CN106356126A - Flame-retarding cross-linked polyethylene power cable capable of being produced in large scale - Google Patents

Abstract

The invention discloses a flame-retarding cross-linked polyethylene power cable capable of being produced in a large scale. The flame-retarding cross-linked polyethylene power cable comprises four parts including a cable core (conductor), an insulating layer, a shielding layer and a protective layer in sequence from inside to outside. The power cable provided by the invention has excellent anti-ageing performance and fireproof and flame-retarding performances, has the advantages of high strength, simple preparation process and good machinable property, can meet market requirements and is worthy of being popularized.

Description

A kind of flame-retardant crosslinking polyethylene power cable that can be mass-produced

Technical field

The present invention relates to field of cable technology, more particularly, to a kind of flame-retardant crosslinking polyethylene electric power electricity that can be mass-produced Cable.

Background technology

Bigger than ac transmission transmission capacity, loss is low, cable accessory structure is simple and safeguards because having for D.C. high voltage transmission Low cost and other advantages and attention.At present, direct current transportation approach has 3 kinds: oil-filled cable transmission of electricity；Oil-paper cable power transmission；Mould Material direct current cables transmission of electricity.Oil-filled cable and oil immersion paper cable due to high cost and maintenance difficulties big the shortcomings of, application is restricted. Plastics direct current cables preparation cost is low, application prospect wide, transmits electricity and the fields such as city transmission of electricity over strait, more and more country, Especially developed country starts to research and develop plastic high voltage direct current cables, and preparing one of crucial problem of high voltage direct current cable is: straight In stream electricity transmission process, conductor can inject electronics and hole to insulating barrier, and insulating barrier easily occurs electronics or hole accumulation, is formed Space-charge effect, causes electric field distortion, when serious, electrical breakdown occurs, causes transmission of electricity accident.Therefore, find effective way suppression empty Between charge buildup, homogenizing insulating barrier Electric Field Distribution, suppression electric branch growth, extend cable service life, be to prepare high-performance Plastics direct current cables technical bottleneck urgently to be resolved hurrily.The appearing as of nanometer composite technology is prepared high-performance direct current cable and is brought newly Technological revolution, interfacial effect that nano-particle is formed due to itself dielectric property and matrix etc., composite can be improved Insulation electrical performance, numerous studies prove crosslinked polyethylene in add nano-particle can effectively suppress space charge gather, Improve breakdown strength and specific insulation, suppression electric branch growth, thus improve insulant electric property.This makes nanometer Grain/Cross-linked Polyethylene Composites increasingly receive publicity.

Author in " preparation of multi-layer mesoporous nano magnesia/LDPE Composite and its insulating properties " literary composition By hydro-thermal reaction, it is prepared for the nano magnesia with multi-layer mesoporous structure, using low boiling point solvent method, by nano magnesia Tentatively uniformly it is attached on Low Density Polyethylene particle surface, is then blended by Haake, finally prepare dispersibility preferably many Layer meso-porous nano mgo/ldpe composite, result shows that nano magnesia is dispersed in ldpe, and adds 1wt%'s The composite of multi-layer mesoporous nano magnesia, under 70kv/mm DC electric field, does not find electrode injection near both positive and negative polarity Electronics and hole, it is suppressed that the generation of heteropolarity space charge, stop the growth of electric branch, have good insulating properties, and Disruptive field intensity is significantly improved, and reduces the dielectric constant of composite, adds the multi-layer mesoporous nanometer of nano-particle in addition Mgo/ldpe composite is highly stable under high and low frequency, can meet the use under wideband, for insulant, low Dielectric constant has low polarizability, and under high electric field, polarizability is lower, and its insulation characterisitic is better, its multi-layer nano mgo/ The dielectric property of ldpe composite meets the use condition of High Performance Insulation material.Although the mgo/ldpe of preparation above is multiple Condensation material has good insulating properties and ageing resistace, but polyethylene easily decomposes at high temperature, and poor fire, combustion Burn produce smog, have great potential safety hazard, thus be directed to this shortcoming, the present invention above on the basis of be modified grinding Study carefully, the cable good, safe, applied widely to reaching practicality.

Content of the invention

The object of the invention is exactly the defect in order to make up prior art, provides a kind of flame-proof cross-linking that can be mass-produced to gather Ethylene power cable.

The present invention is achieved by the following technical solutions:

A kind of flame-retardant crosslinking polyethylene power cable that can be mass-produced, includes core (conductor), insulation from inside to outside successively Layer, screen layer and protective layer four part composition；Wherein, protective layer is made up of the raw material of following weight portion: Tissuemat E 2-4, lanthana 6.5-7, sodium hydroxide 3.8-4.2, isooctyl acid 17-18, No. 200 solvent naphtha 22-24, zinc Isoocatanoate 1.5-2, oil Sour calcium 2-2.5, PEG400 2-3, brucite 1.4-2, Ludox 4-6, No. 42 solvent naphtha 18-22, Low Density Polyethylenes 90-100, maleic anhydride 3-5, tbpo initiator 0.2-0.4, bipb cross-linking agent 1-2, polyurethane resin 20-24, sulfonated oil 2-3, Antiscorching agent ctp0.2-0.4, steel fibre 4-6, expanded vermiculite 12-15, isocyanates 2-2.4, methyl ethylene trifluoro propyl silicon rubber Glue 10-14, appropriate deionized water.

A kind of described flame-retardant crosslinking polyethylene power cable that can be mass-produced, is made up of step in detail below:

(1) lanthana is dissolved with appropriate concentrated hydrochloric acid, add deionized water according still further to mass volume ratio g:ml1:8-8.5, remove Add isooctyl acid and No. 200 solvent naphthas after going precipitation, start to stir, rise high-temperature to 80 DEG C, add 40wt% sodium hydroxide water Solution, is incubated 40-60min after being added dropwise to complete, after being cooled to room temperature, stratification, oil reservoir is washed to not chloride ion-containing, reduces pressure It is standby that dehydration obtains isocaprylic acid lanthanum；

(2) Ludox, PEG400 mixing are added in the dehydrated alcohol of 6-7 times amount, are stirring evenly and then adding into brucite thin Powder, ultrasonic disperse is uniform, then product prepared by zinc Isoocatanoate, calcium oleate, No. 42 solvent naphthas and step (1) is added to above-mentioned mixing In thing, rise high-temperature to 110-120 DEG C of back flow reaction 2-3h, reduce temperature and remove solid impurity to decompression sucking filtration when 50 DEG C, from So it is cooled to room temperature；

(3) expanded vermiculite is added to ultrasonic agitation in the deionized water of 9-10 times amount and obtains suspension, then be added thereto to carboxylic acid Base glycine betaine, controls temperature at 60-75 DEG C and continues stirring 40-50min, filter, solid is dried at 105 DEG C in an oven, then By organically-modified expanded vermiculite and the mixing of isocyanates heated and stirred, at 35-45 DEG C, rotating speed is 600-800r/ to temperature control Min, adds silane coupler kh550 after stirring 30-50min, is cooled to room temperature after continuing stirring 0.6-1h；

(4) 15% Low Density Polyethylene, methyl ethylene trifluoro propyl silicone rubber and maleic anhydride are added at a high speed according to charge ratio Stir in mixer, stirring 10-15min after add Tissuemat E stirring 4-7min, then in mixture add steel fibre, Product prepared by step (3) and tbpo initiator are mediated in kneader, are extruded with extruder, extruder temperature after being sufficiently mixed It is set to 135-145 DEG C, obtain modified compatilizer standby；

(5) product prepared by the product prepared remaining Low Density Polyethylene, polyurethane resin, step (2), step (4) and In addition to bipb cross-linking agent, remaining remaining material mixing, melts compound, prepared nano-complex on torque rheometer, then will Nano-complex and bipb cross-linking agent melt blending on a mill, then in vulcanizing press by complex in temperature be 140-150 DEG C, pressure is hot-forming under 15-20mpa obtaining final product.

The invention has the advantage that the requirement increasing to cable covering with the output of power cable material HVDC is got over Come higher, and polyethylene is susceptible to decompose at high temperature, conventional method is to add stabilizer and antioxidant, with ring Protect the enhancing of consciousness it is necessary to reduce using heavy metal stabilizers such as leaded, cadmiums, the present invention utilizes the rare earth resources of China's abundant, And the toxicity of rare earth is relatively low, all there is improvement to the optics of material, mechanical property, so generating using rare earth modified calcium zinc Complex stabilizer, and form the compound of modification using the formation mixed sols such as Ludox, brucite and complex stabilizer blending Stabilizer, not only increases the heat stability of polyethylene, also improves light stability, weatherability and the anti-flammability of polyethylene, profit With expanded vermiculite is heat-insulated, insulation, nontoxic and chemically inert feature as the filler of cable, improve that PE cable is inflammable, have Cigarette, the defect of non-refractory, are difficult scattered problem for solving expanded vermiculite, using carboxylic acid group's glycine betaine in macromolecular material Modification makes its activity improve, then by one layer of isocyanate-reactive molecule of its surface attachment, carries out crosslinking with silane coupler, generates Modified filler can be uniform, stable be embedded in macromolecule matrix material, given play to the performance of itself, improved cable Combination property；Prepare compatilizer using maleic anhydride etc., and add steel fibre and filler is supported in compatilizer, improve The compatibility in polyethylene for the filler and reinforcing, the addition of modified compatilizer not only improves filler, reinforced resin and matrix The compatibility of resin, improves the dispersity of filler and increased interfacial adhesion, reduce the generation that interfacial stress is concentrated, this Invention provide power cable there is excellent ageing resistace, fire resistant flame retardant performance, and intensity height, preparation process is simple, Processability is good, disclosure satisfy that the demand in market, is worthy to be popularized.

Specific embodiment

A kind of flame-retardant crosslinking polyethylene power cable that can be mass-produced, include successively from inside to outside core (conductor), Insulating barrier, screen layer and protective layer four part composition；Wherein, protective layer is by the raw material preparation system of following weight portion (kilogram) Become: Tissuemat E 2, lanthana 6.5, sodium hydroxide 3.8, isooctyl acid 17, No. 200 solvent naphthas 22, zinc Isoocatanoate 1.5, calcium oleates 2nd, PEG400 2, brucite 1.4, Ludox 4, No. 42 solvent naphthas 18, Low Density Polyethylene 90, maleic anhydride 3, tbpo Initiator 0.2, bipb cross-linking agent 1, polyurethane resin 20, sulfonated oil 2, antiscorching agent ctp0.2, steel fibre 4, expanded vermiculite 12, different Cyanate 2, methyl ethylene trifluoro propyl silicone rubber 10, appropriate deionized water.

A kind of described flame-retardant crosslinking polyethylene power cable that can be mass-produced, is made up of step in detail below:

(1) lanthana is dissolved with appropriate concentrated hydrochloric acid, add deionized water according still further to mass volume ratio g:ml1:8, it is heavy to remove Add isooctyl acid and No. 200 solvent naphthas behind shallow lake, start to stir, rise high-temperature to 80 DEG C, add 40wt% sodium hydroxide water-soluble Liquid, is incubated 40min after being added dropwise to complete, after being cooled to room temperature, stratification, oil reservoir is washed to not chloride ion-containing, decompression dehydration Obtain isocaprylic acid lanthanum standby；

(2) Ludox, PEG400 mixing are added in the dehydrated alcohol of 6 times amount, are stirring evenly and then adding into brucite thin Powder, ultrasonic disperse is uniform, then product prepared by zinc Isoocatanoate, calcium oleate, No. 42 solvent naphthas and step (1) is added to above-mentioned mixing In thing, rise high-temperature to 110 DEG C of back flow reaction 2h, reduce temperature and remove solid impurity, natural cooling to decompression sucking filtration when 50 DEG C To room temperature；

(3) expanded vermiculite is added to ultrasonic agitation in the deionized water of 9 times amount and obtains suspension, then it is sweet to be added thereto to carboxylic acid group Dish alkali, controls temperature at 60 DEG C and continues stirring 40min, filter, solid is dried at 105 DEG C in an oven, then will be organically-modified Expanded vermiculite and isocyanates heated and stirred mixing, temperature control at 35 DEG C, rotating speed be 600r/min, stirring 30min after plus Enter silane coupler kh550, after continuing stirring 0.6h, be cooled to room temperature；

(4) 15% Low Density Polyethylene, methyl ethylene trifluoro propyl silicone rubber and maleic anhydride are added at a high speed according to charge ratio Stir in mixer, add Tissuemat E stirring 4min after stirring 10min, then add steel fibre, step in mixture (3) product prepared and tbpo initiator are mediated in kneader, are extruded with extruder, extruder temperature is arranged after being sufficiently mixed For 135 DEG C, obtain modified compatilizer standby；

(5) product prepared by the product prepared remaining Low Density Polyethylene, polyurethane resin, step (2), step (4) and In addition to bipb cross-linking agent, remaining remaining material mixing, melts compound, prepared nano-complex on torque rheometer, then will Nano-complex and bipb cross-linking agent melt blending on a mill, then in vulcanizing press by complex in temperature be 140 DEG C, pressure is hot-forming under 15mpa obtaining final product.

According to the cable material of embodiment preparation, performance test is carried out to it, result is as follows:

Tensile strength (mpa): 34；Elongation at break (%): 473；Impact strength (j/m): 388；Specific insulation (ω cm): 6.9×10⁵；Dielectric strength (mv/m): 27；Oxygen index (OI): 33.

Claims (2)

1. a kind of flame-retardant crosslinking polyethylene power cable that can be mass-produced is it is characterised in that include line from inside to outside successively Core (conductor), insulating barrier, screen layer and protective layer four part composition；Wherein, protective layer is by the raw material preparation of following weight portion Make: Tissuemat E 2-4, lanthana 6.5-7, sodium hydroxide 3.8-4.2, isooctyl acid 17-18, No. 200 solvent naphtha 22-24, different Zinc octoate 1.5-2, calcium oleate 2-2.5, PEG400 2-3, brucite 1.4-2, Ludox 4-6, No. 42 solvent naphtha 18- 22nd, Low Density Polyethylene 90-100, maleic anhydride 3-5, tbpo initiator 0.2-0.4, bipb cross-linking agent 1-2, polyurethane resin 20-24, sulfonated oil 2-3, antiscorching agent ctp0.2-0.4, steel fibre 4-6, expanded vermiculite 12-15, isocyanates 2-2.4, methyl second Thiazolinyl trifluoro propyl silicone rubber 10-14, appropriate deionized water.

2. according to claim 1 a kind of flame-retardant crosslinking polyethylene power cable that can be mass-produced it is characterised in that by Step is made in detail below:

(1) lanthana is dissolved with appropriate concentrated hydrochloric acid, add deionized water according still further to mass volume ratio g:ml1:8-8.5, remove Add isooctyl acid and No. 200 solvent naphthas after going precipitation, start to stir, rise high-temperature to 80 DEG C, add 40wt% sodium hydroxide water Solution, is incubated 40-60min after being added dropwise to complete, after being cooled to room temperature, stratification, oil reservoir is washed to not chloride ion-containing, reduces pressure It is standby that dehydration obtains isocaprylic acid lanthanum；

(2) Ludox, PEG400 mixing are added in the dehydrated alcohol of 6-7 times amount, are stirring evenly and then adding into brucite thin Powder, ultrasonic disperse is uniform, then product prepared by zinc Isoocatanoate, calcium oleate, No. 42 solvent naphthas and step (1) is added to above-mentioned mixing In thing, rise high-temperature to 110-120 DEG C of back flow reaction 2-3h, reduce temperature and remove solid impurity to decompression sucking filtration when 50 DEG C, from So it is cooled to room temperature；

(3) expanded vermiculite is added to ultrasonic agitation in the deionized water of 9-10 times amount and obtains suspension, then be added thereto to carboxylic acid Base glycine betaine, controls temperature at 60-75 DEG C and continues stirring 40-50min, filter, solid is dried at 105 DEG C in an oven, then By organically-modified expanded vermiculite and the mixing of isocyanates heated and stirred, at 35-45 DEG C, rotating speed is 600-800r/ to temperature control Min, adds silane coupler kh550 after stirring 30-50min, is cooled to room temperature after continuing stirring 0.6-1h；

(4) 15% Low Density Polyethylene, methyl ethylene trifluoro propyl silicone rubber and maleic anhydride are added at a high speed according to charge ratio Stir in mixer, stirring 10-15min after add Tissuemat E stirring 4-7min, then in mixture add steel fibre, Product prepared by step (3) and tbpo initiator are mediated in kneader, are extruded with extruder, extruder temperature after being sufficiently mixed It is set to 135-145 DEG C, obtain modified compatilizer standby；

(5) product prepared by the product prepared remaining Low Density Polyethylene, polyurethane resin, step (2), step (4) and In addition to bipb cross-linking agent, remaining remaining material mixing, melts compound, prepared nano-complex on torque rheometer, then will Nano-complex and bipb cross-linking agent melt blending on a mill, then in vulcanizing press by complex in temperature be 140-150 DEG C, pressure is hot-forming under 15-20mpa obtaining final product.