X-ETFE cable material and preparation method thereof

Abstract

The invention relates to the technical field of cable materials, and particularly discloses an X-ETFE cable material and a preparation method thereof. The X-ETFE cable material is prepared from the following raw materials: ETFE, a sensitizing agent, a flame retardant, a processing aid and a nano inorganic filler. The research shows that the nano inorganic filler is added into the X-ETFE cable material, so that the heat resistance of the X-ETFE cable material can be improved without adding an antioxidant, and the heat resistance of the X-ETFE cable material is superior to that of the X-ETFE cable material obtained by adding the antioxidant. Besides, the inventor also finds that the escape of HF in the X-ETFE cable can be greatly reduced by adding the nano inorganic filler into the X-ETFE cable material in the research. Besides, the nano inorganic filler is added into the X-ETFE cable material, so that the negative synergistic effect between the antioxidant and the cross-linking agent can be avoided, the irradiation dose is reduced, and the degradation of the material is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of cable materials, in particular to an X-ETFE cable material and a preparation method thereof. Background Art

[0002] Cross-linked ethylene-tetrafluoroethylene copolymer (X-ETFE) refers to a high-performance fluorine material made by copolymerizing ethylene and tetrafluoroethylene through chemical or radiation methods. Due to its advantages such as good electrical insulation performance, lightweight, ability to withstand high temperatures, good UV resistance, and resistance to chemical corrosion, it has huge application potential in water treatment, wires and cables, construction engineering and other fields.

[0003] While X-ETFE exhibits moderate high-temperature resistance, it remains insufficient under certain extreme conditions. To further enhance its heat resistance and improve its stability and reliability in applications such as aerospace, published literature often reports the addition of antioxidants. However, while antioxidants inhibit the material's oxidation, they also capture free radicals generated by the crosslinking agent during irradiation, resulting in a decrease in the number of free radicals available for effective crosslinking. To achieve the same degree of crosslinking, the irradiation dose must be increased. However, ETFE undergoes simultaneous crosslinking and degradation under electron beam irradiation, and increasing the irradiation dose also increases the degradation rate. Furthermore, X-ETFE cables generate hydrogen fluoride (HF) gas during electron beam irradiation, which can corrode the conductors and connected electronic components, compromising their safety. Therefore, improving the heat resistance of X-ETFE with antioxidants remains insufficient, making the development of high-performance X-ETFE cable materials of great significance. Summary of the Invention

[0004] In order to overcome at least one of the technical problems existing in the prior art, the present invention provides an X-ETFE cable material and a preparation method thereof.

[0005] The technical solutions of the present invention are as follows:

[0006] The invention first provides an X-ETFE cable material. The raw materials for preparing the X-ETFE cable material comprise ETFE, a sensitizer, a flame retardant, and a processing aid. The raw materials for preparing the X-ETFE cable material also comprise nano inorganic fillers.

[0007] The inventors surprisingly found in their research that adding nano inorganic fillers to X-ETFE cable materials can improve the heat resistance of X-ETFE cable materials without adding antioxidants, and its heat resistance is better than that of X-ETFE cable materials obtained by adding antioxidants.

[0008] In addition, the inventors also found in their research that adding nano inorganic fillers to X-ETFE cable materials can significantly reduce the escape of HF in X-ETFE cables.

[0009] Preferably, the ETFE melt index is 5-20 g / 10 min, measured at 297.5° C. / 5 kg.

[0010] Preferably, the weight percentage of the nano inorganic filler in the raw materials is 1%-5%.

[0011] Preferably, the weight percentage of the nano inorganic filler in the raw materials is 2%-4%.

[0012] Preferably, the weight percentage of the nano inorganic filler in the preparation raw materials is 3%.

[0013] Preferably, the nano inorganic filler is selected from one or a mixture of nano silicon dioxide, nano boron nitride, nano titanium dioxide, and nano aluminum oxide.

[0014] Preferably, the nano inorganic filler is nano titanium dioxide.

[0015] More preferably, the nano inorganic filler is modified nano titanium dioxide.

[0016] Preferably, the modified nano-titanium dioxide is prepared by the following method: adding nano-titanium dioxide to an ethanol aqueous solution, stirring evenly, then adding a modifier, stirring for 3 to 6 hours, filtering and separating the solid, and drying the solid to obtain the modified nano-titanium dioxide.

[0017] The inventors found in further research that adding the modified nano inorganic filler prepared by the above method to the X-ETFE cable material can further reduce the escape of HF in the X-ETFE cable compared to adding the unmodified nano inorganic filler.

[0018] Preferably, the usage ratio of nano-titanium dioxide, modifier and ethanol aqueous solution is 1 kg: 200-400 g: 4-8 L.

[0019] Preferably, the usage ratio of nano-titanium dioxide, modifier and ethanol aqueous solution is 1kg:300g:6L.

[0020] Preferably, the ethanol aqueous solution is an ethanol aqueous solution with an ethanol volume fraction of 50 to 80%.

[0021] Most preferably, the ethanol aqueous solution is an ethanol aqueous solution with an ethanol volume fraction of 60%.

[0022] Preferably, the modifier is selected from one or a combination of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, phenyltrimethoxysilane and sodium diisooctyl sulfosuccinate.

[0023] Preferably, the modifier is selected from a combination of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and sodium diisooctyl sulfosuccinate.

[0024] Preferably, the weight ratio of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane to sodium diisooctylsulfosuccinate is 1-5:1-5.

[0025] Most preferably, the weight ratio of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane to sodium diisooctylsulfosuccinate is 1:1.

[0026] The inventors discovered in further research that the selection of modifiers is crucial in the preparation of modified nano-inorganic fillers. Studies have shown that adding a single modifier, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, phenyltrimethoxysilane, or sodium diisooctylsulfosuccinate, to X-ETFE cable material can further reduce HF emission from X-ETFE cables, but the reduction is modest.

[0027] However, a modified nano-inorganic filler prepared by adding a modifier consisting of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and sodium diisooctyl sulfosuccinate to an X-ETFE cable material can significantly reduce HF emission from the X-ETFE cable. Furthermore, only the modified nano-inorganic filler prepared by adding a modifier consisting of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and sodium diisooctyl sulfosuccinate to an X-ETFE cable material can significantly reduce HF emission from the X-ETFE cable; modified nano-inorganic fillers prepared by adding combinations of other modifiers cannot significantly reduce HF emission from the X-ETFE cable.

[0028] Preferably, the sensitizer is a high temperature resistant sensitizer.

[0029] Preferably, the sensitizer is an allyl ester sensitizer.

[0030] Most preferably, the sensitizer is TAIC.

[0031] Preferably, the flame retardant is an antimony flame retardant.

[0032] Most preferably, the flame retardant is antimony trioxide.

[0033] Preferably, the processing aid is selected from one or a mixture of more than one of a dispersant, a coupling agent and a lubricant.

[0034] Preferably, the X-ETFE cable material comprises the following raw material components in percentage by weight:

[0035]

[0036] The present invention also provides a method for preparing the above-mentioned X-ETFE cable material, which comprises the following steps: uniformly mixing ETFE, a sensitizer, a flame retardant, a processing aid and a nano inorganic filler, adding the mixture into a twin-screw extruder, and performing melt extrusion and molding to obtain the X-ETFE cable material.

[0037] Beneficial Effects: The present invention provides a novel X-ETFE cable material and its preparation method. Research has shown that the addition of nano-inorganic fillers to X-ETFE cable material can improve its heat resistance without the need for antioxidants, and its heat resistance is superior to that of X-ETFE cable material containing antioxidants. Furthermore, the inventors have discovered that the addition of nano-inorganic fillers to X-ETFE cable material can significantly reduce HF emission from X-ETFE cables. Furthermore, the addition of nano-inorganic fillers to X-ETFE cable material can avoid the negative synergistic effect between antioxidants and crosslinking agents, reduce irradiation dose, and minimize material degradation. DETAILED DESCRIPTION

[0038] The present invention is further explained below with reference to specific examples, but the examples do not limit the present invention in any form.

[0039] The ETFE used in the following examples has a melt index of 5-20 g / 10 min, measured at 297.5° C. / 5 kg; the remaining raw materials without specified sources are conventional raw materials that can be purchased by those skilled in the art through conventional purchasing channels.

[0040] Example 1 Preparation of X-ETFE Cable Material

[0041] Raw material weight percentage composition: ETFE (melt index 5-20g / 10min) 89%; sensitizer (TAIC) 4%; flame retardant (antimony trioxide) 3%; nano inorganic filler 3%; processing aid (lubricant) 1%;

[0042] The nano inorganic filler is nano silicon dioxide.

[0043] Preparation method:

[0044] (1) ETFE resin, sensitizer, flame retardant, nano inorganic filler and processing aid are mixed, and auxiliary materials are uniformly dispersed in the resin by stirring with a stirrer;

[0045] (2) The uniformly mixed materials are added into a twin-screw extruder, melt-extruded and molded at 300° C. to obtain an X-ETFE-based composite material.

[0046] Example 2 Preparation of X-ETFE Cable Material

[0047] Raw material weight percentage composition: ETFE (melt index 5-20g / 10min) 89%; sensitizer (TAIC) 4%; flame retardant (antimony trioxide) 3%; nano inorganic filler 3%; processing aid (lubricant) 1%;

[0048] The nano inorganic filler is nano boron nitride.

[0049] The preparation method is the same as that of Example 1.

[0050] Example 3 Preparation of X-ETFE Cable Material

[0051] Raw material weight percentage composition: ETFE (melt index 5-20g / 10min) 89%; sensitizer (TAIC) 4%; flame retardant (antimony trioxide) 3%; nano inorganic filler 3%; processing aid (lubricant) 1%;

[0052] The nano inorganic filler is nano titanium dioxide.

[0053] The preparation method of X-ETFE cable material is the same as that in Example 1.

[0054] Example 4 Preparation of X-ETFE Cable Material

[0055] Raw material weight percentage composition: ETFE (melt index 5-20g / 10min) 89%; sensitizer (TAIC) 4%; flame retardant (antimony trioxide) 3%; nano inorganic filler 3%; processing aid (lubricant) 1%;

[0056] The nano inorganic filler is modified nano titanium dioxide;

[0057] The modified nano-titanium dioxide is prepared by the following method: adding nano-titanium dioxide to an ethanol aqueous solution, stirring evenly, then adding a modifier, stirring for 4 hours, filtering and separating the solid, and drying the solid to obtain the modified nano-titanium dioxide;

[0058] Preferably, the usage ratio of nano-titanium dioxide, modifier and ethanol aqueous solution is 1kg:300g:6L; the ethanol aqueous solution is an ethanol aqueous solution with an ethanol volume fraction of 60%; the modifier is selected from N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane.

[0059] The preparation method of X-ETFE cable material is the same as that in Example 1.

[0060] Example 5 Preparation of X-ETFE Cable Material

[0061] Raw material weight percentage composition: ETFE (melt index 5-20g / 10min) 89%; sensitizer (TAIC) 4%; flame retardant (antimony trioxide) 3%; nano inorganic filler 3%; processing aid (lubricant) 1%;

[0062] The nano inorganic filler is modified nano titanium dioxide;

[0063] The modified nano-titanium dioxide is prepared by the following method: adding nano-titanium dioxide to an ethanol aqueous solution, stirring evenly, then adding a modifier, stirring for 4 hours, filtering and separating the solid, and drying the solid to obtain the modified nano-titanium dioxide;

[0064] Preferably, the usage ratio of nano-titanium dioxide, modifier and ethanol aqueous solution is 1kg:300g:6L; the ethanol aqueous solution is an ethanol aqueous solution with an ethanol volume fraction of 60%; and the modifier is selected from phenyltrimethoxysilane.

[0065] The preparation method of X-ETFE cable material is the same as that in Example 1.

[0066] Example 6 Preparation of X-ETFE Cable Material

[0067] Raw material weight percentage composition: ETFE (melt index 5-20g / 10min) 89%; sensitizer (TAIC) 4%; flame retardant (antimony trioxide) 3%; nano inorganic filler 3%; processing aid (lubricant) 1%;

[0068] The nano inorganic filler is modified nano titanium dioxide;

[0069] The modified nano-titanium dioxide is prepared by the following method: adding nano-titanium dioxide to an ethanol aqueous solution, stirring evenly, then adding a modifier, stirring for 4 hours, filtering and separating the solid, and drying the solid to obtain the modified nano-titanium dioxide;

[0070] Preferably, the usage ratio of nano-titanium dioxide, modifier and ethanol aqueous solution is 1kg:300g:6L; the ethanol aqueous solution is an ethanol aqueous solution with an ethanol volume fraction of 60%; and the modifier is selected from sodium dioctyl sulfosuccinate.

[0071] The preparation method of X-ETFE cable material is the same as that in Example 1.

[0072] Example 7 Preparation of X-ETFE Cable Material

[0073] Raw material weight percentage composition: ETFE (melt index 5-20g / 10min) 89%; sensitizer (TAIC) 4%; flame retardant (antimony trioxide) 3%; nano inorganic filler 3%; processing aid (lubricant) 1%;

[0074] The nano inorganic filler is modified nano titanium dioxide;

[0075] The modified nano-titanium dioxide is prepared by the following method: adding nano-titanium dioxide to an ethanol aqueous solution, stirring evenly, then adding a modifier, stirring for 4 hours, filtering and separating the solid, and drying the solid to obtain the modified nano-titanium dioxide;

[0076] Preferably, the usage ratio of nano-titanium dioxide, modifier and ethanol aqueous solution is 1kg:300g:6L; the ethanol aqueous solution is an ethanol aqueous solution with an ethanol volume fraction of 60%; the modifier is selected from N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and sodium diisooctyl sulfosuccinate in a weight ratio of 1:1.

[0077] The preparation method of X-ETFE cable material is the same as that in Example 1.

[0078] Example 8 Preparation of X-ETFE Cable Material

[0079] Raw material weight percentage composition: ETFE (melt index 5-20g / 10min) 89%; sensitizer (TAIC) 4%; flame retardant (antimony trioxide) 3%; nano inorganic filler 3%; processing aid (lubricant) 1%;

[0080] The nano inorganic filler is modified nano titanium dioxide;

[0081] The modified nano-titanium dioxide is prepared by the following method: adding nano-titanium dioxide to an ethanol aqueous solution, stirring evenly, then adding a modifier, stirring for 4 hours, filtering and separating the solid, and drying the solid to obtain the modified nano-titanium dioxide;

[0082] Preferably, the usage ratio of nano-titanium dioxide, modifier and ethanol aqueous solution is 1kg:300g:6L; the ethanol aqueous solution is an ethanol aqueous solution with an ethanol volume fraction of 60%; the modifier is selected from N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and phenyltrimethoxysilane in a weight ratio of 1:1.

[0083] The preparation method of X-ETFE cable material is the same as that in Example 1.

[0084] Example 9 Preparation of X-ETFE Cable Material

[0085] Raw material weight percentage composition: ETFE (melt index 5-20g / 10min) 89%; sensitizer (TAIC) 4%; flame retardant (antimony trioxide) 3%; nano inorganic filler 3%; processing aid (lubricant) 1%;

[0086] The nano inorganic filler is modified nano titanium dioxide;

[0087] The modified nano-titanium dioxide is prepared by the following method: adding nano-titanium dioxide to an ethanol aqueous solution, stirring evenly, then adding a modifier, stirring for 4 hours, filtering and separating the solid, and drying the solid to obtain the modified nano-titanium dioxide;

[0088] Preferably, the usage ratio of nano-titanium dioxide, modifier and ethanol aqueous solution is 1kg:300g:6L; the ethanol aqueous solution is an ethanol aqueous solution with an ethanol volume fraction of 60%; the modifier is selected from sodium dioctyl sulfosuccinate and phenyltrimethoxysilane in a weight ratio of 1:1.

[0089] The preparation method of X-ETFE cable material is the same as that in Example 1.

[0090] Comparative Example 1 Preparation of X-ETFE Cable Material

[0091] Raw material weight percentage composition: ETFE (melt index 5-20g / 10min) 92%; sensitizer (TAIC) 4%; flame retardant (antimony trioxide) 3%; processing aid (lubricant) 1%;

[0092] Preparation method:

[0093] (1) ETFE resin, sensitizer, flame retardant and processing aid are mixed, and auxiliary materials are uniformly dispersed in the resin by stirring with a stirrer;

[0094] (2) The uniformly mixed materials are added into a twin-screw extruder, melt-extruded and molded at 300° C. to obtain an X-ETFE-based composite material.

[0095] Comparative Example 2 Preparation of X-ETFE Cable Material

[0096] Raw material weight percentage composition: ETFE (melt index 5-20g / 10min) 91.7%; sensitizer (TAIC) 4%; flame retardant (antimony trioxide) 3%; antioxidant 1010 0.3%; processing aid (lubricant) 1%;

[0097] Preparation method:

[0098] (1) ETFE resin, sensitizer, flame retardant, antioxidant 1010, and processing aid are mixed and stirred by a blender so that the auxiliary materials are uniformly dispersed in the resin;

[0099] (2) The uniformly mixed materials are added into a twin-screw extruder, melt-extruded and molded at 300° C. to obtain an X-ETFE-based composite material.

[0100] Experimental Example 1

[0101] 1) The X-ETFE cable materials prepared in Examples 1 to 9 and Comparative Examples 1 to 2 were prepared into wires through a wire extruder. The wire extruder used in this case was a high-temperature resistant 30 wire extruder from Shanghai Kechen. The wire gauge was 20AWG, the conductor was 19 / 0.203mm silver-plated wire, and the insulation outer diameter was 1.27mm.

[0102] 2) The produced electric wire is irradiated with electron beams.

[0103] 3) Verify the degree of cross-linking of the irradiated X-ETFE according to Section 4.6.25 of GJB 773B-2015. After hanging weight treatment at 300°C for 7h, perform a voltage withstand test according to Section 4.6.8.2.

[0104] The irradiated X-ETFE is subjected to a high-temperature life test according to Section 4.6.19 of GJB 773B-2015. After a 230°C / 500h hanging weight treatment, a voltage withstand test is performed according to Section 4.6.8.2.

[0105] Place the irradiated X-ETFE in a 260℃ oven for an extreme temperature resistance test without hanging any weights, and perform a voltage resistance test as specified in 4.6.8.2.

[0106] The irradiated X-ETFE was subjected to a fluoride (HF) emission test according to Section 4.6.46 of GJB 773B-2015.

[0107] The test results are shown in Tables 1 and 2.

[0108] Table 1. Performance test results of X-ETFE cable materials prepared in Examples 1 to 3 and Comparative Examples 1 and 2

[0109] Comparative Example 1 Comparative Example 2 Comparative Example 2 Example 1 Example 2 Example 3 Verification of cross-linking degree pass Fail pass pass pass pass High temperature life pass pass pass pass pass pass Extreme temperature resistance 260℃ / 48h pass pass pass pass pass pass Extreme temperature resistance 260℃ / 72h Fail Fail pass pass pass pass Extreme temperature resistance 260℃ / 96h Fail Fail Fail pass pass pass HF emission 258ppm 275ppm 386ppm 58ppm 65ppm 46ppm Electron beam irradiation dose 16Mrad 16Mrad 20Mrad 16Mrad 16Mrad 12 Mrad

[0110] As can be seen from the comparative examples in Table 1, Comparative Example 1 passed the crosslinking degree verification and high-temperature life tests, but only passed the 260°C / 48h extreme heat resistance test. Antioxidant 1010 was added to Comparative Example 2, but while the antioxidant interrupts the oxidation chain reaction, it also captures the free radicals generated by the crosslinker during irradiation, resulting in insufficient crosslinking at an irradiation dose of 16 Mrad. Increasing the irradiation dose to 20 Mrad in Comparative Example 2 improved heat resistance, passing the 260°C / 72h extreme heat resistance test. However, increasing the irradiation dose also resulted in greater degradation and increased HF emission.

[0111] As can be seen from the embodiments, the embodiment 1 that adds nano silicon dioxide modification and the embodiment 2 that adds nano boron nitride modification have all passed test, and fluoride overflows and reduces significantly.Adopt nano titanium dioxide among the embodiment 3 reducing irradiation dose to 12Mrad, above-mentioned test can both pass through, and the HF overflow amount further reduces.This shows that, on the basis of X-ETFE prescription, introduce nano inorganic filler, can not only improve its ultimate temperature resistance, can also reduce the corrosion of HF that overflows to electronic components.

[0112] Table 2. Performance test results of X-ETFE cable materials prepared in Examples 4 to 9

[0113] Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Verification of cross-linking degree pass pass pass pass pass pass High temperature life pass pass pass pass pass pass Extreme temperature resistance 260℃ / 48h pass pass pass pass pass pass Extreme temperature resistance 260℃ / 72h pass pass pass pass pass pass Extreme temperature resistance 260℃ / 96h pass pass pass pass pass pass HF emission 36ppm 42ppm 38ppm 12ppm 39ppm 40ppm Electron beam irradiation dose 12 Mrad 12 Mrad 12 Mrad 12 Mrad 12 Mrad 12 Mrad

[0114] From the experimental results in Table 2, it can be seen that the HF emission of the X-ETFE cable materials prepared in Examples 4 to 6 is further less than that in Example 3. This indicates that the addition of the modified nano-inorganic filler prepared by the above method to the X-ETFE cable material can further reduce the HF emission in the X-ETFE cable compared to the addition of the unmodified nano-inorganic filler.

[0115] As can be seen from the experimental results in Table 2, the HF emission of the X-ETFE cable material prepared in Example 7 is significantly lower than that in Example 3, and is also significantly lower than that in Examples 4 to 6. This indicates that the modified nano-inorganic filler prepared by adding a modifier consisting of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and sodium diisooctylsulfosuccinate to the X-ETFE cable material can significantly reduce the emission of HF in the X-ETFE cable.

[0116] As can be seen from the experimental results in Table 2, the HF emission of the X-ETFE cable materials prepared in Examples 8 and 9 is not much reduced compared with that in Example 3; the reduction is much smaller than that in Example 7. This shows that only the modified nano-inorganic filler prepared by adding the modifier consisting of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and sodium diisooctylsulfosuccinate to the X-ETFE cable material can significantly reduce the emission of HF in the X-ETFE cable; the modified nano-inorganic fillers prepared by adding other combinations of modifiers cannot significantly reduce the emission of HF in the X-ETFE cable.

Claims

1. An X-ETFE cable material, wherein the raw materials for its preparation include ETFE, a sensitizer, a flame retardant, and a processing aid, characterized in that: The preparation raw materials also contain nano inorganic fillers.

2. The X-ETFE cable material according to claim 1, characterized in that: The weight percentage of the nano inorganic filler in the preparation raw materials is 1%-5%.

3. The X-ETFE cable material according to claim 1, characterized in that: The weight percentage of the nano inorganic filler in the preparation raw materials is 2%-4%.

4. The X-ETFE cable material according to claim 1, characterized in that: The weight percentage of the nano inorganic filler in the preparation raw materials is 3%.

5. The X-ETFE cable material according to claim 1, characterized in that: The nano inorganic filler is selected from one of nano silicon dioxide, nano boron nitride, nano titanium dioxide, and nano aluminum oxide, or a mixture of more than one of the above.

6. The X-ETFE cable material according to claim 1, characterized in that: The sensitizer is a high temperature resistant sensitizer.

7. The X-ETFE cable material according to claim 1, characterized in that: The sensitizer is an allyl ester sensitizer.

8. The X-ETFE cable material according to claim 1, characterized in that: The flame retardant is an antimony flame retardant.

9. The X-ETFE cable material according to claim 1, characterized in that: Contains the following raw material components in weight percentage:

10. The method for preparing the X-ETFE cable material according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: uniformly mixing ETFE, a sensitizer, a flame retardant, a processing aid and a nano inorganic filler, adding the mixture into a twin-screw extruder, and performing melt extrusion and molding to obtain the X-ETFE cable material.

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