CN113583322A - Branch-resistant polyolefin-based micro-nano composite material and preparation method thereof - Google Patents

Branch-resistant polyolefin-based micro-nano composite material and preparation method thereof Download PDF

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CN113583322A
CN113583322A CN202110724556.5A CN202110724556A CN113583322A CN 113583322 A CN113583322 A CN 113583322A CN 202110724556 A CN202110724556 A CN 202110724556A CN 113583322 A CN113583322 A CN 113583322A
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composite material
resistant polyolefin
nano composite
based micro
montmorillonite
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Inventor
张晓虹
马聪聪
王玉龙
郭宁
高俊国
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Harbin University of Science and Technology
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Harbin University of Science and Technology
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    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids

Abstract

The invention discloses an electric branch-resistant polyolefin-based micro-nano composite material and a preparation method thereof, wherein the electric branch-resistant polyolefin-based micro-nano composite material is prepared by taking low-density polyethylene as a base material and taking micro montmorillonite and nano zinc oxide as inorganic fillers through a melt blending method, wherein the content of the montmorillonite is 0.5wt%, and the content of the zinc oxide is 1 wt%. The preparation method comprises the following steps: melting and blending the low-density polyethylene and the montmorillonite modified by the octadecyl ammonium salt in a torque rheometer, uniformly mixing after two minutes, and melting and blending with the nano zinc oxide particles treated by the silane coupling agent to obtain the tree-resistant polyolefin-based micro-nano composite material. The polyethylene insulating material can effectively inhibit the development of electric tree branches in a polyethylene matrix, and has important significance for prolonging the service life of the polyethylene insulating material and safely operating electric equipment.

Description

Branch-resistant polyolefin-based micro-nano composite material and preparation method thereof
Technical Field
The invention belongs to the field of dielectrics and composite materials, and particularly relates to an electric branch-resistant polyolefin-based micro-nano composite material and a preparation method thereof.
Background
With the development of nanotechnology, the function of nanoparticles in polymer-based nanocomposites can effectively improve some or many aspects of polymer performance. Research shows that in polyethylene system with semi-crystalline structure, ZnO and SiO2The introduction of the equispherical nano particles can improve the performances of space charge, breakdown and the like of polyethylene, and the introduction of the layered montmorillonite can effectively improve the treeing resistance of polyethylene. However, the nano composite material has a large specific surface area, high surface energy and extremely unstable single nano particles, and in order to stabilize the nano composite material, the nano particles are easy to attract each other to generate agglomeration, which causes that the nano composite material is not excellent in the current engineering practical application. The existing research work finds that the micron particles and the nano particles with different mesoscopic forms and different properties are blended and introduced into the polymer matrix, so that the agglomeration phenomenon of single nano particles can be effectively avoided, and the excellent characteristics of the nano particles are fully exerted, and meanwhile, the composite synergistic multifunctional characteristic is also provided. The method for improving the dielectric property of the polymer matrix by using the inorganic micro-nano particles gradually becomes a new research hotspot, and meanwhile, a new idea is provided for the modification of the insulating material.
Disclosure of Invention
Aiming at the problem that single montmorillonite particles are easy to agglomerate in a low-density polyethylene matrix, so that the effect of a montmorillonite/low-density polyethylene composite material for inhibiting the development of electric tree branches is not ideal, the invention aims to provide an electric tree-resistant polyolefin-based micro-nano composite material and a preparation method thereof, and the electric tree-resistant effect is better achieved through the composite synergistic effect between two kinds of micro-nano particles.
The invention provides an electric branch-resistant polyolefin-based micro-nano composite material and a preparation method thereof, and is characterized in that low-density polyethylene is used as a matrix, and the electric branch-resistant polyolefin-based micro-nano composite material is prepared by melt blending with modified micro montmorillonite and modified nano zinc oxide, wherein the micro montmorillonite accounts for 0.5wt% of the composite material, and the nano zinc oxide accounts for 1wt% of the composite material.
The preparation method of the branch-resistant polyolefin-based micro-nano composite material comprises the following steps:
1. opening a torque rheometer, setting the temperature to be 140 ℃, the screw rotating speed to be 40r/min, mixing time to be 20min, and starting to heat up;
2. heating to a set temperature, adding low-density polyethylene into the torque rheometer until the low-density polyethylene is completely molten, melting and blending the low-density polyethylene and the modified montmorillonite in the torque rheometer, mixing the low-density polyethylene and the modified montmorillonite uniformly after two minutes, and adding the nano zinc oxide particles for melting and blending for 20 minutes to obtain the tree-resistant polyolefin-based micro-nano composite material.
An electric branch-resistant polyolefin-based micro-nano composite material and a preparation method thereof are characterized in that a treatment method of micro montmorillonite is as follows: octadecyl ammonium salt is used as an intercalating agent to carry out pre-intercalation and organic treatment on the montmorillonite. Organic montmorillonite can be obtained through surface modification, and original inorganic cations among the sheets are replaced by long-chain organic cations with larger volume, so that the interlayer spacing of the montmorillonite is increased and the inotropic property is changed into the organophilic property.
An electric branch-resistant polyolefin-based micro-nano composite material and a preparation method thereof are characterized in that the surface modification method of nano zinc oxide comprises the following steps: the silane coupling agent is utilized to carry out surface modification on the nano zinc oxide particles, and can cover the surfaces of the nano zinc oxide particles through chemical reaction or physical adsorption under certain conditions, so that the macroscopic performance of the composite material is improved through improving the interface effect in the composite material.
The branch-resistant polyolefin-based micro-nano composite material is characterized in that the low-density polyethylene is granular and has the density of about 0.917g/cm3The melting point is 105-112 ℃.
The branch-resistant polyolefin-based micro-nano composite material is characterized in that the micro montmorillonite is in a lamellar structure by utilizing octadecyl ammonium salt as a coupling agent for pre-intercalation and organic treatment.
The branch-resistant polyolefin-based micro-nano composite material is characterized in that the nano zinc oxide is subjected to modification treatment by a silane coupling agent and calcination treatment at 600 ℃, and is spherical, the average particle size is 30nm, and the purity is 99.9%.
The branch-resistant polyolefin-based micro-nano composite material is characterized in that the structural general formula of the silane coupling agent is YSi (OR)3, wherein: y is a reactive organophilic group and OR is a hydrolyzable organophilic group.
The branch-resistant polyolefin-based micro-nano composite material is characterized by comprising the following components in parts by mass: 98.5wt% of low density polyethylene, 0.5wt% of organically treated micro montmorillonite and 1wt% of silane modified nano zinc oxide.
The invention has the following advantages:
1. the addition of two inorganic particles with different particle diameters ensures that the inorganic filler is dispersed in the polymer matrix more uniformly and is not easy to agglomerate, thereby being more beneficial to improving the dielectric property of the polymer matrix;
2. the lamellar structure of the montmorillonite has a barrier effect on the development of electric tree branches, the nano zinc oxide particles have a heterogeneous nucleation effect, the crystallinity of the low-density polyethylene can be improved, the crystalline structure is more compact, and the two have a synergistic effect with each other, so that the composite material has a better tree branch resistance characteristic.
Drawings
FIG. 1 is a DSC curve of low density polyethylene and tree-resistant polyolefin-based micro-nano composite material.
FIG. 2 is an image of the beginning of the tree formation in the low density polyethylene sample after 1 minute of pressurization.
Figure 3 is an image of electrical dendrites in a low density polyethylene sample after 10 minutes of pressurization.
Figure 4 is an image of electrical dendrites in a low density polyethylene sample after 30 minutes of pressurization.
Figure 5 images of electrical dendrites in low density polyethylene samples after 1 hour of pressurization.
Fig. 6 is an image of the beginning of tree formation in the branch-resistant polyolefin-based micro-nanocomposite sample after 1 minute of pressurization.
FIG. 7 is an image of electrical dendrites in a branch-resistant polyolefin-based micro-nano composite sample after being pressurized for 10 minutes.
FIG. 8 is an image of electrical dendrites in a branch-resistant polyolefin-based micro-nano composite sample after being pressurized for 30 minutes.
FIG. 9 is an image of electrical dendrites in a branch-resistant polyolefin-based micro-nano composite sample after being pressurized for 1 hour.
Detailed Description
The technical solutions of the present invention are further described below, but not limited thereto, and all modifications or equivalent substitutions that do not depart from the spirit and scope of the present invention should be included in the protection scope of the present invention.
The invention provides an electric branch-resistant polyolefin-based micro-nano composite material and a preparation method thereof, wherein low-density polyethylene is used as a matrix, and the electric branch-resistant polyolefin-based micro-nano composite material is prepared by melting and blending with modified micro-montmorillonite and modified nano-zinc oxide, and the preparation method comprises the following specific steps:
1. low-density polyethylene, micro montmorillonite and nano zinc oxide are treated in an oven at 60 ℃ for 24 hours in advance, and various materials are prepared according to 98.5wt% of low-density polyethylene, 0.5wt% of micro montmorillonite and 1wt% of nano zinc oxide, wherein the total weight is 40g as an example;
2. opening a torque rheometer, setting the temperature to be 140 ℃, the screw rotating speed to be 40r/min, mixing time to be 20min, and starting to heat up;
3. heating to a set temperature, adding 39.4g of low-density polyethylene into a torque rheometer until the low-density polyethylene is completely molten, adding 0.2g of modified micro-montmorillonite particles and the low-density polyethylene into the torque rheometer, uniformly mixing after 1min, adding 0.4g of modified nano-zinc oxide, mixing for 20min to obtain the branch-resistant polyolefin-based micro-nano composite material, and shearing the branch-resistant polyolefin-based micro-nano composite material into particles by using clean scissors for bagging for later use;
4. and (3) forming the composite material at 140 ℃ by using a flat vulcanizing machine, cooling and demolding to obtain the sheet for various performance tests.
The first embodiment is as follows:
and (3) testing the crystallization property: and measuring the temperature rise melting process of two samples of pure low-density polyethylene and the branch-resistant polyolefin-based micro-nano composite material by using a differential scanning calorimeter. The test is carried out under the protection of dry nitrogen, and the heating rate and the cooling rate are both set to be 10 ℃/min. Weighing about 10 mg of each of the two samples, heating the samples to 140 ℃, and cooling to 25 ℃ after the samples are completely melted so as to completely crystallize the samples. Through the above process, the influence of the thermal history on the specimen has been eliminated. And then, obtaining a curve obtained in the process of uniformly heating the sample to 140 ℃, namely a DSC heating process curve. DSC temperature rising curves of the two samples are shown in figure 1, and the difference of melting peak temperatures of the two samples is not large and is about 101 ℃; and the crystallinity of the low-density polyethylene obtained by calculation is 38.56, and the crystallinity of the tree-resistant polyolefin-based micro-nano composite material is 39.74, which is improved by 3%.
The second embodiment is as follows:
and (3) tree resistance performance test: respectively molding the branch-resistant polyolefin-based micro-nano composite material and the low-density polyethylene at 140 ℃ by using a flat vulcanizing machine, demolding to obtain a sheet with the thickness of 2mm, and further manufacturing into a square polymer thin sample to be measured, wherein the square polymer thin sample is 10 multiplied by 2 mm;
preheating two kinds of polymer thin samples to be detected and a tungsten needle in an oven at 80 ℃ for 30min, inserting the needle, coating conductive silver adhesive on the bottom surface of the sample to enable the needle point to be 2mm away from the conductive adhesive on the bottom surface, finally placing the sample in the oven at 80 ℃ for 24h, and naturally cooling to room temperature to eliminate stress concentration in the needle point area;
carrying out an electric tree initiation test on a sample in an experiment chamber, filling the experiment chamber with transparent insulating oil, enabling one end of the sample coated with a conductive adhesive to be tightly attached to a ground electrode at the bottom of the experiment chamber, applying 8 kilovolt power frequency voltage to the sample through a needle electrode at the other end of the sample, and observing the growth condition of the electric tree of the sample to be tested through an optical microscope to obtain the test results of figures 2 to 9;
fig. 2 to 5 show the electrical tree growth characteristics of the low-density polyethylene after being respectively pressurized for 1min, 10min, 30min and 1h under 8KV power frequency voltage, and fig. 6 to 9 show the electrical tree growth characteristics of the tree-resistant polyolefin-based micro-nano composite material under the same conditions. The result shows that the branch-resistant polyolefin-based micro-nano composite material prepared by the invention has obvious branch inhibition characteristic.
The needle electrode is a tungsten needle prepared by an electrochemical corrosion method in the laboratory, and the curvature radius of the needle tip is 3 +/-0.1 mu m.
The insulating oil is transparent colorless transformer oil, has low loss and better insulating property.

Claims (5)

1. The tree-resistant polyolefin-based micro-nano composite material is characterized in that the composite material is prepared by taking low-density polyethylene as a matrix material and adopting micro montmorillonite and nano zinc oxide as inorganic fillers through a melt blending method, wherein the content of the montmorillonite is 0.5wt%, and the content of the zinc oxide is 1 wt%.
2. The dendrite-resistant polyolefin-based micro-nano composite material of claim 1, wherein the modified nano zinc oxide is surface treated with a silane coupling agent, has a nominal particle size of 30nm and a purity of 99.9%.
3. The branch-resistant polyolefin-based micro-nano composite material of claim 1, wherein the modified micro montmorillonite is pre-intercalated and surface organized with octadecyl ammonium salt.
4. The branch-resistant polyolefin-based micro-nano composite material of claim 1, wherein the low density polyethylene is in the form of particles and has a density of about 0.917g/cm3The melting point is 105-112 ℃, and the melt index is 1.5.
5. The branch-resistant polyolefin-based micro-nano composite material according to claim 1, which is characterized in that the preparation process comprises the following steps:
(1) opening a torque rheometer, setting the temperature to be 140 ℃, the screw rotating speed to be 40r/min, mixing time to be 20min, and starting to heat up;
(2) and adding low-density polyethylene into the torque rheometer to be completely molten after the temperature is raised to the set temperature, melting and blending the low-density polyethylene and the modified montmorillonite in the torque rheometer, uniformly mixing the low-density polyethylene and the modified montmorillonite after two minutes, and adding the nano zinc oxide particles to be molten and blended for 20 minutes to obtain the tree-resistant polyolefin-based micro-nano composite material.
CN202110724556.5A 2021-06-29 2021-06-29 Branch-resistant polyolefin-based micro-nano composite material and preparation method thereof Pending CN113583322A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106397930A (en) * 2016-10-09 2017-02-15 哈尔滨理工大学 Polyvinyl-based micro/nano ZnO composite material and preparation technology thereof
CN106750747A (en) * 2016-11-29 2017-05-31 哈尔滨理工大学 Regulate and control the preparation method of the resistance to electricity tree nano-complex of mesoscopic structure by ultrasonic wave
CN106883486A (en) * 2017-03-14 2017-06-23 哈尔滨理工大学 A kind of polyvinyl nano composite material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106397930A (en) * 2016-10-09 2017-02-15 哈尔滨理工大学 Polyvinyl-based micro/nano ZnO composite material and preparation technology thereof
CN106750747A (en) * 2016-11-29 2017-05-31 哈尔滨理工大学 Regulate and control the preparation method of the resistance to electricity tree nano-complex of mesoscopic structure by ultrasonic wave
CN106883486A (en) * 2017-03-14 2017-06-23 哈尔滨理工大学 A kind of polyvinyl nano composite material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
RUIJIN LIAO等: "Influence of montmorillonite on electrical treeing and breakdown characteristics of low-density polyethylene", 《JOURNAL OF REINFORCED PLASTICS》 *
于广等: "无机纳米ZnO或蒙脱土颗粒掺杂对低密度聚乙烯介电性能的影响", 《复合材料学报》 *

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