CN111004426B - Heat-conducting and insulating polyethylene composite material and preparation method thereof - Google Patents
Heat-conducting and insulating polyethylene composite material and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention relates to a heat-conducting insulating polyethylene composite material and a preparation method thereof, belonging to the technical field of high polymer material processing. The invention uses silane coupling agent KH-550 to modify the silicon micropowder by dry method, and amino (-NH) is grafted on the surface of the silicon micropowder2) Then adding low-density polyethylene resin, a compatilizer, an antioxidant and a catalyst according to a formula, uniformly mixing, and extruding by using a double-screw extruder to obtain a heat-conducting insulating polyethylene composite material; by means of a compatibilizer PE-gEpoxy groups are introduced into GMA, the reaction between amino groups and the epoxy groups is utilized to enhance the connection between the polymer matrix and the inorganic filler, the phonon interface scattering is reduced, and the heat-conducting property, the insulating property and the mechanical property of the composite material are improved. The composite material has the tensile strength of 14.2-15.3 MPa and the heat conductivity of 0.68-0.77 W.m‑1·K‑1The breakdown voltage is 20.1-35.2kV · mm‑1。
Description
Technical Field
The invention belongs to the technical field of high polymer material processing, and particularly relates to a heat-conducting and insulating polyethylene composite material and a preparation method thereof.
Background
The composite material with polyethylene as base body has excellent electric insulating property, dielectric property, mechanical property, corrosion resistance and other excellent performance, and thus is one kind of common polymer material for wire and cable sheath layer and insulating layer. But the heat conductivity coefficient of the cable is low, and the cable is limited in the application of wires and cables with certain requirements on heat dissipation and energy conservation. The high heat conductivity has important significance for prolonging the service life of the wire and cable, reducing the energy consumption in the power transmission process and improving the safety of the wire and cable in the use process. At present, the method for improving the thermal conductivity of the composite material mainly comprises the steps of adding a thermal conductive filler into a matrix, modifying the filler by using a coupling agent or adding a compatilizer to improve the compatibility between the matrix and the filler, using various fillers and preparing the composite filler with a special shape to improve the heat transfer efficiency and the like.
The silicon rubber composite material is prepared by taking silver-loaded fibers and hexagonal boron nitride as heat-conducting fillers, the fillers are in bridging contact with each other, a structural form similar to a three-dimensional net shape or a long chain shape is formed in a high polymer substrate, a heat-conducting network is constructed, and an inorganic filler is treated by a silane coupling agent, so that the compatibility between a matrix and the inorganic filler is improved, and the heat-conducting property and the mechanical property of the composite material are effectively improved. The other preparation method of the heat-conducting nylon composite material takes the styrene-maleic anhydride copolymer or the maleic anhydride grafted polyphenyl ether as the compatilizer, and in the heat-conducting nylon composite material, the addition of the compatilizer increases the compatibility between the matrix and the inorganic filler, so that the heat-conducting property of the obtained nylon composite material is obviously improved.
Disclosure of Invention
The invention aims to provide a heat-conducting and insulating polyethylene composite material and a preparation method of the heat-conducting and insulating polyethylene composite material.
The heat conductivity coefficient of the heat-conducting insulating polyethylene composite material is 0.68-0.77 W.m-1·K-1Tensile strength of 14.2-15.3 MPa, breakdown voltage of 20.1-35.2kV · mm-1；
The heat-conducting insulating polyethylene composite material is prepared from the following raw materials in parts by mass: 450 portions of 490 portions of low-density polyethylene resin, 500 portions of silicon powder, 10 to 50 portions of compatilizer, 0.5 portion of antioxidant, 2.5 to 5 portions of silane coupling agent, 2 to 5 portions of catalyst,
The antioxidant is 1098F;
the silane coupling agent is KH-550;
the catalyst is 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30);
the compatilizer is polyethylene grafted glycidyl methacrylate (PE-g-GMA）；
Firstly, using silane coupling agent KH-550 to make dry modification of silicon micropowder, and grafting amino group (-NH) on the surface of silicon micropowder2) (ii) a Then adding other raw materials according to the formula, uniformly mixing, and extruding by using a double-screw extruder to obtain the heat-conducting insulating polyethylene composite material; introducing a ring by means of a compatibilizer PE-g-GMAAnd an oxygen group, which enhances the connection between the polymer matrix and the inorganic filler by means of a reaction between the amino group and the epoxy group.
The preparation operation steps of the heat-conducting and insulating polyethylene composite material are as follows:
(1) preparation of modified silica micropowder
Uniformly mixing 2.5-5 parts by mass of silane coupling agent KH-550, 2.085-4.170 parts by mass of anhydrous ethanol and 0.611-1.222 parts by mass of distilled water; hydrolyzing in water bath at 30 deg.C for 30min under stirring to obtain KH-550 hydrolysate; adding 500 parts of silicon micro powder into a high-speed mixer, heating to 100-120 ℃, adding the KH-550 hydrolysate, and continuously stirring for 30-45min to obtain modified silicon micro powder; the silicon micro powder is refined silicon micro powder with the particle size of 10 mu m;
(2) preparation of the mixture
490 portions of low-density polyethylene resin, 500 portions of modified silicon powder and 10 to 50 portions of compatilizer PE-g-Adding GMA, 0.5 part of antioxidant 1098F and 2-5 parts of catalyst DMP-30 into a high-speed mixer, and mixing for 5-6min to obtain a mixed material;
(3) preparation of heat-conducting and insulating polyethylene composite material
And adding the mixed material into a double-screw extruder for extrusion, wherein the extrusion temperature is 160-.
The beneficial technical effects of the invention are embodied in the following aspects:
1. the heat-conducting insulating polyethylene composite material prepared by the method has good mechanical property and heat-conducting insulating property, the tensile strength of the material can reach 15.3MPa, and the heat conductivity coefficient can reach 0.77 W.m-1·K-1The breakdown voltage can reach 35.2 kV.mm-1。
2. Compatibilizer PE-used in the inventiongGMA can well improve the compatibility between the polyethylene matrix and the modified silicon micropowder, so that the modified silicon micropowder is more uniformly distributed in the polyethylene matrix, a heat conduction channel is more easily formed in the composite material, and the heat conduction performance of the composite material is improved; the modified silicon micropowder can reduce the accumulation of space charge in the composite material and improve the performance after being uniformly distributed in the polyvinyl bodyBreakdown voltage of the composite material.
3. The invention uses silane coupling agent KH-550 to modify the surface of the silicon micropowder, and the surface of the silicon micropowder is connected with-NH2The added compatibilizer PE-g-GMA containing epoxy groups by-NH2And PE-gThe epoxy group on the GMA reacts, so that the modified silicon micropowder is more tightly connected with the polyethylene matrix, the phonon interface scattering is reduced, more and stable heat conduction channels are formed in the composite material, and the heat conduction performance of the polyethylene composite material is improved.
Detailed Description
The invention will now be further described with reference to specific examples.
Example 1
The raw materials used in this example were as follows: 490g of low-density polyethylene, 500g of silicon micropowder, 10g of compatilizer PE-g-GMA, 0.5g of antioxidant 1089F, 5g of silane coupling agent KH-550 and 2g of catalyst DMP-30.
The specific preparation steps of the heat-conducting and insulating polyethylene composite material are as follows:
(1) preparation of modified silica micropowder
5g of silane coupling agent KH-550, 4.170g of absolute ethyl alcohol and 1.222g of distilled water are uniformly mixed, and then hydrolyzed in water bath at 30 ℃ for 30min while stirring to obtain KH-550 hydrolysate. Then adding 500g of silicon micro powder into a high-speed mixer, heating to 100 ℃ and 120 ℃, adding the hydrolysate, and continuously stirring for 30-45min to obtain modified silicon micro powder;
(2) preparation of the mixture
Weighing 490g of low-density polyethylene, 500g of modified silicon powder, 10g of compatilizer PE-g-GMA, 2g of catalyst DMP-30 and 0.5g of antioxidant 1098F according to a certain formula, and adding into a high-speed mixer to mix for 5-6min to obtain a mixed material;
(3) preparation of heat-conducting and insulating polyethylene composite material
Adding the mixed material into a double-screw extruder to be extruded at the extrusion temperature of 160--1·K-1Breakdown voltage of 22.1kV · mm-1。
Example 2
The raw materials used in this example were as follows: 460g of low-density polyethylene, 500g of silica powder, 40g of compatilizer PE-g-GMA, 0.5g of antioxidant 1098F, 5g of silane coupling agent KH-550 and 2g of catalyst DMP-30, wherein the specific preparation steps of the heat-conducting and insulating polyethylene composite material are as follows:
(1) preparation of modified silica micropowder
5g of silane coupling agent KH-550, 4.170g of absolute ethyl alcohol and 1.222g of distilled water are uniformly mixed, and then hydrolyzed in water bath at 30 ℃ for 30min while stirring to obtain KH-550 hydrolysate. Then adding 500g of silicon micro powder into a high-speed mixer, heating to 100 ℃ and 120 ℃, adding the hydrolysate, and continuously stirring for 30-45min to obtain modified silicon micro powder;
(2) preparation of the mixture
Weighing 460g of low-density polyethylene, 500g of modified silicon micropowder, 40g of compatilizer PE-g-GMA, 2g of catalyst DMP-30 and 0.5g of antioxidant 1098F according to a certain formula, and adding into a high-speed mixer for mixing for 5-6 min;
(3) preparation of heat-conducting and insulating polyethylene composite material
Adding the mixed material into a double-screw extruder to be extruded at the extrusion temperature of 160--1·K-1Breakdown voltage of 30.4kV · mm-1。
Example 3
The raw materials used in this example were as follows: 470g of low-density polyethylene, 500g of silica micropowder, 30g of compatilizer PE-g-GMA, 0.5g of antioxidant 1098F, 2.5g of silane coupling agent KH-550 and 2g of catalyst DMP-30.
The specific preparation steps of the heat-conducting and insulating polyethylene composite material are as follows:
(1) preparation of modified silica micropowder
2.5g of silane coupling agent KH-550, 2.085g of absolute ethyl alcohol and 0.611g of distilled water are uniformly mixed, and then hydrolyzed in water bath at 30 ℃ for 30min while stirring, so as to obtain KH-550 hydrolysate. And then adding 500g of silicon micro powder into a high-speed mixer, heating to 100 ℃ and 120 ℃, adding the hydrolysate, and continuously stirring for 30-45min to obtain the modified silicon micro powder.
(2) Preparation of the mixture
470g of low-density polyethylene, 500g of modified silica powder, 30g of compatilizer PE-g-GMA, 2g of catalyst DMP-30 and 0.5g of antioxidant 1098F are weighed according to a certain formula and then added into a high-speed mixer to be mixed for 5-6 min.
(3) Preparation of heat-conducting and insulating polyethylene composite material
Adding the mixed material into a double-screw extruder to be extruded at the extrusion temperature of 160--1·K-1Breakdown voltage of 33.2kV · mm-1。
Example 4
The raw materials used in this example were as follows: 450g of low-density polyethylene, 500g of silicon micropowder, 50g of compatilizer PE-g-GMA, 0.5g of antioxidant 1098F, 5g of silane coupling agent KH-550 and 5g of catalyst DMP-30.
The specific preparation steps of the heat-conducting and insulating polyethylene composite material are as follows:
(1) preparation of modified silica micropowder
5g of silane coupling agent KH-550, 4.170g of absolute ethyl alcohol and 1.222g of distilled water are uniformly mixed, and then hydrolyzed in water bath at 30 ℃ for 30min while stirring to obtain KH-550 hydrolysate. Then adding 500g of silicon micro powder into a high-speed mixer, heating to 100-120 ℃, adding the hydrolysate, and continuously stirring for 30-45min to obtain modified silicon micro powder;
(2) preparation of the mixture
Weighing 450g of low-density polyethylene, 500g of modified silicon micropowder, 50g of compatilizer PE-g-GMA, 5g of catalyst DMP-30 and 0.5g of antioxidant 1098F according to a certain formula, and adding into a high-speed mixer for mixing for 5-6 min;
(3) preparation of heat-conducting and insulating polyethylene composite material
Adding the mixed material into a double-screw extruder for extrusion, wherein the extrusion temperature is 160-The polyethylene composite material has tensile strength of 15.1MPa and heat conductivity of 0.77 W.m-1·K-1Breakdown voltage of 28.7kV · mm-1。
Example 5
The raw materials used in this example were as follows: 480g of low-density polyethylene, 500g of silicon micropowder, 20g of compatilizer PE-g-GMA, 0.5g of antioxidant 1098F, 5g of silane coupling agent KH-550 and 5g of catalyst DMP-30.
The specific preparation steps of the heat-conducting and insulating polyethylene composite material are as follows:
(1) preparation of modified silica micropowder
5g of silane coupling agent KH-550, 4.170g of absolute ethyl alcohol and 1.222g of distilled water are uniformly mixed, and then hydrolyzed in water bath at 30 ℃ for 30min while stirring to obtain KH-550 hydrolysate. And then adding 500g of silicon micro powder into a high-speed mixer, heating to 100 ℃ and 120 ℃, adding the hydrolysate, and continuously stirring for 30-45min to obtain the modified silicon micro powder.
(2) Preparation of the mixture
480g of low-density polyethylene, 500g of modified silicon micro powder, 20g of compatilizer PE-g-GMA, 5g of catalyst DMP-30 and 0.5g of antioxidant 1098F are weighed according to a certain formula and then added into a high-speed mixer to be mixed for 5-6 min.
(3) Preparation of heat-conducting and insulating polyethylene composite material
Adding the mixed material into a double-screw extruder to be extruded at the extrusion temperature of 160--1·K-1Breakdown voltage of 25.7kV · mm-1。
Example 6
The raw materials used in this example were as follows: 470g of low-density polyethylene, 500g of silica micropowder, 30g of compatilizer PE-g-GMA, 0.5g of antioxidant 1098F, 5g of silane coupling agent KH-550 and 2g of catalyst DMP-30.
The specific preparation steps of the heat-conducting and insulating polyethylene composite material are as follows:
(1) preparation of modified silica micropowder
5g of silane coupling agent KH-550, 4.170g of absolute ethyl alcohol and 1.222g of distilled water are uniformly mixed, and then hydrolyzed in water bath at 30 ℃ for 30min while stirring to obtain KH-550 hydrolysate. Then adding 500g of silicon micro powder into a high-speed mixer, heating to 100 ℃ and 120 ℃, adding the hydrolysate, and continuously stirring for 30-45min to obtain modified silicon micro powder;
(2) preparation of the mixture
Weighing 470g of low-density polyethylene, 500g of modified silicon powder, 30g of compatilizer PE-g-GMA, 2g of catalyst DMP-30 and 0.5g of antioxidant 1098F according to a certain formula, and adding into a high-speed mixer to mix for 5-6 min;
(3) preparation of heat-conducting and insulating polyethylene composite material
Adding the mixed material into a double-screw extruder to be extruded at the extrusion temperature of 160--1·K-1Breakdown voltage of 35.2kV · mm-1。
Claims (1)
1. A heat-conducting insulating polyethylene composite material is characterized in that: the heat conductivity coefficient of the heat-conducting insulating polyethylene composite material is 0.68-0.77 W.m-1·K-1Tensile strength of 14.2-15.3 MPa, breakdown voltage of 20.1-35.2kV · mm-1；
The heat-conducting insulating polyethylene composite material is prepared from the following raw materials in parts by mass: 450 portions of 490 portions of low-density polyethylene resin, 500 portions of silicon powder, 10 to 50 portions of compatilizer, 0.5 portion of antioxidant, 2.5 to 5 portions of silane coupling agent and 2 to 5 portions of catalyst;
the antioxidant is 1098F;
the silane coupling agent is KH-550;
the catalyst is 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30);
the compatilizer is polyethylene grafted glycidyl methacrylate (PE-g-GMA）；
Firstly, using silane coupling agent KH-550 to make dry modification of silicon micropowder, and grafting amino group (-NH) on the surface of silicon micropowder2) (ii) a Then adding other materials according to the formulaThe raw materials are uniformly mixed and extruded by a double-screw extruder to obtain the heat-conducting insulating polyethylene composite material.
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| CN103613828A (en) * | 2013-11-26 | 2014-03-05 | 无锡市明珠电缆有限公司 | High-voltage direct-current cable material as well as preparation method and applications thereof |
| CN105837925A (en) * | 2016-04-22 | 2016-08-10 | 深圳市博赛新材有限公司 | Material and preparation method of heat conducting heat shrink tubing |
| KR20190125731A (en) * | 2018-04-30 | 2019-11-07 | (주) 솔루켐 | Insulation Materials Including Nano Silica And Crosslinked Polyethylene And Cables Using The Same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103613828A (en) * | 2013-11-26 | 2014-03-05 | 无锡市明珠电缆有限公司 | High-voltage direct-current cable material as well as preparation method and applications thereof |
| CN105837925A (en) * | 2016-04-22 | 2016-08-10 | 深圳市博赛新材有限公司 | Material and preparation method of heat conducting heat shrink tubing |
| KR20190125731A (en) * | 2018-04-30 | 2019-11-07 | (주) 솔루켐 | Insulation Materials Including Nano Silica And Crosslinked Polyethylene And Cables Using The Same |
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