel method for preparing a high-toughness soluble naphthalene-biphenyl polyaryl ether resin and the naphthalene-biphenyl polyaryl ether resin itself.

[0007] To achieve the above objectives, the first aspect of this application provides a method for preparing a heteronaphthyl biphenyl polyarylene ether resin, comprising the following steps: Using diazanaphthyl ketone biphenyl bisphenol, carboxylates, halodiphenyl sulfones, and halobenzene as monomers, anhydrous carbonates as catalysts, tetrahydrothiophene oxide as a reaction solvent, and aromatic hydrocarbons as dehydrating agents, the polymerization reaction system had a solid content of 50%. The monomers, catalysts, reaction solvents, and dehydrating agents were added to a three-necked flask, nitrogen gas was introduced for gas replacement, and the three-necked flask was heated to remove water and dehydrating agents from the polymerization reaction system. Then, the temperature was increased to carry out a nucleophilic substitution polycondensation reaction. Tetrahydrothiophene oxide was added during the reaction to maintain the fluidity of the polymerization reaction system. The reaction was stopped when the viscosity of the polymerization reaction system no longer increased. After the nucleophilic substitution polycondensation reaction is completed, the heating temperature is reduced, tetrahydrothiophene oxide is added to the polymerization reaction system, the solid content of the polymerization reaction system is diluted to 20%, and then the diluted polymerization reaction system is added to acidic deionized water to precipitate the polymer. The precipitated polymer is then boiled in deionized water, followed by filtration and drying. The boiling, filtration and drying process is repeated to obtain crude polymer. The crude polymer was dissolved in an organohalogenated hydrocarbon to form a polymer solution, and the polymer solution was filtered. The filtrate was added to anhydrous ethanol for precipitation to obtain a refined polymer. The refined polymer was then boiled and washed in deionized water, and the boiling and washing process was repeated. After drying, the naphthalene-biphenyl polyarylene ether resin was obtained.

[0008] Preferably, the halodiphenyl sulfone is one of 4,4'-difluorodiphenyl sulfone or 4,4'-dichlorodiphenyl sulfone; the halobenzophenone is one of 4,4'-difluorodibenzophenone or 4,4'-dichlorodibenzophenone; the anhydrous carbonate is one of anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous cesium carbonate or anhydrous rubidium carbonate; the tetrahydrothiophene oxide is one of sulfolane, tetrahydrothiophene-1-oxide, 2-methylsulfolane or 3-methylsulfolane; the aromatic hydrocarbon is one of toluene, p-xylene, m-xylene, ethylbenzene or benzene; and the organohalogenated hydrocarbon is one of chloroform, dichloromethane, 1,2-dichloroethane or 1,1,2,2-tetrachloroethane.

[0009] Preferably, the heating temperature for removing moisture from the polymerization reaction system is 140°C and the heating time is 4 hours, and the heating temperature for removing the water-carrying agent from the polymerization reaction system is 150°C and the heating time is 4 hours.

[0010] Preferably, the heating temperature for the nucleophilic substitution polycondensation reaction is 200°C.

[0011] Preferably, the heating temperature for the dilution process of adding tetrahydrothiophene oxide to the polymerization reaction system is 180°C, and the heating time is 1 hour.

[0012] Preferably, the acidic deionized water is deionized water with added concentrated hydrochloric acid, wherein the volume fraction of concentrated hydrochloric acid is 15%, and the temperature of the acidic deionized water is 50-90℃.

[0013] Preferably, the mass fraction of crude polymer in the polymer solution is 10%.

[0014] Preferably, the boiling, filtration and drying processes are repeated 4-6 times.

[0015] Preferably, the boiling and washing process is repeated 4-6 times.

[0016] The second aspect of this application provides a heteronaphthyl biphenyl polyarylene ether resin, obtained according to the preparation method described in the first aspect.

[0017] The beneficial effects of this invention are as follows: This invention uses a flexible monomer to partially replace the molecular structure of diazanaphthyl ketone biphenyl bisphenol, retaining the rigid structures such as the naphthyl biphenyl structure, benzene ring, sulfone group, and carbonyl group in the target polymer molecular chain, while introducing a flexible structure, so that the prepared naphthyl biphenyl polyaryl ether resin has high toughness; through high-temperature solution nucleophilic substitution condensation reaction and acidification precipitation, repeated washing and dissolution-precipitation purification process, a polymer with good solubility can be obtained, while retaining the high-temperature resistance of the naphthyl biphenyl polyaryl ether resin, so that the obtained naphthyl biphenyl polyaryl ether resin has high toughness, solubility and high-temperature resistance. Attached Figure Description

[0018] Figure 1 Typical stress-strain curves of the products obtained in Examples 1 and 2 and PPESK under tensile testing are shown. Figure 2 This is a comparison chart of the elongation at break of the products obtained in Examples 1 and 2 and PPESK under tensile testing. Detailed Implementation

[0019] The specific preparation method of the heteronaphthyl biphenyl polyarylene ether resin proposed in this application includes the following steps. Using diazanaphthyl ketone biphenyl bisphenol, carboxylates, halobenzene sulfones, and halobenzene ketones as monomers, anhydrous carbonates as catalysts, tetrahydrothiophene oxide as a solvent, and aromatic hydrocarbons as dehydrating agents, a polymerization reaction system was formed by adding the above materials to a three-necked flask equipped with a mechanical stirrer, a water separator, a condenser, and a gas interface. The solid content of the polymerization reaction system was 50%. Nitrogen gas was introduced before the reaction to purge air from the apparatus. Then, the oil bath temperature was raised to 140°C to induce an azeotropic reaction between the aromatic hydrocarbons and water in the polymerization reaction system. After maintaining the heating temperature for 4 hours, the aromatic hydrocarbon / water mixture in the water separator was discharged. The oil bath temperature was then raised to 150°C and maintained for 4 hours to remove the aromatic hydrocarbons. Subsequently, the oil bath temperature was raised to 200°C to carry out a nucleophilic substitution polycondensation reaction. During the reaction, the viscosity of the system gradually increased. After 3 hours of reaction... After h, tetrahydrothiophene oxide was added to maintain the fluidity of the polymerization system. The reaction was stopped when the viscosity of the polymerization system no longer increased. After the nucleophilic substitution polycondensation reaction is completed, the oil bath temperature is lowered to 180℃, and tetrahydrothiophene oxide is added to the polymerization reaction system to dilute the solid content of the polymerization reaction system to 20%. After stirring for 1 hour, the diluted polymerization reaction system is poured into acidic deionized water at a temperature of 50-90℃ to precipitate the polymer. The acidic deionized water is deionized water with added concentrated hydrochloric acid, and the volume fraction of concentrated hydrochloric acid is 15%. The precipitated polymer is boiled in deionized water to remove residual solvent, inorganic salts, and acidic components. Then it is filtered and dried. The boiling, filtration, and drying process of the precipitated polymer is repeated 4-6 times to obtain crude polymer. The crude polymer was dissolved in an organohalogenated hydrocarbon to form a polymer solution, and the polymer solution was filtered. The filtrate was added to anhydrous ethanol for precipitation to obtain a refined polymer. The refined polymer was then boiled and washed in deionized water, and the boiling and washing process was repeated. After drying, the naphthalene-biphenyl polyarylene ether resin was obtained.

[0020] The dried crude polymer was dissolved in an organohalogenated hydrocarbon to prepare a polymer solution with a crude polymer mass fraction of 10%. Impurities were removed by filtration, and the filtrate was poured into anhydrous ethanol to precipitate, thus obtaining a refined polymer. The refined polymer was boiled and washed in deionized water, and the boiling and washing were repeated 4-6 times. The boiled and washed refined polymer was dried in a vacuum oven at 120°C for more than 24 hours to obtain a naphthalene-biphenyl polyarylene ether resin.

[0021] In the above process, the carboxylate is 4,4-bis(4-hydroxyphenyl)valerate; the halodiphenyl sulfone is one of 4,4'-difluorodiphenyl sulfone or 4,4'-dichlorodiphenyl sulfone; the halobenzophenone is one of 4,4'-difluorodiphenyl sulfone or 4,4'-dichlorodiphenyl sulfone; the anhydrous carbonate is one of anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous cesium carbonate or anhydrous rubidium carbonate; the tetrahydrothiophene oxide is one of sulfolane, tetrahydrothiophene-1-oxide, 2-methylsulfolane or 3-methylsulfolane; the aromatic hydrocarbon is one of toluene, p-xylene, m-xylene, ethylbenzene or benzene; and the organohalogenated hydrocarbon is one of chloroform, dichloromethane, 1,2-dichloroethane or 1,1,2,2-tetrachloroethane.

[0022] A naphthalene-biphenyl polyarylene ether resin was obtained by the above preparation method.

[0023] The technical solution of the present invention will be further described below with reference to the embodiments.

[0024] Example 1 The following mixture was selected: 25 mmol of diazanaphthone biphenyl bisphenol, 5 mmol of 4,4-bis(4-hydroxyphenyl)valeric acid, 24 mmol of 4,4'-difluorodiphenyl sulfone, 6 mmol of 4,4'-difluorobenzophenone, 45 mmol of anhydrous potassium carbonate, 14.8 ml of sulfolane, and 45 ml of toluene. These materials were added to a three-necked flask. Nitrogen gas was introduced before the reaction began. The oil bath temperature was then raised to 140°C and maintained for 4 hours. The toluene / water mixture in the separator was then discharged. The oil bath temperature was raised to 150°C and maintained for 4 hours to remove the toluene. The oil bath temperature was then raised to 200°C to initiate a nucleophilic substitution polycondensation reaction. During the reaction, the viscosity of the system gradually increased. After 3 hours of reaction, sulfolane was added to maintain the fluidity of the polymerization system. The reaction was stopped when the viscosity of the polymerization system no longer increased. After the nucleophilic substitution polycondensation reaction was completed, the oil bath temperature was raised to 180℃, and sulfolane was added to the polymerization reaction system to dilute the solid content of the polymerization reaction system to 20%. After stirring for 1 hour, the diluted polymerization reaction system was poured into acidic deionized water at a temperature of 50-90℃ to precipitate the polymer. The precipitated polymer was boiled in deionized water, then filtered and dried. The boiling, filtration, and drying process of the precipitated polymer was repeated 5 times to obtain the crude polymer. The dried crude polymer was dissolved in chloroform to prepare a polymer solution with a crude polymer mass fraction of 10%. Impurities were removed by filtration, and the filtrate was poured into anhydrous ethanol to precipitate, resulting in a refined polymer. The refined polymer was boiled and washed in deionized water, and the boiling and washing process was repeated 5 times. The boiled and washed refined polymer was dried in a vacuum oven at 120°C for more than 24 hours to obtain a naphthalene-biphenyl polyarylene ether resin, labeled as product a.

[0025] Example 2 The following materials were selected: 20 mmol of diazanaphthyl biphenyl bisphenol, 10 mmol of 4,4-bis(4-hydroxyphenyl)valerate, 24 mmol of 4,4'-difluorodiphenyl sulfone, 6 mmol of 4,4'-difluorodiphenyl ketone, 45 mmol of anhydrous potassium carbonate, 15.1 ml of sulfolane, and 45 ml of toluene. The above materials were added to a three-necked flask and prepared using the same method as in Example 1 to obtain a diazanaphthyl biphenyl polyarylene ether resin, labeled as product b.

[0026] The tensile and solubility properties of the products obtained in Examples 1 and 2 were compared with those of PPESK (sulfone-ketone ratio of 8:2). Tensile properties such as Figure 1 and Figure 2 As shown, where, Figure 1 The figures show typical stress-strain curves of the products obtained in Examples 1 and 2 and PPESK under tensile testing. Figure 2 The graph shows a comparison of the elongation at break under tensile testing between the products obtained in Examples 1 and 2 and PPESK. Product a from Example 1 has a tensile strength of approximately 90 MPa and an elongation at break of approximately 12.7%. Product b from Example 2 has a tensile strength of approximately 70 MPa and an elongation at break of approximately 12%. PPESK has a tensile strength of approximately 60 MPa and an elongation at break of approximately 9.5%. Compared to PPESK, product a shows an increase in tensile strength of approximately 50% and an increase in elongation at break of approximately 34%, while product b shows an increase in tensile strength of approximately 17% and an increase in elongation at break of approximately 26%.

[0027] The solubility properties are shown in Table 1. Table 1 compares the solubility properties of the products obtained in Examples 1 and 2 with PPESK in different solvents. The products obtained in Examples 1 and 2, along with PPESK, all exhibited good solubility in common solvents such as NMP, DMAc, DMF, and chloroform, forming homogeneous solutions at room temperature. In Table 1, "++" indicates soluble at room temperature; "+" indicates soluble upon heating; and "-" indicates insoluble. Table 1 In summary, the naphthalene-biphenyl polyarylene ether resin product prepared according to the method for preparing naphthalene-biphenyl polyarylene ether resin proposed in this embodiment exhibits superior toughness while retaining the good solubility of PPESK.

[0028] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the inventive concept, and these all fall within the protection scope of this invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A method for preparing a heteronaphthalene-biphenyl polyarylene ether resin, characterized in that, The process includes the following steps: using diazanaphthyl ketone biphenyl bisphenol, carboxylates, halodiphenyl sulfones, and halobenzene as monomers, anhydrous carbonates as catalysts, tetrahydrothiophene oxide as a reaction solvent, and aromatic hydrocarbons as dehydrating agents. The solid content of the polymerization reaction system is 50%. The monomers, catalysts, reaction solvents, and dehydrating agents are added to a three-necked flask, nitrogen is introduced for gas replacement, and the three-necked flask is heated to remove water and dehydrating agents from the polymerization reaction system. Then, the temperature is increased to carry out a nucleophilic substitution polycondensation reaction. Tetrahydrothiophene oxide is added during the reaction to maintain the fluidity of the polymerization reaction system. The reaction is stopped when the viscosity of the polymerization reaction system no longer increases. After the nucleophilic substitution polycondensation reaction is completed, the heating temperature is reduced, tetrahydrothiophene oxide is added to the polymerization reaction system, the solid content of the polymerization reaction system is diluted to 20%, and then the diluted polymerization reaction system is added to acidic deionized water to precipitate the polymer. The precipitated polymer is then boiled in deionized water, followed by filtration and drying. The boiling, filtration and drying process is repeated to obtain crude polymer. The crude polymer was dissolved in an organohalogenated hydrocarbon to form a polymer solution, and the polymer solution was filtered. The filtrate was added to anhydrous ethanol for precipitation to obtain a refined polymer. The refined polymer was then boiled and washed in deionized water, and the boiling and washing process was repeated. After drying, the naphthalene-biphenyl polyarylene ether resin was obtained.

2. The preparation method according to claim 1, characterized in that, The carboxylate is 4,4-bis(4-hydroxyphenyl)valerate, the halodiphenyl sulfone is one of 4,4'-difluorodiphenyl sulfone or 4,4'-dichlorodiphenyl sulfone, the halobenzophenone is one of 4,4'-difluorodibenzophenone or 4,4'-dichlorodibenzophenone, the anhydrous carbonate is one of anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous cesium carbonate or anhydrous rubidium carbonate, the tetrahydrothiophene oxide is one of sulfolane, tetrahydrothiophene-1-oxide, 2-methylsulfolane or 3-methylsulfolane, the aromatic hydrocarbon is one of toluene, p-xylene, m-xylene, ethylbenzene or benzene, and the organohalogenated hydrocarbon is one of chloroform, dichloromethane, 1,2-dichloroethane or 1,1,2,2-tetrachloroethane.

3. The preparation method according to claim 2, characterized in that, The heating temperature for removing moisture from the polymerization reaction system is 140℃, and the heating time is 4 hours. The heating temperature for removing water-carrying agent from the polymerization reaction system is 150℃, and the heating time is 4 hours.

4. The preparation method according to claim 3, characterized in that, The heating temperature for the nucleophilic substitution condensation reaction is 200℃.

5. The preparation method according to claim 4, characterized in that, The heating temperature for diluting the polymerization reaction system with tetrahydrothiophene oxide was 180℃, and the heating time was 1h.

6. The preparation method according to claim 5, characterized in that, The acidic deionized water is deionized water with added concentrated hydrochloric acid, wherein the volume fraction of concentrated hydrochloric acid is 15%, and the temperature of the acidic deionized water is 50-90℃.

7. The preparation method according to claim 6, characterized in that, The crude polymer in the polymer solution has a mass fraction of 10%.

8. The preparation method according to claim 7, characterized in that, The boiling, filtration, and drying processes are repeated 4-6 times.

9. The preparation method according to claim 8, characterized in that, The boiling and washing process is repeated 4-6 times.

10. A polyaryl ether resin of naphthalene-biphenyl, characterized in that, The preparation method according to any one of claims 1-9 is obtained.

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