Matt antistatic elastomer cable material and preparation method thereof

Abstract

The invention discloses a matte antistatic elastomer cable material and a preparation method thereof. The matte antistatic elastomer cable material comprises the following raw materials in parts by weight: 75-100 parts of TPEE, 1-3 parts of a flame retardant, 1-5 parts of a lubricant, 5-8 parts of an antistatic agent, 10-20 parts of carbon black, 5-8 parts of silicon dioxide, 1-3 parts of an antioxidant and 5-10 parts of an auxiliary agent. The preparation method comprises the following steps: adding the raw materials into a mixer, mixing for 5-8min at the rotating speed of 2000-2500r / min to obtain a mixture, feeding the mixture into a double-screw extruder, melting, extruding and granulating to obtain the matte antistatic elastomer cable material. Carbon black and silicon dioxide are added as a delustering agent, so that the cable material can be endowed with a matte effect, and the cable material is endowed with excellent antistatic performance by adding the synthesized antistatic agent.

Description

Technical Field

[0001] The present invention relates to the technical field of cable materials, and particularly relates to a matte antistatic elastomeric cable material and a preparation method thereof. Background Art

[0002] With the continuous improvement of the market's requirements for the quality of cable products, the cable industry is accelerating the replacement of products. Low-smoke halogen-free flame-retardant cables, flexible special cables, cables for new energy vehicles and lighting in Chinese standard multiple units have more stringent requirements for the performance of the above cable products due to their special use environments. On the one hand, as power transmission carriers and signal transmission paths, these cable materials need to simultaneously meet the basic performance requirements such as halogen-free flame retardancy, high strength, bending resistance, wear resistance, tear resistance, high dimensional stability, thin walls, and low toxicity. On the other hand, due to the harsh use environments of these cable materials, such as power energy cables applied to wind power projects, mining machinery projects, and extreme environments such as deserts and ice and snow, while meeting various basic performance requirements, they also need to have good high and low temperature resistance, environmental stress cracking resistance, light aging resistance, oil resistance, hydrolysis resistance, wind erosion resistance, and antioxidant properties.

[0003] Thermoplastic polyester elastomer (TPEE) is a block copolymer formed by polymerizing a polyester hard segment with good crystallinity and a polyether or polyester soft segment. The hard segment endows TPEE with outstanding strength, good high temperature resistance, oil resistance, creep resistance, solvent resistance, and impact resistance, while the soft segment endows TPEE with excellent low temperature resistance and anti-aging properties. The performance characteristics presented by this unique structure have enabled TPEE to develop and be applied rapidly in many fields, such as the fields of automobiles, electronic and electrical, industrial products, and sports goods, and TPEE materials have high recycling value.

[0004] Although TPEE materials have relatively superior comprehensive performance, they are extremely easy to burn, with their limiting oxygen index (LOI) only being about 19%, and they will produce dripping when burning. In the event of a fire, the dripping will cause dangers such as flame spread or scalding, so it is of great significance to improve the flame retardant effect of TPEE materials. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides a matte antistatic elastomeric cable material and a preparation method thereof.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A matte antistatic elastomeric cable material, comprising the following raw materials in parts by weight: 75 - 100 parts of TPEE, 1 - 3 parts of a flame retardant, 1 - 5 parts of a lubricant, 5 - 8 parts of an antistatic agent, 10 - 20 parts of carbon black, 5 - 8 parts of silica, 1 - 3 parts of an antioxidant, and 5 - 10 parts of an auxiliary agent;

[0008] The antistatic agent is prepared through the following steps:

[0009] Step S1: Mix the chloroform solution of hydroxymethyl EDOT and the chloroform solution of phosphorus tribromide, stir evenly for 1 h in an ice-water bath, then raise the temperature to room temperature, continue stirring and reacting for 24 - 30 h. After the reaction, neutralize with saturated sodium carbonate solution and extract to obtain intermediate 1.

[0010]

[0011] In step S1, the chloroform solution of hydroxymethyl EDOT is prepared by mixing hydroxymethyl EDOT and chloroform at a dosage ratio of 3 - 5 g:10 mL; the chloroform solution of phosphorus tribromide is prepared by mixing phosphorus tribromide and chloroform at a dosage ratio of 10 - 12 g:20 mL.

[0012] In step S1, the hydroxyl group on hydroxymethyl EDOT undergoes a substitution reaction with phosphorus tribromide to form a brominated compound, which is intermediate 1.

[0013] Step S2: Add intermediate 1 and potassium phthalimide into dimethylformamide, raise the temperature to 75 - 90 °C, keep warm and react for 18 h. After the reaction, cool to room temperature to obtain intermediate 2.

[0014] Control the dosage ratio of intermediate 1, potassium phthalimide and dimethylformamide to be 10 - 15 mmol:10 - 15 mmol:50 mL.

[0015] In step S2, intermediate 1 reacts with potassium phthalimide to prepare intermediate 2, and the reaction process is as follows:

[0016]

[0017] Intermediate 2 is a thiophene derivative monomer in terms of structure.

[0018] Step S3: Add intermediate 2 into n - hexane, stir evenly for 15 min to obtain solution a for standby; add ferric chloride into acetonitrile, stir evenly for 15 min to obtain solution b; mix solution a and solution b, raise the temperature to 35 - 45 °C, stir evenly and react for 12 h. After the reaction, the antistatic agent is obtained.

[0019] Control the dosage ratio of intermediate 2 and n - hexane to be 3 - 5 mmol:10 - 15 mL, and the dosage ratio of ferric chloride and acetonitrile to be 2 - 3 mmol:3 - 5 mL.

[0020] In step S3, using ferric chloride as an oxidant, intermediate 2 polymerizes to form an antistatic agent, which has a polythiophene derivative structure. By introducing

[0021] Further, the flame retardant is aluminum hydroxide or magnesium hydroxide.

[0022] Further, the lubricant is one or more of methyl silicone oil, paraffin wax, and PE wax mixed in any proportion.

[0023] Further, the antioxidant is antioxidant 1010 or antioxidant 168.

[0024] Further, the auxiliary agent is aluminum diethyl phosphonate salt.

[0025] A preparation method of a matte antistatic elastomer cable compound includes the following steps:

[0026] Add each raw material into a mixer, mix at a rotation speed of 2000 - 2500 r / min for 5 - 8 min to obtain a mixed material, and then send the mixed material into a twin-screw extruder for melting, extrusion, and pelletizing to obtain the matte antistatic elastomer cable compound.

[0027] Further, the rotation speed of the twin-screw extruder is 60 r / min, the first temperature zone: 160 - 180 °C; the second temperature zone: 200 - 220 °C; the third temperature zone: 200 - 220 °C; the fourth temperature zone: 190 - 210 °C; the fifth temperature zone: 190 - 200 °C, and the die head temperature: 220 - 235 °C.

[0028] The beneficial effects of the present invention: The present invention discloses a matte antistatic elastomer cable compound. By adding carbon black and silica as matting agents, the cable compound can be given a matte effect. By adding a synthesized antistatic agent, the cable compound is given excellent antistatic performance. In the preparation process of the antistatic agent, first, the hydroxyl group on hydroxymethyl EDOT undergoes a substitution reaction with phosphorus tribromide to generate a brominated compound, which is intermediate 1. Then, intermediate 1 reacts with potassium phthalimide to prepare intermediate 2. Intermediate 2 is a thiophene derivative monomer in terms of structure. Using ferric chloride as an oxidant, intermediate 2 polymerizes to form an antistatic agent, which has a polythiophene derivative structure. Introducing the polythiophene structure can synergistically conduct electricity with carbon black to achieve organic / inorganic synergistic conductivity, improve the antistatic performance of the matrix, and the introduced phthalimide structure can endow the matrix with good corrosion resistance and improve the service life of the cable compound in harsh environments. Specific Embodiments

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0030] Example 1: A matte antistatic elastomeric cable compound, comprising the following raw materials in parts by weight: 75 parts of TPEE, 1 part of flame retardant, 1 part of lubricant, 5 parts of antistatic agent, 10 parts of carbon black, 5 parts of silica, 1 part of antioxidant, and 5 parts of auxiliary agent;

[0031] A method for preparing a matte antistatic elastomeric cable compound, comprising the following steps:

[0032] Add each raw material into a mixer, mix at a speed of 2000 r / min for 5 min to obtain a mixed material, and then send the mixed material into a twin-screw extruder for melting, extrusion, and pelletizing to obtain the matte antistatic elastomeric cable compound.

[0033] The speed of the twin-screw extruder is 60 r / min. The first temperature zone: 160 - 180 °C; the second temperature zone: 200 - 220 °C; the third temperature zone: 200 - 220 °C; the fourth temperature zone: 190 - 210 °C; the fifth temperature zone: 190 - 200 °C, and the die head temperature: 220 - 235 °C.

[0034] The antistatic agent is prepared through the following steps:

[0035] Step S1: Mix the chloroform solution of hydroxymethyl EDOT and the chloroform solution of phosphorus tribromide, stir evenly in an ice-water bath for 1 h, then raise the temperature to room temperature, continue stirring and reacting for 24 h. After the reaction is completed, neutralize with saturated sodium carbonate solution and extract to obtain intermediate 1;

[0036] In step S1, the chloroform solution of hydroxymethyl EDOT is prepared by mixing hydroxymethyl EDOT and chloroform according to a dosage ratio of 3 g:10 mL; the chloroform solution of phosphorus tribromide is prepared by mixing phosphorus tribromide and chloroform according to a dosage ratio of 10 g:20 mL.

[0037] Step S2: Add intermediate 1 and potassium phthalimide into dimethylformamide, raise the temperature to 75 °C, keep warm and react for 18 h. After the reaction is completed, cool to room temperature to obtain intermediate 2;

[0038] Control the dosage ratio of intermediate 1, potassium phthalimide, and dimethylformamide to be 10 mmol:10 mmol:50 mL.

[0039] Step S3: Add intermediate 2 into n-hexane, stir evenly for 15 min to obtain solution a for standby; add ferric chloride into acetonitrile, stir evenly for 15 min to obtain solution b; mix solution a and solution b, raise the temperature to 35 °C, stir evenly and react for 12 h. After the reaction is completed, obtain the antistatic agent.

[0040] Control the dosage ratio of intermediate 2 and n-hexane to be 3 mmol:10 mL, and the dosage ratio of ferric chloride and acetonitrile to be 2 mmol:3 mL.

[0041] The flame retardant is aluminum hydroxide or magnesium hydroxide.

[0042] The lubricant is composed of one or more of methyl silicone oil, paraffin wax and PE wax mixed in any proportion.

[0043] The antioxidant is antioxidant 1010 or antioxidant 168.

[0044] The auxiliary agent is aluminum diethyl phosphite salt.

[0045] Example 2: A matte antistatic elastomer cable compound, comprising the following raw materials in parts by weight: 85 parts of TPEE, 2 parts of flame retardant, 3 parts of lubricant, 6 parts of antistatic agent, 15 parts of carbon black, 6 parts of silica, 2 parts of antioxidant, 8 parts of auxiliary agent;

[0046] A method for preparing a matte antistatic elastomer cable compound, comprising the following steps:

[0047] Add the raw materials into a mixer and mix at a speed of 2400 r / min for 6 min to obtain a mixed material. Then, send the mixed material into a twin-screw extruder for melting, extrusion and pelletizing to obtain the matte antistatic elastomer cable compound.

[0048] The speed of the twin-screw extruder is 60 r / min. The first temperature zone: 160 - 180 °C; the second temperature zone: 200 - 220 °C; the third temperature zone: 200 - 220 °C; the fourth temperature zone: 190 - 210 °C; the fifth temperature zone: 190 - 200 °C, and the die head temperature: 220 - 235 °C.

[0049] The antistatic agent is prepared through the following steps:

[0050] Step S1: Mix the chloroform solution of hydroxymethyl EDOT and the chloroform solution of phosphorus tribromide, stir evenly in an ice-water bath for 1 h, then raise the temperature to room temperature, continue stirring and reacting for 28 h. After the reaction, neutralize with saturated sodium carbonate solution and extract to obtain intermediate 1;

[0051] In step S1, the chloroform solution of hydroxymethyl EDOT is prepared by mixing hydroxymethyl EDOT and chloroform according to a dosage ratio of 4 g:10 mL; the chloroform solution of phosphorus tribromide is prepared by mixing phosphorus tribromide and chloroform according to a dosage ratio of 11 g:20 mL.

[0052] Step S2: Add intermediate 1 and potassium phthalimide to dimethylformamide, raise the temperature to 85 °C, keep warm and react for 18 h. After the reaction, cool to room temperature to obtain intermediate 2;

[0053] The dosage ratio of the control intermediate 1, potassium phthalimide and dimethylformamide is 12 mmol: 12 mmol: 50 mL.

[0054] Step S3: Add intermediate 2 into n-hexane and stir evenly for 15 min to obtain solution a for standby; add ferric trichloride into acetonitrile and stir evenly for 15 min to obtain solution b; mix solution a and solution b, heat up to 40 °C, stir evenly and react for 12 h, and an antistatic agent is obtained after the reaction ends.

[0055] Control the dosage ratio of intermediate 2 to n-hexane to be 4 mmol: 12 mL, and the dosage ratio of ferric trichloride to acetonitrile to be 3 mmol: 5 mL.

[0056] The flame retardant is aluminum hydroxide or magnesium hydroxide.

[0057] The lubricant is one or more of methyl silicone oil, paraffin wax and PE wax mixed in any proportion.

[0058] The antioxidant is antioxidant 1010 or antioxidant 168.

[0059] The auxiliary agent is aluminum diethyl phosphonate.

[0060] Example 3: A matte antistatic elastomer cable material, comprising the following raw materials in parts by weight: 100 parts of TPEE, 3 parts of flame retardant, 5 parts of lubricant, 8 parts of antistatic agent, 20 parts of carbon black, 8 parts of silica, 3 parts of antioxidant, 10 parts of auxiliary agent;

[0061] A preparation method of a matte antistatic elastomer cable material, comprising the following steps:

[0062] Add each raw material into a mixer, mix at a speed of 2500 r / min for 8 min to obtain a mixed material, and then send the mixed material into a twin-screw extruder for melting, extrusion and pelletizing to obtain a matte antistatic elastomer cable material.

[0063] The speed of the twin-screw extruder is 60 r / min, the first temperature zone: 160 - 180 °C; the second temperature zone: 200 - 220 °C; the third temperature zone: 200 - 220 °C; the fourth temperature zone: 190 - 210 °C; the fifth temperature zone: 190 - 200 °C, and the die head temperature: 220 - 235 °C.

[0064] The antistatic agent is prepared through the following steps:

[0065] Step S1: Mix the chloroform solution of hydroxymethyl EDOT and the chloroform solution of phosphorus tribromide, stir evenly in an ice-water bath for 1 h, then heat up to room temperature, continue stirring and reacting for 30 h, and neutralize with saturated sodium carbonate solution after the reaction ends, and extract to obtain intermediate 1;

[0066] The chloroform solution of hydroxymethyl EDOT described in step S1 is prepared by mixing hydroxymethyl EDOT and chloroform in a dosage ratio of 5 g: 10 mL; the chloroform solution of phosphorus tribromide is prepared by mixing phosphorus tribromide and chloroform in a dosage ratio of 12 g: 20 mL.

[0067] Step S2: Add intermediate 1 and potassium phthalimide into dimethylformamide, heat up to 90 °C, keep warm and react for 18 h, and after the reaction is completed, cool to room temperature to obtain intermediate 2;

[0068] Control the dosage ratio of intermediate 1, potassium phthalimide and dimethylformamide to be 15 mmol: 15 mmol: 50 mL.

[0069] Step S3: Add intermediate 2 into n-hexane, stir evenly for 15 min to obtain solution a for standby; add ferric chloride into acetonitrile, stir evenly for 15 min to obtain solution b; mix solution a and solution b, heat up to 45 °C, stir evenly and react for 12 h, and obtain an antistatic agent after the reaction is completed.

[0070] Control the dosage ratio of intermediate 2 and n-hexane to be 5 mmol: 15 mL, and the dosage ratio of ferric chloride and acetonitrile to be 3 mmol: 5 mL.

[0071] The flame retardant is aluminum hydroxide or magnesium hydroxide.

[0072] The lubricant is composed of one or more of methyl silicone oil, paraffin wax and PE wax mixed in any proportion.

[0073] The antioxidant is antioxidant 1010 or antioxidant 168.

[0074] The auxiliary agent is aluminum diethylphosphonate.

[0075] Comparative example 1: Compared with example 1, no antistatic agent was added in this comparative example, and the rest was the same as in example 1.

[0076] Test the properties of the cable materials prepared in examples 1-3 and comparative example 1, and the results are shown in Table 1 below:

[0077] Test of surface resistance: IEC60093, sample thickness 2 mm;

[0078] Mechanical properties: Adopt ASTM D638-89 standard;

[0079] Table 1

[0080]

[0081] It can be seen from Table 1 above that the cable materials prepared in Examples 1-3 of the present invention not only have good antistatic performance but also excellent corrosion resistance.

[0082] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution, as long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.

Claims

1. A matte antistatic elastomer cable material, characterized in that: The invention comprises the following raw materials in parts by weight: 75-100 parts of TPEE, 1-3 parts of flame retardant, 1-5 parts of lubricant, 5-8 parts of antistatic agent, 10-20 parts of carbon black, 5-8 parts of silicon dioxide, 1-3 parts of antioxidant, and 5-10 parts of auxiliary agent; The antistatic agent is prepared by the following steps: Step S1, mixing a chloroform solution of hydroxymethyl EDOT and a chloroform solution of phosphorus tribromide, stirring at a constant speed for 1 hour in an ice-water bath, then heating to room temperature, continuing to stir and react for 24-30 hours, and after the reaction is completed, neutralizing with a saturated sodium carbonate solution, extracting, and obtaining an intermediate 1; Step S2, adding intermediate 1 and potassium phthalimide to dimethylformamide, heating to 75-90° C., keeping the temperature and reacting for 18 hours, cooling to room temperature after the reaction is completed, to obtain intermediate 2; Step S3, adding intermediate 2 to n-hexane, stirring at a constant speed for 15 minutes to obtain solution a, which is set aside; adding ferric chloride to acetonitrile, stirring at a constant speed for 15 minutes to obtain solution b; mixing solution a and solution b, heating to 35-45° C., stirring at a constant speed and reacting for 12 hours, and obtaining an antistatic agent after the reaction is completed.

2. The matte antistatic elastomer cable material according to claim 1, characterized in that: The flame retardant is aluminum hydroxide or magnesium hydroxide.

3. The matte antistatic elastomer cable material according to claim 1, characterized in that: The lubricant is a mixture of one or more of methyl silicone oil, paraffin wax and PE wax in any proportion.

4. The matte antistatic elastic cable material according to claim 1, characterized in that: The antioxidant is antioxidant 1010 or antioxidant 168.

5. The matte antistatic elastic cable material according to claim 1, characterized in that: The auxiliary agent is aluminum diethylphosphite.

6. The matte antistatic elastic cable material according to claim 1, characterized in that: The chloroform solution of hydroxymethyl EDOT in step S1 is prepared by mixing hydroxymethyl EDOT and chloroform in a ratio of 3-5 g:10 mL; the chloroform solution of phosphorus tribromide is prepared by mixing phosphorus tribromide and chloroform in a ratio of 10-12 g:20 mL.

7. The matte antistatic elastic cable material according to claim 1, characterized in that: In step S2, the dosage ratio of intermediate 1, potassium phthalimide and dimethylformamide is controlled to be 10-15 mmol: 10-15 mmol: 50 mL.

8. The matte antistatic elastic cable material according to claim 1, characterized in that: In step S3, the usage ratio of intermediate 2 and n-hexane is controlled to be 3-5 mmol:10-15 mL, and the usage ratio of ferric chloride and acetonitrile is controlled to be 2-3 mmol:3-5 mL.

9. The method for preparing a matte antistatic elastic cable material according to claim 1, characterized in that: The steps include: The raw materials are added into a mixer, mixed at a speed of 2000-2500 r / min for 5-8 minutes to obtain a mixture, and then the mixture is sent into a twin-screw extruder for melting, extrusion and granulation to obtain a matte antistatic elastomer cable material.

10. The method for preparing a matte antistatic elastic cable material according to claim 9, characterized in that: The speed of the twin-screw extruder is 60r / min, the first temperature zone: 160-180°C; the second temperature zone: 200-220°C; the third temperature zone: 200-220°C; the fourth temperature zone: 190-210°C; the fifth temperature zone: 190-200°C, and the die head temperature: 220-235°C.

Images