CN103319774B - Crosslinkable inorganic nano LDPE/SiOx polymer composites - Google Patents
Crosslinkable inorganic nano LDPE/SiOx polymer composites Download PDFInfo
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- CN103319774B CN103319774B CN201310269709.7A CN201310269709A CN103319774B CN 103319774 B CN103319774 B CN 103319774B CN 201310269709 A CN201310269709 A CN 201310269709A CN 103319774 B CN103319774 B CN 103319774B
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- 229920001684 low density polyethylene Polymers 0.000 title claims abstract description 48
- 239000004702 low-density polyethylene Substances 0.000 title claims abstract description 48
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 229920000642 polymer Polymers 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 36
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- -1 pentaerythritol ester Chemical class 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims abstract description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims abstract description 4
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical group OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003490 Thiodipropionic acid Substances 0.000 claims abstract description 4
- WHKRHWSQMCFENF-UHFFFAOYSA-N [Si].OCCO Chemical compound [Si].OCCO WHKRHWSQMCFENF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229930016911 cinnamic acid Natural products 0.000 claims abstract description 4
- 235000013985 cinnamic acid Nutrition 0.000 claims abstract description 4
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 4
- 235000019303 thiodipropionic acid Nutrition 0.000 claims abstract description 4
- 239000002114 nanocomposite Substances 0.000 claims description 21
- 238000009792 diffusion process Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 33
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 15
- 229920000573 polyethylene Polymers 0.000 description 15
- 239000004698 Polyethylene Substances 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000004154 testing of material Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- SAEZBIIRXDZCAB-UHFFFAOYSA-N 1,1,1-trimethoxyoctane Chemical compound CCCCCCCC(OC)(OC)OC SAEZBIIRXDZCAB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A kind of crosslinkable inorganic nano LDPE/SiOx polymer composites and preparation method thereof, comprise organic silicon sol, Low Density Polyethylene, primary antioxidant, auxiliary antioxidant and linking agent, described organic silicon sol is ethylene glycol silicon sol, primary antioxidant is four [B-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is thiodipropionic acid dilauryl cinnamic acid ester, and linking agent is dicumyl peroxide.Instant invention overcomes the existing bad dispersibility prepared olefin polymerization nanometer composite material and exist, the problems such as particle aggregation is serious, adopt molten-molten blending method successfully to obtain SiO
xsize of particles is the crosslinkable SiO of 55nm ~ 100nm
x/ LDPE nano-cable material, effectively prevents the reunion of inorganic particulate, significantly better than crosslinkable SiO
2/ LDPE nano-cable material contrasts.
Description
Technical field
The present invention relates to polymer inorganic nano composite material technical field, refer in particular to a kind of crosslinkable inorganic nano LDPE/ SiOx polymer composites.
Background technology
Compared with polyethylene, crosslinkable polyethylene nano composite material has excellent electric property (as high in breaking down field strength, volume specific resistance is high) and mechanical property, has become one of focus of electric wire and cable material area research.But, inorganic nano-particle and polyethylene interfacial energy differ greatly, poor compatibility, easy generation secondary agglomeration, and, under high temperature fused state, the easy decomposition causing linking agent of mixing produces crosslinked, is difficult to the crosslinkable polyethylene nano composite material being prepared into nano-scale dispersion, can not improves electric property and mechanical property.In order to make nano polythene composite material, usual employing coupling agent processes inorganic nano-particle sub-surface, to increase and poly consistency, melt blending, prepare nano polythene composite material, because polyethylene viscosity is comparatively large, nanoparticle dispersion difficulty, reunite more serious, simultaneously add linking agent easily produce when melting mixing plumage be cross-linked, affect performance, crosslinkable Polyethylene Nanocomposites can not be prepared; Huang utilizes trimethoxy octane coupling agent treatment silicon-dioxide (SiO
2), then toluene by process silicon oxide particle chloroform in, meanwhile, LLDPE is dissolved in 100 DEG C of xylene solvents, makes solution; At 100 DEG C, two kinds of solution mixing, then use methanol extraction, 140 DEG C, the nano polythene composite material of good dispersity is prepared in vacuum-drying, and disruptive strength and resistance to electricity tree performance significantly improve.But this preparation is complicated, can not prepare crosslinkable nano composite material, not easily realize industrialization.
Summary of the invention
The object of this invention is to provide a kind of crosslinkable inorganic nano LDPE/ SiOx polymer composites.
The object of the invention is to realize as follows: a kind of crosslinkable inorganic nano LDPE/ SiOx polymer composites, comprise organic silicon sol, Low Density Polyethylene, primary antioxidant, auxiliary antioxidant and linking agent, described organic silicon sol is ethylene glycol silicon sol, primary antioxidant is four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is thiodipropionic acid dilauryl cinnamic acid ester, and linking agent is dicumyl peroxide;
First, be the organic silicon sol of 5-15wt% by total mass percentage ratio, mass percent is the Low Density Polyethylene of 90-97wt%, the auxiliary antioxidant of the primary antioxidant of mass percent 0.1-0.4wt% and mass percent 0.2-0.8wt% mixes in high-speed mixer, place mass percent sum is absolutely;
Then, the material mixed is adopted molten-molten blending method through twin screw degassing extruder heat up further vacuum outgas, extrude, melting to enter in single screw extrusion machine more degassed, extrude, earnestly granulation, air-cooled, obtain LDPE/ SiO
xnanocomposite particles;
Finally, then by SiO
x/ LDPE nanocomposite particles and mass percent are that 1.8-2.2wt% linking agent mixes and infiltrates 30min at 50-80 DEG C of temperature, become crosslinkable SiO by linking agent diffusion
x/ LDPE nano-cable material.
The invention has the beneficial effects as follows: instant invention overcomes the existing bad dispersibility prepared olefin polymerization nanometer composite material and exist, the problems such as particle aggregation is serious, propose a kind of novel method preparing crosslinkable polyolefin nano composite material simultaneously; Molten-molten blending method is adopted successfully to obtain SiO
xsize of particles is the crosslinkable SiO of 55nm ~ 100nm
x/ LDPE nano-cable material, effectively prevents the reunion of inorganic particulate, significantly better than crosslinkable SiO
2/ LDPE nano-cable material contrasts.Add SiO
xnanoparticle effectively can improve electrical property; Work as SiO
xwhen addition is 1.5wt%, over-all properties is best, particle diameter 60-90nm, crosslinkable SiO
2the volume specific resistance of/LDPE nano-cable material compared with pure LDPE improves 82.6%, and the breaking down field strength of material, tensile strength, elongation at break and Young's modulus improve 14.3%, 12.5%, 35.2% and 23.8% respectively.
embodiment:
The crosslinkable inorganic nano LDPE/ SiOx polymer composites that following examples obtain, comprise organic silicon sol, Low Density Polyethylene, primary antioxidant, auxiliary antioxidant and linking agent, described organic silicon sol is ethylene glycol silicon sol, primary antioxidant is four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is thiodipropionic acid dilauryl cinnamic acid ester, and linking agent is dicumyl peroxide;
First, be the organic silicon sol of 5-15wt% by total mass percentage ratio, mass percent is the Low Density Polyethylene of 90-97wt%, the auxiliary antioxidant of the primary antioxidant of mass percent 0.1-0.4wt% and mass percent 0.2-0.8wt% mixes in high-speed mixer, the weight percentage sum of all components is absolutely;
Then, the material mixed is adopted molten-molten blending method through twin screw degassing extruder heat up further vacuum outgas, extrude, melting to enter in single screw extrusion machine more degassed, extrude, earnestly granulation, air-cooled, obtain LDPE/ SiO
xnanocomposite particles;
Finally, then by LDPE/ SiO
xnanocomposite particles and mass percent are that 1.8-2.2wt% linking agent mixes and infiltrates 30min at 50-80 DEG C of temperature, become crosslinkable SiO by linking agent diffusion
x/ LDPE nano-cable material.
The preparation method of organic silicon sol: adopt and add 50ml tetraethoxy (TEOS) in four-hole bottle, be heated with stirring to 120-140 DEG C, after temperature-stable, often drip 3-9s with rate of addition drip Organic Alcohol in TEOS, the mol ratio of Organic Alcohol and TEOS is 1.9, reaction times 2-8h, obtains boiling point 120-160 DEG C, solids content is 20-37wt% organic silicon sol.
Because high boiling point silicon sol is close with polyethylene melt temperature, favourable mixing each other, heating up in degassed process further, has silicon sol in polyethylene melt, form homodisperse SiO
xnanoparticle, thus will form the SiO that is evenly distributed
x/ LDPE nano composite material; Because solid linking agent more than 50 DEG C is melt into liquid, with nano composite material, the molecular diffusion effect crosslinked by liquid state infiltrates, and prepares crosslinkable SiO
x/ LDPE nano-cable material.
embodiment 1
Take 192gLDPE, 10g solids content 20% organic silicon sol (actual solid SiO
xaccount for the mass percent 1.0% of whole matrix material), 0.6g primary antioxidant, 1.4g auxiliary antioxidant mix in mixing machine; After the principle of mixing is melt extruded through twin screw extruder, being vented, then be vented through singe screw, cool, be a granulated into nanocomposite particles; This matrix material is heated up 80 DEG C with 4g linking agent in mixing machine and mixes 30min, make crosslinkable SiO
x/ LDPE nano-cable material is sample 1.
To add the SiO of 50nm
2inorganic nano SiOx/LDPE and LDPE prepares crosslinkable CABLE MATERIALS in contrast.SiO2 inorganic nano SiOx/LDPE, 0.6g primary antioxidant, the 1.4g auxiliary antioxidant that take 192gLDPE, 2g 50nm mix in mixing machine; After the principle of mixing is melt extruded through twin screw extruder, being vented, then be vented through singe screw, cool, be a granulated into nanocomposite particles; This matrix material is heated up 80 DEG C with 4g linking agent in mixing machine and mixes 30min, make crosslinkable SiO
2/ LDPE nano-cable material is sample 2.
With the crosslinkable CABLE MATERIALS of non-plus nano silicon oxide inorganic particulate in contrast.Take 192gLDPE, 0.6g primary antioxidant, 1.4g auxiliary antioxidant mixes in mixing machine; After the principle of mixing is melt extruded through twin screw extruder, being vented, then be vented through singe screw, cool, be a granulated into nanocomposite particles; Heated up 80 DEG C with 4g linking agent in mixing machine by this matrix material and mix 30min, making crosslinkable LDPE nano-cable material is sample 3.
HT-100 breakdown voltage tester that voltage breakdown test adopts Zhejiang Univ to manufacture, sample: square sheet specimens, size 100mm × 100mm, thickness is about 1mm.Electrode: circular on-gauge plate-plate copper electrode, electrode diameter 25mm.Boosting mode: boost continuously.The rate of rise: 10kV/s.
ZC-36 megger that volume specific resistance test adopts Shanghai City the 6th ammeter factory to manufacture.Test sample is of a size of 100mm × 100mm, and thickness is about the square plate tensile sample of 1mm.Electrode materials is annealing aluminium foil, applies electric field 500V/mm.The volume specific resistance of sample is measured according to GB 1410-89.
The AG-J10 KN electronic universal material testing machine that Mechanics Performance Testing adopts Japanese Shimadzu Corporation to manufacture; Material is hot pressed under vulcanizing press the print of 10cm × 10cm × 1mm, with reference to the dumbbell shape batten of GB/ T1040-92 standards for calibration, sample basic size is 100mm × 6mm × 1mm, maximum pull is 500N, draw speed is 200mm/min, the Young's modulus of test material, tensile strength and elongation at break.
Heat extends the index representing degree of crosslinking, the hot elongation test instrument of WSK-49b that its test adopts Jiangdu, Jiangsu experimental machine factory to manufacture; Prepare sample with reference to GB/T2951.1 test method and test after measuring sectional area.Dumbbell thickness of test piece should be not less than 0.8mm, is not more than 2.0mm.
The dispersion particle diameter test of inorganic particulate adopts FEI Sirion 200 scanning electron microscope analysis instrument (SEM) of Dutch PHILIPS Co. manufacture to observe the SiO of fracture
xsize of particles.First by sample brittle failure in liquid nitrogen, the test conductive resin after brittle failure is fixed in stainless steel sample table, utilizes spraying plating instrument, at Fracture Profile in Metallic Materials place metal spraying.
The breaking down field strength of the crosslinkable polyethylene cable material prepared, volume specific resistance and mechanical property and other performance value are in table 1:
Table 1 breaking down field strength, volume specific resistance, mechanical property and other the performance test results
T
| Sample number into spectrum | Sample 1 | Sample 2 | Sample 3 |
| Breaking down field strength/kV/mm | 27.8 | 25.7 | 25.1 |
| Volume specific resistance/Ω m (× 10 15) | 2.64 | 2.22 | 1.95 |
| Tensile strength/MPa | 13.4 | 10.9 | 11.2 |
| Elongation at break/% | 889.4 | 592.1.4 | 634.8 |
| Young's modulus/Nmm -2 | 156.8 | 136.7 | 126.0 |
| Hot extension/% | 75 | 80 | 78 |
| The dispersion particle diameter (nm) of inorganic particulate | 55-96 | 80-180 | 0 |
Table 1
embodiment 2:
Take 191gLDPE, 15g solids content 20% organic silicon sol (actual solid SiO
xaccount for the mass percent 1.5% of whole matrix material), 0.6g primary antioxidant, 1.4g auxiliary antioxidant mix in mixing machine; After the principle of mixing is melt extruded through twin screw extruder, being vented, then be vented through singe screw, cool, be a granulated into nanocomposite particles; This matrix material is heated up 80 DEG C with 4g linking agent in mixing machine and mixes 30min, make crosslinkable SiO
x/ LDPE nano-cable material is sample 4.
To add the SiO of 50nm
2inorganic nano SiOx/LDPE and LDPE prepares crosslinkable CABLE MATERIALS in contrast.SiO2 inorganic nano SiOx/LDPE, 0.6g primary antioxidant, the 1.4g auxiliary antioxidant that take 192gLDPE, 3g 50nm mix in mixing machine; After the principle of mixing is melt extruded through twin screw extruder, being vented, then be vented through singe screw, cool, be a granulated into nanocomposite particles; This matrix material is heated up 80 DEG C with 4g linking agent in mixing machine and mixes 30min, make crosslinkable SiO
2/ LDPE nano-cable material is sample 5.
With the crosslinkable CABLE MATERIALS of non-plus nano silicon oxide inorganic particulate in contrast.With sample 3.
HT-100 breakdown voltage tester that voltage breakdown test adopts Zhejiang Univ to manufacture, sample: square sheet specimens, size 100mm × 100mm, thickness is about 1mm.Electrode: circular on-gauge plate-plate copper electrode, electrode diameter 25mm.Boosting mode: boost continuously.The rate of rise: 10kV/s.
ZC-36 megger that volume specific resistance test adopts Shanghai City the 6th ammeter factory to manufacture.Test sample is of a size of 100mm × 100mm, and thickness is about the square plate tensile sample of 1mm.Electrode materials is annealing aluminium foil, applies electric field 500V/mm.The volume specific resistance of sample is measured according to GB 1410-89.
The AG-J10 KN electronic universal material testing machine that Mechanics Performance Testing adopts Japanese Shimadzu Corporation to manufacture; Material is hot pressed under vulcanizing press the print of 10cm × 10cm × 1mm, with reference to the dumbbell shape batten of GB/ T1040-92 standards for calibration, sample basic size is 100mm × 6mm × 1mm, maximum pull is 500N, draw speed is 200mm/min, the Young's modulus of test material, tensile strength and elongation at break.
Heat extends the index representing degree of crosslinking, the hot elongation test instrument of WSK-49b that its test adopts Jiangdu, Jiangsu experimental machine factory to manufacture; Prepare sample with reference to GB/T2951.1 test method and test after measuring sectional area.Dumbbell thickness of test piece should be not less than 0.8mm, is not more than 2.0mm.
The dispersion particle diameter test of inorganic particulate adopts FEI Sirion 200 scanning electron microscope analysis instrument (SEM) of Dutch PHILIPS Co. manufacture to observe the SiO of fracture
xsize of particles.First by sample brittle failure in liquid nitrogen, the test conductive resin after brittle failure is fixed in stainless steel sample table, utilizes spraying plating instrument, at Fracture Profile in Metallic Materials place metal spraying.
The breaking down field strength of the crosslinkable polyethylene cable material prepared, volume specific resistance and mechanical property and other performance value are in table 2:
Table 2 breaking down field strength, volume specific resistance, mechanical property and other the performance test results
T
| Sample number into spectrum | Sample 4 | Sample 5 | Sample 3 |
| Breaking down field strength/kV/mm | 28.7 | 25.7 | 25.1 |
| Volume specific resistance/Ω m (× 10 15) | 3.56 | 2.22 | 1.95 |
| Tensile strength/MPa | 12.6 | 10.2 | 11.2 |
| Elongation at break/% | 858.5 | 508.2 | 634.8 |
| Young's modulus/Nmm -2 | 139.0 | 127.9 | 126.0 |
| Hot extension/% | 77 | 81 | 78 |
| The dispersion particle diameter (nm) of inorganic particulate | 55-90 | 80-180 | 0 |
Table 2
embodiment 3:
Take 190gLDPE, 20g solids content 20% organic silicon sol (actual solid SiO
xaccount for the mass percent 1.5% of whole matrix material), 0.6g primary antioxidant, 1.4g auxiliary antioxidant mix in mixing machine; After the principle of mixing is melt extruded through twin screw extruder, being vented, then be vented through singe screw, cool, be a granulated into nanocomposite particles; This matrix material is heated up 80 DEG C with 4g linking agent in mixing machine and mixes 30min, make crosslinkable SiO
x/ LDPE nano-cable material is sample 6.
To add the SiO of 50nm
2inorganic nano SiOx/LDPE and LDPE prepares crosslinkable CABLE MATERIALS in contrast.SiO2 inorganic nano SiOx/LDPE, 0.6g primary antioxidant, the 1.4g auxiliary antioxidant that take 190gLDPE, 4g 50nm mix in mixing machine; After the principle of mixing is melt extruded through twin screw extruder, being vented, then be vented through singe screw, cool, be a granulated into nanocomposite particles; This matrix material is heated up 80 DEG C with 4g linking agent in mixing machine and mixes 30min, make crosslinkable SiO
2/ LDPE nano-cable material is sample 7.
With the crosslinkable CABLE MATERIALS of non-plus nano silicon oxide inorganic particulate in contrast.With sample 3.
HT-100 breakdown voltage tester that voltage breakdown test adopts Zhejiang Univ to manufacture, sample: square sheet specimens, size 100mm × 100mm, thickness is about 1mm.Electrode: circular on-gauge plate-plate copper electrode, electrode diameter 25mm.Boosting mode: boost continuously.The rate of rise: 10kV/s.
ZC-36 megger that volume specific resistance test adopts Shanghai City the 6th ammeter factory to manufacture.Test sample is of a size of 100mm × 100mm, and thickness is about the square plate tensile sample of 1mm.Electrode materials is annealing aluminium foil, applies electric field 500V/mm.The volume specific resistance of sample is measured according to GB 1410-89.
The AG-J10 KN electronic universal material testing machine that Mechanics Performance Testing adopts Japanese Shimadzu Corporation to manufacture; Material is hot pressed under vulcanizing press the print of 10cm × 10cm × 1mm, with reference to the dumbbell shape batten of GB/ T1040-92 standards for calibration, sample basic size is 100mm × 6mm × 1mm, maximum pull is 500N, draw speed is 200mm/min, the Young's modulus of test material, tensile strength and elongation at break.
Heat extends the index representing degree of crosslinking, the hot elongation test instrument of WSK-49b that its test adopts Jiangdu, Jiangsu experimental machine factory to manufacture; Prepare sample with reference to GB/T2951.1 test method and test after measuring sectional area.Dumbbell thickness of test piece should be not less than 0.8mm, is not more than 2.0mm.
The dispersion particle diameter test of inorganic particulate adopts FEI Sirion 200 scanning electron microscope analysis instrument (SEM) of Dutch PHILIPS Co. manufacture to observe the SiO of fracture
xsize of particles.First by sample brittle failure in liquid nitrogen, the test conductive resin after brittle failure is fixed in sample table (stainless steel), utilizes spraying plating instrument, at Fracture Profile in Metallic Materials place metal spraying.
The breaking down field strength of the crosslinkable polyethylene cable material prepared, volume specific resistance and mechanical property and other performance value are in table 3:
Table 3 breaking down field strength, volume specific resistance, mechanical property and other the performance test results
T
| Sample number into spectrum | Sample 6 | Sample 7 | Sample 3 |
| Breaking down field strength/kV/mm | 26.8 | 24.7 | 25.1 |
| Volume specific resistance/Ω m (× 10 15) | 3.35 | 2.64 | 1.95 |
| Tensile strength/MPa | 11.3 | 9.3 | 11.2 |
| Elongation at break/% | 692.6 | 504.4 | 634.8 |
| Young's modulus/Nmm -2 | 141.8 | 123.6 | 126.0 |
| Hot extension/% | 81 | 85 | 78 |
| The dispersion particle diameter (nm) of inorganic particulate | 60-100 | 80-200 | 0 |
Table 3
The breaking down field strength of crosslinkable polyethylene cable material, volume specific resistance and mechanical property and other performance brief summaries.
Claims (1)
1. a crosslinkable inorganic nano LDPE/ SiOx polymer composites, it is characterized in that, comprise organic silicon sol, Low Density Polyethylene, primary antioxidant, auxiliary antioxidant and linking agent, described organic silicon sol is ethylene glycol silicon sol, primary antioxidant is four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is thiodipropionic acid dilauryl cinnamic acid ester, and linking agent is dicumyl peroxide;
First, be the organic silicon sol of 5-15wt% by total mass percentage ratio, mass percent is the Low Density Polyethylene of 90-97wt%, the auxiliary antioxidant of the primary antioxidant of mass percent 0.1-0.4wt% and mass percent 0.2-0.8wt% mixes in high-speed mixer, the weight percentage sum of all components is absolutely;
Then, the material mixed is adopted molten-molten blending method through twin screw degassing extruder heat up further vacuum outgas, extrude, melting to enter in single screw extrusion machine more degassed, extrude, earnestly granulation, air-cooled, obtain LDPE/ SiO
xnanocomposite particles;
Finally, then by LDPE/ SiO
xnanocomposite particles and mass percent are that 1.8-2.2wt% linking agent mixes and infiltrates 30min at 50-80 DEG C of temperature, become crosslinkable LDPE/SiO by linking agent diffusion
xnano-cable material.
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