Self-healing polyurethane anti-corrosion cable and production method thereof
By introducing ditelluride bonds and nano-zinc oxide-modified graphene oxide into the polyurethane main chain, room temperature self-healing of self-healing anti-corrosion polyurethane was achieved, which solved the problem of decreased protective performance of polyurethane materials in complex environments and improved the mechanical properties and corrosion resistance of the cable.
Patent Information
- Application Number
- CN202510701588.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-28
- Publication Date
- 2025-10-10
AI Technical Summary
Existing polyurethane materials are difficult to achieve self-healing at room temperature in complex environments, resulting in a decrease in the protective performance of cable sheaths and the creation of safety hazards such as leakage, short circuits and fire.
By introducing ditelluride bonds and nano-zinc oxide-modified graphene oxide into the polyurethane main chain, a self-healing anti-corrosion polyurethane is formed, which achieves self-healing at room temperature through dynamic covalent exchange reaction, and functional anti-corrosion fillers are added to construct an anti-corrosion barrier.
It significantly improves the reliability and durability of the cable protective layer, enhances the mechanical properties and corrosion resistance, and extends the service life of the cable.
Smart Images
Figure BDA0005424667110000061 
Figure BDA0005424667110000071
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of self-healing polymer material preparation, in particular to a self-healing polyurethane anti-corrosion cable and a production method thereof. Background Art
[0002] With the rapid development of modern industry, energy transmission and communication technology, cables, as the core carriers of power transmission and signal transmission, have a performance reliability that is directly related to the safety and operational efficiency of infrastructure. However, when cables are used for a long time in complex environments (such as high humidity, highly corrosive media, temperature changes or mechanical vibrations), the sheath is susceptible to chemical corrosion, physical wear or micro cracks, resulting in a decrease in protective performance, which in turn leads to safety hazards such as leakage, short circuit and even fire. In recent years, polyurethane materials have been widely used in the field of cable sheaths due to their excellent mechanical properties, wear resistance and chemical corrosion resistance.
[0003] However, ordinary polyurethane materials still have certain limitations when facing the above problems. At present, the self-healing of polyurethane is mainly divided into two categories: non-dynamic covalent bonds and dynamic covalent bonds. Among them, non-covalent dynamic exchange reactions (such as π-π stacking, metal coordination bonds, hydrogen bonds, host-guest interactions, etc.) require a relatively low external environment to achieve self-healing of the material; while dynamic covalent exchange reactions usually (such as disulfide bonds, hydrazone bonds, imine bonds, boric acid bonds, alkoxyamine bonds and diaryldibenzofuran bonds) require external stimulation or the action of a catalyst to achieve self-healing of the material. In practical applications, especially in the field of cable sheaths, these conditions are often difficult to meet. Therefore, the development of anti-corrosion polyurethane materials that can self-heal at room temperature is of great practical significance. Summary of the Invention
[0004] In view of the above-mentioned deficiencies in the prior art, the present invention provides a self-healing polyurethane anti-corrosion cable with high-efficiency self-healing ability at room temperature, and at the same time introduces functional anti-corrosion fillers to construct an anti-corrosion barrier, and a production method thereof.
[0005] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is:
[0006] A method for preparing a self-healing anti-corrosion polyurethane is provided, comprising the following steps:
[0007] S1: dissolving zinc oxide in N-methylpyrrolidone by ultrasonication to obtain a mixed solution, adding silane coupling agent KH550 to the mixed solution, and then ultrasonically dispersing and mixing the solution, allowing the solution to stand for stratification, removing the supernatant, and washing and drying to obtain pretreated zinc oxide;
[0008] S2: Graphene oxide was ultrasonically dispersed in dimethylacetamide, and then pretreated zinc oxide was slowly added. The ZnO / GO composite was obtained after washing with ethanol and drying.
[0009] S3: The ZnO / GO composite was dissolved in a mixed solution of 2,2-dihydroxymethylpropionic acid and N-methylpyrrolidone, and sodium octamethylstannate was added to react for 1 hour. After the reaction was completed, polytetramethylene glycol and polyethylene glycol were added. The mixture was degassed at 80°C for 6 hours, cooled to 60°C, and then 4,4'-diphenylmethane diisocyanate was added under argon atmosphere and stirred for 1.5 hours to obtain a ZnO / GO prepolymer.
[0010] S4: The ZnO / GO prepolymer and di-(1-hydroxyethyl) ditelluride were added to N,N-dimethylformamide and stirred for 3 hours. After the reaction was complete, the solid was precipitated into ether to obtain a red solid. The solid was then vacuum dried to obtain a self-healing, anti-corrosion polyurethane PUTeTe-GO containing ditelluride and graphene oxide.
[0011] Furthermore, in step S1, silane coupling agent KH550 is added to adjust the pH value of the mixed solution to 4-5.
[0012] Furthermore, the mass ratio of zinc oxide to graphene oxide is 1:2;
[0013] The mass ratio of ZnO / GO composite, sodium octamethylstannate, polytetramethylene glycol, polyethylene glycol and 4,4'-diphenylmethane diisocyanate is 15:8:65:65:35.
[0014] Furthermore, the mass ratio of ZnO / GO prepolymer, di-(1-hydroxyethyl) ditelluride and N,N-dimethylformamide is 3:75:125.
[0015] Furthermore, in step S3, after sodium octamethylstannate is added and reacted for 1 hour, acetone is added before adding polytetramethylene glycol and polyethylene glycol, and the stirring reaction is continued for 1 hour; the mass ratio of sodium octamethylstannate to acetone is 8:1.5.
[0016] Furthermore, the preparation method of the di-(1-hydroxyethyl) ditelluride is:
[0017] A1: Tellurium, sodium borohydride, and distilled water were stirred at 40°C under argon atmosphere for 3 h, and then cooled to room temperature to obtain a purple-red aqueous solution;
[0018] A2: Dissolve 2-bromoethanol in degassed tetrahydrofuran, add the purple-red aqueous solution, and stir under argon for 5 h.
[0019] A3: After the reaction is completed, extraction is performed with dichloromethane. The organic phase is dried over anhydrous magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure and purified by silica gel column chromatography using ethyl acetate:dichloromethane (1:1) to obtain di-(1-hydroxyethyl)ditelluride.
[0020] Further, the molar ratio of tellurium, sodium borohydride and 2-bromoethanol is 60:22:55.
[0021] The application also provides a self-healing anticorrosive polyurethane as described above.
[0022] The application also provides a self-healing anticorrosive polyurethane cable prepared by using the self-healing anticorrosive polyurethane as described above, and the self-healing anticorrosive polyurethane is used for preparing a cable core protection layer.
[0023] Further, the cable core protection layer is prepared by uniformly mixing 85 parts of the self-healing anticorrosive polyurethane, 10 parts of a flame retardant, 3 parts of an antioxidant, 1 part of a lubricant and 5 parts of an ultraviolet absorber, and then extruding the mixture through a screw extruder to coat the outside of the cable core.
[0024] The application has the following beneficial effects:
[0025] The application introduces a double telluride bond into the main chain to synthesize a novel self-healing double telluride-containing polyurethane. Based on the dynamic characteristics of the double telluride bond, the polyurethane can self-heal at room temperature and in the dark without external intervention, which significantly improves the reliability and durability of the cable protection layer.
[0026] The application adds nano zinc oxide modified graphene oxide to the polyurethane system. The nano zinc oxide modification not only improves the dispersibility of graphene oxide in the polyurethane matrix, but also enhances the interaction between organic molecules in the polyurethane. This synergistic effect not only significantly improves the overall mechanical properties of the material, making it exhibit higher strength and toughness when facing external mechanical stress, but also enhances the corrosion resistance of the polyurethane, enabling it to better resist the erosion of external chemical environments, thereby prolonging the service life of the cable and providing a strong guarantee for the long-term stable operation of the cable in complex environments. DETAILED DESCRIPTION
[0027] The specific embodiments of the application are described below to facilitate understanding of the application by those skilled in the art, but it should be clear that the application is not limited to the scope of the specific embodiments. It is obvious to those skilled in the art that any changes within the spirit and scope of the application as defined in the appended claims are obvious, and all applications utilizing the concept of the application are within the scope of protection.
[0028] The raw materials used in the embodiments of the application are commercially available from the National Pharmaceutical Group Chemical Reagent Co., Ltd. and Shanghai Maikelin Biochemical Technology Co., Ltd. if not specifically stated.
[0029] Preparation of di-(1-hydroxyethyl) ditelluride in Example 1
[0030] Di-(1-hydroxyethyl)ditelluride was prepared by the following method:
[0031] A1: Add 60 parts of tellurium and 22 parts of sodium borohydride to a round-bottom flask containing distilled water, stir at 40°C under argon atmosphere for 3 hours, and cool to room temperature to obtain a purple-red aqueous solution;
[0032] A2: Dissolve 55 parts of 2-bromoethanol in degassed tetrahydrofuran, add the purple-red aqueous solution, and stir under argon for 5 hours;
[0033] A3: After the reaction is completed, extraction is performed with dichloromethane. The organic phase is dried over anhydrous magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure and purified by silica gel column chromatography using ethyl acetate:dichloromethane (1:1) to obtain di-(1-hydroxyethyl)ditelluride.
[0034] Example 2 Preparation of self-healing anti-corrosion polyurethane PUTeTe-GO
[0035] The self-healing anti-corrosion polyurethane PUTeTe-GO was prepared by the following method:
[0036] S1: Dissolve 5 parts of zinc oxide in 100 mL of N-methylpyrrolidone and sonicate for 4 hours to obtain a mixed solution, add 0.01 M silane coupling agent KH550 to the mixed solution to adjust the pH of the mixed solution to 4-5, sonicate for 2 hours to disperse and mix, let the solution stand for stratification, remove the supernatant, wash with deionized water and anhydrous ethanol three times, vacuum filter, and dry at 60°C for 24 hours to obtain pretreated zinc oxide;
[0037] S2: 10 parts of graphene oxide were dispersed in dimethylacetamide and sonicated for 4 h, and then pretreated zinc oxide was slowly added. The mixture was washed three times with ethanol, and the recovered composite was centrifuged and then dried in an oven at 60 °C for 24 h to obtain a ZnO / GO composite.
[0038] S3: Dissolve 15 parts of ZnO / GO composite in 50 ml of a mixed solution of 2,2-dihydroxymethylpropionic acid and N-methylpyrrolidone in a ratio of 2:1; continue to add 8 parts of sodium octamethylstannate and react for 1 hour; then add 1.5 parts of acetone to adjust the viscosity to avoid gelation and continue to react for 1 hour. After the reaction is complete, continue to add 65 parts of polytetramethylene glycol and 65 parts of polyethylene glycol; degas under vacuum at 80°C for 6 hours, cool to 60°C, and then add 35 parts of 4,4'-diphenylmethane diisocyanate under argon and stir for 1.5 hours to obtain ZnO / GO prepolymer;
[0039] S4: 3 parts of ZnO / GO prepolymer and 75 parts of di-(1-hydroxyethyl) ditelluride prepared in Example 1 were added to 125 parts of N,N-dimethylformamide and stirred for 3 hours. After the reaction was complete, the solid was precipitated into ether to obtain a red solid. The solid was vacuum dried and fermented for 4 hours to obtain a self-healing, anti-corrosion polyurethane PUTeTe-GO containing ditelluride and graphene oxide.
[0040] Example 3
[0041] The difference between this embodiment and embodiment 2 is that the amount of the ZnO / GO composite used in step S3 is 30 parts.
[0042] Example 4
[0043] The difference between this embodiment and embodiment 2 is that the amount of di-(1-hydroxyethyl)ditelluride used in step S4 is 105 parts.
[0044] Comparative Example 1
[0045] The difference between this embodiment and embodiment 2 is that in step S4, di-(1-hydroxyethyl)ditelluride is replaced by 1,4-butanediol.
[0046] Comparative Example 2
[0047] The difference between this embodiment and embodiment 2 is that the amount of the ZnO / GO composite used in step S3 is 0.
[0048] Example 7
[0049] The polyurethanes prepared in Examples 2 to 4 and Comparative Examples 1 to 2 were tested for corrosion resistance by electrochemical impedance spectroscopy (EIS). EIS can detect the material's ability to block corrosive media. A high impedance value indicates that the material effectively prevents the penetration of the corrosive medium. When the material is damaged or fails, the impedance value drops significantly, indicating that the corrosive medium has invaded. The tensile strength and elongation at break were tested in accordance with GB / T8804.2-2016. At the same time, in order to test the self-healing property of the polyurethane, an ordinary blade was used to cut it into two pieces and attached to the surface of a fresh crack. The samples were then placed in a dark environment and allowed to stand at room temperature. After a period of repair, the tensile strength and elongation at break of the material were tested again, and the self-healing rate of the material was calculated using the following formula:
[0050]
[0051] The results are shown in Table 1 below;
[0052] Table 1
[0053]
[0054] As can be seen from Table 1, the polyurethane prepared by the method of the present invention has a good self-healing rate. After standing, the tensile strength and elongation at break can both approximately return to the levels before cutting. And they all have large resistance values, that is, corrosion resistance. Although the corrosion resistance of Comparative Example 1 is better than that of Example 3 and Example 4, it is weaker than that of Example 2, and Comparative Example 1 does not have self-healing properties. Although Comparative Example 2 has similar self-healing properties to Examples 2 to 4, its resistance value is the lowest and it does not have good corrosion resistance. In summary, the method of the present invention has prepared a cable with both good corrosion resistance and an excellent (greater than or equal to 93%) self-healing rate, which provides a strong guarantee for the long-term stable operation of the cable in a complex environment.
[0055] Example 8
[0056] A method for preparing a self-healing polyurethane anti-corrosion cable comprises the following steps: uniformly mixing 85 parts of self-healing anti-corrosion polyurethane, 10 parts of flame retardant, 3 parts of antioxidant, 1 part of lubricant, and 5 parts of ultraviolet absorber, extruding the mixture through a screw extruder, and coating the mixture on the outside of a cable core.
[0057] In a specific implementation, the thermal flame retardant is one or a combination of nitrogen-based flame retardants and phosphorus-based flame retardants; the antioxidant is one or a combination of tetrakis[pentaerythritol 3,5-di-tert-butyl-4-hydroxyphenylpropionate], octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, diethylene sulfonate bis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionate)], and bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite. The lubricant is one or a combination of hydroxystearic acid, stearyl alcohol, N,N-ethylenebisstearamide (EBS), and N,N-ethylenebisricinoleamide. The ultraviolet absorber is one or a combination of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)-benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-(2'-hydroxy-5-methylphenyl)-benzotriazole, and phenyl salicylate. The extrusion molding temperature is 100-200°C.
Claims
1. A method for preparing a self-healing anti-corrosion polyurethane, characterized in that: The following steps are involved: S1: dissolving zinc oxide in N-methylpyrrolidone by ultrasonication to obtain a mixed solution, adding silane coupling agent KH550 to the mixed solution, and then ultrasonically dispersing and mixing the solution, allowing the solution to stand for stratification, removing the supernatant, and washing and drying to obtain pretreated zinc oxide; S2: Graphene oxide was ultrasonically dispersed in dimethylacetamide, and then pretreated zinc oxide was slowly added. The ZnO / GO composite was obtained after washing with ethanol and drying. S3: The ZnO / GO composite was dissolved in a mixed solution of 2,2-dihydroxymethylpropionic acid and N-methylpyrrolidone, and sodium octamethylstannate was added to react for 1 hour. After the reaction was completed, polytetramethylene glycol and polyethylene glycol were added. The mixture was degassed at 80°C for 6 hours, cooled to 60°C, and then 4,4'-diphenylmethane diisocyanate was added under argon atmosphere and stirred for 1.5 hours to obtain a ZnO / GO prepolymer. S4: The ZnO / GO prepolymer and di-(1-hydroxyethyl) ditelluride were added to N,N-dimethylformamide and stirred for 3 hours. After the reaction was complete, the solid was precipitated into ether to obtain a red solid. The solid was then vacuum dried to obtain a self-healing, anti-corrosion polyurethane PUTeTe-GO containing ditelluride and graphene oxide.
2. The method for preparing the self-healing anti-corrosion polyurethane according to claim 1, wherein: In step S1, silane coupling agent KH550 is added to adjust the pH value of the mixed solution to 4-5.
3. The method for preparing the self-healing anti-corrosion polyurethane according to claim 2, wherein: The mass ratio of zinc oxide to graphene oxide is 1:2; The mass ratio of ZnO / GO composite, sodium octamethylstannate, polytetramethylene glycol, polyethylene glycol and 4,4'-diphenylmethane diisocyanate is 15:8:65:65:
35.
4. The method for preparing the self-healing anti-corrosion polyurethane according to claim 3, wherein: The mass ratio of ZnO / GO prepolymer, di-(1-hydroxyethyl) ditelluride and N,N-dimethylformamide is 3:75:
125.
5. The method for preparing the self-healing anti-corrosion polyurethane according to claim 4, characterized in that: In step S3, after sodium octamethylstannate is added and reacted for 1 hour, acetone is added before adding polytetramethylene glycol and polyethylene glycol, and the reaction is continued with stirring for 1 hour; the mass ratio of sodium octamethylstannate to acetone is 8:1.
5.
6. The method for preparing the self-healing anti-corrosion polyurethane according to claim 1, characterized in that: The preparation method of the di-(1-hydroxyethyl) ditelluride is: A1: Tellurium, sodium borohydride, and distilled water were stirred at 40°C under argon atmosphere for 3 h, and then cooled to room temperature to obtain a purple-red aqueous solution; A2: Dissolve 2-bromoethanol in degassed tetrahydrofuran, add the purple-red aqueous solution, and stir under argon for 5 h. A3: After the reaction is completed, extraction is performed with dichloromethane. The organic phase is dried over anhydrous magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure and purified by silica gel column chromatography using ethyl acetate:dichloromethane (1:1) to obtain di-(1-hydroxyethyl)ditelluride.
7. The method for preparing the self-healing anti-corrosion polyurethane according to claim 6, characterized in that: The mass ratio of tellurium, sodium borohydride and 2-bromoethanol is 60:22:
55.
8. A self-healing anti-corrosion polyurethane according to claim 5 or 6.
9. A self-healing polyurethane anti-corrosion cable prepared using the self-healing anti-corrosion polyurethane according to claim 8, characterized in that: Self-healing anti-corrosion polyurethane is used to prepare the cable core protective layer.
10. The self-healing polyurethane anti-corrosion cable according to claim 9, characterized in that: The cable core protective layer is made by mixing 85 parts of self-healing anti-corrosion polyurethane, 10 parts of flame retardant, 3 parts of antioxidant, 1 part of lubricant and 5 parts of ultraviolet absorber evenly, extruding it through a screw extruder, and coating it on the outside of the cable core to obtain a self-healing anti-corrosion cable core protective layer.