Polyether sulfone-nylon composite material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of synthesis of nylon composite materials, and discloses a polyethersulfone-nylon composite material and a preparation method and application thereof to solve the problem of poor compatibility of blending of polyethersulfone and PA6 in the prior art, the polyethersulfone-nylon composite material is modified by introducing carboxyl into a side group of polyethersulfone and then grafting PA6, and the polyethersulfone-nylon composite material is obtained. Further, the compatibility of polyether sulfone and nylon 6 is remarkably improved, and the polyether sulfone-nylon composite material with excellent comprehensive performance is obtained in a hydrolytic polymerization in-situ production mode; the composite material prepared by the method provided by the invention not only has the excellent performance of nylon 6, but also has higher thermal stability and rigidity, lower water absorption and more excellent flame retardant property compared with pure nylon 6, and is suitable for engineering application with higher requirements on high temperature, humidity or flame retardant property.

Description

Technical Field

[0001] The present invention relates to a nylon composite material, in particular to a polyethersulfone-nylon composite material and a preparation method and application thereof, belonging to the technical field of nylon composite materials. Background Art

[0002] Nylon 6 (PA6) is an engineering plastic with excellent performance, but pure PA6 has high hygroscopicity, poor dimensional stability and heat resistance. Unmodified PA6 cannot fully meet application requirements.

[0003] In the prior art, blending two or more polymers is a common method for obtaining nylon materials with higher overall performance. Compared to PA6, polyethersulfone (PES) exhibits superior mechanical properties, including high rigidity, high thermal stability, good dimensional stability, and resistance to hydrolysis, radiation, and flame retardancy. Blending PES with PA6 can improve certain performance deficiencies of PA6. Lin Zhiyong et al. (Engineering Plastics Applications, 2012, Vol. 40, No. 1, pp. 4-7; Engineering Plastics Applications, 2012, Vol. 40, No. 2, pp. 8-11; CN200610040169.5; Plastics Industry, January 2009, Vol. 37, No. 1, pp. 13-16) reported an anionic in-situ preparation method for polyethersulfone / MCPA6 composites. However, due to the significant differences in the chemical structures of PES and PA6, their compatibility was poor, resulting in performance far below expectations. Therefore, how to increase the interaction between the two phases of polyethersulfone and PA6 is an effective way to improve the performance of polyethersulfone / PA6 composite materials. Summary of the Invention

[0004] In response to the problem of poor compatibility in the blending of polyethersulfone and PA6 in the prior art, the present invention provides a polyethersulfone-nylon composite material, a preparation method, and uses thereof. By introducing carboxyl groups into the side groups of polyethersulfone and then grafting PA6 to modify the polyethersulfone, the interfacial interaction between polyethersulfone and PA6 can be greatly improved, ultimately obtaining a polyethersulfone-nylon composite material with excellent comprehensive performance. The composite material not only has the excellent properties of nylon 6, but also has higher thermal stability and rigidity, lower water absorption, and better flame retardant properties than pure nylon 6. It is suitable for engineering applications with high requirements for high temperature, humidity or flame retardant properties.

[0005] In order to achieve the above technical objectives, the technical solutions adopted by the present invention are as follows:

[0006] According to a first embodiment of the present invention, a polyethersulfone-nylon composite material is provided:

[0007] A polyethersulfone-nylon composite material, comprising or consisting of nylon 6 and a polymer having a general structural formula (I). The polymer having a general structural formula (I) is as follows:

[0008]

[0009] In the general structural formula (I), Ar1 is one or more of diphenylalkyl, diphenylhaloalkyl, diphenylsulfone, and biphenyl. Ar2 is one or both of diphenylalkyl and triphenylalkyl. n is 10 to 200. 0 < x < 1, and y = 1-x.

[0010] Preferably, Ar1 is one or more of diphenyl C1-C10 alkyl, diphenyl halogenated C1-C10 alkyl, diphenyl sulfone, and biphenyl. Ar2 is one or both of diphenyl C1-C10 alkyl and triphenyl C1-C10 alkyl.

[0011] Preferably, Ar1 is one or more of 2,2-diphenylpropane, 2,2-diphenylperfluoropropane, diphenylsulfone, and biphenyl. Ar2 is one or two of 2,2-bisphenylbutyl and triphenylmethane.

[0012] Preferably, n is 30 to 150, and more preferably, n is 40 to 100.

[0013] It should be noted that, in the present invention, the size of the degree of polymerization n can be regulated by regulating the reaction time (the specific value can be calculated after the molecular weight is tested by GPC). Generally, the larger the degree of polymerization, the greater the viscosity will increase. Therefore, when n is too large, the viscosity of the entire system will be too large, which is not conducive to discharging and processing. If n is too small, the carboxyl content will be very low, the modification effect will be poor, and the performance improvement of the composite material will not be large. In addition, in the general structural formula (I), the size of y determines the content of the side carboxyl group. The larger the y value, the higher the side carboxyl content, the shorter the side-chain PA6, and the worse the toughness. The lower the y value, the longer the side-chain PA6, but too low a value will result in excessive overall viscosity. In a preferred embodiment of the present invention, the value of y is preferably between 0.02 and 0.5 (preferably 0.05 to 0.2).

[0014] Preferably, the polymer having the general structural formula (I) in the composite material comprises 1-30% by weight, preferably 5-20% by weight. Experimental verification has shown that excessive amounts of the polymer having the general structural formula (I) shorten the PA6 chain length, leading to decreased toughness, reduced impact resistance, and embrittlement of the composite material. However, excessive amounts of the polymer having the general structural formula (I) have little effect on the mechanical and heat resistance properties of the composite material.

[0015] According to a second embodiment of the present invention, a method for preparing a polyethersulfone-nylon composite material is provided:

[0016] A method for preparing a polyethersulfone-nylon composite material or a method for preparing a polyethersulfone-nylon composite material as described in the first embodiment, the preparation method comprising the following steps:

[0017] 1) 4,4'-dichlorodiphenyl sulfone, a diphenol monomer having the general structural formula (II), a diphenol monomer having a side carboxyl group having the general structural formula (III), a salt-forming agent, a solvent, and a water-carrying agent are added to a reaction kettle, and water separation, salt formation, and polymerization reactions are carried out in sequence. The mixture is then neutralized and condensed in an aqueous phase, washed with water, and dried to obtain a side carboxyl group polyethersulfone resin having the general structural formula (IV). The reaction process is as follows:

[0018]

[0019] 2) A pendant carboxyl polyethersulfone resin having the general structural formula (IV), caprolactam, and water are added to an autoclave, and a hydrolysis reaction is first carried out under a protective atmosphere. The reaction is then subjected to heating, degassing, reduced pressure polymerization, water washing, and drying to obtain a composite material containing a polymer having the general structural formula (I). The reaction flow is as follows:

[0020]

[0021] Wherein: Ar1 is one or more of diphenylalkyl, diphenylhaloalkyl, diphenylsulfone, and biphenyl. Ar2 is one or both of 4,4-diphenylpentanoic acid and 2-carboxytriphenylmethane. n is 10 to 200, preferably 30 to 150, and more preferably 60 to 100. 0 < x < 1, y = 1 - x.

[0022] Preferably, Ar1 is one or more of diphenyl C1-C10 alkyl, diphenyl halogenated C1-C10 alkyl, diphenyl sulfone, and biphenyl. Ar2 is one or both of diphenyl C1-C10 alkyl and triphenyl C1-C10 alkyl.

[0023] Preferably, Ar1 is one or more of the following groups:

[0024] 2,2-Diphenylpropane:

[0025] (The diphenol monomer formed after combining with hydroxyl group is ),

[0026] 2,2-Diphenylperfluoropropane:

[0027] (The diphenol monomer formed after combining with hydroxyl group is ), diphenyl sulfone:

[0028] (The diphenol monomer formed after combining with hydroxyl group is ),

[0029] Biphenyl:

[0030] (The diphenol monomer formed after combining with hydroxyl group is ).

[0031] Preferably, Ar2 is one or two of the following groups:

[0032] 2,2-Bisphenylbutyl:

[0033] (The diphenol monomer formed by combining it with hydroxyl and carboxyl groups is ),

[0034] Triphenylmethane:

[0035] (The diphenol monomer formed by combining it with hydroxyl and carboxyl groups is

[0036] Preferably, in step 1), the salt-forming agent is selected from one or more of an alkali, an alkali metal carbonate, and an alkali metal bicarbonate, preferably one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. Preferably, the molar amount of the salt-forming agent is 1.8 to 2.5 times the molar amount of 4,4'-dichlorodiphenyl sulfone.

[0037] Preferably, in step 1), the solvent is an aprotic polar solvent, preferably one or more of diphenyl sulfone, sulfolane, dimethyl sulfone, N-methylpyrrolidone, dimethyl sulfoxide, N,N'-dimethylformamide, and N,N'-dimethylacetamide. Preferably, the volume of the solvent used is 3 to 10 times the mass of 4,4'-dichlorodiphenyl sulfone used.

[0038] Preferably, in step 1), the water-carrying agent is selected from one or more of toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, and diethylidene benzene, preferably toluene. Preferably, the volumetric amount of the water-carrying agent is 1.5 to 6 times the mass amount of 4,4'-dichlorodiphenyl sulfone.

[0039] Preferably, in step 1), the molar ratio of 4,4'-dichlorodiphenyl sulfone, the diphenol monomer having the general structural formula (II), and the diphenol monomer containing a pendant carboxyl group having the general structural formula (III) is 1-1.05:0.5-1.03:0.02-0.53, preferably 1-1.02:0.8-1:0.05-0.21.

[0040] Preferably, in step 2), the weight ratio of the pendant carboxyl polyethersulfone resin having the general structural formula (IV) to caprolactam is 2-30:70-98, preferably 3-25:75-97, and more preferably 5-20:80-95. The weight ratio of water is 3-10%, preferably 4-8%, of the total weight of the pendant carboxyl polyethersulfone resin having the general structural formula (IV) and caprolactam.

[0041] Preferably, in step 2), the protective atmosphere is a nitrogen atmosphere or an inert gas atmosphere.

[0042] Preferably, step 1) is specifically as follows: 4,4'-dichlorodiphenyl sulfone, a diphenol monomer having the general structural formula (II), a diphenol monomer having a side carboxyl group having the general structural formula (III), a salt-forming agent, a solvent and a water-carrying agent are added to a reaction kettle in proportion, firstly separated into salts at a temperature of 100-180°C (preferably 120-160°C) for 1-8h (preferably 2-6h), and then polymerized at a temperature of 150-280°C (preferably 160-240°C) for 1-8h (preferably 2 ~6h), after the reaction is completed, the reaction system is poured into a dilute hydrochloric acid solution (preferably with a mass concentration of 10-30%) under stirring (preferably at a stirring rate of not less than 300r / min) for aqueous phase neutralization and coagulation, and after the coagulation is completed, solid-liquid separation is performed, and the obtained solid is washed with deionized water for 1 to 10 times, and finally dried in an oven (preferably at a drying temperature of 60 to 100°C and a drying time of 0.5 to 5h) to obtain a side carboxyl polyethersulfone resin having the general structural formula (IV).

[0043] Preferably, step 2) is specifically as follows: adding a side carboxyl polyethersulfone resin having a general structural formula (IV), caprolactam and water into a high-pressure reactor in proportion, introducing a protective gas to replace the air in the reactor 1 to 10 times, first heating to 180 to 280° C. (preferably 200 to 260° C.) for hydrolysis reaction for 0.5 to 6 h (preferably 1 to 4 h), then heating to 220 to 300° C. (preferably 240 to 280° C.) for further reaction for 0.5 to 6 h (preferably 1 to 4 h), and exhausting to normal pressure after the reaction is completed. Then, the reaction mixture is polymerized under reduced pressure until the viscosity is acceptable (preferably, the reaction mixture is polymerized under reduced pressure stepwise within 0.5 to 6 hours (preferably 1 to 3 hours) until the negative pressure value is -0.05 MPa to -0.09 MPa, preferably -0.06 MPa to -0.08 MPa, for example, -0.07 MPa), and then pelletized to obtain solid particles. The solid particles are washed with deionized water for 1 to 10 times, and finally dried in an oven (preferably at a drying temperature of 60 to 100° C. and for 0.5 to 5 hours) to obtain a composite material containing a polymer having the general structural formula (I).

[0044] According to a third embodiment of the present invention, there is provided a use of a polyethersulfone-nylon composite material:

[0045] A use of a polyethersulfone-nylon composite material, or the use of the polyethersulfone-nylon composite material as described in the first embodiment, or the use of the polyethersulfone-nylon composite material prepared by the preparation method as described in the second embodiment, wherein the polyethersulfone-nylon composite material is used as a plastic.

[0046] In the present invention, experimental studies have found that when carboxyl groups are introduced into the side groups of polyethersulfone and then grafted onto PA6, a side carboxyl polyethersulfone resin can be obtained. This side carboxyl polyethersulfone resin and a PA6 monomer (such as caprolactam) are used as raw materials for hydrolysis and polymerization, thereby in situ preparing a composite material including or consisting of nylon 6 (i.e., PA6) and a polymer having the general structural formula (I) (i.e., PSU-g-PA6). The composite material has good compatibility between PA6 and PSU-g-PA6, high thermal stability and rigidity, low water absorption, and excellent flame retardant properties.

[0047] Compared with the prior art, the beneficial technical effects of the present invention are as follows:

[0048] 1: In the composite material of the present invention, since PA6 is grafted to the polymer having the general structural formula (I) through a pendant carboxyl group, the polymer having the general structural formula (I) and PA6 have good compatibility, and thus the composite material has good mechanical properties, heat resistance, flame retardancy and dimensional stability.

[0049] 2: In the method for preparing the composite material of the present invention, the target composite material is prepared by in-situ hydrolysis polymerization, the overall process is short, the process is easy to control, the production efficiency is high, and it is conducive to promoting and further improving the comprehensive performance of the target product. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 The schematic diagram of the synthetic route for preparing the polymer having the general structural formula (I) of the present invention is shown.

[0051] Figure 2 1 is a hydrogen nuclear magnetic resonance spectrum of polyethersulfone (PSU) and the side carboxyl polyethersulfone prepared in Example 3 of the present invention.

[0052] Figure 3 1 and 2 are hydrogen nuclear magnetic resonance spectra of the polyethersulfone-nylon composite material described in Comparative Example 1 and the polyethersulfone-nylon composite material prepared in Example 3 of the present invention.

[0053] Figure 4 3 are the DSC curves of PA6 and the composite materials obtained in Examples 1, 2 and 3 of the present invention during the second heating under a nitrogen atmosphere.

[0054] Figure 5 3 are thermogravimetric analysis curves of PA6 and the composite materials obtained in Examples 1, 2, and 3 of the present invention.

[0055] Figure 6 1 is a stress-strain curve of the tensile strength of PA6 and the composite materials obtained in Examples 1, 2, and 3 of the present invention.

[0056] Figure 7 This is a field emission scanning electron microscope image of the brittle fracture surface of comparative example 1 after etching.

[0057] Figure 8 This is a field emission scanning electron microscope image of the brittle fracture surface of the composite material of Example 3 of the present invention after etching. DETAILED DESCRIPTION

[0058] The technical solutions of the present invention are illustrated below with examples, and the scope of protection requested by the present invention includes but is not limited to the following embodiments.

[0059] Example 1

[0060] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 102.7g (0.45mol) of bisphenol A, 14.3g (0.05mol) of diphenolic acid, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, and then further heated to 180°C for polymerization reaction for 4 hours. After the reaction is completed, it is slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase is condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0061] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 950g of caprolactam, 50g of the side carboxyl polyethersulfone resin prepared above and 47.5mL of water were added to an autoclave. The air was replaced by nitrogen three times and then the temperature was raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the air was exhausted to normal pressure and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0062] Example 2

[0063] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 102.7g (0.45mol) of bisphenol A, 14.3g (0.05mol) of diphenolic acid, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, and then further heated to 180°C for polymerization reaction for 4 hours. After the reaction is completed, it is slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase is condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0064] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 900g of caprolactam, 100g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the pressure was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0065] Example 3

[0066] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 102.7g (0.45mol) of bisphenol A, 14.3g (0.05mol) of diphenolic acid, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, and then further heated to 180°C for polymerization reaction for 4 hours. After the reaction is completed, it is slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase is condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0067] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 850g of caprolactam, 150g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the air was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0068] Example 4

[0069] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 91.3g (0.40mol) of bisphenol A, 28.6g (0.10mol) of diphenolic acid, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, then further heated to 180°C for polymerization reaction for 4 hours. After the reaction was completed, it was slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase was condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0070] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 900g of caprolactam, 100g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the pressure was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0071] Example 5

[0072] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 112.6g (0.45mol) of bisphenol S, 14.3g (0.05mol) of diphenolic acid, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, and then further heated to 200°C for polymerization reaction for 4 hours. After the reaction is completed, it is slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase is condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0073] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 900g of caprolactam, 100g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the pressure was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0074] Example 6

[0075] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 83.8g (0.45mol) of 4,4'-biphenol, 14.3g (0.05mol) of diphenolic acid, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, and then further heated to 180°C for polymerization reaction for 4 hours. After the reaction is completed, it is slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase is condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0076] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 900g of caprolactam, 100g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the pressure was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0077] Example 7

[0078] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 102.7g (0.45mol) of bisphenol A, 16.0g (0.05mol) of phenolphthalein, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, then further heated to 180°C for polymerization reaction for 4 hours. After the reaction was completed, it was slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase was condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0079] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 900g of caprolactam, 100g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the pressure was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0080] Example 8

[0081] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 112.6g (0.45mol) of bisphenol S, 16.0g (0.05mol) of phenolphthalein, 138.2g (1.0mol) of potassium carbonate, 600mL of cyclopentane and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, then further heated to 180°C for polymerization reaction for 4 hours, and after the reaction was completed, slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase was condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0082] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 900g of caprolactam, 100g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the pressure was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0083] Example 9

[0084] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 68.5g (0.30mol) of bisphenol A, 57.2g (0.20mol) of diphenolic acid, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, then further heated to 180°C for polymerization reaction for 4 hours, and after the reaction was completed, slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase was condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0085] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 850g of caprolactam, 150g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the air was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0086] Example 10

[0087] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 57.0g (0.25mol) of bisphenol A, 71.5g (0.25mol) of diphenolic acid, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, and then further heated to 180°C for polymerization reaction for 4 hours. After the reaction is completed, it is slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase is condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0088] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 850g of caprolactam, 150g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the air was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0089] Example 11

[0090] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 45.6g (0.20mol) of bisphenol A, 85.3g (0.30mol) of diphenolic acid, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, and then further heated to 180°C for polymerization reaction for 4 hours. After the reaction is completed, it is slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase is condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0091] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 850g of caprolactam, 150g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the air was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0092] Example 12

[0093] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) 4,4'-dichlorodiphenyl sulfone, 34.2g (0.15mol) bisphenol A, 100.1g (0.35mol) diphenolic acid, 138.2g (1.0mol) potassium carbonate, 600mL dimethyl sulfoxide and 300mL toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, then further heated to 180°C for polymerization reaction for 4 hours. After the reaction was completed, it was slowly poured into 1000mL dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase was condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0094] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 850g of caprolactam, 150g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the air was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0095] Example 13

[0096] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 102.7g (0.45mol) of bisphenol A, 14.3g (0.05mol) of diphenolic acid, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, and then further heated to 180°C for polymerization reaction for 4 hours. After the reaction is completed, it is slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase is condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0097] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 800g of caprolactam, 200g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the pressure was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0098] Example 14

[0099] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 102.7g (0.45mol) of bisphenol A, 14.3g (0.05mol) of diphenolic acid, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, and then further heated to 180°C for polymerization reaction for 4 hours. After the reaction is completed, it is slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase is condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0100] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 700g of caprolactam, 300g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the pressure was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0101] Example 15

[0102] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 102.7g (0.45mol) of bisphenol A, 14.3g (0.05mol) of diphenolic acid, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, and then further heated to 180°C for polymerization reaction for 4 hours. After the reaction is completed, it is slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase is condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0103] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 980g of caprolactam, 20g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the air was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0104] Example 16

[0105] Preparation of side carboxyl polyether sulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenyl sulfone, 102.7g (0.45mol) of bisphenol A, 14.3g (0.05mol) of diphenolic acid, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, and then further heated to 180°C for polymerization reaction for 4 hours. After the reaction is completed, it is slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase is condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain side carboxyl polyether sulfone resin.

[0106] Side carboxyl polyethersulfone / caprolactam hydrolysis polymerization: 990g of caprolactam, 10g of the side carboxyl polyethersulfone resin prepared above and 45mL of water were added to an autoclave. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the air was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0107] Comparative Example 1

[0108] Preparation of polyethersulfone resin: 143.6g (0.5mol) of 4,4'-dichlorodiphenylsulfone, 114.4g (0.50mol) of bisphenol A, 138.2g (1.0mol) of potassium carbonate, 600mL of dimethyl sulfoxide and 300mL of toluene were added to a reactor, first heated to 140°C for water separation and salt formation reaction for 4 hours, then further heated to 180°C for polymerization reaction for 4 hours. After the reaction was completed, it was slowly poured into 1000mL of dilute hydrochloric acid with a mass concentration of 10% under high-speed stirring (500r / min), the aqueous phase was condensed, washed with deionized water 3 times, and dried at 80°C for 3h to obtain polyethersulfone resin.

[0109] Polyethersulfone / caprolactam hydrolysis polymerization: 900g of caprolactam, 100g of the above-prepared polyethersulfone resin and 45mL of water were added to a high-pressure reactor. After replacing the air with nitrogen three times, the temperature was first raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the pressure was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0110] Comparative Example 2

[0111] Polyethersulfone / caprolactam hydrolysis polymerization: 850g of caprolactam, 150g of the carboxyl polyethersulfone resin prepared in Comparative Example 1 and 45mL of water were added to a high-pressure reactor. The air was replaced with nitrogen three times and then the temperature was raised to 220°C for hydrolysis reaction for 2 hours, and then the temperature was raised to 260°C for reaction for 2 hours. After the reaction was completed, the air was exhausted to normal pressure and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07MPa within 2h). The material was pelletized, washed with deionized water three times, and dried at 80°C for 3h to obtain a polyethersulfone-nylon composite material.

[0112] Comparative Example 3

[0113] 1000 g of caprolactam and 50 mL of water were added to a high-pressure reactor. The air was replaced by nitrogen three times, and the temperature was first raised to 220° C. for hydrolysis reaction for 2 hours, and then raised to 260° C. for reaction for 2 hours. After the reaction was completed, the pressure was exhausted to normal pressure, and the pressure was slowly reduced to polymerize until the viscosity was qualified (i.e., the relative viscosity was not less than 2.0, and the negative pressure value dropped to about -0.07 MPa within 2 hours). The material was pelletized, washed with deionized water three times, and dried at 80° C. for 3 hours to obtain nylon 6 material.

[0114] Performance Testing

[0115] Test conditions: Tensile properties were tested according to GB / T 1040.2-2006, with a gauge length of 50 mm, an initial distance between fixtures of 115 mm, a preferred thickness of 4 mm, a narrow portion of 10 mm, I-type splines, and a test rate of 50 mm / min.

[0116] The bending properties were tested according to GB / T 9341-2008, with a sample size of 80 mm × 10 mm × 4 mm, a support span of 64 mm, and a test rate of 2 mm / min.

[0117] Crystallinity (X c ) by formula Calculate, where ΔH m is the melting enthalpy of the sample, ΔH* m (230.1 J / g) is the melting enthalpy of PA6 when it is completely crystallized. The melting enthalpy of the sample was measured by DSC.

[0118] The heat deformation temperature is tested according to the national standard GB / T1634-2004. The sample is placed flat, the sample size is 80mm×10mm×4mm, the pressure is 1.8MPa, and the heating rate is 120℃ / h.

[0119] Water absorption is tested according to ASTM D570. The sample is a 60mm×60mm×2mm flat plate. The sample is placed in an 80°C oven and dried until its mass no longer changes. The mass of the dried sample is recorded as the initial mass W0. The dried sample is soaked in room temperature water for 24 hours. The sample is removed and the surface moisture is wiped off. The mass is then measured immediately and recorded as the wet weight W. t .

[0120]

[0121] The limiting oxygen index (LOI) value is determined according to the national standard GB / T 2406.2-2009 using a JYW-111 oxygen index tester. The ambient conditions are a temperature of 26°C, a humidity of 61%, a gas concentration of 99.99% oxygen and nitrogen, and top surface ignition.

[0122] The results of the above tests on the composite materials of the embodiments and comparative examples are shown in Table 1 below:

[0123] Table 1 is a comparison of the test results of the composite materials obtained in each embodiment and comparative example

[0124]

[0125]

[0126] from Figure 7 and Figure 8It can be seen from the field emission scanning electron microscope image of the composite material brittle fracture after etching of Comparative Example 1 ( Figure 7 ) showed obvious phase separation phenomenon. The field emission scanning electron microscope image of the composite material brittle fracture after etching in Example 3 of the present invention ( Figure 8 ) without obvious phase separation.

[0127] The sources of the reagents used in the present invention are as follows:

[0128] 4,4'-Dichlorodiphenyl sulfone was purchased from Anaiji Pharmaceutical Chemical Co., Ltd.

[0129] Bisphenol A was purchased from Anaiji Pharmaceutical Chemical Co., Ltd.

[0130] 4,4'-Bisphenol A was purchased from Anaiji Pharmaceutical Chemical Co., Ltd.

[0131] Diphenolic acid was purchased from Anhui Zesheng Technology Co., Ltd.

[0132] Phenolphthalein was purchased from Anhui Zesheng Technology Co., Ltd.

[0133] Potassium carbonate was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0134] Dimethyl sulfoxide was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0135] Sulfolane was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0136] Toluene was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0137] Dilute hydrochloric acid was purchased from China Airlines Trading Co., Ltd.

[0138] Caprolactam was purchased from Sinopec Hunan Petrochemical Co., Ltd.

Claims

1. A polyethersulfone-nylon composite material, characterized in that: The composite material comprises or consists of nylon 6 and a polymer having a general structural formula (I); wherein the polymer having a general structural formula (I) is as follows: In the general structural formula (I), Ar1 is one or more of diphenylalkyl, diphenylhaloalkyl, diphenylsulfone, and biphenyl; Ar2 is one or two of diphenylalkyl and triphenylalkyl; n is 10 to 200; 0<x<1, y=1-x.

2. The composite material according to claim 1, characterized in that: Ar1 is one or more of diphenyl C1-C10 alkyl, diphenyl halogenated C1-C10 alkyl, diphenyl sulfone, and biphenyl; Ar2 is one or two of diphenyl C1-C10 alkyl and triphenyl C1-C10 alkyl.

3. The composite material according to claim 1 or 2, characterized in that: Ar1 is one or more of 2,2-diphenylpropane, 2,2-diphenylperfluoropropane, diphenylsulfone, and biphenyl; Ar2 is one or two of 2,2-bisphenylbutyl and triphenylmethane.

4. The composite material according to any one of claims 1 to 3, characterized in that: n is 30 to 150, preferably 40 to 100; and / or In the composite material, the mass content of the polymer having the general structural formula (I) is 1 to 30%, preferably 5 to 20%.

5. A method for preparing a polyethersulfone-nylon composite material or a method for preparing a polyethersulfone-nylon composite material according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: 1) 4,4'-dichlorodiphenyl sulfone, a diphenol monomer having a general structural formula (II), a diphenol monomer having a side carboxyl group having a general structural formula (III), a salt-forming agent, a solvent, and a water-carrying agent are added to a reaction kettle, and water separation, salt formation, and polymerization reactions are sequentially performed, followed by aqueous phase neutralization, coagulation, water washing, and drying to obtain a side carboxyl group polyethersulfone resin having a general structural formula (IV). The reaction process is shown below: 2) Adding a pendant carboxyl polyethersulfone resin having the general structural formula (IV), caprolactam, and water into an autoclave, first performing a hydrolysis reaction under a protective atmosphere, and then sequentially performing heating and exhausting, reduced pressure polymerization, water washing, and drying to obtain a composite material containing a polymer having the general structural formula (I); the reaction process is shown below: Wherein: Ar1 is one or more of diphenylalkyl, diphenylhaloalkyl, diphenylsulfone, and biphenyl; Ar2 is one or two of diphenylalkyl and triphenylalkyl; n is 10 to 200, preferably 30 to 150, and more preferably 40 to 100; 0<x<1, y=1-x.

6. The preparation method according to claim 5, characterized in that: Ar1 is one or more of diphenyl C1-C10 alkyl, diphenyl halogenated C1-C10 alkyl, diphenyl sulfone, and biphenyl; Ar2 is one or two of diphenyl C1-C10 alkyl and triphenyl C1-C10 alkyl; Preferably, Ar1 is one or more of 2,2-diphenylpropane, 2,2-diphenylperfluoropropane, diphenylsulfone, and biphenyl; and Ar2 is one or two of 2,2-diphenylbutyl and triphenylmethane.

7. The preparation method according to claim 5 or 6, characterized in that: In step 1), the salt-forming agent is selected from one or more of alkali, alkali metal carbonate, and alkali metal bicarbonate, preferably one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; preferably, the molar amount of the salt-forming agent is 1.8 to 2.5 times the molar amount of 4,4'-dichlorodiphenyl sulfone; and / or The solvent is an aprotic polar solvent, preferably one or more of diphenyl sulfone, sulfolane, dimethyl sulfone, N-methylpyrrolidone, dimethyl sulfoxide, N,N'-dimethylformamide, and N,N'-dimethylacetamide; preferably, the volume amount of the solvent is 3 to 10 times the mass amount of 4,4'-dichlorodiphenyl sulfone; and / or The water-carrying agent is selected from one or more of toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, and diethylidene benzene, preferably toluene; preferably, the volume amount of the water-carrying agent is 1.5 to 6 times the mass amount of 4,4'-dichlorodiphenyl sulfone; Preferably, in step 1), the molar ratio of 4,4'-dichlorodiphenyl sulfone, the diphenol monomer having the general structural formula (II), and the diphenol monomer containing a pendant carboxyl group having the general structural formula (III) is 1-1.05:0.5-1.03:0.02-0.53, preferably 1-1.02:0.8-1:0.05-0.

21.

8. The preparation method according to any one of claims 5 to 7, characterized in that: In step 2), the weight ratio of the side carboxyl polyethersulfone resin having the general structural formula (IV) to caprolactam is 2-30:70-98, preferably 3-25:75-97, and more preferably 5-20:80-95; the weight ratio of water is 3-10% of the total weight of the side carboxyl polyethersulfone resin having the general structural formula (IV) and caprolactam, preferably 4-8%; Preferably, in step 2), the protective atmosphere is a nitrogen atmosphere or an inert gas atmosphere.

9. The preparation method according to any one of claims 5 to 8, characterized in that: Step 1) is specifically as follows: 4,4'-dichlorodiphenyl sulfone, a diphenol monomer having a general structural formula (II), a diphenol monomer having a side carboxyl group having a general structural formula (III), a salt-forming agent, a solvent, and a water-carrying agent are added to a reaction kettle in proportion, firstly separated into salts at a temperature of 100-180°C (preferably 120-160°C) for 1-8 hours (preferably 2-6 hours), and then polymerized at a temperature of 150-280°C (preferably 160-240°C) for 1-8 hours (preferably 2-6 hours). After the reaction is completed, the reaction system is poured into a dilute hydrochloric acid solution (preferably with a mass concentration of 10-30%) under stirring (preferably at a stirring rate of not less than 300 r / min) for aqueous phase neutralization and coagulation. After the coagulation is completed, solid-liquid separation is performed, and the obtained solid is washed with deionized water for 1-10 times, and finally dried in an oven (preferably at a drying temperature of 60-100° C. and a drying time of 0.5-5 h) to obtain a side carboxyl polyether sulfone resin having the general structural formula (IV); and / or Step 2) is specifically as follows: a side carboxyl polyethersulfone resin having a structural formula (IV), caprolactam and water are added to a high-pressure reactor in proportion, a protective gas is introduced to replace the air in the reactor 1 to 10 times, the temperature is first raised to 180 to 280° C. (preferably 200 to 260° C.) for a hydrolysis reaction for 0.5 to 6 hours (preferably 1 to 4 hours), and then the temperature is raised to 220 to 300° C. (preferably 240 to 280° C.) and the reaction is continued for 0.5 to 6 hours (preferably 1 to 4 hours). After the reaction is completed, the mixture is evacuated to normal pressure and then decompressed and polymerized until the viscosity is qualified, and then pelletized to obtain solid particles, the solid particles are washed with deionized water 1 to 10 times, and finally dried in an oven (preferably at a drying temperature of 60 to 100° C. and a drying time of 0.5 to 5 hours) to obtain a composite material containing a polymer having a structural formula (I).

10. Use of a polyethersulfone-nylon composite material, or use of the polyethersulfone-nylon composite material according to any one of claims 1 to 4, or use of the polyethersulfone-nylon composite material prepared by the preparation method according to any one of claims 5 to 9, characterized in that: The polyethersulfone-nylon composite material is used as the plastic.

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