Low-voltage cable with self-cleaning function and preparation method thereof

Abstract

The invention relates to the technical field of cables, and discloses a low-voltage cable with a self-cleaning function and a preparation method thereof.The low-voltage cable is prepared by adding an ethylene-propylene copolymer, polypropylene, amino-modified fluorosilane, epoxy nano-silicon dioxide, an antioxidant 1010 and modified phenolic resin into an internal mixer, mixing, extruding and molding. And carrying out hot press molding on the mixed material in a press vulcanizer to obtain the low-voltage cable with the self-cleaning function. In the banburying process, amino groups in the amino-modified fluorosilane, hydroxyl groups in the modified phenolic resin and epoxy groups in the epoxy nano silicon dioxide are subjected to ring-opening reaction, and a cross-linked network is formed among the amino groups and the hydroxyl groups, so that more cross-linked fulcrums exist, and the tensile property is better. A quaternary ammonium salt group contained in the amino-modified fluorosilane has a good self-cleaning function, and fluorine is introduced into the amino-modified fluorosilane, so that a smooth fluorine carbonization layer which is not easy to adhere to an object can be formed on the surface of the amino-modified fluorosilane, and therefore, the amino-modified fluorosilane also has a good self-cleaning effect.

Description

Technical Field

[0001] The present invention relates to the technical field of cables, and in particular to a low-voltage cable with a self-cleaning function and a preparation method thereof. Background Art

[0002] Cables are important materials that are indispensable in industrial and agricultural production and modern life. With the development of my country's petrochemical, communications, transportation, construction, electricity and other industries, long-term placement of submarine cables during use will cause a large amount of pollutants on their surface. Therefore, how to avoid this phenomenon is the key to solving the problem. For example, patent CN118335405B discloses a fire-retardant cable and its preparation method. In this invention, by filling the surface of the cable core with composite fiber filling yarn, it is beneficial to improve the flame retardant and wear resistance of the cable; by applying a fire retardant coating for the cable on the surface of the cable, the obtained fire-retardant cable has good fire retardant properties, but its self-cleaning effect is not improved. Summary of the invention

[0003] 1. Technical issues to be solved

[0004] In view of the deficiencies in the prior art, the present invention provides a low-voltage cable with a self-cleaning function and a preparation method thereof, which has good self-cleaning and stretching effects.

[0005] (II) Technical solution

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solutions: a low-voltage cable with self-cleaning function and a preparation method thereof, a low-voltage cable with self-cleaning function, comprising the following weight components: 75-90 parts by weight of ethylene-propylene copolymer, 40-80 parts by weight of polypropylene, 10-12 parts by weight of amino-modified fluorosilane, 4-9 parts by weight of epoxy nano-silica, 1-2 parts by weight of antioxidant 1010, and 4-6 parts by weight of modified phenolic resin.

[0007] Preferably, the preparation method of the amino-modified fluorosilane is:

[0008] (1) adding hexamethyldisilazane and 4-maleimidophenol to N,N-dimethylformamide solvent, introducing nitrogen protection, adding chloroplatinic acid catalyst, reacting at 50-75° C. for 40-65 min, cooling to room temperature after reaction, filtering and drying to obtain tertiary aminophenol;

[0009] (2) adding perfluorooctanoyl chloride and tertiary aminophenol to tetrahydrofuran solvent, and then adding triethylamine catalyst thereto, reacting at 30-60° C. for 5-10 hours, and after the reaction, removing the solvent by reduced pressure distillation, washing, and recrystallizing to obtain a fluorine-modified tertiary amine group;

[0010] (3) adding fluorine-modified tertiary amine and bromoethanol to N,N-dimethylformamide solvent, stirring and dissolving, and carrying out quaternization reaction at 75-90° C. for 6-8 hours. After completion, distilling under reduced pressure, washing, and drying to obtain intermediate 1;

[0011] (4) Add 4-aminophenylboronic acid and intermediate 1 to ether solvent, stir and disperse, heat to 70-85° C., react for 6-12 hours, distill and wash after reaction, and obtain amino-modified fluorosilane.

[0012] Preferably, the mass ratio of hexamethyldisilazane, 4-maleimidophenol and chloroplatinic acid catalyst in (1) is 1:1.1-1.3:0.01-0.03.

[0013] Preferably, the mass ratio of perfluorooctanoyl chloride, tertiary aminophenol and triethylamine catalyst in (2) is 1.2-1.6:1:0.02-0.04.

[0014] Preferably, the mass ratio of the fluorine-modified tertiary amine group to bromoethanol in (3) is 1:2.2-2.6.

[0015] Preferably, the mass ratio of 4-aminophenylboronic acid to intermediate 1 in (4) is 1.5-1.8:1.

[0016] Preferably, the preparation method of the modified phenolic resin is:

[0017] S1. 5-12 parts by weight of a phenolic resin and 7-15 parts by weight of epichlorohydrin are mixed uniformly, reacted at 80-95 ° C for 6-10h, and then concentrated under reduced pressure and washed to obtain an epoxidized phenolic resin;

[0018] S2. Add 6-9 parts by weight of intermediate 1 to 1,4-dioxane, stir and disperse, then add 4-7 parts by weight of epoxidized phenolic resin and 0.1-0.3 parts by weight of boron trifluoride etherate, react at 75-90° C. for 7-12 hours, filter after reaction, wash and dry to obtain modified phenolic resin.

[0019] Preferably, the preparation method of the low-voltage cable with self-cleaning function is: add ethylene-propylene copolymer, polypropylene, amino-modified fluorosilane, epoxy nano-silica, antioxidant 1010, and modified phenolic resin into an internal mixer, mix them at 140-155°C for 12-18 minutes, and then hot-press the mixed materials in a flat vulcanizer, and mold them at a pressure of 8-11 MPa for 6-10 minutes to obtain a low-voltage cable with self-cleaning function.

[0020] (III) Beneficial technical effects

[0021] The present invention obtains a low-voltage cable with a self-cleaning function by adding ethylene-propylene copolymer, polypropylene, amino-modified fluorosilane, epoxy nano-silica, antioxidant 1010, and modified phenolic resin into an internal mixer, mixing, and then hot-pressing the mixed materials in a flat vulcanizer.

[0022] During the mixing process, the amino groups in the amino-modified fluorosilane and the hydroxyl groups in the modified phenolic resin will undergo a ring-opening reaction with the epoxy groups in the epoxy nano-silica, forming a cross-linked network, and further forming a network interpenetration with the ethylene-propylene copolymer and polypropylene, so that it has more cross-linking fulcrums and can disperse more force when subjected to external force, so it has better tensile properties. The quaternary ammonium salt group contained in the amino-modified fluorosilane has a good self-cleaning function. The introduction of fluorine element can form a smooth fluorocarbon layer on its surface that is not easy to adhere to objects, so it also has a good self-cleaning effect. DETAILED DESCRIPTION

[0023] Example 1

[0024] (1) adding hexamethyldisilazane and 4-maleimidophenol to an N,N-dimethylformamide solvent, introducing nitrogen protection, and continuously adding a chloroplatinic acid catalyst thereto, wherein the mass ratio of hexamethyldisilazane, 4-maleimidophenol, and chloroplatinic acid catalyst is 1:1.1:0.01, reacting at 50° C. for 40 minutes, cooling to room temperature after completion, filtering, and drying to obtain a tertiary aminophenol;

[0025] (2) adding perfluorooctanoyl chloride and tertiary aminophenol to tetrahydrofuran solvent, and then continuing to add triethylamine catalyst thereto, wherein the mass ratio of perfluorooctanoyl chloride, tertiary aminophenol and triethylamine catalyst is 1.2:1:0.02, reacting at 30° C. for 5 hours, and after the reaction is completed, removing the solvent by reduced pressure distillation, washing and recrystallizing to obtain a fluorine-modified tertiary amine group;

[0026] (3) adding fluorine-modified tertiary amine and bromoethanol to N,N-dimethylformamide solvent, wherein the mass ratio of fluorine-modified tertiary amine to bromoethanol is 1:2.2, stirring and dissolving, and performing quaternization reaction at 75° C. for 6 h. After the reaction, performing reduced pressure distillation, washing, and drying to obtain intermediate 1;

[0027] (4) adding 4-aminophenylboronic acid and intermediate 1 to an ether solvent, wherein the mass ratio of 4-aminophenylboronic acid to intermediate 1 is 1.5:1, stirring and dispersing, heating to 70° C. to react for 6 h, and then distilling and washing to obtain amino-modified fluorosilane;

[0028] (5) 5 parts by weight of phenolic resin and 7 parts by weight of epichlorohydrin are uniformly mixed, reacted at 80° C. for 6 hours, and then concentrated under reduced pressure and washed to obtain an epoxidized phenolic resin;

[0029] (6) adding 6 parts by weight of the intermediate 1 to 1,4-dioxane, stirring and dispersing, then adding 4 parts by weight of an epoxidized phenolic resin and 0.1 parts by weight of boron trifluoride etherate, reacting at 75° C. for 7 h, filtering after completion, washing and drying to obtain a modified phenolic resin;

[0030] (7) 75 parts by weight of ethylene-propylene copolymer, 40 parts by weight of polypropylene, 10 parts by weight of amino-modified fluorosilane, 4 parts by weight of epoxy nanosilica, 1 part by weight of antioxidant 1010, and 4 parts by weight of modified phenolic resin were added to an internal mixer and mixed at 140° C. for 12 min. The mixed material was then hot-pressed in a flat vulcanizer and molded at a pressure of 8 MPa for 6 min to obtain a low-voltage cable with a self-cleaning function.

[0031] Example 2

[0032] (1) adding hexamethyldisilazane and 4-maleimidophenol to an N,N-dimethylformamide solvent, introducing nitrogen protection, and continuously adding a chloroplatinic acid catalyst thereto, wherein the mass ratio of hexamethyldisilazane, 4-maleimidophenol, and chloroplatinic acid catalyst is 1:1.3:0.03, reacting at 75° C. for 65 minutes, cooling to room temperature after completion, filtering, and drying to obtain a tertiary aminophenol;

[0033] (2) adding perfluorooctanoyl chloride and tertiary aminophenol to tetrahydrofuran solvent, and then continuing to add triethylamine catalyst thereto, wherein the mass ratio of perfluorooctanoyl chloride, tertiary aminophenol and triethylamine catalyst is 1.6:1:0.04, reacting at 60° C. for 10 hours, and after the reaction is completed, removing the solvent by reduced pressure distillation, washing and recrystallizing to obtain a fluorine-modified tertiary amine group;

[0034] (3) adding fluorine-modified tertiary amine and bromoethanol to N,N-dimethylformamide solvent, wherein the mass ratio of fluorine-modified tertiary amine to bromoethanol is 1:2.6, stirring and dissolving, and performing quaternization reaction at 90° C. for 8 h. After the reaction, performing reduced pressure distillation, washing, and drying to obtain intermediate 1;

[0035] (4) adding 4-aminophenylboronic acid and intermediate 1 to an ether solvent, wherein the mass ratio of 4-aminophenylboronic acid to intermediate 1 is 1.8:1, stirring and dispersing, heating to 85° C. to react for 12 h, and then distilling and washing to obtain amino-modified fluorosilane;

[0036] (5) 12 parts by weight of phenolic resin and 15 parts by weight of epichlorohydrin are uniformly mixed, reacted at 95° C. for 10 hours, and then concentrated under reduced pressure and washed to obtain an epoxidized phenolic resin;

[0037] (6) adding 9 parts by weight of the intermediate 1 to 1,4-dioxane, stirring and dispersing, then adding 7 parts by weight of an epoxidized phenolic resin and 0.3 parts by weight of boron trifluoride etherate, reacting at 90° C. for 12 h, filtering after completion, washing and drying to obtain a modified phenolic resin;

[0038] (7) 90 parts by weight of ethylene-propylene copolymer, 80 parts by weight of polypropylene, 12 parts by weight of amino-modified fluorosilane, 9 parts by weight of epoxy nano-silica, 2 parts by weight of antioxidant 1010, and 6 parts by weight of modified phenolic resin were added to an internal mixer and mixed at 155° C. for 18 min. The mixed material was then hot-pressed in a flat vulcanizer and molded at a pressure of 11 MPa for 10 min to obtain a low-voltage cable with a self-cleaning function.

[0039] Example 3

[0040] (1) adding hexamethyldisilazane and 4-maleimidophenol to an N,N-dimethylformamide solvent, introducing nitrogen protection, and continuously adding a chloroplatinic acid catalyst thereto, wherein the mass ratio of hexamethyldisilazane, 4-maleimidophenol, and chloroplatinic acid catalyst is 1:1.2:0.02, reacting at 62° C. for 52 minutes, cooling to room temperature after completion, filtering, and drying to obtain a tertiary aminophenol;

[0041] (2) adding perfluorooctanoyl chloride and tertiary aminophenol to tetrahydrofuran solvent, and then continuing to add triethylamine catalyst thereto, wherein the mass ratio of perfluorooctanoyl chloride, tertiary aminophenol, and triethylamine catalyst is 1.4:1:0.03, reacting at 45° C. for 7.5 hours, and after the reaction is completed, removing the solvent by reduced pressure distillation, washing, and recrystallizing to obtain a fluorine-modified tertiary amine group;

[0042] (3) adding fluorine-modified tertiary amine and bromoethanol to N,N-dimethylformamide solvent, wherein the mass ratio of fluorine-modified tertiary amine to bromoethanol is 1:2.4, stirring and dissolving, and performing quaternization reaction at 82° C. for 7 h. After completion, performing reduced pressure distillation, washing, and drying to obtain intermediate 1;

[0043] (4) adding 4-aminophenylboronic acid and intermediate 1 to an ether solvent, wherein the mass ratio of 4-aminophenylboronic acid to intermediate 1 is 1.6:1, stirring and dispersing, heating to 77° C. to react for 9 h, and then distilling and washing to obtain amino-modified fluorosilane;

[0044] (5) 8 parts by weight of phenolic resin and 11 parts by weight of epichlorohydrin were uniformly mixed, reacted at 87° C. for 8 hours, and then concentrated under reduced pressure and washed to obtain an epoxidized phenolic resin;

[0045] (6) adding 7 parts by weight of the intermediate 1 to 1,4-dioxane, stirring and dispersing, then adding 5.5 parts by weight of an epoxidized phenolic resin and 0.2 parts by weight of boron trifluoride etherate, reacting at 82° C. for 9 hours, filtering after completion, washing and drying to obtain a modified phenolic resin;

[0046] (7) 82 parts by weight of ethylene-propylene copolymer, 60 parts by weight of polypropylene, 11 parts by weight of amino-modified fluorosilane, 6 parts by weight of epoxy nano-silica, 1.5 parts by weight of antioxidant 1010, and 5 parts by weight of modified phenolic resin were added to an internal mixer and mixed at 147° C. for 15 min. The mixed material was then hot-pressed in a flat vulcanizer and molded at a pressure of 9 MPa for 8 min to obtain a low-voltage cable with a self-cleaning function.

[0047] Comparative Example 1

[0048] 82 parts by weight of ethylene-propylene copolymer, 60 parts by weight of polypropylene, 6 parts by weight of epoxy nano-silica, 1.5 parts by weight of antioxidant 1010, and 5 parts by weight of modified phenolic resin were added to an internal mixer and mixed at 147°C for 15 minutes. The mixed material was then hot-pressed in a flat vulcanizer and molded at a pressure of 9 MPa for 8 minutes to obtain a low-voltage cable with self-cleaning function.

[0049] Comparative Example 2

[0050] 82 parts by weight of ethylene-propylene copolymer, 60 parts by weight of polypropylene, 11 parts by weight of amino-modified fluorosilane, 6 parts by weight of epoxy nano-silica, and 1.5 parts by weight of antioxidant 1010 were added to an internal mixer and mixed at 147°C for 15 minutes. The mixed material was then hot-pressed in a flat vulcanizer and molded at a pressure of 9 MPa for 8 minutes to obtain a low-voltage cable with self-cleaning function.

[0051] The tensile test was carried out in accordance with GB / T 1040.1-2018. The test results are shown in Table 1.

[0052] Table 1: Tensile strength test.

[0053] project Tensile strength(MPa) Example 1 54.6 Example 2 56.7 Example 3 55.8 Comparative Example 1 36.7 Comparative Example 2 38.1

[0054] It can be seen from Table 2 that the low-voltage cable embodiments 1-3 with self-cleaning function of the present invention have better tensile properties than the comparative examples 1-2.

[0055] The surface wettability of the low-voltage cables with self-cleaning function of Examples 1-3 and Comparative Examples 1-2 was characterized according to JC2000D, and a contact angle test was performed.

[0056] Table 2: Contact angle tests.

[0057] project Contact angle Example 1 126.8° Example 2 127.6° Example 3 126.4° Comparative Example 1 105.1° Comparative Example 2 104.8°

[0058] It can be seen from Table 2 that compared with Comparative Example 1-2, the contact angle of Example 1-3 is larger, resulting in that the water droplets cannot spread and are very easy to slide, indicating that the low-voltage cable with self-cleaning function prepared by the present invention has a good self-cleaning function.

[0059] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A low-voltage cable with self-cleaning function, characterized in that: The invention comprises the following components by weight: 75-90 parts by weight of ethylene-propylene copolymer, 40-80 parts by weight of polypropylene, 10-12 parts by weight of amino-modified fluorosilane, 4-9 parts by weight of epoxy nano-silica, 1-2 parts by weight of antioxidant 1010 and 4-6 parts by weight of modified phenolic resin.

2. The low-voltage cable with self-cleaning function according to claim 1, characterized in that: The preparation method of the amino-modified fluorosilane is: (1) adding hexamethyldisilazane and 4-maleimidophenol to N,N-dimethylformamide solvent, introducing nitrogen protection, adding chloroplatinic acid catalyst, reacting at 50-75° C. for 40-65 min, cooling to room temperature after reaction, filtering and drying to obtain tertiary aminophenol; (2) adding perfluorooctanoyl chloride and tertiary aminophenol to tetrahydrofuran solvent, and then adding triethylamine catalyst thereto, reacting at 30-60° C. for 5-10 hours, and after the reaction, removing the solvent by reduced pressure distillation, washing, and recrystallizing to obtain a fluorine-modified tertiary amine group; (3) adding fluorine-modified tertiary amine and bromoethanol to N,N-dimethylformamide solvent, stirring and dissolving, and carrying out quaternization reaction at 75-90° C. for 6-8 hours. After completion, distilling under reduced pressure, washing, and drying to obtain intermediate 1; (4) Add 4-aminophenylboronic acid and intermediate 1 to ether solvent, stir and disperse, heat to 70-85° C., react for 6-12 hours, distill and wash after reaction, and obtain amino-modified fluorosilane.

3. The low-voltage cable with self-cleaning function according to claim 2, characterized in that: The mass ratio of hexamethyldisilazane, 4-maleimidophenol and chloroplatinic acid catalyst in (1) is 1:1.1-1.3:0.01-0.

03.

4. The low-voltage cable with self-cleaning function according to claim 2, characterized in that: The mass ratio of perfluorooctanoyl chloride, tertiary aminophenol and triethylamine catalyst in (2) is 1.2-1.6:1:0.02-0.

04.

5. The low-voltage cable with self-cleaning function according to claim 2, characterized in that: The mass ratio of the fluorine-modified tertiary amine group to bromoethanol in (3) is 1:2.2-2.

6.

6. The low-voltage cable with self-cleaning function according to claim 2, characterized in that: The mass ratio of 4-aminophenylboronic acid to intermediate 1 in (4) is 1.5-1.8:

1.

7. The low-voltage cable with self-cleaning function according to claim 1, characterized in that: The preparation method of the modified phenolic resin is: S1. 5-12 parts by weight of a phenolic resin and 7-15 parts by weight of epichlorohydrin are mixed uniformly, reacted at 80-95 ° C for 6-10h, and then concentrated under reduced pressure and washed to obtain an epoxidized phenolic resin; S2. Add 6-9 parts by weight of intermediate 1 to 1,4-dioxane, stir and disperse, then add 4-7 parts by weight of epoxidized phenolic resin and 0.1-0.3 parts by weight of boron trifluoride etherate, react at 75-90° C. for 7-12 hours, filter after reaction, wash and dry to obtain modified phenolic resin.

8. A method for preparing a low-voltage cable with a self-cleaning function according to any one of claims 1 to 7, characterized in that: The preparation method of the low-voltage cable with self-cleaning function is as follows: ethylene-propylene copolymer, polypropylene, amino-modified fluorosilane, epoxy nano-silica, antioxidant 1010, and modified phenolic resin are added to an internal mixer, mixed at 140-155° C. for 12-18 minutes, and then the mixed materials are hot-pressed in a flat vulcanizer, and molded at a pressure of 8-11 MPa for 6-10 minutes to obtain a low-voltage cable with self-cleaning function.