A matte antistatic elastomeric cable compound and method of making the same

Abstract

This invention discloses a matte antistatic elastomer cable material and its preparation method, comprising the following raw materials in parts by weight: 75-100 parts TPEE, 1-3 parts flame retardant, 1-5 parts lubricant, 5-8 parts antistatic agent, 10-20 parts carbon black, 5-8 parts silica, 1-3 parts antioxidant, and 5-10 parts additives. The raw materials are added to a mixer and mixed for 5-8 minutes at a speed of 2000-2500 r / min to obtain a mixture. The mixture is then fed into a twin-screw extruder for melting, extrusion, and granulation to obtain the matte antistatic elastomer cable material. The addition of carbon black and silica as matting agents imparts a matte finish to the cable material, while the addition of the synthesized antistatic agent gives the cable material excellent antistatic properties.

Description

Technical Field

[0001] This invention relates to the field of cable material technology, specifically to a matte antistatic elastomer cable material and its preparation method. Background Technology

[0002] As market demands for cable product quality continue to rise, the cable industry is accelerating product upgrades. Low-smoke halogen-free flame-retardant cables, flexible special cables, and lighting cables for new energy vehicles and China Standard EMU trains face particularly stringent performance requirements due to their unique operating environments. On one hand, these cable materials, serving as power transmission carriers and signal transmission paths, must simultaneously meet basic performance requirements such as halogen-free flame retardancy, high strength, bending resistance, abrasion resistance, tear resistance, high dimensional stability, thin walls, and low toxicity. On the other hand, due to the harsh operating environments—such as those used in wind power generation projects, mining machinery projects, and power cables in extreme environments like deserts and snowy landscapes—they must not only meet various basic performance requirements but also possess excellent resistance to high and low temperatures, environmental stress cracking, light aging, oil, hydrolysis, wind erosion, and oxidation.

[0003] Thermoplastic polyester elastomer (TPEE) is a block copolymer formed by polymerizing well-crystallized polyester hard segments and polyether or polyester soft segments. The hard segments give TPEE outstanding strength and good high-temperature resistance, oil resistance, creep resistance, solvent resistance, and impact resistance, while the soft segments endow TPEE with excellent low-temperature resistance and aging resistance. These unique structural characteristics have led to the rapid development and application of TPEE in many fields, such as automotive, electronics, industrial products, and sporting goods. Furthermore, TPEE materials have high recycling value.

[0004] Although TPEE material has superior overall performance, it is extremely flammable, with a limiting oxygen index (LOI) of only around 19%, and it drips when burning. In the event of a fire, these drips can cause the flames to spread or cause burns, making it crucial to improve the flame-retardant properties of TPEE material. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a matte antistatic elastomer cable material and its preparation method.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A matte antistatic elastomer cable material comprises the following raw materials in parts by weight: 75-100 parts TPEE, 1-3 parts flame retardant, 1-5 parts lubricant, 5-8 parts antistatic agent, 10-20 parts carbon black, 5-8 parts silica, 1-3 parts antioxidant, and 5-10 parts additives.

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

[0009] Step S1: Mix the chloroform solution of hydroxymethyl EDOT and the chloroform solution of phosphorus tribromide, stir at a constant speed in an ice-water bath for 1 hour, then heat to room temperature, continue stirring and react for 24-30 hours. After the reaction is completed, neutralize with saturated sodium carbonate solution and extract to obtain intermediate 1.

[0010]

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

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

[0013] Step S2: Add intermediate 1 and potassium phthalimide to dimethylformamide, heat to 75-90℃, keep warm and react for 18h, cool to room temperature after the reaction is completed to obtain intermediate 2.

[0014] The ratio of intermediate 1, potassium phthalimide, and dimethylformamide was controlled to be 10-15 mmol: 10-15 mmol: 50 mL.

[0015] In step S2, intermediate 1 reacts with potassium phthalimide to prepare intermediate 2. The reaction process is shown below:

[0016]

[0017] Structurally, intermediate 2 is a thiophene derivative monomer.

[0018] Step S3: Add intermediate 2 to n-hexane and stir at a constant speed for 15 min to obtain solution a, which is set aside; add ferric chloride to acetonitrile and stir at a constant speed for 15 min to obtain solution b; mix solution a and solution b, heat to 35-45℃, stir at a constant speed and react for 12 h, and after the reaction is completed, the antistatic agent is obtained.

[0019] The ratio of intermediate 2 to n-hexane was controlled at 3-5 mmol: 10-15 mL, and the ratio of ferric chloride to acetonitrile was controlled at 2-3 mmol: 3-5 mL.

[0020] In step S3, ferric chloride is used as an oxidant, and intermediate 2 polymerizes to form an antistatic agent, which is a polythiophene derivative structure. This is achieved by introducing...

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

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

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

[0024] Furthermore, the additive is aluminum diethylphosphonate.

[0025] A method for preparing a matte antistatic elastomer cable material includes the following steps:

[0026] Add all raw materials to a mixer and mix for 5-8 minutes at a speed of 2000-2500 r / min to obtain a mixture. Then, feed the mixture into a twin-screw extruder for melting, extrusion, and granulation to obtain a matte antistatic elastomer cable material.

[0027] Furthermore, the twin-screw extruder has a rotational speed of 60 r / min, a first temperature zone of 160-180℃, a second temperature zone of 200-220℃, a third temperature zone of 200-220℃, a fourth temperature zone of 190-210℃, a fifth temperature zone of 190-200℃, and a die temperature of 220-235℃.

[0028] The beneficial effects of this invention are as follows: This invention discloses a matte antistatic elastomer cable material. By adding carbon black and silica as matting agents, a matte effect can be given to the cable material. The addition of a synthesized antistatic agent gives the cable material excellent antistatic properties. In the preparation process, the antistatic agent first undergoes a substitution reaction between the hydroxyl group on hydroxymethyl EDOT and phosphorus tribromide to generate a brominated compound, namely intermediate 1. Then, intermediate 1 reacts with potassium phthalimide to prepare intermediate 2. Structurally, intermediate 2 is a thiophene derivative monomer. Using ferric chloride as an oxidant, intermediate 2 polymerizes to form an antistatic agent, which is a polythiophene derivative structure. The introduction of the polythiophene structure can synergistically achieve organic / inorganic conductivity with carbon black, improving the antistatic properties of the matrix. Moreover, the introduced phthalimide structure can give the matrix good corrosion resistance, improving the service life of the cable material in harsh environments. Detailed Implementation

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] Example 1: A matte antistatic elastomer cable material, comprising the following raw materials in parts by weight: 75 parts TPEE, 1 part flame retardant, 1 part lubricant, 5 parts antistatic agent, 10 parts carbon black, 5 parts silica, 1 part antioxidant, and 5 parts additives.

[0031] A method for preparing a matte antistatic elastomer cable material includes the following steps:

[0032] The raw materials are added to a mixer and mixed for 5 minutes at a speed of 2000 r / min to obtain a mixture. The mixture is then fed into a twin-screw extruder for melting, extrusion, and granulation to obtain a matte antistatic elastomer cable material.

[0033] The twin-screw extruder has a rotation speed of 60 r / min, a first temperature zone of 160-180℃, a second temperature zone of 200-220℃, a third temperature zone of 200-220℃, a fourth temperature zone of 190-210℃, a fifth temperature zone of 190-200℃, and a die temperature of 220-235℃.

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

[0035] Step S1: Mix the chloroform solution of hydroxymethyl EDOT and the chloroform solution of phosphorus tribromide, stir at a constant speed in an ice-water bath for 1 hour, then heat to room temperature, continue stirring and react for 24 hours. After the reaction is completed, neutralize with saturated sodium carbonate solution and extract to obtain intermediate 1.

[0036] The chloroform solution of hydroxymethyl EDOT mentioned in step S1 is prepared by mixing hydroxymethyl EDOT and chloroform at a ratio of 3g:10mL; the chloroform solution of phosphorus tribromide is prepared by mixing phosphorus tribromide and chloroform at a ratio of 10g:20mL.

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

[0038] The ratio of intermediate 1, potassium phthalimide, and dimethylformamide was controlled to be 10 mmol: 10 mmol: 50 mL.

[0039] Step S3: Add intermediate 2 to n-hexane and stir at a constant speed for 15 min to obtain solution a, which is set aside; add ferric chloride to acetonitrile and stir at a constant speed for 15 min to obtain solution b; mix solution a and solution b, heat to 35℃, stir at a constant speed and react for 12 h, and after the reaction is completed, the antistatic agent is obtained.

[0040] The ratio of intermediate 2 to n-hexane was controlled at 3 mmol:10 mL, and the ratio of ferric chloride to acetonitrile was controlled at 2 mmol:3 mL.

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

[0042] The lubricant is 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 additive is aluminum diethylphosphonate.

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

[0046] A method for preparing a matte antistatic elastomer cable material includes the following steps:

[0047] The raw materials are added to a mixer and mixed at 2400 r / min for 6 minutes to obtain a mixture. The mixture is then fed into a twin-screw extruder for melting, extrusion, and granulation to obtain a matte antistatic elastomer cable material.

[0048] The twin-screw extruder has a rotation speed of 60 r / min, a first temperature zone of 160-180℃, a second temperature zone of 200-220℃, a third temperature zone of 200-220℃, a fourth temperature zone of 190-210℃, a fifth temperature zone of 190-200℃, and a die temperature of 220-235℃.

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

[0050] Step S1: Mix the chloroform solution of hydroxymethyl EDOT and the chloroform solution of phosphorus tribromide, stir at a constant speed in an ice-water bath for 1 hour, then heat to room temperature, continue stirring and react for 28 hours. After the reaction is completed, neutralize with saturated sodium carbonate solution and extract to obtain intermediate 1.

[0051] The chloroform solution of hydroxymethyl EDOT mentioned in step S1 is prepared by mixing hydroxymethyl EDOT and chloroform at a ratio of 4g:10mL; the chloroform solution of phosphorus tribromide is prepared by mixing phosphorus tribromide and chloroform at a ratio of 11g:20mL.

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

[0053] The ratio of intermediate 1, potassium phthalimide, and dimethylformamide was controlled to be 12 mmol: 12 mmol: 50 mL.

[0054] Step S3: Add intermediate 2 to n-hexane and stir at a constant speed for 15 min to obtain solution a, which is set aside; add ferric chloride to acetonitrile and stir at a constant speed for 15 min to obtain solution b; mix solution a and solution b, heat to 40℃, stir at a constant speed and react for 12 h, and after the reaction is completed, the antistatic agent is obtained.

[0055] The ratio of intermediate 2 to n-hexane was controlled at 4 mmol:12 mL, and the ratio of ferric chloride to acetonitrile was controlled at 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 additive is aluminum diethylphosphonate.

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

[0061] A method for preparing a matte antistatic elastomer cable material includes the following steps:

[0062] The raw materials are added to a mixer and mixed for 8 minutes at a speed of 2500 r / min to obtain a mixture. The mixture is then fed into a twin-screw extruder for melting, extrusion, and granulation to obtain a matte antistatic elastomer cable material.

[0063] The twin-screw extruder has a rotation speed of 60 r / min, a first temperature zone of 160-180℃, a second temperature zone of 200-220℃, a third temperature zone of 200-220℃, a fourth temperature zone of 190-210℃, a fifth temperature zone of 190-200℃, and a die temperature of 220-235℃.

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

[0065] Step S1: Mix the chloroform solution of hydroxymethyl EDOT and the chloroform solution of phosphorus tribromide, stir at a constant speed in an ice-water bath for 1 hour, then heat to room temperature, continue stirring and react for 30 hours. After the reaction is completed, neutralize with saturated sodium carbonate solution and extract to obtain intermediate 1.

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

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

[0068] The ratio of intermediate 1, potassium phthalimide, and dimethylformamide was controlled to be 15 mmol: 15 mmol: 50 mL.

[0069] Step S3: Add intermediate 2 to n-hexane and stir at a constant speed for 15 min to obtain solution a, which is set aside; add ferric chloride to acetonitrile and stir at a constant speed for 15 min to obtain solution b; mix solution a and solution b, heat to 45℃, stir at a constant speed and react for 12 h, and after the reaction is completed, the antistatic agent is obtained.

[0070] The ratio of intermediate 2 to n-hexane was controlled at 5 mmol:15 mL, and the ratio of ferric chloride to acetonitrile was controlled at 3 mmol:5 mL.

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

[0072] The lubricant is 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 additive is aluminum diethylphosphonate.

[0075] Comparative Example 1: This comparative example is the same as Example 1 except that no antistatic agent was added.

[0076] The performance of the cable materials prepared in Examples 1-3 and Comparative Example 1 was tested, and the results are shown in Table 1 below:

[0077] Surface resistivity test: IEC60093, sample thickness 2mm;

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

[0079] Table 1

[0080]

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

[0082] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A matte antistatic elastomeric cable compound characterized in that, The flame retardant agent is aluminum hydroxide or magnesium hydroxide. The antistatic agent is prepared by the following steps: Step S1, the chloroform solution of hydroxymethyl EDOT and the chloroform solution of phosphorus tribromide are mixed, and stirred at a uniform speed under ice water bath for 1h, then warmed to room temperature, continue to stir and react for 24-30h, after the reaction is completed, neutralized with saturated sodium carbonate solution, extracted, and the prepared intermediate 1 is obtained, the chloroform solution of hydroxymethyl EDOT is mixed according to the usage ratio of 3-5g:10mL; the chloroform solution of phosphorus tribromide is mixed according to the usage ratio of 10-12g:20mL; Step S2, intermediate 1 and potassium phthalimide are added to dimethylformamide, and heated to 75-90℃, and incubated and reacted for 18h, after the reaction is completed, cooled to room temperature, and intermediate 2 is obtained, the usage ratio of intermediate 1, potassium phthalimide and dimethylformamide is controlled to be 10-15mmol:10-15mmol:50mL; Step S3, intermediate 2 is added to n-hexane, and stirred at a uniform speed for 15min to prepare solution a; iron trichloride is added to acetonitrile, and stirred at a uniform speed for 15min to prepare solution b; solution a and solution b are mixed, heated to 35-45℃, and stirred at a uniform speed and reacted for 12h, after the reaction is completed, the antistatic agent is prepared, the usage ratio of intermediate 2 and n-hexane is controlled to be 3-5mmol:10-15mL, and the usage ratio of iron trichloride and acetonitrile is controlled to be 2-3mmol:3-5mL.

2. A matte, antistatic elastomeric cable compound according to claim 1, wherein The lubricant is one or more of methyl silicone oil, paraffin wax and PE wax mixed in any ratio.

3. A matte, antistatic elastomeric cable compound according to claim 1, wherein The antioxidant is antioxidant 1010 or antioxidant 168.

4. A matte, antistatic elastomeric cable compound according to claim 1 wherein, The auxiliary agent is aluminum diethyl phosphite.

5. A matte, antistatic elastomeric cable compound according to claim 1 wherein, The method comprises the following steps:

6. The method for preparing a matte antistatic elastomer cable material according to claim 1, characterized in that, Each raw material is added to a mixer, mixed at a rotating speed of 2000-2500r / min for 5-8min to prepare a mixture, and then the mixture is sent into a double screw extruder to melt, extrude and granulate to prepare the matte antistatic elastomer cable material. The rotating speed of the double screw extruder is 60r / min, the first temperature zone is 160-180℃, the second temperature zone is 200-220℃, the third temperature zone is 200-220℃, the fourth temperature zone is 190-210℃, the fifth temperature zone is 190-200℃, and the die temperature is 220-235℃.

7. The process for preparing a matte antistatic elastomeric cable compound according to claim 6, characterized in that, ​

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