CN102532636A - Nanometer modified water-tree resistant polyolefin composition - Google Patents
Nanometer modified water-tree resistant polyolefin composition Download PDFInfo
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Abstract
The invention provides a polyolefin resin composition which comprises polyolefin and hydrophilic nanometer inorganic oxide powder, wherein the polyolefin resin composition has a water-tree growth speed of 0.08-0.25 mm/day, a dielectric strength of 38-100 MV/mm, and a dielectric loss tangent of 0-5.0*10<-4>. The invention also provides an insulating material for cables and a cable. The polyolefin resin composition, the insulating material containing the polyolefin resin composition, and the cable provided by the invention have strong water-tree resistance, good dielectric properties and applicability, and the problem of additive precipitation for cables during application is prevented.
Description
Technical field
The present invention relates to a kind of polyolefine resin composition, also relate to comprise this resin combination cable with insulating material and cable.
Background technology
Crosslinked polyethylene (XLPE) because of advantages such as its performance are remarkable, ME is simple, maintenance is easy, has obtained widespread use in electrical power trans mission/distribution system since the fifties comes out.
People just find plastic cable insulation layer dendritic discharge channel of its inner meeting generation tree under the effect of electric field and water as far back as the sixties in last century, are called the water tree.Water tree meeting continued growth along with the increase of time finally causes insulation layer breakdown, becomes the early stage major reason of damaging of cable.
The water tree catabiosis of XLPE cable mainly can reduce following some: just water tree can take place when there is the power and water field simultaneously in (1), even under lower electric field, also water tree can take place; (2) water tree is that diameter is gathered at 0.1 to several μ m water-filled air gap; (3) the local high electric field position that the inhomogeneous place of outer semiconductor layer forms in impurity, pore and the Surface Insulation that exists in the insulation is the starting point that water tree takes place; (4) under alternating-electric field than under DC electric field, more being easy to generate water tree, ac frequency is high more, the speed of growth is fast more; Water tree takes place when (5) temperature is high easily.
Along with the research of water tree is carried out extensively and profoundly constantly; Adopt the method for many raising cable long term life characteristics, comprised the processing condition of the insulating material of the anti-water tree effect of employing, the construction of cable that extrudes semi-conductive screen, design waterproof and improvement insulation manufacturing etc.
People have proposed the method for many improvement insulating material water tree resistant properties, and these methods can reduce two types: first method is with having the additive of affinity interaction to mix with polymer materials to obtain anti-water tree characteristic with the polymer materials molecular chain.This method is representative with Dow Chemical company.Second method is the character that changes polymer materials itself, promptly changes polymer molecular structure, polymer architecture form, perhaps adopts the blend of various polymerization thing material, perhaps adopts polymer alloy.This method uses polyolefine supplier Borealis to be representative with the topmost cable in Europe.
At present people have adopted multiple measure to solve the water tree problem in the Insulation Material, comprise that the method for using additives polyethylene glycol (PEG) improves the water tree resistant property of Insulation Material.Though yet various technology before have certain effect aspect the anti-Shui Shu, electrical properties such as processing characteristics of Insulation Material (separating out problem) and dielectric loss but are affected.Thereby in Insulation Material, add different additive in order to obtain the needed various performances of power cable during production; In order to guarantee ability very compatible between additive and the base material; Must add solubilizing agent again, so not only have influence on the purity of cable insulation material, change the aggregated structure of original polymer materials simultaneously to a great extent; Thereby influenced performance of products, be difficult in and reach a kind of suitable balance between the various performances.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art; A kind of polyolefine resin composition is provided; This polyolefine resin composition comprises polyolefine and hydrophilic nano inorganic oxide powder, and wherein, the water of the said polyolefine resin composition tree speed of growth is 0.08-0.25mm/ days; Dielectric strength is 38-100MV/mm, and dielectric loss angle tangent is in 0-5 * 10
-4
Another object of the present invention is to provide a kind of cable to use insulating material, and this cable insulation material comprises polyolefine resin composition of the present invention.
Another object of the present invention is to provide a kind of cable, and this cable comprises that cable of the present invention uses insulating material.
According to polyolefine resin composition provided by the invention, can change the inner crystalline structure of polyolefine material on the one hand through in polyolefine, adding the hydrophilic nano inorganic oxide powder, make the speed of growth of water tree slow down; On the other hand, because the wetting ability of nano inorganic oxide makes that water is difficult for accumulating in together.Thereby can make this material have stronger water tree resistant property, dielectric properties and suitability preferably, and can prevent the cable problem such as separate out of additive in use.Polyolefine resin composition provided by the invention and cable insulation material and cable; The related request of the complete National standard JB/T10437-2004 of its performance " electric wire is used the crosslinkable polyethylene Insulation Material "; And its water tree length compares with the common cable material and can reduce by 40～60%, and have better manufacturability can and suitability.
Description of drawings
Fig. 1 is water tree culture experiment schematic representation of apparatus.
Embodiment
Term as used herein " Vilaterm " is meant the homopolymer of ethene.
Polyolefine resin composition provided by the invention comprises polyolefine and hydrophilic nano inorganic oxide powder, and based on 100 mass parts polyolefine, the content of said hydrophilic nano inorganic oxide powder is 0.2-20 mass parts, preferred 0.5-5 mass parts.
According to polyolefine resin composition of the present invention,, can improve the inner crystalline structure of polyolefine on the one hand through in polyolefine, adding the hydrophilic nano inorganic oxide powder; A spot of inorganic nano material plays a part nucleator, and incorgruous nucleation has improved percent crystallinity, and nano material is dispersed in the polymkeric substance; Preoccupy those free volume part and large-sized traps; Thereby reduce the number of free volume, and deep trap is converted into shallow trap, make the speed of growth of water tree slow down; On the other hand because the wetting ability of this inorganic oxide powder, thereby make water be difficult for accumulating in together, reduced the speed of growth of water tree.Thereby can make this material have stronger water tree resistant property, dielectric properties and suitability preferably, and can prevent the cable problem such as separate out of additive in use.Prolonged the work-ing life of cable thus widely.
According to polyolefine resin composition provided by the invention; Under preferable case; In order to overcome the easy agglomeration of hydrophilic nano inorganic oxide powder; This powder is disperseed in hydrophobic polyolefine more equably, and said hydrophilic nano inorganic oxide powder can be the hydrophilic nano inorganic oxide powder of crossing with coupling agent treatment.The mass ratio of said hydrophilic nano inorganic oxide powder and said coupling agent is unrestricted, for example can be 100: 0.5-3.0, be preferably 100: 0.8-2.0.
Said coupling agent can be coupling agent usually used in this field, for example at least a in titanate coupling agent, silane coupling agent, stearic acid coupling agent, aluminium esters of gallic acid coupling agent, rare-earth coupling agent, aluminium titanium composite coupler, the zirconium aluminate coupling agent.Wherein, owing to the reasons such as influence that after coupling agent price and the coupling agent adding product the subject of knowledge and the object of knowledge produced, preferably this coupling agent is titanate coupling agent, silane coupling agent and stearic acid coupling agent.
With coupling agent the hydrophilic nano inorganic oxide powder is carried out the surface-treated method and can adopt the whole bag of tricks well known by persons skilled in the art; The hydrophilic nano powder of for example ethanolic soln (30-60 quality %) and the high temperature (under 200-250 ℃) of coupling agent being handled evenly stirred 10-20 minute under 70-150 ℃ temperature.
Above-mentioned titanate coupling agent can be selected from least a in sec.-propyl three (stearyl-) titanic acid ester, sec.-propyl three (different capryloyl) titanic acid ester, sec.-propyl three (decanoyl) titanic acid ester, sec.-propyl three oily acyloxy titanic acid ester, sec.-propyl three (dodecyl benzenesulfonyl) titanic acid ester.Said titanate coupling agent can be through being purchased acquisition.
Above-mentioned silane coupling agent can be selected from least a in chain alkyl Trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-chloropropyl triethoxysilane, two-[γ-(triethoxysilicane) propyl group] tetrasulfide, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicon, the γ-mercaptopropyl trimethoxysilane.Said silane coupling agent can be through being purchased acquisition.
According to polyolefine resin composition provided by the invention, be easy to homodisperse in order to make the hydrophilic nano inorganic oxide powder, the particle diameter of said hydrophilic nano inorganic oxide powder be preferably 1-100nm, more preferably 30-70nm, most preferably be 50-70nm.
Above-mentioned hydrophilic nano inorganic oxide powder can be the inorganic oxide powder of various possess hydrophilic properties, and preferably this powder is selected from least a in zinc oxide, Natural manganese dioxide, aluminum oxide, the silicon-dioxide.Wherein silicon-dioxide can be fumed silica and solid phase method silicon-dioxide.Above-mentioned hydrophilic nano inorganic oxide powder can be through being purchased acquisition.
Under preferable case; Polyolefine resin composition provided by the invention can also contain polyoxyethylene glycol; Polyoxyethylene glycol and hydrophilic nano inorganic oxide powder have synergy to suppressing the Shui Shu aspect, thereby strengthen the anti-water tree effect of polyolefine resin composition of the present invention.Generally, based on 100 mass parts polyolefine resin compositions, the content of said polyoxyethylene glycol can be the 0.5-10 mass parts.
According to polyolefine resin composition provided by the invention, said polyolefine can be selected from the conventional polyolefine that uses of those skilled in the art, and under the preferable case, this polyolefinic density is generally 0.860-0.950g/cm
3, 0.870-0.930g/cm more preferably
3, melting index is approximately 0.1-50g/10min, is preferably 1-5g/10min, more preferably 1.5-3g/10min (190 ℃, 2.16kg).
Said polyolefine can be for having 3-12, the ethylene copolymer of the copolymerization of ethylene copolymer, ethene and (methyl) propenoate of the alhpa olefin copolymerization of preferred 4-8 carbon atom or their mixture as the Vilaterm of Alathon, ethene and at least a.Alhpa olefin can be propylene, 1-butylene, 1-hexene, 4 Methyl-1-pentenes, 1-octene.The therein ethylene multipolymer includes but not limited at least a in ethylene-propylene copolymer, ethylene-butene copolymer, vinyl-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer and the ethylene-methyl acrylate copolymer.Wherein, the content of vinyl monomer can be the 80-98% molar percentage in this multipolymer.
Polyolefine among the present invention can be homogeneous phase or out-phase.The polyolefinic molecular weight distributing index of homogeneous phase (Mw/Mn) scope is at 1.5-3 and have well-proportioned comonomer distribution, shows as 105 ℃ of single relatively low fusing points.The molecular weight distributing index of heterophasic polyolefin (Mw/Mn) is greater than 3.5, and the polymer monomers skewness.
In said polyolefins; Preferably polyethylene; And more preferably new LDPE (film grade) or linear low density polyethylene; This new LDPE (film grade) or linear low density polyethylene can for example adopt Oil of Shanghai Petrochemical Company (DJ210, DJ200A) through being purchased acquisition, raise sub-BASF petrochemical industry (2220H), import Iran's petrochemical industry (2102TX00) etc.
According to polyolefine resin composition provided by the invention, under preferable case, said polyolefine resin composition can also comprise primary antioxidant, with the oxidation resistant ability of improvement polyolefine resin composition, thus the work-ing life of prolongation cable.The content of said primary antioxidant can be the normally used various content of those skilled in the art, and generally, the content of said primary antioxidant is the 0.2-0.6 mass parts based on 100 mass parts polyolefine.
Above-mentioned primary antioxidant can be selected various oxidation inhibitor usually used in this field for use; Four [methyl-β-(3 for example; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester (antioxidant 1010), 4; 4 '-thiobis (6-tertiary butyl meta-cresol) (antioxidant 300), DBPC 2,6 ditertiary butyl p cresol (antioxidant 264), 2,2 '-at least a in methylene-bis-(4-methyl-6-tert butyl phenol) (antioxidant 2246).Above-mentioned primary antioxidant can be through being purchased acquisition.
According to polyolefine resin composition provided by the invention, under preferable case, said polyolefine resin composition can also comprise auxiliary antioxidant.The content of said auxiliary antioxidant can be the normally used various content of those skilled in the art, and generally, the content of said auxiliary antioxidant is the 0.05-0.2 mass parts based on 100 mass parts polyolefine.
Above-mentioned auxiliary antioxidant can be selected auxiliary antioxidant usually used in this field for use; For example be selected from three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters (phosphite ester kind antioxidant 168), Tyox B (organic sulfide DLTP) and thio-2 acid SUNSOFT Q-182S (organic sulfide DSTP).Above-mentioned auxiliary antioxidant can be through being purchased acquisition.
According to polyolefine resin composition provided by the invention, in order to improve the thermotolerance of said composition, under preferable case, said polyolefine resin composition also comprises initiator.The content of said initiator can be the normally used content of those skilled in the art, and generally, the content of said initiator is the 1-3 mass parts based on 100 mass parts polyolefine.
Above-mentioned initiator can for example can be the peroxide initiator for usually used in this field in order to improve the stable on heating initiator of resin.Said peroxide initiator can comprise inorganic peroxide and organo-peroxide.
Said inorganic peroxide initiator can be used as aqueous solution polymerization, letex polymerization, and the example of inorganic peroxide initiator includes but not limited to hydrogen peroxide, ammonium persulphate or Potassium Persulphate etc.; Said organic peroxide evocating agent can cause the polymerization of vinyl monomers such as the sulfuration, vinylchlorid, vinylbenzene of polymerization, the rubber of unsaturated polyester, and organic peroxide evocating agent includes but not limited to Lucidol, the Lucidol tert-butyl ester, methylethyl ketone peroxide and Di Cumyl Peroxide 99.Above-mentioned initiator can be through being purchased acquisition.
According to polyolefine resin composition provided by the invention; Under preferable case; Said composition can also be included in conventional other additive that uses in this area; For example nucleator (can make polyolefinic crystal littler, thereby make its physicals uniformity), thermo-stabilizer, photostabilizer, UV absorption agent, lubricant, processing aid, fire retardant and static inhibitor etc.Above-mentioned auxiliary agent can be through being purchased acquisition.
The consumption of above-mentioned other additive based on 100 mass parts polyolefine can be for the 0.05-5.0 mass parts, be preferably the 0.5-2.0 mass parts.
The water of said polyolefine resin composition is set length and is 0-2.5mm/15 days, is preferably 0-1.5mm/15 days, and the water tree speed of growth is 0.08-0.25mm/ days, and dielectric strength is 38-100MV/mm, is preferably 40-70MV/mm that dielectric loss angle tangent is 0-5.0 * 10
-4
The preparation method of polyolefine resin composition of the present invention can adopt the whole bag of tricks commonly used in this area; For example (1) in high mixer for example under 70-150 ℃ temperature with coupling agent and the mixing of hydrophilic nano inorganic oxide powder 10-20 minute, so that the hydrophilic nano inorganic oxide powder is carried out surface treatment; (2) under 120-130 ℃ temperature; The part hydrophilic nano inorganic oxide powder and the part polyolefine that in Banbury mixer, will carry out after the surface treatment carry out the mixing masterbatch of processing, and making hydrophilic nano inorganic oxide powder content is the 2-30 quality % of polyolefine amount; (3) the hydrophilic nano inorganic oxide powder after the surface treatment of resulting masterbatch and residual content and polyolefine and primary antioxidant, auxiliary antioxidant, initiator and optional at least a other additive of residual content are mixed by proportion scale; Under 90-125 ℃, extruding pelletization in twin screw extruder for example.
Employed high mixer, Banbury mixer, twin screw extruder etc. all can adopt the conventional equipment that uses in this area in aforesaid method.
Application Areas to polyolefine resin composition of the present invention has no particular limits, and comprising needs the various fields of insulating, like the manufacturing of the sheet material of cable sheath or sheath.This resin combination especially is suitable for cable sheath or sheath.
The present invention also provides cable to use insulating material, and this cable insulation material comprises the said polyolefins resin combination.
The present invention also provides cable, and this cable comprises that above-mentioned cable uses insulating material.
Adopt the mode of embodiment below, technical scheme of the present invention is described further.Yet these embodiment do not constitute limitation of the scope of the invention.Various device that is adopted in following examples and raw material are commercial equipment and raw material.
Embodiment 1
Employed poly density is 0.910g/cm
3, melting index be 2.0g/10min (190 ℃, 2.16kg).
1, the hydrophilic nano inorganic oxide powder is carried out surface treatment
With 100 mass parts particle diameters is the Natural manganese dioxide of 50nm and titanate coupling agent sec.-propyl three (stearyl-) titanic acid ester of 2 mass parts, in high mixer, mixes 15 minutes down at 120 ℃, obtains the magnesium oxide powder after the surface treatment.
2, the preparation of polyolefine resin composition
(1) magnesium oxide powder after pre-mixing Vilaterm and the surface treatment is processed masterbatch
In Banbury mixer, the magnesium oxide powder after the Vilaterm of 3800 mass parts and the 1200 mass parts surface treatments is mixed under 125 ℃, making the content of the magnesium oxide powder after the surface treatment is 24% of total mass, obtains masterbatch.
(2) acquisition of polyolefine resin composition
With 90 mass parts Vilaterm, the above-mentioned masterbatch that obtains of 10 mass parts, 0.2 mass parts antioxidant 300,0.1 mass parts oxidation inhibitor DSTP, 2 mass parts initiator Di Cumyl Peroxide 99s together in twin screw extruder under 110 ℃ temperature extruding pelletization, obtain polyolefine resin composition.
Embodiment 2
Employed poly density is 0.910g/cm
3, melting index be 2.0g/10min (190 ℃, 2.16kg).
1, the hydrophilic nano inorganic oxide powder is carried out surface treatment
The zinc oxide that with 100 mass parts particle diameters is 50nm mixed under 120 ℃ 15 minutes in high mixer with the silane coupling agent vinyl triethoxyl silane of 0.8 mass parts, obtained the Zinc oxide powder after the surface treatment.
2, the preparation of polyolefine resin composition
(1) Zinc oxide powder after pre-mixing Vilaterm and the surface treatment is processed masterbatch
In Banbury mixer, the Zinc oxide powder after the Vilaterm of 95 mass parts and the 5 mass parts surface treatments is mixed under 120 ℃, making the content of the Zinc oxide powder after the surface treatment is total mass 5%, obtains masterbatch.
(2) acquisition of polyolefine resin composition
With the Zinc oxide powder of the above-mentioned masterbatch that obtains after 80 mass parts Vilaterm, 17.5 mass parts surface treatments, 0.35 mass parts antioxidant 300,0.2 mass parts oxidation inhibitor DSTP, 2 mass parts initiator Di Cumyl Peroxide 99s in twin screw extruder under 110 ℃ temperature extruding pelletization, obtain polyolefine resin composition.
Embodiment 3
1, the hydrophilic nano inorganic oxide powder is carried out surface treatment
The aerosil powder that with 100 mass parts particle diameters is 50nm mixed under 120 ℃ 15 minutes in high mixer with the silane coupling agent vinyl triethoxyl silane of 0.8 mass parts, obtained the aerosil powder after the surface treatment.
2, the preparation of polyolefine resin composition
(1) magnesium oxide powder after pre-mixing Vilaterm and the surface treatment is processed masterbatch
In Banbury mixer, the aerosil powder after the Vilaterm of 95 mass parts and the 5 mass parts surface treatments is mixed under 130 ℃, making the content of the aerosil powder after the surface treatment is 5% of total mass, obtains masterbatch.
(2) acquisition of polyolefine resin composition
With the aerosil powder of the above-mentioned masterbatch that obtains after 80 mass parts Vilaterm, 8 mass parts surface treatments, 1 mass parts antioxidant 300,0.15 mass parts oxidation inhibitor DSTP, 2 mass parts initiator Di Cumyl Peroxide 99s in twin screw extruder under 90 ℃ temperature extruding pelletization, obtain polyolefine resin composition.
Embodiment 4
1, the hydrophilic nano inorganic oxide powder is carried out surface treatment
The Natural manganese dioxide that with 100 mass parts particle diameters is 50nm mixed under 120 ℃ 15 minutes in high mixer with titanate coupling agent sec.-propyl three (stearyl-) titanic acid ester of 2 mass parts, obtained the magnesium oxide powder after the surface treatment.
2, the preparation of polyolefine resin composition
(1) magnesium oxide powder after pre-mixing Vilaterm and the surface treatment is processed masterbatch
In Banbury mixer, the magnesium oxide powder after the Vilaterm of 90 mass parts and the 5 mass parts surface treatments and the polyoxyethylene glycol of 5 mass parts are mixed under 125 ℃, making the content of the magnesium oxide powder after the surface treatment is 5% of total mass, obtains masterbatch.
(2) acquisition of polyolefine resin composition
With the magnesium oxide powder order material of the above-mentioned masterbatch that obtains after 90 mass parts Vilaterm, 10 mass parts surface treatments, 1 mass parts antioxidant 300,0.1 mass parts oxidation inhibitor DSTP, 2 mass parts initiator Di Cumyl Peroxide 99s in twin screw extruder under 110 ℃ temperature extruding pelletization, obtain polyolefine resin composition.
Embodiment 5
In not using embodiment 4 in the step 2 polyoxyethylene glycol in (1) step, with embodiment 4 in identical method prepare polyolefine resin composition (in order to relatively to add the effect before and after the polyoxyethylene glycol).
Comparative example 1
In twin screw extruder, under 125 ℃ temperature, the new LDPE (film grade) of 97.8 quality %, the initiator Di Cumyl Peroxide 99 of 2 quality % and the antioxidant 300 of 0.2 quality % are extruded and granulation, obtain polyolefine resin composition.
Performance test
1, the preparation of sample
Getting polyolefine resin composition and be placed on the vulcanizing press, is 190 ℃ at crosslinking temperature, and oil press pressure is under the 15MPa, is cooled to room temperature then.Respectively make II type dumb-bell shape, thickness is each a slice of coupons of 1.0 ± 0.1mm and 4 ± 0.1mm, coupons is should be smooth bright and clean, thickness evenly, no bubble.
2, the testing method of sample performance
(1) density
The above-mentioned sample for preparing is tested by the regulation among the GB/T 1033.
(2) tensile strength velocity of variation and elongation at break velocity of variation after tensile strength, elongation at break, the thermal ageing
Employing is shaped as II type dumb-bell shape, thickness is the coupons of (1.0 ± 0.1) mm, according to the regulation among the GB/T 1040, with draw speed tested for tensile strength and the elongation at break experiment of (250 ± 50) mm/min.The air chest temperature is 135 ℃, and thermal aging time is 168 hours.
(3) heat is extended elongation and cooling back permanent set down
Employing is shaped as II type dumb-bell shape, thickness is the coupons of (1.0 ± 0.1) mm, carries out heat according to the regulation among the GB/T 5470 and extends experiment.Temperature is 200 ℃, loads to be that 0.2MPa, stretching time are 15 minutes.
(4) specific inductivity and dielectric loss angle tangent
Adopting thickness is the coupons of (1.0 ± 0.1) mm, carries out relative permittivity and dielectric dissipation factor test according to the regulation among the GB/T 1409.
(5) volume specific resistance
Adopting thickness is the coupons of (1.0 ± 0.1) mm, tests according to the regulation among the GB/T 1410.
(6) dielectric strength
Adopting thickness be the coupons of (1.0 ± 0.1) mm, and the employing electrode diameter is 25mm, and the arc radius of electrode edge is the symmetry electrode of 2.5mm, carries out the test of dielectric strength according to the regulation among the GB/T1408.1-1999.Experiment should be near 2.3 with the transformer oil relative permittivity, and enough dielectric strengths are arranged.Initial experimental voltage is zero, can boost with speed faster from 0 to 6kV, and until puncture, rate of pressure rise should be not more than 3kV/S from 6kV.
(7) water tree length and water tree relative length
Adopting thickness is the coupons of (4.0 ± 0.1) mm, and the experiment of water tree is carried out in the experiment of water tree in water tree culture apparatus in water tree culture apparatus as shown in Figure 1.Wherein, 1 is high voltage terminal, and 2 is coupons, and 3 for diameter is the pin hole of 3mm, and 4 is semiconductor varnish, and 5 is the NaCl aqueous solution, and 6 is lid.
Water tree device high pressure termination output voltage is no less than 7kv, and frequency is 1kHz, and output rating is no less than the high-frequency and high-voltage sine-wave power of 3kVA.The volumetric molar concentration of the NaCl aqueous solution is 0.1mol/L.
Resulting polyolefine resin composition in the foregoing description 1-5 and the comparative example 1 is prepared coupons by the method for making sample in the above-mentioned performance test, and carry out performance test according to above-mentioned testing method, the result sees table 1.
Table 1
Can find out by last table data; YJ-35 requirement among the embodiment 1-3 among the complete conformance with standard JB/T 10437-2002 of performance resulting and polyolefine resin composition " electric wire is used the crosslinkable polyethylene Insulation Material ", and its water tree length is compared the about 50%-60% of reduction with the common cable material.In addition, can find out that magnesium oxide powder is suppressing to have synergy with polyoxyethylene glycol in the growth of water tree, makes anti-water tree effect more excellent from embodiment 4 and 5.
Claims (17)
1. polyolefine resin composition, this polyolefine resin composition comprises polyolefine and hydrophilic nano inorganic oxide powder,
Wherein, the water of the said polyolefine resin composition tree speed of growth is 0.08-0.25mm/ days, and dielectric strength is 38-100MV/mm, and dielectric loss angle tangent is 0-5.0 * 10
-4
2. polyolefine resin composition according to claim 1, based on 100 mass parts polyolefine, the content of said hydrophilic nano inorganic oxide powder is the 0.2-20 mass parts.
3. polyolefine resin composition according to claim 1 and 2; Wherein, The inorganic oxide powder of said hydrophilic nano inorganic oxide powder for crossing with coupling agent treatment, the mass ratio of said hydrophilic nano inorganic oxide powder and said coupling agent is 100: 0.5-3; Said coupling agent is selected from least a in titanate coupling agent, silane coupling agent, stearic acid coupling agent, aluminium esters of gallic acid coupling agent, rare-earth coupling agent, aluminium titanium composite coupler, the zirconium aluminate coupling agent.
4. according to claim 1,2 or 3 described polyolefine resin compositions, wherein, the particle diameter of said hydrophilic nano inorganic oxide powder is 1-100nm.
5. according to each described polyolefine resin composition among the claim 1-4, wherein, said hydrophilic nano inorganic oxide powder is selected from least a in zinc oxide, Natural manganese dioxide, aluminum oxide, the silicon-dioxide.
6. polyolefine resin composition according to claim 1 and 2, wherein, said polyolefinic density is 0.860-0.950g/cm
3, melting index be 0.1-50g/10min (190 ℃, 2.16kg).
7. polyolefine resin composition according to claim 6; Wherein, said polyolefine is Vilaterm, ethene and at least a ethylene copolymer, ethene and ethylene copolymer of (methyl) acrylic ester copolymer or their mixture with alhpa olefin copolymerization of 3-12 carbon atom as Alathon.
8. polyolefine resin composition according to claim 7, wherein, said polyolefine is new LDPE (film grade) or linear low density polyethylene.
9. according to each described polyolefine resin composition among the claim 1-8, wherein, said polyolefine resin composition also contains polyoxyethylene glycol, and based on 100 mass parts polyolefine, the content of said polyoxyethylene glycol is the 0.5-10 mass parts.
10. according to each described polyolefine resin composition among the claim 1-9, wherein, said polyolefine resin composition also comprises primary antioxidant, and based on 100 mass parts polyolefine, the content of said primary antioxidant is the 0.2-0.6 mass parts.
11. polyolefine resin composition according to claim 10; Wherein, Said primary antioxidant be selected from four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, 4,4 '-thiobis (6-tertiary butyl meta-cresol), 2; 6-ditertbutylparacresol, 2,2 '-at least a in methylene-bis-(the 4-methyl-6-tert butyl phenol).
12. according to each described polyolefine resin composition among the claim 1-11, wherein, said polyolefine resin composition also comprises auxiliary antioxidant, and based on 100 mass parts polyolefine, the content of said auxiliary antioxidant is the 0.05-0.2 mass parts.
13. polyolefine resin composition according to claim 12, wherein, said auxiliary antioxidant is selected from three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, Tyox B and thio-2 acid SUNSOFT Q-182S.
14. according to each described polyolefine resin composition among the claim 1-13, wherein, said polyolefine resin composition also comprises initiator, based on 100 mass parts polyolefine, the content of said initiator is the 1-3 mass parts.
15. polyolefine resin composition according to claim 14; Said initiator is selected from the peroxide initiator, and this peroxide initiator is selected from least a in hydrogen peroxide, ammonium persulphate, Potassium Persulphate, Lucidol, the Lucidol tert-butyl ester, methylethyl ketone peroxide and the Di Cumyl Peroxide 99.
16. a cable is used insulating material, this cable insulation material comprises each described polyolefine resin composition among the claim 1-15.
17. a cable, this cable comprise that the described cable of claim 16 uses insulating material.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911417A (en) * | 2012-10-16 | 2013-02-06 | 濮阳市义达塑料化工有限公司 | Water-tree-retardant crosslinkable polyethylene cable material compound and preparation method thereof |
| CN103400639A (en) * | 2013-08-12 | 2013-11-20 | 句容骏成电子有限公司 | Insulating material on inner surface of glass and application of same |
| CN105111564A (en) * | 2015-08-31 | 2015-12-02 | 无锡市嘉邦电力管道厂 | Water tree resistant cross-linked polyethylene (XLPE) insulating material used below 35KV and preparation method thereof |
| CN107189154A (en) * | 2017-05-23 | 2017-09-22 | 江苏德威新材料股份有限公司 | A kind of water resistant tree processes for chemically crosslinked polyethylene Insulation Material |
| CN110024051A (en) * | 2017-10-25 | 2019-07-16 | 住友电气工业株式会社 | Biaxial cable and multicore cable |
| CN110305387A (en) * | 2019-07-12 | 2019-10-08 | 无锡工艺职业技术学院 | A kind of high pressure fire-resistant cable material and preparation method thereof |
| CN116457899A (en) * | 2021-01-29 | 2023-07-18 | 住友电气工业株式会社 | Resin composition and power cable |
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| US20090090536A1 (en) * | 2005-07-01 | 2009-04-09 | Do-Hyun Park | Flame retardant composition for cable covering material and ocean cable using the same |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911417A (en) * | 2012-10-16 | 2013-02-06 | 濮阳市义达塑料化工有限公司 | Water-tree-retardant crosslinkable polyethylene cable material compound and preparation method thereof |
| CN103400639A (en) * | 2013-08-12 | 2013-11-20 | 句容骏成电子有限公司 | Insulating material on inner surface of glass and application of same |
| CN103400639B (en) * | 2013-08-12 | 2016-04-06 | 句容骏成电子有限公司 | A kind of insulating material of interior surfaces of glass and application thereof |
| CN105111564A (en) * | 2015-08-31 | 2015-12-02 | 无锡市嘉邦电力管道厂 | Water tree resistant cross-linked polyethylene (XLPE) insulating material used below 35KV and preparation method thereof |
| CN107189154A (en) * | 2017-05-23 | 2017-09-22 | 江苏德威新材料股份有限公司 | A kind of water resistant tree processes for chemically crosslinked polyethylene Insulation Material |
| CN107189154B (en) * | 2017-05-23 | 2020-09-04 | 江苏德威新材料股份有限公司 | Water tree resistant chemical crosslinked polyethylene insulating material |
| CN110024051A (en) * | 2017-10-25 | 2019-07-16 | 住友电气工业株式会社 | Biaxial cable and multicore cable |
| CN110305387A (en) * | 2019-07-12 | 2019-10-08 | 无锡工艺职业技术学院 | A kind of high pressure fire-resistant cable material and preparation method thereof |
| CN116457899A (en) * | 2021-01-29 | 2023-07-18 | 住友电气工业株式会社 | Resin composition and power cable |
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Address after: 311305 No. 63, South Ring Road, Ling'an Economic Development Zone, Zhejiang Applicant after: Zhejiang Wanma Macromolecule Material Co., Ltd. Address before: 311305 No. 63, South Ring Road, Ling'an Economic Development Zone, Zhejiang Applicant before: Zhejiang Wanma Macromolecule Material Co., Ltd. |
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Application publication date: 20120704 |