WO2024045419A1 - 基于复配树脂的半导电屏蔽料及其制备方法和应用 - Google Patents

基于复配树脂的半导电屏蔽料及其制备方法和应用 Download PDF

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WO2024045419A1
WO2024045419A1 PCT/CN2022/139563 CN2022139563W WO2024045419A1 WO 2024045419 A1 WO2024045419 A1 WO 2024045419A1 CN 2022139563 W CN2022139563 W CN 2022139563W WO 2024045419 A1 WO2024045419 A1 WO 2024045419A1
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parts
resin
shielding material
ethylene
material based
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PCT/CN2022/139563
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English (en)
French (fr)
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侯帅
傅明利
黎小林
贾磊
展云鹏
惠宝军
朱闻博
冯宾
张逸凡
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南方电网科学研究院有限责任公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Definitions

  • the present application relates to the technical field of high-voltage cables, and in particular to a semi-conductive shielding material based on compound resin and its preparation method and application.
  • the semi-conductive shielding material based on compound resin has a low PTC coefficient and can be well used as a semi-conductive shielding material for high-voltage cables.
  • a semi-conductive shielding material based on compound resin includes the following components by mass: 55 to 65 parts of compound resin, 20 to 30 parts of conductive filler and 0.9 to 2 parts of cross-linking agent. ;
  • the compound resin is compounded by low-density polyethylene resin and ethylene-acrylic acid resin;
  • the ethylene-acrylic acid resin is at least one of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin.
  • the raw materials for preparing the semiconductive shielding material based on compound resin include the following mass parts of each component: 61 to 64 parts of compound resin, 25 to 30 parts of conductive filler, and 1 part of cross-linking agent. ⁇ 1.5 servings.
  • the mass ratio of the low-density polyethylene resin and the ethylene-acrylic resin is 1:4 to 1:1.
  • the low-density polyethylene resin has a melt index of 0.25g/10min to 2g/10min.
  • the low-density polyethylene resin has a density of 0.918g/cm 3 to 0.932g/cm 3 .
  • the ethylene-acrylic resin has a melt index ⁇ 10 g/min.
  • the ethylene-acrylic resin has an elongation at break ⁇ 700%.
  • the raw materials for preparing the semiconductive shielding material based on compound resin also include a dispersant; the mass fraction of the dispersant is 0.5 to 2 parts.
  • the raw materials for preparing the compound resin-based semiconductive shielding material also include processing aids; the mass parts of the processing aids are 2 to 6 parts.
  • the processing aid is made of components including the following mass parts: 1 to 2 parts of coupling agent, 1 to 3 parts of lubricant, and 0.6 to 1 part of antioxidant.
  • a method for preparing the above-mentioned semi-conductive shielding material based on compound resin including the following steps:
  • the low-density polyethylene resin, the ethylene-acrylic resin and the conductive filler are kneaded and pelletized to obtain pellets;
  • the pre-finished product is subjected to heat treatment.
  • mixing the low-density polyethylene resin, the ethylene-acrylic resin and the conductive filler includes the following steps: mixing the low-density polyethylene resin and the ethylene-acrylic resin, and then adding the conductive filler Continue mixing.
  • the mixing speed is 80 rpm to 150 rpm, and the mixing temperature is 150°C to 180°C.
  • the temperature of the heat treatment is 50°C to 70°C.
  • a semiconductive shielding product whose preparation raw materials include the above-mentioned semi-conductive shielding material or the semi-conductive shielding material prepared by the above-mentioned preparation method.
  • the above-mentioned semi-conductive shielding material based on compound resin is mainly prepared by using 55 to 65 parts by mass of compound resin, 20 to 30 parts of conductive filler and 0.9 to 2 parts of cross-linking agent.
  • this shielding material is used as a semi-conductive shielding material for high-voltage cables, as the temperature rises during the use of the cable, the melting expansion of the ethylene-acrylic resin will be suppressed by the low-density polyethylene resin, which can cause damage to the conductive network when the temperature rises. to a good fixation effect.
  • conductive fillers are mainly distributed in low-density polyethylene resin. As the temperature rises, the low-density polyethylene resin expands to a smaller extent.
  • the conductive network is less affected by temperature changes, and the expansion of ethylene-acrylic resin will further Extruding low-density polyethylene can promote contact between conductive fillers, strengthen the conductive network, thereby reducing the PTC coefficient of the shielding material, suppressing the PTC effect of the shielding material, and reducing the adverse impact of the PTC effect on the use of high-voltage cables.
  • the conductive filler is mainly distributed in the low-density polyethylene resin.
  • the low-density polyethylene resin When vinyl resin forms a continuous phase, a shielding material with higher conductivity can be obtained while reducing the amount of conductive filler.
  • the above-mentioned semi-conductive shielding material based on compound resin has good interface compatibility with the insulating layer of high-voltage cables, which can improve the bonding force between the semi-conducting shielding material and the insulating layer of high-voltage cables. This makes the semi-conductive shielding material less likely to be peeled off, thereby extending the service life of the high-voltage cable.
  • Figure 1 is a scanning electron microscope image of the shielding material obtained in Example 2 of the present application.
  • An embodiment of the present application provides a semi-conductive shielding material based on compound resin.
  • the raw materials for preparing the semi-conductive shielding material include the following components by mass: 55 to 65 parts of compound resin, 20 to 30 parts of conductive filler, and 0.9 to 2 parts of cross-linking agent; wherein, the compound resin is composed of Low-density polyethylene resin and ethylene-acrylic acid resin are compounded; the ethylene-acrylic acid resin is at least one of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin.
  • the resin matrix will expand due to heat, thereby destroying the conductive mesh in the semi-conductive shielding material, causing the 90°C volume resistivity of the semi-conductive shielding material to rise sharply, the PTC coefficient to increase, and the PTC The effect is significantly increased.
  • the semi-conductive shielding material in this embodiment is used as a semi-conductive shielding material for high-voltage cables, as the temperature rises during the use of the cable, the melting expansion of the ethylene-acrylic resin will be suppressed by the low-density polyethylene resin, so that the temperature can be increased It plays a good role in fixing the conductive network when rising.
  • conductive fillers are mainly distributed in low-density polyethylene resin.
  • the low-density polyethylene resin expands to a smaller extent.
  • the conductive network is less affected by temperature changes, and the expansion of ethylene-acrylic resin will further Extruding low-density polyethylene can promote contact between conductive fillers, strengthen the conductive network, thereby reducing the PTC coefficient of the shielding material, suppressing the PTC effect of the shielding material, and reducing the adverse impact of the PTC effect on the use of high-voltage cables.
  • the conductive filler is mainly distributed in the low-density polyethylene resin.
  • the low-density polyethylene resin When vinyl resin forms a continuous phase, a shielding material with higher conductivity can be obtained while reducing the amount of conductive filler.
  • the above-mentioned semi-conductive shielding material based on compound resin has good interface compatibility with the insulating layer of high-voltage cables, which can improve the bonding force between the semi-conducting shielding material and the insulating layer of high-voltage cables. This makes the semi-conductive shielding material less likely to be peeled off, thereby extending the service life of the high-voltage cable.
  • the low density polyethylene resin has a melting point higher than the melting point of the ethylene-acrylic resin. At this time, the melt expansion of the ethylene-acrylic resin can be better suppressed by low-density polyethylene resin to further fix the conductive network.
  • the raw materials for preparing the semiconductive shielding material based on compound resin include the following mass parts of each component: 61 to 64 parts of compound resin, 25 to 30 parts of conductive filler, and 1 cross-linking agent. serving ⁇ 1.5 servings.
  • the mass ratio of low-density polyethylene resin and ethylene-acrylic resin is 1:4 to 1:1.
  • the mass ratio of low-density polyethylene resin and ethylene-acrylic resin is 1:4, 3:7, 2:3 or 1:1, etc. It is understandable that the mass ratio of low-density polyethylene resin and ethylene-acrylic resin can be other suitable choices in the range of 1:4 to 1:1.
  • the melt index of the low-density polyethylene resin is 0.25g/10min ⁇ 2g/10min.
  • the melt index of low-density polyethylene resin is 0.5g/10min, 0.6g/10min, 0.8g/10min, 1g/10min, 1.5g/10min, 1.8g/10min or 2g/10min, etc. It is understandable that the melt index of low-density polyethylene resin can also be appropriately selected within the range of 0.25g/10min ⁇ 2g/10min.
  • the density of the low-density polyethylene resin is 0.918g/cm 3 to 0.932g/cm 3 .
  • the density of low-density polyethylene resin is 0.918g/cm 3 , 0.92g/cm 3 , 0.925g/cm 3 , 0.928g/cm 3 , 0.93g/cm 3 , etc. It is understandable that the density of low-density polyethylene resin can also be appropriately selected within the range of 0.918g/cm 3 to 0.932g/cm 3 .
  • the melt index of the ethylene-acrylic resin is ⁇ 10 g/min.
  • the melt index of the ethylene-acrylic resin at 190°C and 2.16kg is ⁇ 10g/min.
  • the melt index of ethylene-acrylic resin at 190°C and 2.16kg is ⁇ 9g/min; the melting index of ethylene-acrylic resin at 190°C and 2.16kg is ⁇ 8g/min; the melting index of ethylene-acrylic resin at 190°C and 2.16kg
  • the melt index under the condition is ⁇ 5g/min, etc.
  • the elongation at break of the ethylene-acrylic resin is ⁇ 700%.
  • the elongation at break of the ethylene-acrylic resin is ⁇ 800%; the elongation at break of the ethylene-acrylic resin is ⁇ 900%, etc.
  • the mass parts of the compound resin can be but are not limited to 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63, 64 or 65 servings.
  • the mass fraction of the compound resin can also be appropriately selected in the range of 55 to 65 parts.
  • the mass parts of the conductive filler can be but are not limited to 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts , 29 servings or 30 servings. It is understandable that the mass fraction of the conductive filler can also be appropriately selected within the range of 20 to 30 parts.
  • the conductive filler is conductive carbon black.
  • the oil absorption value of the conductive carbon black is 130ml/100g ⁇ 200ml/100g.
  • the oil absorption value of conductive carbon black is 140ml/100g, 150ml/100g, 180ml/100g, etc.
  • the mass fraction of the cross-linking agent may be, but is not limited to, 0.9 parts, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts or 2 parts. It is understandable that the mass fraction of the cross-linking agent can also be appropriately selected in the range of 0.9 to 2 parts.
  • the cross-linking agent is at least one of di-tert-butyl cumene peroxide and dicumyl peroxide.
  • the raw materials for preparing the semi-conductive shielding material based on compound resin are the following components by mass: 55 to 65 parts of compound resin, 20 to 30 parts of conductive filler and 0.9 parts of cross-linking agent parts to 2 parts; wherein, the compound resin is compounded of low-density polyethylene resin and ethylene-acrylic acid resin; the ethylene-acrylic acid resin is at least one of ethylene-ethyl acrylate resin and ethylene-butyl acrylate resin.
  • the raw materials for preparing the semiconductive shielding material based on compound resin also include a dispersant; the mass fraction of the dispersant is 0.5 to 2 parts.
  • the mass parts of the dispersant may be, but are not limited to, 0.5 parts, 0.8 parts, 1 part, 1.1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.7 parts, 1.9 parts or 2 parts. It is understandable that the mass fraction of the dispersant can also be appropriately selected in the range of 0.5 to 2 parts.
  • the dispersant is at least one of ethylene bisstearamide and oleic acid amide.
  • the raw materials for preparing the semiconductive shielding material based on compound resin also include processing aids; the mass parts of the processing aids are 2 to 6 parts.
  • the mass parts of the processing aid may be, but are not limited to, 2 parts, 2.5 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.8 parts, 5 parts, 5.2 servings, 5.5 servings, 5.8 servings or 6 servings. It is understandable that the mass fraction of the processing aid can also be appropriately selected in the range of 2 to 6 parts.
  • the processing aid is made of components including the following mass parts: 1 to 2 parts of coupling agent, 1 to 3 parts of lubricant, and 0.6 to 1 part of antioxidant.
  • the coupling agent is a silane coupling agent.
  • the lubricant is zinc stearate.
  • the antioxidant is at least one of antioxidant 1010 and antioxidant 168.
  • the silane coupling agent is KH550.
  • the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 at a mass ratio of (1.5 ⁇ 2.5):1.
  • the mass ratio of the antioxidant 1010 and the antioxidant 168 may be, but is not limited to, 1.8:1, 2:1, 2.2:1, or 2.5:1.
  • the processing aid is a mixture of coupling agents, lubricants and antioxidants.
  • the mass fraction of the coupling agent can be, but is not limited to, 1 part, 1.2 parts, 1.5 parts, 1.8 parts or 2 parts, etc.
  • the mass parts of the lubricant may be, but are not limited to, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts or 3 parts, etc.
  • the mass parts of the antioxidant may be, but are not limited to, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts or 1 part, etc. It can also be understood that the mass fraction of the coupling agent can also be made in the range of 1 to 2 parts, and the mass fraction of the lubricant can also be made in the range of 1 to 3 parts. , the mass fraction of the antioxidant can also be appropriately selected within the range of 0.6 to 1 part.
  • the raw materials for preparing the semi-conductive shielding material based on compound resin are the following components by mass: 55 to 65 parts of compound resin, 20 to 30 parts of conductive filler, and 0.9 parts of cross-linking agent. parts to 2 parts and 0.5 to 2 parts of dispersant; among them, the compound resin is compounded of low-density polyethylene resin and ethylene-acrylic acid resin; the ethylene-acrylic acid resin is ethylene-ethyl acrylate resin and ethylene-butyl acrylate. At least one of the ester resins.
  • the raw materials for preparing the semi-conductive shielding material based on compound resin are the following components by mass: 55 to 65 parts of compound resin, 20 to 30 parts of conductive filler, and 0.9 parts of cross-linking agent. 0.5 to 2 parts of dispersant and 2 to 6 parts of processing aids; among them, the compound resin is compounded of low-density polyethylene resin and ethylene-acrylic resin; the ethylene-acrylic resin is ethylene- At least one of ethyl acrylate resin and ethylene-butyl acrylate resin.
  • Another embodiment of the present application provides a method for preparing the above-mentioned semi-conductive shielding material based on compound resin.
  • the preparation method includes the following steps: mix and dice low-density polyethylene resin, ethylene-acrylic resin and conductive filler to obtain pellets; mix the pellets and cross-linking agent to obtain a pre-finished product; conduct Heat treatment.
  • the mixing speed is 80 rpm to 150 rpm, and the mixing temperature is 150°C to 180°C.
  • mixing is performed in torque.
  • the mixing speed may be, but is not limited to, 80rpm, 90rpm, 100rpm, 110rpm, 120rpm, 130rpm or 140rpm, etc.
  • the mixing temperature is 150°C, 160°C, 170°C or 180°C, etc.
  • the mixing time is 10 to 20 minutes.
  • the mixing time is 10min, 12min, 15min, 18min or 20min, etc.
  • mixing low-density polyethylene resin, ethylene-acrylic resin and conductive filler includes the following steps: mixing low-density polyethylene resin and ethylene-acrylic resin, and then adding conductive filler and continuing mixing. Further, the low-density polyethylene resin and the ethylene-acrylic resin are mixed for 4 to 6 minutes, and then the conductive filler is added and mixed for 8 to 12 minutes. Further, the low-density polyethylene resin and the ethylene-acrylic resin were mixed for 5 minutes, and then the conductive filler was added and the mixture was continued for 10 minutes.
  • the mixing conditions for mixing the low-density polyethylene resin and the ethylene-acrylic resin, and adding the conductive filler to continue the mixing can be independently selected from the mixing speed of 80 rpm to 150 rpm, and the mixing temperature of 150°C ⁇ 180°C.
  • the conditions for kneading the low-density polyethylene resin and the ethylene-acrylic resin, and adding the conductive filler and continuing the kneading are the same.
  • the temperature of the heat treatment is 50°C to 70°C.
  • the temperature of the heat treatment is 50°C, 55°C, 60°C, 65°C, or 70°C, etc.
  • the heat treatment time is 5h to 10h.
  • the heating treatment time is 5h, 6h, 7h, 8h, 9h or 10h, etc.
  • the following steps are also included: keeping the pellets warm at 50°C to 70°C.
  • the insulation temperature is 50°C, 55°C, 60°C, 65°C, or 70°C, etc.
  • the holding time is 3h to 6h.
  • the holding time is 3h, 4h, 5h or 6h, etc.
  • the grinding time is 8min ⁇ 20min. Specifically, the grinding time is 8 min, 10 min, 15 min or 20 min, etc. It will be appreciated that grinding can be performed in a grinder.
  • the following steps are also included before mixing low-density polyethylene resin, ethylene-acrylic acid resin and conductive filler: mixing low-density polyethylene resin, ethylene-acrylic acid
  • the resin, conductive filler and cross-linking agent are dried to remove moisture from each raw material.
  • the low-density polyethylene resin, ethylene-acrylic resin, conductive filler, dispersant, processing aid and cross-linking agent are dried to remove moisture in each raw material.
  • the raw materials for preparing the conductive shielding product include the above-mentioned semi-conductive shielding material or the semi-conductive shielding material prepared by the above-mentioned preparation method.
  • the semi-conductive shielding product is made by extrusion molding of raw materials including the above-mentioned semi-conductive shielding material.
  • the semiconductive shielding product is a semiconductive shielding sleeve.
  • the semiconductive shielding product is a high-voltage cable semiconducting shielding product.
  • the raw materials for preparing the semiconductive shielding product also include insulating materials.
  • Semiconducting shielding products are made by extrusion molding of raw materials including the above-mentioned semiconducting shielding materials and insulation materials.
  • a cable including a conductor, an insulating layer and a semiconducting shielding layer; the conductor is located inside the insulating layer, and the semiconducting shielding layer is located on at least one surface of the insulating layer; the semiconducting shielding layer is composed of the above complex based It is made of a semi-conductive shielding material mixed with resin or a semi-conductive shielding material based on compound resin prepared by the above preparation method.
  • semiconductive shielding layers are located on both surfaces of the insulating layer.
  • the cable includes a conductor, an inner shielding layer, an insulation layer and an outer shielding layer arranged in sequence from the inside to the outside.
  • the inner shielding layer and the outer shielding layer are both semi-conductive shielding layers.
  • the raw materials for preparing the semi-conductive shielding material based on compound resin in this embodiment are: 63.5 parts of compound resin, 30 parts of conductive filler, 1 part of dispersant, 4.5 parts of processing aids and 1 part of cross-linking agent share.
  • the compound resin is low-density polyethylene resin and ethylene-butyl acrylate resin.
  • the mass ratio of low-density polyethylene resin and ethylene-butyl acrylate resin is 2:3.
  • the melt index of low-density polyethylene resin is 0.5g.
  • the density of low-density polyethylene resin is 0.918g/cm 3
  • the melt index of ethylene-butyl acrylate resin at 190°C and 2.16kg is ⁇ 10g/min
  • the elongation at break of ethylene-butyl acrylate resin is ⁇ 700%.
  • the conductive filler is conductive carbon black.
  • the dispersant is ethylene bisstearamide.
  • the cross-linking agent is bis-tert-butylperoxycumylbenzene (BIBP).
  • the processing aid is mixed with the following raw materials: 2 parts of coupling agent, 2 parts of lubricant and 0.5 part of antioxidant.
  • the coupling agent is silane coupling agent KH550.
  • the lubricant is zinc stearate.
  • the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 at a mass ratio of 2:1.
  • the preparation method of the semiconductive shielding material based on compound resin includes the following steps:
  • S101 Dry low-density polyethylene resin, ethylene-butyl acrylate resin, conductive carbon black, dispersant, processing aids and cross-linking agent to remove moisture in each raw material.
  • S102 Mix low-density polyethylene resin, ethylene-butyl acrylate resin, dispersant and processing aids for 5 minutes, then add conductive filler and continue mixing for 10 minutes, then pelletize to obtain pellets.
  • the kneading is performed under torque, the kneading rotation speed is 100 rpm, and the kneading temperature is 160°C.
  • S104 Grind the cross-linking agent in a grinder for 10 minutes.
  • the semiconductive shielding material based on compound resin in this embodiment is obtained.
  • Example 1 Compared with Example 1, the difference in this example is that in S102, the low-density polyethylene resin is kneaded for 5 minutes, then the conductive filler is added and kneaded for 5 minutes, and finally ethylene-butyl acrylate resin is added and kneaded for 5 minutes, and then cut Granules to obtain cut pellets.
  • Example 1 Compared with Example 1, the difference in this example is that in S102, the ethylene-butyl acrylate resin is mixed for 5 minutes, then the conductive filler is added and mixed for 5 minutes, and finally the low-density polyethylene resin is added and mixed for 5 minutes, and then cut Granules to obtain cut pellets.
  • the difference in this example is that the raw materials for preparing the semiconductive shielding material based on compound resin are: 63.5 parts of compound resin, 30 parts of conductive filler and 1 part of cross-linking agent.
  • the difference in this example is that the raw materials for preparing the semiconductive shielding material based on compound resin are: 55 parts of compound resin, 20 parts of conductive filler, 1 part of dispersant, and 4.5 parts of processing aid. parts and 0.9 parts of cross-linking agent.
  • the difference in this example is that the raw materials for preparing the semiconductive shielding material based on compound resin are: 60 parts of compound resin, 25 parts of conductive filler, 1 part of dispersant, and 4.5 parts of processing aid. parts and 1.5 parts of cross-linking agent.
  • the difference in this example is that the raw materials for preparing the semiconductive shielding material based on compound resin are: 65 parts of compound resin, 30 parts of conductive filler, 1 part of dispersant, and 4.5 parts of processing aid. parts and 2 parts of cross-linking agent.
  • Example 1 Compared with Example 1, the difference of this comparative example is that the compound resin is replaced with ethylene-butyl acrylate resin.
  • the difference of this comparative example is that the raw materials for preparing the semiconductive shielding material based on compound resin are: 50 parts of compound resin, 15 parts of conductive filler and 0.5 part of cross-linking agent.
  • Example 1 Compared with Example 1, the difference of this comparative example is that the raw materials for preparing the semi-conductive shielding material based on compound resin are: 70 parts of compound resin, 35 parts of conductive filler and 2.5 parts of cross-linking agent.
  • Example 1 Compared with Example 1, the difference of this comparative example is that the raw materials for preparing the semi-conductive shielding material based on compound resin are: 63.5 parts of compound resin, 35 parts of conductive filler and 0.5 part of cross-linking agent.
  • the shielding materials obtained in the examples and comparative examples were pressed into test plates with a thickness of 1 mm. Then the test plates were tested for tensile strength, elongation at break, room temperature volume resistivity, 90°C volume resistivity and PTC coefficient. The test results are shown in Table 1.
  • the PTC coefficients of Examples 1 to 3 are smaller than Comparative Example 1, indicating that the use of compound resin can reduce the PTC effect and reduce the influence of temperature on the shielding material.
  • the overall performance of Example 1 is better, the resistivity at 23°C and the resistivity at 90°C are 8.85 ⁇ cm and 98.4 ⁇ cm respectively, and the PTC coefficient is 11.1.
  • the decrease in PTC coefficient has been greatly suppressed.
  • Example 2 the microstructure of the shielding material obtained in Example 2 was analyzed, as shown in Figure 1. It can be seen from Figure 1 that a bicontinuous phase is formed in the shielding material, and the conductive carbon black is mainly distributed in one of the phases. , indicating that the double-threshold penetration structure can suppress the PTC effect of the shielding material and enhance its conductive network.

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Abstract

一种基于复配树脂的半导电屏蔽料，其制备原料包括如下质量份数的各组分：复配树脂55份~65份、导电填料20份～30份以及交联剂0.9份~2份；其中，所述复配树脂由低密度聚乙烯树脂和乙烯-丙烯酸树脂复配而成；所述乙烯-丙烯酸树脂为乙烯-丙烯酸乙酯树脂和乙烯-丙烯酸丁酯树脂中的至少一种。

Description

基于复配树脂的半导电屏蔽料及其制备方法和应用
本申请要求于2022年08月30日提交中国专利局、申请号为2022110570792、发明名称为“基于复配树脂的半导电屏蔽料及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及高压电缆技术领域，尤其是涉及一种基于复配树脂的半导电屏蔽料及其制备方法和应用。
背景技术
随着电力工业的高速发展，高压电力电缆的生产和应用也进入了一个快速的发展期。目前，在中低电压领域，电缆半导电屏蔽料通常可以表现出较好的综合性能而稳定使用。但是当电压升高时，比如在220kV级的高压领域，电缆半导电屏蔽料的使用受到了较大的制约。其受制约的重要原因之一在于，传统的高压电缆半导电屏蔽料在使用过程中PTC系数(正的温度系数)较高，使得电缆在高压条件下运行时电阻变化幅度大，进而影响了高压电缆的稳定使用。
发明内容
基于此，有必要提供一种基于复配树脂的半导电屏蔽料及其制备方法和应用。所述基于复配树脂的半导电屏蔽料具有较低的PTC系数，可以较好地作为高压电缆半导电屏蔽料使用。
为了解决以上技术问题，本申请一实施例的技术方案为：
一种基于复配树脂的半导电屏蔽料，其制备原料包括如下质量份数的 各组分：复配树脂55份～65份、导电填料20份～30份以及交联剂0.9份～2份；其中，所述复配树脂由低密度聚乙烯树脂和乙烯-丙烯酸树脂复配而成；所述乙烯-丙烯酸树脂为乙烯-丙烯酸乙酯树脂和乙烯-丙烯酸丁酯树脂中的至少一种。
在一些实施方式中，基于复配树脂的半导电屏蔽料的制备原料包括如下质量份数的各组分：复配树脂61份～64份、导电填料25份～30份以及交联剂1份～1.5份。
在一些实施方式中，所述低密度聚乙烯树脂和所述乙烯-丙烯酸树脂的质量比为1:4～1:1。
在一些实施方式中，所述低密度聚乙烯树脂的熔融指数为0.25g/10min～2g/10min。
在一些实施方式中，所述低密度聚乙烯树脂的密度为0.918g/cm 3～0.932g/cm 3。
在一些实施方式中，所述乙烯-丙烯酸树脂的熔融指数≤10g/min。
在一些实施方式中，所述乙烯-丙烯酸树脂的断裂伸长率≥700％。
在一些实施方式中，基于复配树脂的半导电屏蔽料的制备原料还包括分散剂；所述分散剂的质量份数为0.5份～2份。
在一些实施方式中，基于复配树脂的半导电屏蔽料的制备原料还包括加工助剂；所述加工助剂的质量份数为2份～6份。
在一些实施方式中，所述加工助剂由包括如下质量份数的组分制成：偶联剂1份～2份、润滑剂1份～3份以及抗氧剂0.6份～1份。
一种上述基于复配树脂的半导电屏蔽料的制备方法，包括如下步骤：
将所述低密度聚乙烯树脂、所述乙烯-丙烯酸树脂以及所述导电填料混炼、切粒，得到切粒料；
将所述切粒料与所述交联剂混合，得到预成品；
对所述预成品进行加热处理。
在一些实施方式中，将低密度聚乙烯树脂、乙烯-丙烯酸树脂以及导电填料混炼包括如下步骤：将所述低密度聚乙烯树脂和所述乙烯-丙烯酸树脂混炼，然后加入所述导电填料继续混炼。
在一些实施方式中，所述混炼的转速为80rpm～150rpm，所述混炼的温度为150℃～180℃。
在一些实施方式中，所述加热处理的温度为50℃～70℃。
一种半导电屏蔽制品，其制备原料包括上述半导电屏蔽料或者上述制备方法制备的半导电屏蔽料。
上述基于复配树脂的半导电屏蔽料主要通过质量份数分别为55份～65份的复配树脂、20份～30份的导电填料以及0.9份～2份的交联剂制备而成。将该屏蔽料作为高压电缆半导电屏蔽料使用时，随着电缆使用过程中温度的上升，乙烯-丙烯酸树脂的熔融膨胀会被低密度聚乙烯树脂抑制，这样可以在温度上升时对导电网络起到良好的固定作用。另外，导电填料主要分布在低密度聚乙烯树脂中，在温度上升的过程中，低密度聚乙烯树脂膨胀程度较小，导电网络受温度变化的影响较小，且乙烯-丙烯酸树脂的膨胀会进一步挤压低密度聚乙烯，这样可以促进导电填料之间的接触，强化导电网络，进而降低屏蔽料的PTC系数，抑制屏蔽料的PTC效应，降低PTC效应对高压电缆使用的不利影响。
进一步地，在上述基于复配树脂的半导电屏蔽料，低密度聚乙烯树脂和乙烯-丙烯酸树脂之间存在双阈渗透效果，并且导电填料主要分布在低密度聚乙烯树脂中，当低密度聚乙烯树脂形成连续相时，能够在减少导电填料用量的基础上，获得导电能力较高的屏蔽料。
再进一步地，在制备高压电缆时，上述基于复配树脂的半导电屏蔽料与高压电缆的绝缘层的界面相容性好，可以提高半导电屏蔽料与高压电缆绝 缘层之间的结合力，使得半导电屏蔽料不易被剥离，进而可以提高高压电缆的使用寿命。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍。显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其它的附图。
图1为本申请实施例2中得到的屏蔽料的扫描电子显微镜图。
具体实施方式
为使本申请的上述目的、特征和优点能够更加明显易懂，下面结合附图对本申请的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本申请。但是本申请能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本申请内涵的情况下做类似改进，因此本申请不受下面公开的具体实施例的限制。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
本申请一实施例提供了一种基于复配树脂的半导电屏蔽料。该半导电屏蔽料的制备原料包括如下质量份数的各组分：复配树脂55份～65份、导电填料20份～30份以及交联剂0.9份～2份；其中，复配树脂由低密度聚乙烯树脂和乙烯-丙烯酸树脂复配而成；乙烯-丙烯酸树脂为乙烯-丙烯酸乙酯 树脂和乙烯-丙烯酸丁酯树脂中的至少一种。
可以理解的是，在电缆的使用过程中，树脂基体会受热膨胀，进而破坏半导电屏蔽料中的导电网格，使得半导电屏蔽料的90℃体积电阻率急剧上升，PTC系数升高，PTC效应显著增大。将本实施例中的半导电屏蔽料作为高压电缆半导电屏蔽料使用时，随着电缆使用过程中温度的上升，乙烯-丙烯酸树脂的熔融膨胀会被低密度聚乙烯树脂抑制，这样可以在温度上升时对导电网络起到良好的固定作用。另外，导电填料主要分布在低密度聚乙烯树脂中，在温度上升的过程中，低密度聚乙烯树脂膨胀程度较小，导电网络受温度变化的影响较小，且乙烯-丙烯酸树脂的膨胀会进一步挤压低密度聚乙烯，这样可以促进导电填料之间的接触，强化导电网络，进而降低屏蔽料的PTC系数，抑制屏蔽料的PTC效应，降低PTC效应对高压电缆使用的不利影响。
进一步地，在上述基于复配树脂的半导电屏蔽料，低密度聚乙烯树脂和乙烯-丙烯酸树脂之间存在双阈渗透效果，并且导电填料主要分布在低密度聚乙烯树脂中，当低密度聚乙烯树脂形成连续相时，能够在减少导电填料用量的基础上，获得导电能力较高的屏蔽料。
再进一步地，在制备高压电缆时，上述基于复配树脂的半导电屏蔽料与高压电缆的绝缘层的界面相容性好，可以提高半导电屏蔽料与高压电缆绝缘层之间的结合力，使得半导电屏蔽料不易被剥离，进而可以提高高压电缆的使用寿命。
在一个具体的示例中，低密度聚乙烯树脂的熔点高于乙烯-丙烯酸树脂的熔点。此时，可以通过低密度聚乙烯树脂对乙烯-丙烯酸树脂的熔融膨胀进行更好地抑制，进一步固定导电网络。
在一个具体的示例中，基于复配树脂的半导电屏蔽料的制备原料包括如下质量份数的各组分：复配树脂61份～64份、导电填料25份～30份以及 交联剂1份～1.5份。
在一个具体的示例中，低密度聚乙烯树脂和乙烯-丙烯酸树脂的质量比为1:4～1:1。比如，低密度聚乙烯树脂和乙烯-丙烯酸树脂的质量比为1:4、3:7、2:3或者1:1等。可理解的是，低密度聚乙烯树脂和乙烯-丙烯酸树脂的质量比还可以在1:4～1:1范围内做其他合适的选择。
进一步地，低密度聚乙烯树脂的熔融指数为0.25g/10min～2g/10min。譬如，低密度聚乙烯树脂的熔融指数为0.5g/10min、0.6g/10min、0.8g/10min、1g/10min、1.5g/10min、1.8g/10min或2g/10min等。可理解的是，低密度聚乙烯树脂的熔融指数还可以在0.25g/10min～2g/10min范围内做其他合适的选择。
可选地，低密度聚乙烯树脂的密度为0.918g/cm 3～0.932g/cm 3。譬如，低密度聚乙烯树脂的密度为0.918g/cm 3、0.92g/cm 3、0.925g/cm 3、0.928g/cm 3、0.93g/cm 3等。可理解的是，低密度聚乙烯树脂的密度还可以在0.918g/cm 3～0.932g/cm 3范围内做其他合适的选择。
在一个具体的示例中，乙烯-丙烯酸树脂的熔融指数≤10g/min。可选地，乙烯-丙烯酸树脂在190℃和2.16kg下的熔融指数≤10g/min。比如，乙烯-丙烯酸树脂在190℃和2.16kg下的熔融指数≤9g/min；乙烯-丙烯酸树脂在190℃和2.16kg下的熔融指数≤8g/min；乙烯-丙烯酸树脂在190℃和2.16kg下的熔融指数≤5g/min等。进一步地，乙烯-丙烯酸树脂的断裂伸长率≥700％。可选地，乙烯-丙烯酸树脂的断裂伸长率≥800％；乙烯-丙烯酸树脂的断裂伸长率≥900％等。
作为复配树脂的质量份数的可选示例，复配树脂的质量份数可以是但不限定为55份、56份、57份、58份、59份、60份、61份、62份、63份、64份或65份。可选地，复配树脂的质量份数也可以在55份～65份范围内做其他合适的选择。
作为导电填料的质量份数的可选示例，导电填料的质量份数可以是但不限定为20份、21份、22份、23份、24份、25份、26份、27份、28份、29份或30份。可理解的是，导电填料的质量份数也可以在20份～30份范围内作其他合适的选择。可选地，导电填料为导电炭黑。进一步可选地，导电炭黑的吸油值为130ml/100g～200ml/100g。比如，导电炭黑的吸油值为140ml/100g、150ml/100g、180ml/100g等。
作为交联剂的质量份数的可选示例，交联剂的质量份数可以是但不限定为0.9份、1份、1.1份、1.2份、1.3份、1.4份、1.5份、1.6份、1.7份、1.8份、1.9份或2份。可理解的是，交联剂的质量份数也可以在0.9份～2份范围内作其他合适的选择。可选地，交联剂为双叔丁基过氧异丙基苯和过氧化二异丙苯中的至少一种。
在一个具体的示例中，基于复配树脂的半导电屏蔽料的制备原料为如下质量份数的各组分：复配树脂55份～65份、导电填料20份～30份以及交联剂0.9份～2份；其中，复配树脂由低密度聚乙烯树脂和乙烯-丙烯酸树脂复配而成；乙烯-丙烯酸树脂为乙烯-丙烯酸乙酯树脂和乙烯-丙烯酸丁酯树脂中的至少一种。
在另一个具体的示例中，基于复配树脂的半导电屏蔽料的制备原料还包括分散剂；分散剂的质量份数为0.5份～2份。可选地，分散剂的质量份数可以是但不限定为0.5份、0.8份、1份、1.1份、1.2份、1.4份、1.5份、1.7份、1.9份或2份。可理解的是，分散剂的质量份数也可以在0.5份～2份范围内作其他合适的选择。进一步可选地，分散剂为乙撑双硬脂酰胺和油酸酰胺中的至少一种。
在另一个具体的示例中，基于复配树脂的半导电屏蔽料的制备原料还包括加工助剂；加工助剂的质量份数为2份～6份。可选地，加工助剂的质量份数可以是但不限定为2份、2.5份、3份、3.2份、3.5份、3.8份、4份、 4.2份、4.5份、4.8份、5份、5.2份、5.5份、5.8份或6份。可理解的是，加工助剂的质量份数也可以在2份～6份范围内作其他合适的选择。
具体地，加工助剂由包括如下质量份数的组分制成：偶联剂1份～2份、润滑剂1份～3份以及抗氧剂0.6份～1份。可选地，偶联剂为硅烷偶联剂。润滑剂为硬脂酸锌。抗氧剂为抗氧剂1010和抗氧剂168中的至少一种。进一步地可选地，硅烷偶联剂为KH550。抗氧剂为抗氧剂1010和抗氧剂168按质量比为(1.5～2.5):1混合而成。更进一步地，抗氧剂1010和抗氧剂168的质量比可以是但不限定为1.8:1、2:1、2.2:1、2.5:1。可选地，加工助剂由偶联剂、润滑剂以及抗氧剂混合而成。
可以理解的是，在加工助剂中，偶联剂的质量份数可以是但不限定为1份、1.2份、1.5份、1.8份或2份等。润滑剂的质量份数可以是但不限定为1份、1.2份、1.5份、1.8份、2份、2.2份、2.5份、2.8份或3份等。抗氧剂的质量份数可以是但不限定为0.6份、0.7份、0.8份、0.9份或1份等。还可以理解的是，偶联剂的质量份数也可以在1份～2份范围内做其他合适的选择，润滑剂的质量份数也可以在1份～3份范围内做其他合适的选择，抗氧剂的质量份数也可以在0.6份～1份范围内做其他合适的选择。
在一个具体的示例中，基于复配树脂的半导电屏蔽料的制备原料为如下质量份数的各组分：复配树脂55份～65份、导电填料20份～30份、交联剂0.9份～2份以及分散剂0.5份～2份；其中，复配树脂由低密度聚乙烯树脂和乙烯-丙烯酸树脂复配而成；乙烯-丙烯酸树脂为乙烯-丙烯酸乙酯树脂和乙烯-丙烯酸丁酯树脂中的至少一种。
在一个具体的示例中，基于复配树脂的半导电屏蔽料的制备原料为如下质量份数的各组分：复配树脂55份～65份、导电填料20份～30份、交联剂0.9份～2份、分散剂0.5份～2份以及加工助剂2份～6份；其中，复配树脂由低密度聚乙烯树脂和乙烯-丙烯酸树脂复配而成；乙烯-丙烯酸树脂为乙 烯-丙烯酸乙酯树脂和乙烯-丙烯酸丁酯树脂中的至少一种。
本申请还有一实施例提供了一种上述基于复配树脂的半导电屏蔽料的制备方法。该制备方法包括如下步骤：将低密度聚乙烯树脂、乙烯-丙烯酸树脂以及导电填料混炼、切粒，得到切粒料；将切粒料与交联剂混合，得到预成品；对预成品进行加热处理。
在一个具体的示例中，混炼的转速为80rpm～150rpm，混炼的温度为150℃～180℃。可选地，混炼在转矩中进行。进一步可选地，混炼的转速可以是但不限定为80rpm、90rpm、100rpm、110rpm、120rpm、130rpm或140rpm等。混炼的温度为150℃、160℃、170℃或180℃等。再进一步可选地，混炼的时间为10min～20min。比如，混炼的时间为10min、12min、15min、18min或20min等。
在一个具体的示例中，将低密度聚乙烯树脂、乙烯-丙烯酸树脂以及导电填料混炼包括如下步骤：将低密度聚乙烯树脂和乙烯-丙烯酸树脂混炼，然后加入导电填料继续混炼。进一步地，将低密度聚乙烯树脂和乙烯-丙烯酸树脂混炼4min～6min，然后加入导电填料继续混炼8min～12min。再进一步地，将低密度聚乙烯树脂和乙烯-丙烯酸树脂混炼5min，然后加入导电填料继续混炼10min。可以理解的是，将低密度聚乙烯树脂和乙烯-丙烯酸树脂混炼，以及加入导电填料继续混炼中混炼的条件可以独立选自于混炼的转速为80rpm～150rpm，混炼的温度为150℃～180℃。可选地，将低密度聚乙烯树脂和乙烯-丙烯酸树脂混炼，以及加入导电填料继续混炼中混炼的条件相同。
在一个具体的示例中，加热处理的温度为50℃～70℃。可选地，加热处理的温度为50℃、55℃、60℃、65℃、或70℃等。进一步地，加热处理的时间为5h～10h。可选地，加热处理的时间为5h、6h、7h、8h、9h或10h等。通过加热处理，可以使交联剂被切粒料充分吸收，以提高半导电屏蔽料的性 能。
在将切粒料与交联剂混合之前，还包括如下步骤：将切粒料在50℃～70℃保温。可选地，保温温度为50℃、55℃、60℃、65℃、或70℃等。再进一步地，保温时间3h～6h。可选地，保温时间为3h、4h、5h或6h等。
在将切粒料与交联剂混合之前，还包括如下步骤：对交联剂进行研磨处理。研磨时间为8min～20min。具体地，研磨时间为8min、10min、15min或20min等。可理解的是，研磨可以在研磨机中进行。
可以理解的是，在制备基于复配树脂的半导电屏蔽料中，将低密度聚乙烯树脂、乙烯-丙烯酸树脂以及导电填料混炼之前还包括如下步骤：将低密度聚乙烯树脂、乙烯-丙烯酸树脂、导电填料以及交联剂烘干以去除各原料中的水分。进一步地，将低密度聚乙烯树脂、乙烯-丙烯酸树脂、导电填料、分散剂、加工助剂以及交联剂烘干以去除各原料中的水分。
本申请还有一实施例提供了一种半导电屏蔽制品。该导电屏蔽制品的制备原料包括上述半导电屏蔽料或者上述制备方法制备的半导电屏蔽料。可选地，半导电屏蔽制品由包括上述半导电屏蔽料的原料挤出成型制成。进一步可选地，半导电屏蔽制品为半导电屏蔽套。可选地，半导电屏蔽制品为高压电缆半导电屏蔽制品。
在一个具体的示例中，半导电屏蔽制品的制备原料中还包括绝缘料。半导电屏蔽制品由包括上述半导电屏蔽料和绝缘料的原料挤出成型制成。
本申请还有一实施例提供了一种电缆，包括导体、绝缘层以及半导电屏蔽层；导体位于绝缘层的内侧，半导电屏蔽层位于绝缘层的至少一个表面；半导电屏蔽层由上述基于复配树脂的半导电屏蔽料或者上述制备方法制备的基于复配树脂的半导电屏蔽料制成。
在一个具体的示例中，半导电屏蔽层位于绝缘层的两个表面。此时，电缆包括由内到外依次设置的导体、内屏蔽层、绝缘层和外屏蔽层，其中内屏 蔽层和外屏蔽层均为半导电屏蔽层。
以下为具体实施例。
实施例1
按质量份数计，本实施例中基于复配树脂的半导电屏蔽料的制备原料为：复配树脂63.5份、导电填料30份、分散剂1份、加工助剂4.5份以及交联剂1份。其中，复配树脂为低密度聚乙烯树脂和乙烯-丙烯酸丁酯树脂，低密度聚乙烯树脂和乙烯-丙烯酸丁酯树脂的质量比为2：3，低密度聚乙烯树脂的熔融指数为0.5g/10min，低密度聚乙烯树脂的密度为0.918g/cm 3，乙烯-丙烯酸丁酯树脂在190℃和2.16kg下的熔融指数≤10g/min，乙烯-丙烯酸丁酯树脂的断裂伸长率≥700％。导电填料为导电炭黑。分散剂为乙撑双硬脂酰胺。交联剂为双叔丁基过氧异丙基苯(BIBP)。
按质量份数计，加工助剂由以下原料混合而成：偶联剂2份、润滑剂2份以及抗氧剂0.5份。其中，偶联剂为硅烷偶联剂KH550。润滑剂为硬脂酸锌。抗氧剂为抗氧剂1010和抗氧剂168按质量比为2:1混合而成。
本实施例中基于复配树脂的半导电屏蔽料的制备方法包括如下步骤：
S101：将低密度聚乙烯树脂、乙烯-丙烯酸丁酯树脂、导电炭黑、分散剂、加工助剂以及交联剂烘干以去除各原料中的水分。
S102：将低密度聚乙烯树脂、乙烯-丙烯酸丁酯树脂、分散剂以及加工助剂混炼5min，然后加入导电填料继续混炼10min、切粒，得到切粒料。其中，混炼在转矩中进行，混炼的转速为100rpm、混炼的温度为160℃。
S103：将切粒料烘干去除水分，再在60℃保温4h。
S104：将交联剂在研磨机中研磨10min。
S105：将保温之后的切粒料与研磨之后的交联剂混合，得到预成品。
S106：对预成品在60℃加热8h。
加热之后得到本实施例中的基于复配树脂的半导电屏蔽料。
实施例2
与实施例1相比，本实施例的不同之处在于，S102中，将低密度聚乙烯树脂混炼5min，再加入导电填料混炼5min，最后加入乙烯-丙烯酸丁酯树脂混炼5min、切粒，得到切粒料。
实施例3
与实施例1相比，本实施例的不同之处在于，S102中，将乙烯-丙烯酸丁酯树脂混炼5min，再加入导电填料混炼5min，最后加入低密度聚乙烯树脂混炼5min、切粒，得到切粒料。
实施例4
与实施例1相比，本实施例的不同之处在于，基于复配树脂的半导电屏蔽料的制备原料为：复配树脂63.5份、导电填料30份以及交联剂1份。
实施例5
与实施例1相比，本实施例的不同之处在于，基于复配树脂的半导电屏蔽料的制备原料为：复配树脂55份、导电填料20份、分散剂1份、加工助剂4.5份以及交联剂0.9份。
实施例6
与实施例1相比，本实施例的不同之处在于，基于复配树脂的半导电屏蔽料的制备原料为：复配树脂60份、导电填料25份、分散剂1份、加工助剂4.5份以及交联剂1.5份。
实施例7
与实施例1相比，本实施例的不同之处在于，基于复配树脂的半导电屏蔽料的制备原料为：复配树脂65份、导电填料30份、分散剂1份、加工助剂4.5份以及交联剂2份。
对比例1
与实施例1相比，本对比例的不同之处在于，将复配树脂替换成乙烯- 丙烯酸丁酯树脂。
对比例2
与实施例1相比，本对比例的不同之处在于，基于复配树脂的半导电屏蔽料的制备原料为：复配树脂50份、导电填料15份以及交联剂0.5份。
对比例3
与实施例1相比，本对比例的不同之处在于，基于复配树脂的半导电屏蔽料的制备原料为：复配树脂70份、导电填料35份以及交联剂2.5份。
对比例4
与实施例1相比，本对比例的不同之处在于，基于复配树脂的半导电屏蔽料的制备原料为：复配树脂63.5份、导电填料35份以及交联剂0.5份。
测试例
将实施例和对比例中得到的屏蔽料分别压板制成厚度为1mm的测试板。然后对测试板分别测试拉伸强度、断裂伸长率、常温体积电阻率、90℃体积电阻率以及PTC系数。测试结果如表1所示。
表1
Figure PCTCN2022139563-appb-000001
Figure PCTCN2022139563-appb-000002
由表1可知，实施例1～3的PTC系数小于对比例1，表明复配树脂的使用可以降低PTC效应，减小屏蔽料受温度的影响。其中，由表1可以看出，实施例1综合性能较优，23℃电阻率和90℃电阻率分别为8.85Ω·cm和98.4Ω·cm，PTC系数为11.1，相比于对比例1，PTC系数降低得到了大幅度抑制。
进一步地，对实施例2得到的屏蔽料进行显微结构分析，如图1所示，从图1中可以看出在屏蔽料中形成了双连续相，导电炭黑主要分布在其中一相中，表明了双阈渗透结构可以抑制屏蔽料的PTC效应，增强其导电网络。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准，说明书及附图可以用于解释权利要求的内容。

Claims (15)

  1. 一种基于复配树脂的半导电屏蔽料，其特征在于，其制备原料包括如下质量份数的各组分：复配树脂55份～65份、导电填料20份～30份以及交联剂0.9份～2份；其中，所述复配树脂由低密度聚乙烯树脂和乙烯-丙烯酸树脂复配而成；所述乙烯-丙烯酸树脂为乙烯-丙烯酸乙酯树脂和乙烯-丙烯酸丁酯树脂中的至少一种。
  2. 根据权利要求1所述的基于复配树脂的半导电屏蔽料，其特征在于，其制备原料包括如下质量份数的各组分：复配树脂61份～64份、导电填料25份～30份以及交联剂1份～1.5份。
  3. 根据权利要求1～2任一项所述的基于复配树脂的半导电屏蔽料，其特征在于，所述低密度聚乙烯树脂和所述乙烯-丙烯酸树脂的质量比为1:4～1:1。
  4. 根据权利要求1～3任一项所述的基于复配树脂的半导电屏蔽料，其特征在于，所述低密度聚乙烯树脂的熔融指数为0.25g/10min～2g/10min。
  5. 根据权利要求1～4任一项所述的基于复配树脂的半导电屏蔽料，其特征在于，所述低密度聚乙烯树脂的密度为0.918g/cm 3～0.932g/cm 3。
  6. 根据权利要求1～5任一项所述的基于复配树脂的半导电屏蔽料，其特征在于，所述乙烯-丙烯酸树脂的熔融指数≤10g/min。
  7. 根据权利要求1～6任一项所述的基于复配树脂的半导电屏蔽料，其特征在于，所述乙烯-丙烯酸树脂的断裂伸长率≥700％。
  8. 根据权利要求1～7中任一项所述的基于复配树脂的半导电屏蔽料，其特征在于，其制备原料还包括分散剂；所述分散剂的质量份数为0.5份～2份。
  9. 根据权利要求1～8中任一项所述的基于复配树脂的半导电屏蔽料，其特征在于，其制备原料还包括加工助剂；所述加工助剂的质量份数为2份～6份。
  10. 根据权利要求9所述的基于复配树脂的半导电屏蔽料，其特征在于，所述加工助剂由包括如下质量份数的组分制成：偶联剂1份～2份、润滑剂1份～3份以及抗氧剂0.6份～1份。
  11. 一种权利要求1～10任一项所述的基于复配树脂的半导电屏蔽料的制备方法，其特征在于，包括如下步骤：
    将所述低密度聚乙烯树脂、所述乙烯-丙烯酸树脂以及所述导电填料混炼、切粒，得到切粒料；
    将所述切粒料与所述交联剂混合，得到预成品；
    对所述预成品进行加热处理。
  12. 根据权利要求11所述的基于复配树脂的半导电屏蔽料的制备方法，其特征在于，将低密度聚乙烯树脂、乙烯-丙烯酸树脂以及导电填料混炼包括如下步骤：将所述低密度聚乙烯树脂和所述乙烯-丙烯酸树脂混炼，然后加入所述导电填料继续混炼。
  13. 根据权利要求11～12任一项所述的基于复配树脂的半导电屏蔽料的制备方法，其特征在于，所述混炼的转速为80rpm～150rpm，所述混炼的温度为150℃～180℃。
  14. 根据权利要求11～13任一项所述的基于复配树脂的半导电屏蔽料的制备方法，其特征在于，所述加热处理的温度为50℃～70℃。
  15. 一种半导电屏蔽制品，其特征在于，其制备原料包括权利要求1～10任一项所述的半导电屏蔽料或者权利要求11～14任一项所述的制备方法制备的半导电屏蔽料。
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