CN105778233A - High-strength nanometer magnesia doped polyethylene direct-current cable composite material and preparing method thereof - Google Patents

High-strength nanometer magnesia doped polyethylene direct-current cable composite material and preparing method thereof Download PDF

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Publication number
CN105778233A
CN105778233A CN201610246992.5A CN201610246992A CN105778233A CN 105778233 A CN105778233 A CN 105778233A CN 201610246992 A CN201610246992 A CN 201610246992A CN 105778233 A CN105778233 A CN 105778233A
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parts
nano
nanometer
composite material
magnesium oxide
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CN201610246992.5A
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Chinese (zh)
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祝春菊
祝永芳
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Anhui Zhong Hong Cable Co Ltd
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Anhui Zhong Hong Cable Co Ltd
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Priority to CN201610246992.5A priority Critical patent/CN105778233A/en
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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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • 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
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

Abstract

The invention discloses a high-strength nanometer magnesia doped polyethylene direct-current cable composite material. The composite material is prepared from, by weight, 8-10 parts of ethyl alcohol, 2-2.5 parts of nanometer rubber fiber, 0.3-0.5 part of sodium borohydride, 1.5-1.6 parts of acrylic acid graft-modified CR/SBS, 10-11 parts of nanometer magnesia, 90-91 parts of polyethylene, 30-35 parts of N,N-dimethylformamide, 200-220 parts of 20% sulfuric acid solution, 100-120 parts of perfluoro caprylic acid, 23-27 parts of nanometer polytetrafluoroethylene micro powder, 70-75 parts of chloroform, 2.4-2.5 parts of methyl methacrylate, 0.1-0.2 part of potassium peroxodisulfate and 1.5-1.6 parts of nonionic boric acid ester. Nano-powder is modified through nanometer rubber fiber and acrylic acid graft-modified CR/SBS, so that the tensile strength and crack resistance of the composite material are improved; the abrasion resistance and oxidation resistance of the composite material are improved through sodium borohydride.

Description

A kind of high-strength nano magnesium oxide doping polyethylene direct current cables composite and preparation method thereof
Technical field
The present invention relates to CABLE MATERIALS technical field, particularly relate to a kind of high-strength nano magnesium oxide doping polyethylene direct current cables composite and preparation method thereof.
Background technology
Mixed nanometer has been widely used for improving the heat conductivility of material, mechanical property, electrical property etc..In recent decades, initial micron particle, micro-nano particle it is compound to nano-particle doping and makes material property be promoted further, develop many novel special type function materials.In insulant field, mixed nanometer improves the electrical property of material and is also gradually paid attention to.Currently, saving the energy has become the important step of social development, and traditional ac transmission is owing in electric energy course of conveying, loss is big, adnexa is complicated, high in cost of production shortcoming, and direct current transportation can make up these shortcomings.Direct current transportation has three kinds of modes: oil-filled cable is transmitted electricity；Oil-paper cable power transmission；Plastics direct current cables is transmitted electricity.Wherein plastics direct current cables has powerful potentiality, is mainly used in transmission of electricity over strait, Urban Underground power grid construction etc..But plastic cable is when direct current transportation, it may occur that conductor injects electronics and hole to insulating barrier, and insulating barrier is owing to being inhomogeneous medium, easily it is susceptible to electronics or hole accumulation, forms Space-charge effect, cause electric field distortion, there is electrical breakdown time serious, cause transmission of electricity accident.The application of mixed nanometer technology, provides direction for solving plastics direct current cables space charge accumulation problems.
Research shows, adds a small amount of nano-particle ZnO, TiO in insulated cable material2、SiO2Deng, a space charge accumulation difficult problem can be improved.Research finds, adds nano-particle and can effectively suppress space charge to gather in crosslinked polyethylene (XLPE), improves breakdown strength and specific insulation, suppression electric branch growth, improves the electric property of insulant.This makes nano-particle/XLPE composite more and more concerned, and people are referred to as third generation insulant.At present, Japanese Scientists has successfully passed and has added a small amount of MgO in polyethylene, prepares the high voltage direct current cable of 250kV/mm and 500kV/mm, is just waiting that business is applied.Also there is the nano modification CABLE MATERIALS of commercialization in DOW company of the U.S..But, how the mechanism that space charge gathers is suppressed for nano-particle, does not the most also have consistent conclusion.
Research shows, adds a small amount of nano-particle ZnO, TiO in insulated cable material2、SiO2Deng, a space charge accumulation difficult problem can be improved.Research finds, adds nano-particle and can effectively suppress space charge to gather in crosslinked polyethylene (XLPE), improves breakdown strength and specific insulation, suppression electric branch growth, improves the electric property of insulant.This makes nano-particle/XLPE composite more and more concerned, and people are referred to as third generation insulant.At present, Japanese Scientists has successfully passed and has added a small amount of MgO in polyethylene, prepares the high voltage direct current cable of 250kV/mm and 500kV/mm, is just waiting that business is applied.Also there is the nano modification CABLE MATERIALS of commercialization in DOW company of the U.S..But, how the mechanism that space charge gathers is suppressed for nano-particle, does not the most also have consistent conclusion.
" preparation of nano-MgO doping polyethylene direct current cables composite and performance " literary composition obtains the MgO granule on surface not hydroxyl (OH) by heat treatment method, mother material is used to be prepared for 10wt%MgO/ polyethylene (LDPE) composite, and have studied MgO/LDPE composite space charge characteristic under 70kV/mm DC electric field, have evaluated the method effect scattered to nano-particle and industrial applications promotional value.Additionally, be investigated MgO surface hydroxylation (OH) to the nano-MgO granule doping space charge characteristic of LDPE, alternating temperature specific insulation and the impact of dielectric property, and probe into MgO suppression space charge mechanism.
But 10 wt% MgO/ polyethylene (LDPE) composites that this article uses mother material to prepare can absorb moisture in wet environment, magnesium hydroxide can be generated, affect the space charge characteristic of composite, alternating temperature specific insulation and dielectric property, need to improve.Additionally the thermostability of this composite, soil resistance, static electricity resistance, toughness, intensity need to improve.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of high-strength nano magnesium oxide doping polyethylene direct current cables composite and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of high-strength nano magnesium oxide doping polyethylene direct current cables composite, it is prepared by the raw materials in: ethanol 8-10, nano-rubber fiber 2-2.5, sodium borohydride 0.3-0.5, acrylic graft-modified CR/SBS1.5-1.6, nano magnesia 10-11, polyethylene 90-91, N, N '-dimethyl Methanamide 30-35, the sulfuric acid solution 200-220 of 20%, perfluoro caprylic acid 100-120, nanometer polytetrafluoroethylcomposite micropowder 23-27, chloroform 70-75, methyl methacrylate 2.4-2.5, potassium peroxydisulfate 0.1-0.2, nonionic borate 1.5-1.6.
The preparation method of described high-strength nano magnesium oxide doping polyethylene direct current cables composite, comprises the following steps:
(1) nano magnesia and perfluoro caprylic acid are carried out being mixed to join N, in N '-dimethyl Methanamide, ultrasonic 30-35 minute, drip sulfuric acid solution the most while stirring, be again heated to 80-85 DEG C of stirring reaction 20-30 minute, after terminating reaction, filtering, vacuum drying obtains fluorinated nano magnesium oxide；
(2) fluorinated nano magnesium oxide mixes with nanometer polytetrafluoroethylcomposite micropowder, joins in chloroform, ultrasonic disperse 1-1.2h, and volatilization removes chloroform, is dried to obtain nanometer powder；
(3) nano-rubber fiber is joined in ethanol, stir, add acrylic graft-modified CR/SBS, it is heated to 75-78 DEG C, continue stirring to ethanol to be evaporated completely, mix homogeneously with methyl methacrylate, sodium borohydride, nonionic borate, described nanometer powder again, add potassium peroxydisulfate mix homogeneously, obtain mixed material；
(4) mixed material (3rd) step obtained and other surplus stocks, send in high-speed mixer and mix, mix homogeneously at 135-140 DEG C, then through pelletize and get final product.
The invention have the advantage that nano magnesia is fluorinated by the present invention, Nano microsphere is made with nanometer polytetrafluoroethylcomposite micropowder, prevent CABLE MATERIALS water suction magnesium oxide from becoming magnesium hydroxide and affect the specific insulation of composite, improve the breakdown strength of composite, and improve the dispersibility of nano magnesia, reduce agglomeration, improve the lubricity of composite；Re-use methyl methacrylate, nonionic borate is modified, and improves the compatibility of nanometer powder and polyethylene, prevent powder body and sub polyethylene from, intensity reduces.By using nano-rubber fiber, acrylic graft-modified CR/SBS that nano-powder is modified, improve the compatibility of nano-powder and polyethylene, and improve tensile strength and the crack resistance of composite；By using sodium borohydride can improve the wearability of composite, improve non-oxidizability.
Detailed description of the invention
A kind of high-strength nano magnesium oxide doping polyethylene direct current cables composite, it is made up of the raw material of following weight portion (kilogram): ethanol 8, nano-rubber fiber 2, sodium borohydride 0.3, acrylic graft-modified CR/SBS1.5, nano magnesia 10, polyethylene 90, N, the sulfuric acid solution 200 of N '-dimethyl Methanamide 30,20%, perfluoro caprylic acid 100, nanometer polytetrafluoroethylcomposite micropowder 23, chloroform 70, methyl methacrylate 2.4, potassium peroxydisulfate 0.1, nonionic borate 1.5.
The preparation method of described high-strength nano magnesium oxide doping polyethylene direct current cables composite, comprises the following steps:
(1) nano magnesia and perfluoro caprylic acid are carried out being mixed to join N, in N '-dimethyl Methanamide, ultrasonic 30 minutes, drip sulfuric acid solution the most while stirring, be again heated to 80 DEG C of stirring reactions 20 minutes, after terminating reaction, filtering, vacuum drying obtains fluorinated nano magnesium oxide；
(2) fluorinated nano magnesium oxide mixes with nanometer polytetrafluoroethylcomposite micropowder, joins in chloroform, ultrasonic disperse 1h, and volatilization removes chloroform, is dried to obtain nanometer powder；
(3) nano-rubber fiber is joined in ethanol, stir, add acrylic graft-modified CR/SBS, it is heated to 75 DEG C, continue stirring to ethanol to be evaporated completely, mix homogeneously with methyl methacrylate, sodium borohydride, nonionic borate, described nanometer powder again, add potassium peroxydisulfate mix homogeneously, obtain mixed material；
(4) mixed material (3rd) step obtained and other surplus stocks, send in high-speed mixer and mix, mix homogeneously at 135 DEG C, then through pelletize and get final product.
The fusing point of this embodiment composite is 113 DEG C, under 70kV/mm electric field, does not occur that space charge gathers in pressurization 90min, and dielectric constant is 2.29；Carry out Mechanics Performance Testing, be fabricated to the sample of thickness 3 mm and test for oxygen index (OI), knot test result be hot strength be 27MPa, elongation at break is 268%, and oxygen index (OI) is 37.9, electrical strength is 45MV/m.

Claims (2)

1. a high-strength nano magnesium oxide doping polyethylene direct current cables composite, it is characterized in that: be prepared by the raw materials in: ethanol 8-10, nano-rubber fiber 2-2.5, sodium borohydride 0.3-0.5, acrylic graft-modified CR/SBS1.5-1.6, nano magnesia 10-11, polyethylene 90-91, N, N '-dimethyl Methanamide 30-35, the sulfuric acid solution 200-220 of 20%, perfluoro caprylic acid 100-120, nanometer polytetrafluoroethylcomposite micropowder 23-27, chloroform 70-75, methyl methacrylate 2.4-2.5, potassium peroxydisulfate 0.1-0.2, nonionic borate 1.5-1.6.
The preparation method of high-strength nano magnesium oxide doping polyethylene direct current cables composite the most according to claim 1, it is characterised in that comprise the following steps:
(1) nano magnesia and perfluoro caprylic acid are carried out being mixed to join N, in N '-dimethyl Methanamide, ultrasonic 30-35 minute, drip sulfuric acid solution the most while stirring, be again heated to 80-85 DEG C of stirring reaction 20-30 minute, after terminating reaction, filtering, vacuum drying obtains fluorinated nano magnesium oxide；
(2) fluorinated nano magnesium oxide mixes with nanometer polytetrafluoroethylcomposite micropowder, joins in chloroform, ultrasonic disperse 1-1.2h, and volatilization removes chloroform, is dried to obtain nanometer powder；
(3) nano-rubber fiber is joined in ethanol, stir, add acrylic graft-modified CR/SBS, it is heated to 75-78 DEG C, continue stirring to ethanol to be evaporated completely, mix homogeneously with methyl methacrylate, sodium borohydride, nonionic borate, described nanometer powder again, add potassium peroxydisulfate mix homogeneously, obtain mixed material；
(4) mixed material (3rd) step obtained and other surplus stocks, send in high-speed mixer and mix, mix homogeneously at 135-140 DEG C, then through pelletize and get final product.
CN201610246992.5A 2016-04-20 2016-04-20 High-strength nanometer magnesia doped polyethylene direct-current cable composite material and preparing method thereof Pending CN105778233A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1417249A (en) * 2002-12-13 2003-05-14 清华大学 Composite polyolefin/sio2 nano particle and its prepn
CN1654488A (en) * 2005-01-26 2005-08-17 清华大学 Process for preparing reaction functional macromolecule/Al2O3 nano composite particles
CN101440163A (en) * 2007-11-22 2009-05-27 中国科学院兰州化学物理研究所 Preparation of polytetrafluorethylene nano-microsphere
CN103834332A (en) * 2014-03-25 2014-06-04 南京承佑树脂有限公司 SBS (styrene-butadiene-styrene)-neoprene graft polymerization composite adhesive and preparation method thereof
CN104910495A (en) * 2015-06-19 2015-09-16 国网智能电网研究院 High-voltage direct-current cable material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1417249A (en) * 2002-12-13 2003-05-14 清华大学 Composite polyolefin/sio2 nano particle and its prepn
CN1654488A (en) * 2005-01-26 2005-08-17 清华大学 Process for preparing reaction functional macromolecule/Al2O3 nano composite particles
CN101440163A (en) * 2007-11-22 2009-05-27 中国科学院兰州化学物理研究所 Preparation of polytetrafluorethylene nano-microsphere
CN103834332A (en) * 2014-03-25 2014-06-04 南京承佑树脂有限公司 SBS (styrene-butadiene-styrene)-neoprene graft polymerization composite adhesive and preparation method thereof
CN104910495A (en) * 2015-06-19 2015-09-16 国网智能电网研究院 High-voltage direct-current cable material and preparation method thereof

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Application publication date: 20160720