A hyperbranched polyphenylene sulfide-modified nanomaterial, its preparation method and application

Abstract

This invention discloses a method for preparing hyperbranched polyphenylene sulfide-modified nanomaterials. By modifying the ends of mesoporous nanomaterials with amino groups, and reacting the amino groups with acyl halides at low temperature, terminal halogen-modified mesoporous nanomaterials are obtained. Then, polyphenylene sulfide is grown on the surface of the mesoporous nanomaterials through an electrophilic substitution reaction. The resulting nanomaterials are in-situ polymerized with oligophenylene sulfide resin, which greatly enhances the compatibility between the nanomaterials and polyphenylene sulfide resin, while improving the corrosion resistance of thermoplastic resins and extending the service life of thermoplastic resin coatings in geothermal environments.

Description

Technical Field

[0001] This invention relates to the field of nanomaterials technology, specifically to a hyperbranched polyphenylene sulfide-modified nanomaterial, its preparation method, and its application. Background Technology

[0002] In clean and green energy sources such as geothermal water and nuclear power plants, the structural metals operate under harsh temperature and pressure conditions. Currently, thermoplastic resins and corrosion inhibitors are widely used in this field. However, corrosion inhibitors require continuous addition, resulting in high chemical consumption and potential contamination of reinjection water. The use of nano-residue technology to immobilize corrosion inhibitors has not yet been applied in geothermal applications, primarily because its poor compatibility with thermoplastic resins easily leads to coating defects, especially with mesoporous nano-silica, which is most suitable for geothermal environments.

[0003] Polyphenylene sulfide (PPS) is a thermoplastic resin with phenyl sulfide groups in its molecular chain. The chain structure composed of alternating benzene rings and sulfur atoms gives PPS good rigidity and regularity, resulting in high strength, good dimensional stability, creep resistance, fatigue resistance, solvent resistance, chemical corrosion resistance, good flame retardancy, and molding processability. It can be used as a major material for thermoplastic resins.

[0004] Chinese patent document CN119614074A discloses a high-temperature and high-pressure water environment resistant composite coating. It uses SiO2 as a pretreatment layer, silicone resin as the main resin skeleton, high-temperature resistant organic resin materials as nanoparticles, zirconium and cerium composite oxide nanoparticles as high-temperature corrosion inhibitors, and isocyanate polymers as crosslinking and curing agents for the above components, thus preparing a high-temperature sintered high-temperature and high-pressure water environment resistant coating. However, because the above method directly combines nano-mesoporous silica and other nano-memory storage devices through the silicon in the composite coating, the weather resistance of the resulting composite coating is inferior to that of a pure polyphenylene sulfide coating.

[0005] Chinese patent document CN113337205A discloses a polyphenylene sulfide (PPS) coating with high corrosion resistance. The method involves mixing and ultrasonically dispersing a superhydrophobic nano-silica sol, a fluoropolymer, and PPS to obtain a PPS / fluoropolymer / superhydrophobic nano-silica suspension. This suspension is then coated onto a substrate, dried, and cured to obtain the highly corrosion-resistant PPS coating. However, the PPS coating prepared by this method has significant defects, poor compatibility among the three materials, and low practical feasibility.

[0006] Therefore, it is particularly important to develop a method and application for modifying the surface of mesoporous nano-silica suitable for thermoplastic resins. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention provides a method for preparing hyperbranched polyphenylene sulfide-modified nanomaterials. This method generates oligomeric polyphenylene sulfide on the surface of the nanomaterials in situ, which greatly enhances the compatibility between the modified nanomaterials and thermoplastic resins. At the same time, it improves the corrosion resistance of the thermoplastic resins and extends the service life of the thermoplastic resin coatings in geothermal environments.

[0008] A method for preparing hyperbranched polyphenylene sulfide-modified nanomaterials includes the following steps: (1) Preparation of amino-modified mesoporous nanomaterials; (2) The amino-modified mesoporous nanomaterials obtained in step (1) are reacted with acyl halide reagents to obtain terminal halogen-modified mesoporous nanomaterials. (3) The mesoporous nanomaterials modified with terminal halogens obtained in step (2) are heated and reacted with dichlorobenzylthiophenol under the action of an alkaline catalyst, and after post-treatment, hyperbranched polyphenylene sulfide modified nanomaterials are obtained.

[0009] In this invention, mesoporous nanomaterials are modified with amino groups at their ends. The amino groups react with acyl halogen reagents at low temperatures to obtain terminally halogenated mesoporous nanomaterials. Then, polyphenylene sulfide is grown on the surface of the mesoporous nanomaterials through an electrophilic substitution reaction. Since there are two reactive chlorine atoms on dichlorophenylthiophenol, the reaction can grow in multiple directions to form a hyperbranched structure instead of a linear structure. This yields in-situ polymerized oligophenylene sulfide resins of hyperbranched polyphenylene sulfide-modified nanomaterials, which greatly enhances the compatibility between the nanomaterials and polyphenylene sulfide resins.

[0010] Preferably, in step (1), the mesoporous nanomaterial is at least one of silicon dioxide, titanium dioxide, or layered double hydroxide (LDH).

[0011] In this invention, the preparation method can be changed to correspond to the type of mesoporous nanomaterial selected.

[0012] Preferably, in step (2), the acyl halide reagent is 2-bromoisobutyryl bromide (BIBB) or 2-bromoisobutyryl chloride (BIBC).

[0013] In this invention, the highly active acyl halide group (-COX) in acyl halide reagents (such as BIBB or BIBC) acts as an electrophilic center, which attacks the lone pair electrons on the amino group in the amino-modified mesoporous nanomaterial, undergoes a nucleophilic substitution reaction, and loses one molecule of hydrogen halide (HX) to form a stable amide bond (-CONH-).

[0014] Preferably, in step (2), the mass-to-volume ratio of the amino-modified mesoporous nanomaterial to the acyl halide reagent is 1:8~120 g / mL.

[0015] Preferably, in step (3), the alkaline catalyst is potassium hydroxide or potassium carbonate.

[0016] Preferably, in step (3), the amount of alkaline catalyst added is 0.5 wt% to 2.5 wt% of the terminal halogen modified mesoporous nanomaterial.

[0017] Preferably, in step (3), the dichlorothiophenol is at least one of 2,4-dichlorothiophenol, 2,5-dichlorothiophenol, and 2,6-dichlorothiophenol.

[0018] Preferably, in step (3), the mass ratio of the terminal halogen-modified mesoporous nanomaterial to dichlorobenzylthiophenol is 1~2:1~2.

[0019] In this invention, the dichlorosubstitution position and amount of thiophene exhibit a significant synergistic relationship, jointly determining the degree of polymerization and final structure of the hyperbranched polyphenylene sulfide. The substitution position directly determines the intrinsic reactivity of dichlorobenzenethiophene; highly reactive dichlorobenzenethiophenes (such as those at the 2,4-position) readily form a compact hyperbranched structure. By controlling its addition amount within the aforementioned range, the degree of polymerization and structure of the hyperbranched polyphenylene sulfide-modified nanomaterials can be synergistically controlled with the type of dichlorobenzenethiophene.

[0020] Preferably, in step (3), the heating reaction temperature is 150~170 ℃ and the time is 5~12 h.

[0021] Preferably, in step (3), the post-processing step is as follows: after the reaction is completed, water and hydrochloric acid solution are added, the mixture is aged overnight, washed with water and ethanol, and dried to obtain the hyperbranched polyphenylene sulfide modified nanomaterial.

[0022] The present invention also provides hyperbranched polyphenylene sulfide modified nanomaterials prepared by the above preparation method.

[0023] The present invention also provides the application of the above-mentioned hyperbranched polyphenylene sulfide modified nanomaterials in the preparation of thermoplastic resin coatings for geothermal environments.

[0024] Preferably, the polyphenylene sulfide coating for geothermal environments is prepared by the following method: the above-mentioned hyperbranched polyphenylene sulfide modified nanomaterials are dispersed in a corrosion inhibitor solution, dried to obtain hyperbranched polyphenylene sulfide modified nanomaterials loaded with corrosion inhibitors, mixed with thermoplastic resin, and electrostatically sprayed onto a metal surface to obtain a thermoplastic resin coating for geothermal environments.

[0025] The traditional method involves adding a large amount of corrosion inhibitor directly to the water to prepare the coating. However, this invention loads the corrosion inhibitor directly onto the nanomaterial during the coating preparation process and then mixes it with the thermoplastic resin to obtain the coating, which greatly reduces the use of corrosion inhibitor.

[0026] Preferably, the corrosion inhibitor is at least one of sodium metavanadate, sodium molybdate, and sodium silicate.

[0027] Preferably, the mass ratio of the hyperbranched polyphenylene sulfide-modified nanomaterial to the corrosion inhibitor is 10~20:1~2.

[0028] Preferably, the thermoplastic resin is at least one of polyphenylene sulfide, oxidized polyphenylene sulfide, and carboxylated polyphenylene sulfide.

[0029] Preferably, the proportion of the nanomaterial modified with hyperbranched polyphenylene sulfide loaded with corrosion inhibitor in the thermoplastic resin is 0.1~1 wt%.

[0030] In this invention, the hyperbranched polyphenylene sulfide-modified nanomaterials prepared by the above method can reduce the use of corrosion inhibitors, are more environmentally friendly, and improve the service life of thermoplastic resin coatings in geothermal environments.

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows: In this invention, by modifying the ends of mesoporous nanomaterials with amino groups, and then reacting the amino groups with acyl halide reagents at low temperature to obtain terminal halogen-modified mesoporous nanomaterials, polyphenylene sulfide is grown on the surface of the mesoporous nanomaterials through an electrophilic substitution reaction, thereby preparing hyperbranched polyphenylene sulfide-modified nanomaterials in situ polymerized resin oligophenylene sulfide. This greatly enhances the compatibility between the nanomaterials and thermoplastic resin coatings, improves the corrosion resistance of the prepared thermoplastic resin coatings, and thus extends the service life of the thermoplastic resin coatings in geothermal environments. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of the preparation process for hyperbranched polyphenylene sulfide-modified mesoporous nano silica (MSN-HPPS) in Example 1.

[0033] Figure 2 The images show the transmission electron microscope (TEM) image and infrared spectrum of the hyperbranched polyphenylene sulfide-modified mesoporous nano-silica (MSN-HPPS) of Example 1, where a and b are the TEM image and infrared spectrum, respectively.

[0034] Figure 3 Images of the hyperbranched polyphenylene sulfide-modified mesoporous nano silica polyphenylene sulfide coating (MSN-HPPS-PPS coating) and the silica polyphenylene sulfide coating (MSN-PPS coating) of Example 1.

[0035] Figure 4 Images show the changes in the polyphenylene sulfide (PPS) coatings (MSN-HPPS-PPS coating), silica-modified mesoporous nano-silica coating, and pure PPS coating under a simulated geothermal environment, as described in Example 1. Images a1 and a2 are of the pure PPS coating on day 0 and day 22, respectively; images b1 and b2 are of the MSN-PPS coating on day 0 and day 22, respectively; and images c1 and c2 are of the MSN-HPPS-PPS coating on day 0 and day 22, respectively. Detailed Implementation

[0036] The present invention will be further described in detail below with reference to the embodiments, but the implementation of the present invention is not limited to the following embodiments.

[0037] All raw materials used in this invention are commercially available.

[0038] Example 1 Preparation process as follows Figure 1 As shown, the details are as follows: (1) Preparation of amino-modified mesoporous nano silica 0.75 g of hexadecyltrimethylammonium bromide (CTAB) was dissolved in 336 mL of aqueous solution, and 3.75 mL of tetraethyl orthosilicate was added. After stirring for 0.5 h, 0.21 g of sodium hydroxide was added, and the mixture was stirred at 80 °C for 2 h. After centrifugation, template-modified mesoporous nano-silica (MSN-CTAB) was obtained. 0.5 g of MSN-CTAB was dispersed in 50 mL of toluene, and 1 mL of aminotriethoxysilane (APTES) was added. After oil bath at 110 °C for 12 h, the mixture was centrifuged, washed, and dried under vacuum at 60 °C to obtain MSN-APTES-CTAB. MSN-CTAB and MSN-APTES-CTAB were dispersed separately in 2 M hydrochloric acid in alcohol solution and stirred at 60 °C for 12 h to remove the CTAB template. After centrifugation, washing, and drying under vacuum at 60 °C, mesoporous nano-silica and amino-modified mesoporous nano-silica (i.e., MSN and MSN-NH2) were obtained.

[0039] (2) 5 g of MSN-NH2 was ultrasonically dispersed in 100 mL of tetrahydrofuran (THF), and then 40 mL of THF was added. 40 mL of BIBB was added. The mixture was placed in an ice-water bath under a nitrogen atmosphere for 12 h. After centrifugation, washing with anhydrous ethanol, and vacuum drying at 60 °C, mesoporous nano silica modified with terminal bromine (i.e., MSN-Br) was obtained.

[0040] (3) 1.5 g of MSN-Br was dispersed in 200 mL of N-methylpyrrolidone (NMP), 0.015 g of potassium hydroxide and 0.005 mol of 2,4-dichlorothiophenol were added, and the reaction was carried out at 160 °C for 6 h under a nitrogen atmosphere. After heating, water of equal volume to the solution was added and stirred for 0.5 h, followed by the addition of 10% hydrochloric acid solution of equal volume to the solution, stirring for 10 min and aging overnight. After centrifugation, the mixture was washed with water and ethanol in sequence, and dried under vacuum at 60 °C to obtain hyperbranched polyphenylene sulfide modified mesoporous nano-silica (i.e., MSN-HPPS). Its transmission electron microscopy image is shown below. Figure 2 As shown in a, the hyperbranched MSN-HPPS retains its mesoporous structure while having an outer layer of HPPS. Infrared results. Figure 2 As shown in b, the infrared spectrum after HPPS modification is in the range of 1380~1500 cm⁻¹. -1 A distinct benzene ring skeleton absorption peak appears between the peaks, with the peak at 880 cm⁻¹ in the figure. -1 and 700 cm -1 These are the CH absorption peak and the C-Br absorption peak on the benzene ring, respectively.

[0041] Sample Analysis: 1 g of the above-mentioned MSN-HPPS or MSN was dispersed in 200 mL of 0.1 M sodium molybdate aqueous solution, stirred for 6 h, centrifuged, and dried at 60 °C to obtain Na2MoO4@MSN-HPPS and Na2MoO4@MSN, respectively. 1 g of Na2MoO4@MSN-HPPS or Na2MoO4@MSN was mixed with 100 g of polyphenylene sulfide (PPS) using a ball mill, electrostatically sprayed onto the surface of Q235B, and cured at 320 °C to obtain MSN-PPS coating and MSN-HPPS-PPS coating, respectively.

[0042] like Figure 3 As shown, compared to the unmodified MSN, no obvious defects were observed in the polyphenylene sulfide coating with MSN-HPPS added according to this application, while the aggregation of MSN was clearly observed in the MSN-PPS coating.

[0043] Pure PPS coating, MSN-PPS coating, and MSN-HPPS-PPS coating were placed in a 3.5% sodium chloride solution at 120 °C and 0.15 mPa, respectively, and images were recorded on day 0 (before placement) and day 22. Figure 4 As shown, after 22 days, the pure PPS coating and the MSN-PPS coating showed significant separation of nanoparticles from the coating due to water penetration from defects, resulting in blistering and worsening of defects. However, the MSN-PPS-PPS coating did not show significant changes and was more corrosion resistant than the pure PPS coating and the MSN-PPS coating.

[0044] Example 2 (1) Preparation of amino-modified mesoporous nano silica 0.75 g of hexadecyltrimethylammonium bromide (CTAB) was dissolved in 336 mL of aqueous solution. 3.75 mL of tetraethyl orthosilicate was added, and the mixture was stirred for 0.5 h. Then, 0.21 g of sodium hydroxide was added, and the mixture was stirred at 80 °C for 2 h. After centrifugation, template-modified mesoporous nano-silica (MSN-CTAB) was obtained. 0.5 g of MSN-CTAB was dispersed in 50 mL of toluene, and 0.8 mL of N-aminoethyl-3-aminopropyltriethoxysilane (AAPTES) was added. The mixture was heated in an oil bath at 110 °C for 12 h, centrifuged, washed, and vacuum dried at 60 °C to obtain MSN-AAPTES-CTAB. This CTAB template was then removed by dispersing it in a 2 M hydrochloric acid-alcoholic solution and stirring at 60 °C for 12 h. After centrifugation, washing, and vacuum drying at 60 °C, amino-modified mesoporous nano-silica (MSN-NH-CH2-CH2-NH2) was obtained.

[0045] (2) 5 g of MSN-NH-CH2-CH2-NH2 was ultrasonically dispersed in 100 mL of tetrahydrofuran (THF), and then 40 mL of THF was added. 45 mL of BIBB was added. The mixture was placed in an ice-water bath under a nitrogen atmosphere for 12 h. After centrifugation, washing with anhydrous ethanol, and vacuum drying at 60 °C, mesoporous nano silica modified with terminal bromine (i.e., MSN-NH-CH2-CH2-Br) was obtained.

[0046] (3) 1.5 g of MSN-NH-CH2-CH2-Br was dispersed in 200 mL of N-methylpyrrolidone (NMP), 0.02 g of potassium hydroxide and 0.005 mol of 2,4-dichlorothiophenol were added, and the reaction was carried out at 160 °C for 6 h under a nitrogen atmosphere. After heating, an equal volume of water was added and stirred for 0.5 h, and then an equal volume of 10% hydrochloric acid solution was added. After stirring for 10 min, the mixture was aged overnight. After centrifugation, the mixture was washed with water and ethanol in sequence, and then dried under vacuum at 60 °C to obtain hyperbranched polyphenylene sulfide modified mesoporous nano silica (i.e., MSN-NH-HPPS).

[0047] Sample Analysis: 1 g of the above-mentioned MSN-NH-HPPS was dispersed in 200 mL of 0.1 M sodium molybdate aqueous solution, stirred for 6 h, centrifuged, and dried at 60 °C to obtain Na2MoO4@MSN-NH-HPPS. 1 g of Na2MoO4@MSN-NH-HPPS was mixed with 100 g of polyphenylene sulfide (PPS) using a ball mill, electrostatically sprayed onto the surface of Q235B, and cured at 315 °C to obtain an MSN-NH-HPPS-PPS coating.

[0048] When the MSN-NH-HPPS-PPS coating was placed in a 3.5% sodium chloride solution at 120 °C and 0.15 mPa, the MSN-NH-HPPS-PPS coating showed no significant changes over 18 days.

[0049] Example 3 (1) Preparation of amino-modified mesoporous nano-titanium dioxide Anhydrous ethanol and glacial acetic acid were mixed in a volume ratio of 6:1 to prepare a solution. 0.85 mL of tetrabutyl titanate was added to 336 mL of the mixed solution and stirred for 2 h. The solution was then transferred to a hydrothermal reactor and reacted at 200 °C for 4 h. After centrifugation and washing, the solution was dried under vacuum at 60 °C to obtain mesoporous nano-titanium dioxide (MTNs). 0.8 g of MTNs was dispersed in 100 mL of water, and 0.5 mL of 25% ammonia and 0.8 mL of APTES were added. The mixture was reacted at 80 °C for 6 h, centrifuged, washed, and dried under vacuum at 60 °C to obtain amino-modified mesoporous nano-titanium dioxide peptides (MTNs-NH2).

[0050] (2) 5 g of MTNs-NH2 was ultrasonically dispersed in 100 mL of tetrahydrofuran (THF), and then 40 mL of THF was added. 45 mL of BIBC was added. The mixture was placed in an ice-water bath under a nitrogen atmosphere for 16 h. After centrifugation, washing with anhydrous ethanol, and vacuum drying at 60 °C, mesoporous nano-dioxide peptides with terminal chlorine modification (i.e., MTNs-Cl) were obtained.

[0051] (3) 1.5 g of MTNs-Cl was dispersed in 200 mL of N-methylpyrrolidone (NMP), 0.13 g of potassium carbonate and 0.005 mol of 2,4-dichlorothiophenol were added, and the reaction was carried out at 170 °C for 8 h under a nitrogen atmosphere. After heating, an equal volume of water was added and stirred for 0.5 h, and then an equal volume of 10% hydrochloric acid solution was added. After stirring for 10 min, the mixture was aged overnight. After centrifugation, the mixture was washed with water and ethanol in sequence, and then dried under vacuum at 60 °C to obtain hyperbranched polyphenylene sulfide modified mesoporous nano-dioxide peptides (i.e., MTNs-HPPS).

[0052] Sample analysis: 1 g of the above-mentioned MTNs-HPPS was dispersed in 200 mL of 0.1 M sodium molybdate aqueous solution, stirred for 6 h, centrifuged, and dried at 60 ℃ to obtain Na2MoO4@MTNs-HPPS. 1 g of Na2MoO4@MTNs-HPPS was mixed with 100 g of polyphenylene sulfide (PPS) using a ball mill, electrostatically sprayed onto the surface of Q235B, and cured at 320 ℃ to obtain an MTNs-HPPS-PPS coating.

[0053] When the MTNs-HPPS-PPS coating was placed in a 3.5% sodium chloride solution at 120 °C and 0.15 mPa, the MTNs-HPPS-PPS coating showed no significant changes over 13 days.

[0054] Example 4 (1) Preparation of amino-modified mesoporous nanolayered double hydroxides 19.2 g of Mg(NO3)2·6H2O and 9.4 g of Al(NO3)3·9H2O were dissolved in 90 mL of deionized water (solution A); approximately 8 g of NaOH and 6.5 g of sodium dodecyl sulfonate were dissolved in 50 mL of deionized water (solution B); 5 mL of APTES was added to 50 mL of ethanol, followed by solutions A and B, and the pH was adjusted to 10. The mixture was stirred at 80 °C for 12 h, centrifuged and washed, and then vacuum dried at 60 °C to obtain an amino-modified mesoporous layered double hydroxide (LDH-NH2).

[0055] (2) 5 g of LDH-NH2 was ultrasonically dispersed in 100 mL of tetrahydrofuran (THF), and then 40 mL of THF was added. 45 mL of BIBB was added. The mixture was placed in an ice-water bath under a nitrogen atmosphere for 16 h. After centrifugation, washing with anhydrous ethanol, and vacuum drying at 60 °C, mesoporous nano-dioxide peptides with terminal chlorine modification (i.e., LDH-Br) were obtained.

[0056] (3) 1.5 g of LDH-Br was dispersed in 200 mL of N-methylpyrrolidone (NMP), 0.14 g of potassium hydroxide and 0.005 mol of 2,5-dichlorothiophenol were added, and the reaction was carried out at 160 °C for 8 h under a nitrogen atmosphere. After heating, water of equal volume to the solution was added and stirred for 0.5 h, and then 10% hydrochloric acid solution of equal volume to the solution was added. After stirring for 10 min, the mixture was aged overnight. After centrifugation, the mixture was washed with water and ethanol in sequence, and then dried under vacuum at 60 °C to obtain the mesoporous nanolayered double hydroxide modified with hyperbranched polyphenylene sulfide (i.e., LDH-HPPS).

[0057] Sample analysis: 1 g of the above-mentioned LDH-HPPS was dispersed in 200 mL of 0.1 M sodium molybdate aqueous solution, stirred for 6 h, centrifuged, and dried at 60 ℃ to obtain Na2MoO4@MTNs-HPPS. 1 g of Na2MoO4@LDH-HPPS was mixed with 100 g of polyphenylene sulfide (PPS) using a ball mill, electrostatically sprayed onto the surface of Q235B, and cured at 320 ℃ to obtain an LDH-HPPS-PPS coating.

[0058] When the LDH-HPPS-PPS coating was placed in a 3.5% sodium chloride solution at 120 °C and 0.15 mPa, the LDH-HPPS-PPS coating showed no significant changes over 16 days.

[0059] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing hyperbranched polyphenylene sulfide-modified nanomaterials, characterized in that, Includes the following steps: (1) Preparation of amino-modified mesoporous nanomaterials; (2) The amino-modified mesoporous nanomaterials obtained in step (1) are reacted with acyl halide reagents to obtain terminal halogen-modified mesoporous nanomaterials. (3) The mesoporous nanomaterials modified with terminal halogens obtained in step (2) are heated and reacted with dichlorobenzylthiophenol under the action of an alkaline catalyst, and after post-treatment, hyperbranched polyphenylene sulfide modified nanomaterials are obtained.

2. The method for preparing hyperbranched polyphenylene sulfide-modified nanomaterials according to claim 1, characterized in that, In step (1), the mesoporous nanomaterial is at least one of silicon dioxide, titanium dioxide, or layered double hydroxide.

3. The method for preparing hyperbranched polyphenylene sulfide-modified nanomaterials according to claim 1, characterized in that, In step (2), the acyl halide reagent is 2-bromoisobutyryl bromide or 2-bromoisobutyryl chloride; the mass-to-volume ratio of the amino-modified mesoporous nanomaterial to the acyl halide reagent is 1:8~120 g / mL.

4. The method for preparing hyperbranched polyphenylene sulfide-modified nanomaterials according to claim 1, characterized in that, In step (3), the alkaline catalyst is potassium hydroxide or potassium carbonate; the amount of alkaline catalyst added is 0.5 wt% to 2.5 wt% of the terminal halogen modified mesoporous nanomaterial.

5. The method for preparing hyperbranched polyphenylene sulfide-modified nanomaterials according to claim 1, characterized in that, In step (3), the dichlorothiophenol is at least one of 2,4-dichlorothiophenol, 2,5-dichlorothiophenol, and 2,6-dichlorothiophenol; the mass ratio of the terminal halogen-modified mesoporous nanomaterial to dichlorothiophenol is 1~2:1~2.

6. The method for preparing hyperbranched polyphenylene sulfide-modified nanomaterials according to claim 1, characterized in that, In step (3), the heating reaction is carried out at a temperature of 150~170 ℃ for 5~12 h.

7. Hyperbranched polyphenylene sulfide-modified nanomaterials prepared by any one of the preparation methods according to claims 1 to 6.

8. The application of the hyperbranched polyphenylene sulfide-modified nanomaterials according to claim 7 in the preparation of thermoplastic resin coatings for geothermal environments.

9. The application according to claim 8, characterized in that, The polyphenylene sulfide coating for geothermal environments is prepared by the following method: the hyperbranched polyphenylene sulfide modified nanomaterials of claim 7 are dispersed in a corrosion inhibitor solution, dried to obtain hyperbranched polyphenylene sulfide modified nanomaterials loaded with corrosion inhibitors, mixed with thermoplastic resin, and electrostatically sprayed onto a metal surface to obtain a thermoplastic resin coating for geothermal environments.

10. The application according to claim 9, characterized in that, In the thermoplastic resin coating for geothermal environments, the proportion of hyperbranched polyphenylene sulfide-modified nanomaterials loaded with corrosion inhibitors is 0.1~1 wt%.

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