CN105949581A - Preparation method and application of flame-retardant cable insulating material comprising nano perovskite oxide LaxSr[1-x]CoO3 - Google Patents
Preparation method and application of flame-retardant cable insulating material comprising nano perovskite oxide LaxSr[1-x]CoO3 Download PDFInfo
- Publication number
- CN105949581A CN105949581A CN201610458518.9A CN201610458518A CN105949581A CN 105949581 A CN105949581 A CN 105949581A CN 201610458518 A CN201610458518 A CN 201610458518A CN 105949581 A CN105949581 A CN 105949581A
- Authority
- CN
- China
- Prior art keywords
- preparation
- nano
- coo
- insulant
- citric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003063 flame retardant Substances 0.000 title abstract description 36
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 19
- 239000011810 insulating material Substances 0.000 title abstract 5
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 15
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 15
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 11
- 239000005011 phenolic resin Substances 0.000 claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 90
- 239000000243 solution Substances 0.000 claims description 36
- 239000013207 UiO-66 Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000012774 insulation material Substances 0.000 claims description 20
- 229910002651 NO3 Inorganic materials 0.000 claims description 15
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002134 carbon nanofiber Substances 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 10
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 10
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 229910018307 LaxSr1−x Inorganic materials 0.000 claims description 9
- 239000004014 plasticizer Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010445 mica Substances 0.000 claims description 6
- 229910052618 mica group Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000004567 concrete Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical group CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 43
- 230000032683 aging Effects 0.000 abstract description 21
- -1 polyene ester Chemical class 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 15
- 230000009471 action Effects 0.000 abstract description 5
- 239000012621 metal-organic framework Substances 0.000 abstract description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000004904 shortening Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 19
- 239000002131 composite material Substances 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 230000005684 electric field Effects 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004079 fireproofing Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 229920003020 cross-linked polyethylene Polymers 0.000 description 2
- 239000004703 cross-linked polyethylene Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910018921 CoO 3 Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910019828 La0.7Sr0.3CoO3 Inorganic materials 0.000 description 1
- 229910002187 La0.8Sr0.2CoO3 Inorganic materials 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 241000907903 Shorea Species 0.000 description 1
- 229910003508 Sr0.3CoO3 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003124 biologic agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical compound [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003434 inspiratory effect Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229950000845 politef Drugs 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0853—Ethene vinyl acetate copolymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/02—Disposition of insulation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B9/00—Power cables
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Insulating Materials (AREA)
- Insulated Conductors (AREA)
Abstract
The invention relates to a preparation method of a flame-retardant cable insulating material comprising nano perovskite oxide LaxSr[1-x]CoO3. Nano perovskite oxide and a metal organic framework UIO material are together added into a three-element polyene ester material (LDPE (low-density polyethylene)/EVA (ethylene-vinyl acetate)/phenolic resin) to enhance the heat resistance and strength of the insulating material and shortening the aging time of the insulating material. The insulating material can keep undegraded for a long time under the action of high temperature, and can keep favorable flame-retardant effect; and the LOI (loss on ignition) index is greatly enhanced.
Description
Technical field
The present invention relates to the preparation method of a kind of Fire retardation electric cable insulation material comprising nano-perovskite granule, described nano-perovskite oxide LaxSr1-xCoO3There is special structure, can be as the inorganic nanometer oxide material of high-quality, it is jointly added in polyalkenylesters material with organometallic skeletal UIO material, improve thermostability and the intensity of insulant, reduce the ageing time of insulant, can keep the most non-degradable under high temperature action, and preferable flame retardant effect can also be kept, LOI loss on ignition index is greatly improved.
Background technology
Insulant conventional in cable has oil-paper, polrvinyl chloride, polyethylene, crosslinked polyethylene, rubber etc..On electrotechnics, by specific insulation more than 109The material that the material of Ω cm is constituted is referred to as insulant, is namely used for making device at the material that electric current electrically can be stoped to pass through.Crosslinked polyethylene has excellent dielectric properties and mechanical performance, and oneself is widely used in high pressure and supertension plastic insulating power cable.Along with supertension, the development of extra-high voltage direct-current power transmission and transformation system, the insulation ageing problem in running is increasingly severe, and oneself becomes the major obstacle that insulated cable develops to supertension.When the working field strength of insulating polymer reach breakdown field strength ten/for the moment, the Electric Power Equipment Insulation worked long hours can cause poplar bundles, reduce cable service life.The high voltage power cable insulant being made up of Low Density Polyethylene, is affected the most aging by various aging actions in During Process of Long-term Operation, causes the dielectric properties of material and the decline of mechanical performance.Classification according to aging action can be divided into voltage ageing, heat ageing, mechanical aging and Electrochemical Ageing.Wherein heat ageing is the main inducing of PE cable insulation infringement, and different thermal aging time and condition can cause the difference of polyethylene inner molecular structure, and then affect its space charge characteristic.
Research shows, under DC electric field effect, easily forms space charge, and space charge can make Electric Field Distribution be distorted in polymer insulation, and aggravation polymer insulation is aging, the aging decline that result in material electric property of material.Space Charge in Polymer is mainly ionized the heteropolarity electricity of generation under electric field action by the same polarity space charge entering sunken carrier or transportable current-carrying of electrode injection and organic or inorganic impurity in insulator.In order to suppress the formation of space charge, need, to PE modified thus change trap energy therein and distribution, to change distribution of space charge, lower distortion probability, improve the dielectric properties of polymer, reduce polymer insulation aging, and do not affect the processing characteristics of polymer simultaneously.
Low Density Polyethylene is cable insulation material commonly used in the art, but fire resistance is unsatisfactory.Fire resistance for insulant is improved at present, and adding suitable fire retardant is one of major way.Become charcoal that the anti-flammability of polymer is had to have a significant impact.Therefore, research and development can promote that the fire retardant of the more participation charcoal of polyalkenylesters material self or carbonized agent are significant efficiently.In recent years, in order to improve the char yield of fire-retardant polyethylene material, improve carbon-coating structure and become quality with improving charcoal, for cooperative flame retardant, siloxanes is fire-retardant, polymer nanocomposite is fire-retardant etc., and there is primary study in aspect.
Summary of the invention
Research proves, space charge is to cause power cable electric field distortion, causes shelf depreciation, electric branch and the major reason of dielectric breakdown accident.The at present research to the space charge in polymer focuses primarily upon the generation of space charge in suppression medium and migrates characteristic, generally, space charge in insulant (such as polyethylene) is mainly made up of 2 parts: one be high field pretend with under enter sunken carrier or transportable carrier, referred to as like charges from the electrode injection contacted with medium；Another part is under relatively low field intensity effect, and the impurity in medium ionizes under electric field action and occurs to migrate and the space charge that formed, referred to as heterocharge.The doping of CNFS orientation successful change of carrier transfer ways in medium, reduce trap level, make carrier be prone to along being perpendicular to thickness direction to transport, effectively inhibiting injection and the space charge accumulation in medium of carrier through-thickness. semi-conductive layer weakens extra electric field on thickness of sample direction to a certain extent, reduce the field intensity at semi-conductive layer and interfacial dielectric layer, decrease the space charge amount that negative electrode injects, after short circuit, in sample, the interpolation of final residual a small amount of space charge .CNFS changes the transfer ways of carrier, inhibit space charge by electrode injection in insulating barrier, contribute to fire-retardant, hinder the electric charge polymerization of polymer, improve the service life of insulant.
Phosphorus and phosphorus-containing compound fire retardant are listed as three big flame-retardant systems with halogen system, inorganic system.The flame retardant effect of phosphorus series compound is preferable, because the Metaphosphoric acid generated during burning can be grouped to stable poly state, becomes the protective layer of burning point, can completely cut off and be fired contacting of thing and oxygen.The phosphoric acid and the poly-Metaphosphoric acid that generate are the most all strong acid, have the strongest dehydration property, it is possible to make polymer dehydration carbonization, and form charring layer at polymer surfaces, reach starvation and stop the purpose of burning.
When nitrogenous flame ratardant burns when breaking out of fire, it is heated and easily releases the non-flammable gases such as HCN, N2, NH3, NO2 and NO.The concentration of the imflammable gas produced when oxygen in these gas dilutions air and high polymer decomposes, nitrogenous flame ratardant catabolic process also absorbs a part of heat simultaneously, additionally nitrogen can also catch free radical, the chain reaction of suppression high polymer, reach to remove the effect of free radical, thus reach fire-retardant purpose.
Tripolycyanamide has Halogen, low toxicity, the advantage of low cigarette, nitrogenous flame ratardant is preferable at the flame retardant effect of polyester plastics, is especially combined with phosphorus flame retardant, can form Intumscent Flame Retardant System, by the synergism of the two, the flame retardant effect of polyalkenylesters hydrocarbon insulant can be greatly improved.The application have employed tripolycyanamide and is applied in combination with triethyl phosphate, hydroxyapatite, and adjust the ratio of three, make three play synergism, form Intumscent Flame Retardant System, test shows, the optimal mass ratio of three's (tripolycyanamide: triethyl phosphate: hydroxyapatite) is 1:1:1.Flame retardant effect can be greatly improved.Applicant thinks that mainly containing phosphorus component is jointly to be acted on Phos form by organophosphor, on the basis of different phosphorus forms, in conjunction with nitrogenated flame retardant, structurally can increase swelling degree, and Phos can also occupy intermediate active position in Intumescent Retardant System, the performances such as fire-retardant, the intensity forming the rock-steady structures such as stable system, such as intercalation, link layer, polyhedron, beneficially polyalkenylesters insulant with organophosphor, organic nitrogen.
Nano inorganic oxide is the good selection of fire retardant, and such as nano magnesia, nano zine oxide etc. can serve as nano inorganic oxide fire retardant and joins in polyalkenylesters material.Due to nano effect, it is incomparable a little that Preparing Organic-inorganic Nano Hybrid Material has more conventional polymer/filler compound, and such as density is little, mechanical strength is high, inspiratory and permeability, and particularly thermostability and anti-flammability can be greatly improved.Further, also having the fire resistance of the clay class laminated nm-silicate composite materials such as scholar's research attapulgite, montmorillonite, above-mentioned inorganic material all has flame retardant effect in various degree.Perovskite structure oxide ABO3 has optics, electricity and the magnetic performance of uniqueness, it is widely used in terms of biological agent pottery, having Heat stability is good, low cost, can carry out adsorbing oxygen according to the selection of B position, A, B atom can mention regulation Lattice Oxygen quantity and activity.There is presently no the more excellent nano-perovskite material of employing structure or similar polymetallic metal composite oxide as fire proofing.
The aerial burning of macromolecular compound is the fiercest a kind of oxidation reaction, belongs to chain reaction course.Combustion process is bred the most active hydroxyl free radical, when hydroxyl free radical and macromolecular compound meet, generates Hydrocarbon free radical and water, in the presence of oxygen, Hydrocarbon radical decomposition, form again new hydroxyl free radical.So circulation, makes combustion reaction constantly continue.The mechanism of action of fire retardant is more complicated, comprises many factors, but mainly either physically or chemically stops burn cycle by employing.
Someone use inorganic material zeolite as the fire retardant of insulant, but zeolite is rigid structure, bridging oxygen key is relatively short, and lack flexibility, there is certain defect.A kind of MOF with ultrastability, is labeled as UiO-66, and chemical formula is
Zr6O4 (OH) 4 (CO2) 12, its structure collapse temperature is higher than 500 DEG C.Its stability carrys out inorganic metal unit Zr6O4 (OH) 4 of high degree of symmetry, and this Zr6 octahedron core and the strong interaction of carboxyl oxygen O in part.One Zr6 octahedron core and 12 p-phthalic acid ligands, form tetrahedron and octahedron two kinds of hole cage, on eight faces of each octahedra cage, be all connected with a tetrahedron cage, this connected mode constantly extends at three dimensions, thus forms the MOFs with 6 apertures.It addition, chemical stability test shows, UiO-66 has good water-resistance, acid-resisting.
Therefore, the application sounds out UIO-66 material as the material of composite flame-retardant agent, can improve the resistance to elevated temperatures of cable insulation material, thus improve service life.Owing to metal-organic framework materials is the coordination polymer with metal ion as junction point, when being combined with polythene material, both imidazole skeleton and the polythene material compatibility on high molecular chemical characters in polymer can have been utilized, it is formed with efficient construction, utilize the tetrahedral structure can effective dispersion space electric charge, avoid the gathering of space charge, improve high temperature resistant, ageing-resistant performance；On the other hand, containing metal ion in ZIFS, inorganic compound can be formed, and inorganic compound such as nano inorganic magnesium oxide, ferrum oxide etc. are one of fire retardants of this area, the complementary action of inorganic material can be utilized with polythene material after being combined, the charge transport efficiency of heavy insulation material further, improves fire resistance, improves high temperature resistant, the ageing-resistant performance of insulant.
Conductive polymeric composite is to be filled in polymeric matrix with processing technique (as compound in dispersion, lamination is combined, forms surface electrolemma etc.) in a different manner by various electroconductive stuffings.The matrix resin that conducing composite material is conventional has: EVA, PS, PE (LDPE, HDPE), PP, PVC, ABS,
PA, PBT, PET, PC, PI, PPS, the polymer such as phenolic resin, epoxy resin, poly-virtue are soughed, polypropylene vinegar, butyronitrile rubber, organic silicon rubber.Conductive polymeric composite has more ripe advantage than structural conductive macromolecular material technically, and compared with metal, conductive composite material has the advantages such as processability is good, technique is simple, corrosion-resistant, resistivity adjustable extent is big, price is low.The function of the processing characteristics of macromolecular material and the electric conductivity of conductive filler has together decided on polymer-based conducing composite material to be had and can need to regulate its electricity, mechanics and other performances according to use in a big way, chemical stability is preferable, with low cost, it is prone to molding and large-scale production etc., often make antistatic and electromagnetic shielding material, be widely used in the industry such as electronics, electrical equipment, weaving, colliery.Additionally, composite conductive polymer also has many unique physical phenomenons, such as insulator-conductor jumping phenomenon (percolation phenomena), resistivity is to temperature, pressure, gas concentration sensitivity, current-voltage non-linear behavior, current noise etc..
The present invention uses nano-perovskite oxide La firstxSr1-xCoO3(0.6 < x < 1) is as inorganic nano flame retardant constituent, join in polyalkenylesters material, addition due to nano-perovskite, carrier transfer ways in medium can be changed, reduce trap level, make carrier be prone to along being perpendicular to thickness direction to transport, effectively inhibiting injection and the space charge accumulation in medium of carrier through-thickness. semi-conductive layer weakens extra electric field on thickness of sample direction to a certain extent, reduce the field intensity at semi-conductive layer and interfacial dielectric layer, decrease the space charge amount that negative electrode injects, the a small amount of space charge of final residual in sample after short circuit, reduce the aggregation of electric charge, improve the electricity saving performance of material, improve the aging resistance of insulant, resistance to elevated temperatures, play efficient fire-retardant purpose.
The application polyalkenylesters main material is ternary material (LDPE/EVA/ phenolic resin): low density polyethylene, EVA, phenolic resin mix, composite high-molecular kind is expanded, be conducive to the complementary structure of various macromolecular materials, composite flame-proof agent material directly contacts with polyalkenylesters, combine closely, form active surface to cover and space invasion and attack, occupy suitable flame retardant activity position, and add trap quantity, improve electric charge flowing, add average breakdown strength, be conducive to improving the service life of insulant.Therefore, the insulant of the application both can improve service life, ageing-resistant, impact resistance, and intensity is high, and can also keep preferable flame retardant effect, and LOI loss on ignition index is greatly improved.
The present invention relates to a kind of cable insulation material comprising nano-perovskite oxide particle, described cable insulation material includes LDPE 80-100 part, phenolic resin 50-60 part, EVA60-80 part, white carbon 10-20 part, plasticizer 5-10 part, tripolycyanamide 5-15 part, triethyl phosphate 5-15 part, hydroxyapatite 5-15 part, mica sheet 5-15 part, carbon nano-fiber 5-10 part, LaxSr1-xCoO310-20 part and UIO-66 5-10 part.
Described plasticizer is trioctyl trimellitate (TOTM).Described nano-perovskite oxide LaxSr1-xCoO3Mean diameter be 20-85nm, preferably 20-60nm.Preferably, in cable material, nano-perovskite oxide LaxSr1-xCoO3: the mass ratio of UIO is 2-4:1, preferably 2-3:1；The wherein preferred UIO-66 of UiO material.
Preferably, dicyandiamide in cable material: triethyl phosphate: the mass ratio of hydroxyapatite is 1-3:1:1, most preferably 1:1:1, preferably carbon nano-fiber a length of 10-20 micron.
Described insulant is to prepare in accordance with the following steps:
(1) complex La is preparedxSr1-xCoO3(0.6 < x < 1) and UIO-66:
A () weighs Lanthanum (III) nitrate, cobalt nitrate, strontium nitrate and nitric acid in proportion, be dissolved in deionized water, be configured to nitrate solution, wherein nitric acid: metal ion: the mol ratio of water is (1-4): (2 ~ 4): 70；Separately weighing citric acid to be dissolved in deionized water, be configured to citric acid solution, wherein the mol ratio of citric acid and water is (4 ~ 8): 40；
B nitrate solution is heated to 70 ~ 80 DEG C by (), drip citric acid solution under stirring, and the citric acid amount of addition and the mol ratio of metal ion are 1:1 ~ 1:2；Nitrate solution and citric acid solution adjust pH value of solution to 7 with strong aqua ammonia after being sufficiently mixed uniformly；Gel is obtained after keeping 2 ~ 3 hours at 75 ~ 80 DEG C；
C () is dried into xerogel gained gel at 90 ~ 100 DEG C, then process 0.5 ~ 1 hour at 350 ~ 400 DEG C, obtain nano-perovskite catalyst La1-XSrXCoO3。
Prepared by UIO-66: weigh 0.932g ZrC14 and 1.32 respectively
G p-phthalic acid, in polytetrafluoroethylliner liner, add 24 mL DMF solvent and dissolved, be subsequently adding 0.665 mL concentrated hydrochloric acid, mix homogeneously, supersound process 5 min, seals inner bag, puts in baking oven in 120 DEG C of reacting by heating 16h, then room temperature is reduced the temperature to, by mixture after reaction is centrifuged, bottom centrifuge tube, obtains white precipitate, be UiO-66.
(2) La that LDPE 80-100 part, phenolic resin 50-60 part, EVA60-80 part, white carbon 10-20 part, plasticizer 5-10 part, tripolycyanamide 5-15 part, triethyl phosphate 5-15 part, hydroxyapatite 5-15 part, mica sheet 5-15 part and carbon nano-fiber 5-10 part and above-mentioned steps obtainxSr1-xCoO310-20 part, the mixing of UIO-66 5-10 part, pour homogenizer into, the speed first using 1100 revs/min under room temperature stirs 30 minutes, then 30min is stirred at 60 DEG C with the speed of 4000 revs/min, the batch mixing stirred is discharged, then melt, injection mo(u)lding, obtain described cable insulation material.
Preferably, in described step (2), melt temperature is 200-260 DEG C, and described injection mo(u)lding temperature is 120-150 DEG C, preferably 130-150 DEG C.
Further, present invention employs the carbon nano-fiber that nitrogen is modified, add nitrogenous flame retardance element, and optimize specific surface area and the pore structure of carbon nano-fiber, be beneficial to the anti-flammability to cable material further and improve.
Wherein, in described nitrogen modified carbon nano tube fiber NCNFS, the content of N is 1-5wt%, based on NCNFS overall calculation.Concrete preparation method is: being immersed by carbon nano-fiber in the solution containing ammonia, 120-180 DEG C of hydro-thermal reaction in politef hydrothermal reaction kettle, retention time 0.5-5h, obtain N-CNFS, the doping controlling N is 1-5wt%.
The cable insulation material of the present invention is owing to using nano-perovskite oxide material first, utilize its advantage space structure, and with UIO Material cladding, a part can produce more inorganic nano flame-retardant composition, and another part can utilize the vacant framing structure with ZIF in space, the carbon-forming performance of aggregation thing material, improve LOI index, and the organic backbone in UIO can be combined further with polyalkenylesters material, beneficially comprehensive covering of fire proofing, is greatly improved fire resistance.This cable insulation material is the application in high pressure and supertension plastic insulating power cable, can be substantially reduced aging, improves high temperature resistant, the use intensity of cable insulation material and resistance to fire resistance.
The application have studied and includes composite L axSr1-xCoO3With metallic organic framework UIO-66 to the fire-retardant of LDPE/EVA/ phenolic resin composite and mechanical property, by having limited oxygen index, vertical combustion and mechanical property tests to measure, understand composite cable material high comprehensive performance, stable performance, oxygen index (OI) height, good flame retardation effect, effect are persistently, cheap;By non-volatile, smog is little, avirulence, this composite flame-proof material have concurrently fire-retardant, press down cigarette and reduce the function of toxic gas, be that a kind of non-environmental-pollution fire proofing has prospects for commercial application.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further detailed explanation.
Embodiment
1
(1) complex La is prepared0.7Sr0.3CoO3With UIO-66:
A () weighs Lanthanum (III) nitrate, cobalt nitrate, strontium nitrate and nitric acid in proportion, be dissolved in deionized water, be configured to nitrate solution, wherein nitric acid: metal ion: the mol ratio of water is 1:4:70；Separately weighing citric acid to be dissolved in deionized water, be configured to citric acid solution, wherein the mol ratio of citric acid and water is 6:40；
B mixed nitrate solution is heated to 70 DEG C by (), drip citric acid solution under stirring, and the citric acid amount of addition and the mol ratio of metal ion are 1:1；Nitrate solution and citric acid solution adjust pH value of solution to 7 with strong aqua ammonia after being sufficiently mixed uniformly；Gel is obtained after keeping 2 hours at 80 DEG C；
C () is dried into xerogel gained gel at 100 DEG C, then process 1 hour at 400 DEG C, obtain nano-perovskite catalyst La0.7Sr0.3CoO3。
Prepared by UIO-66: weigh 0.932gZrC14 and 1.32 respectively
G p-phthalic acid, in polytetrafluoroethylliner liner, add 24 mL DMF solvent and dissolved, be subsequently adding 0.665 mL concentrated hydrochloric acid, mix homogeneously, supersound process 5 min, seals inner bag, puts in baking oven in 120 DEG C of reacting by heating 16h, then room temperature is reduced the temperature to, by mixture after reaction is centrifuged, bottom centrifuge tube, obtains white precipitate, be UiO-66.
(2) La that LDPE 80 parts, 50 parts of phenolic resin, EVA60 part, white carbon 10 parts, plasticizer 5 parts, tripolycyanamide 5 parts, triethyl phosphate 5 parts, hydroxyapatite 5 parts, mica sheet 5 parts and carbon nano-fiber 5 parts and above-mentioned steps obtainxSr1-xCoO310 parts, UIO-66 5 parts mixing, pour homogenizer into, first uses the speed of 1100 revs/min to stir under room temperature 30 minutes, then stir 30min at 60 DEG C with the speed of 4000 revs/min, the batch mixing stirred is discharged, then melts, injection mo(u)lding, obtains described cable insulation material.
Embodiment
2
(1) complex La is prepared0.8Sr0.2CoO3With UIO-66:
A () weighs Lanthanum (III) nitrate, cobalt nitrate, strontium nitrate and nitric acid in proportion, be dissolved in deionized water, be configured to mixed nitrate solution, wherein nitric acid: metal ion: the mol ratio of water is 2:4:70；Separately weighing citric acid to be dissolved in deionized water, be configured to citric acid solution, wherein the mol ratio of citric acid and water is 8:40；
B mixed nitrate solution is heated to 70 DEG C by (), drip citric acid solution under stirring, and the citric acid amount of addition and the mol ratio of metal ion are 1:2；Nitrate solution and citric acid solution adjust pH value of solution to 7 with strong aqua ammonia after being sufficiently mixed uniformly；Gel is obtained after keeping 3 hours at 75 DEG C；
C () is dried into xerogel gained gel at 100 DEG C, then process 1 hour at 350 DEG C, obtain nano-perovskite catalyst La0.8Sr0.2CoO3。
Prepared by UIO-66: weigh 0.932g ZrC14 and 1.32 respectively
G p-phthalic acid, in polytetrafluoroethylliner liner, add 24 mL DMF solvent and dissolved, be subsequently adding 0.665 mL concentrated hydrochloric acid, mix homogeneously, supersound process 5 min, seals inner bag, puts in baking oven in 120 DEG C of reacting by heating 16h, then room temperature is reduced the temperature to, by mixture after reaction is centrifuged, bottom centrifuge tube, obtains white precipitate, be UiO-66.
(2) La that LDPE 80 parts, 50 parts of phenolic resin, EVA60 part, white carbon 20 parts, plasticizer 10 parts, tripolycyanamide 5 parts, triethyl phosphate 5 parts, hydroxyapatite 5 parts, mica sheet 10 parts and carbon nano-fiber 10 parts and above-mentioned steps obtainxSr1-xCoO3
20 parts, UIO-66 10 parts mixing, pour homogenizer into, first uses the speed of 1100 revs/min to stir under room temperature 30 minutes, then stir 30min at 60 DEG C with the speed of 4000 revs/min, the batch mixing stirred is discharged, then melts, injection mo(u)lding, obtains described cable insulation material.
Embodiment
3
(1) complex La is prepared0.9Sr0.1CoO3With UIO-66:
A () weighs Lanthanum (III) nitrate, cobalt nitrate, strontium nitrate and nitric acid in proportion, be dissolved in deionized water, be configured to nitrate solution, wherein nitric acid: metal ion: the mol ratio of water is 1:3:70；Separately weighing citric acid to be dissolved in deionized water, be configured to citric acid solution, wherein the mol ratio of citric acid and water is 5:40；
B mixed nitrate solution is heated to 80 DEG C by (), drip citric acid solution under stirring, and the citric acid amount of addition and the mol ratio of metal ion are 1:1；Nitrate solution and citric acid solution adjust pH value of solution to 7 with strong aqua ammonia after being sufficiently mixed uniformly；Gel is obtained after keeping 2 hours at 80 DEG C；
C () is dried into xerogel gained gel at 90 DEG C, then process 1 hour at 400 DEG C, obtain nano-perovskite catalyst La0.9Sr0.1CoO3。
Prepared by UIO-66: weigh 0.932g ZrC14 and 1.32 respectively
G p-phthalic acid, in polytetrafluoroethylliner liner, add 24 mL DMF solvent and dissolved, be subsequently adding 0.665 mL concentrated hydrochloric acid, mix homogeneously, supersound process 5 min, seals inner bag, puts in baking oven in 120 DEG C of reacting by heating 16h, then room temperature is reduced the temperature to, by mixture after reaction is centrifuged, bottom centrifuge tube, obtains white precipitate, be UiO-66.
(2) La that the carbon nano-fiber 10 parts of LDPE 80 parts, 50 parts of phenolic resin, EVA80 part, white carbon 20 parts, plasticizer 8 parts, tripolycyanamide 10 parts, triethyl phosphate 10 parts, hydroxyapatite 10 parts, mica sheet 5 parts and N doping and above-mentioned steps obtainxSr1-xCoO3
15 parts, UIO-66 5 parts mixing, pour homogenizer into, first uses the speed of 1100 revs/min to stir under room temperature 30 minutes, then stir 30min at 60 DEG C with the speed of 4000 revs/min, the batch mixing stirred is discharged, then melts, injection mo(u)lding, obtains described cable insulation material.Wherein N doping amount is 3wt%.
Comparative example
1
It is added without nano-perovskite LaxSr1-xCoO3, other experiment parameters are with embodiment 1.
Comparative example
2
Being added without UIO material, other experiment parameters are with embodiment 1.
Comparative example
3
Attapulgite is used to replace the La of the present inventionxSr1-xCoO3, other experiment parameters are with embodiment 1.
Comparative example
4
Using 4A molecular sieve to replace the UIO-66 of the present invention, other experiment parameters are with embodiment 1.
Concrete detection
Detect the hot strength (σ t/MPa) of above-mentioned aging resistance cable insulation material, elongation at break (δ/ %), carbon left, hardness, LOI index then above-mentioned aging resistance cable insulation material is all over the world carried out hot air aging through 200 DEG C × 30, then detect stretching strength retentivity (E1/ %) and elongation at break conservation rate (E2/ %), concrete outcome is shown in Table 1.
Table 1 each Testing index of Electric insulation material
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Carbon residue, wt% | 22 | 23 | 25 | 5.8 | 7.7 | 3.9 | 6.6 |
| Hardness, ShoreA | 91 | 90 | 88 | 77 | 72 | 70 | 69 |
| Hot strength, MPa | 50 | 51 | 49 | 40 | 37 | 42 | 40 |
| Elongation at break % | 540 | 520 | 550 | 390 | 389 | 338 | 360 |
| LOI | 35.5 | 35.2 | 38.1 | 19.2 | 14.1 | 17.9 | 16.9 |
| 200 DEG C × 30 days, LOI | 33.3 | 34.4 | 33.1 | 14.6 | 11.9 | 10.7 | 12.8 |
| 200 DEG C × 30 days, E1/ % | 95.5 | 93.8 | 93.0 | 66.0 | 63.0 | 65 | 70.1 |
| 200 DEG C × 30 days, E2/ % | 90.4 | 90.8 | 91.4 | 60.9 | 60.8 | 52.7 | 57.7 |
There is the above results it can be seen that LaxSr1-xCoO3With metallic organic framework UIO-66 modified polyolefin material LDPE/PP, advantageously reduce the density of insulant, improve thermostability and the intensity of insulant, reduce the ageing time of insulant, improve LOI index, there is good anti-flammability, long-time (200 DEG C × 30 days) under high temperature action can be kept non-degradable, and through long-time (200 DEG C × 30 days), still there is higher LOI index, fire resistance is preferable.
The above; it is only the detailed description of the invention of the present invention; but protection scope of the present invention is not limited thereto; any those of ordinary skill in the art are in the technical scope that disclosed herein; the change can expected without creative work or replacement, all should contain within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims are limited.
Claims (8)
1. one kind comprises nano-perovskite oxide LaxSr1-xCoO3The preparation method of Fire retardation electric cable insulation material, it is characterised in that concrete preparation process includes:
(1) La is preparedxSr1-xCoO3With UIO-66,
(2) La that LDPE 80-100 part, phenolic resin 50-60 part, EVA60-80 part, white carbon 10-20 part, plasticizer 5-10 part, tripolycyanamide 5-15 part, triethyl phosphate 5-15 part, hydroxyapatite 5-15 part, mica sheet 5-15 part, carbon nano-fiber 5-10 part and above-mentioned steps are obtainedxSr1-xCoO310-20 part, the mixing of UIO-66 5-10 part, pour homogenizer into, the speed first using 1100 revs/min under room temperature stirs 30 minutes, then 30min is stirred at 60 DEG C with the speed of 4000 revs/min, the batch mixing stirred is discharged, then melt, injection mo(u)lding, obtain described cable insulation material；Wherein nano-perovskite oxide LaxSr1-xCoO3In, 0.6 < x < 1.
2. the preparation method of insulant as claimed in claim 1, it is characterised in that nano-perovskite La in step (1)xSr1-xCoO3Preparation method be:
A () weighs Lanthanum (III) nitrate, cobalt nitrate, strontium nitrate and nitric acid in proportion, be dissolved in deionized water, be configured to mixed nitrate solution, wherein nitric acid: metal ion: the mol ratio of water is (1-4): (2 ~ 4): 70；Separately weighing citric acid to be dissolved in deionized water, be configured to citric acid solution, wherein the mol ratio of citric acid and water is (4 ~ 8): 40；
B nitrate solution is heated to 70 ~ 80 DEG C by (), drip citric acid solution under stirring, and the citric acid amount of addition and the mol ratio of metal ion are 1:1 ~ 1:2；Nitrate solution and citric acid solution adjust pH value of solution to 7 with strong aqua ammonia after being sufficiently mixed uniformly；Gel is obtained after keeping 2 ~ 3 hours at 75 ~ 80 DEG C；
C () is dried into xerogel gained gel at 90 ~ 100 DEG C, then process 0.5 ~ 1 hour at 350 ~ 400 DEG C, obtain nano-perovskite oxide La1-XSrXCoO3。
3. the preparation method of insulant as claimed in claim 1 or 2, it is characterised in that in step (1), the preparation method of UIO-66 is: weigh 0.932g ZrC1 respectively4With 1.32 g p-phthalic acids, in polytetrafluoroethylliner liner, add 24 mL DMF solvent and dissolved, be subsequently adding 0.665 mL concentrated hydrochloric acid, mix homogeneously, supersound process 5 min, inner bag sealed, puts in baking oven in 120
DEG C reacting by heating 16h, then reduces the temperature to room temperature, by being centrifuged mixture after reaction, obtains white precipitate, be UiO-66 bottom centrifuge tube.
4. the preparation method of insulant as claimed in claim 1, it is characterised in that in step (2), melt temperature is 200-280 DEG C, and described injection mo(u)lding temperature is 120-150 DEG C, preferably 130-150 DEG C.
5. the preparation method of insulant as claimed in claim 1, it is characterised in that described plasticizer is trioctyl trimellitate (TOTM)；Described nano-perovskite oxide LaxSr1-xCoO3Mean diameter be 20-85nm, preferably 20-60nm.
6. the preparation method of insulant as claimed in claim 1, it is characterised in that tripolycyanamide: triethyl phosphate: the mass ratio of hydroxyapatite is 1-3:1:1, most preferably 1:1:1.
7. the preparation method of insulant as claimed in claim 1, it is characterised in that carbon nano-fiber a length of 10-20 micron, it is preferred that carbon nano-fiber can also use nitrogen modified, and nitrogen content is 1-5wt%.
8. the cable insulation material that the preparation method as described in any one of claim 1-7 obtains application in high pressure or supertension plastic insulating power cable.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610458518.9A CN105949581A (en) | 2016-06-23 | 2016-06-23 | Preparation method and application of flame-retardant cable insulating material comprising nano perovskite oxide LaxSr[1-x]CoO3 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610458518.9A CN105949581A (en) | 2016-06-23 | 2016-06-23 | Preparation method and application of flame-retardant cable insulating material comprising nano perovskite oxide LaxSr[1-x]CoO3 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105949581A true CN105949581A (en) | 2016-09-21 |
Family
ID=56904319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610458518.9A Pending CN105949581A (en) | 2016-06-23 | 2016-06-23 | Preparation method and application of flame-retardant cable insulating material comprising nano perovskite oxide LaxSr[1-x]CoO3 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105949581A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107093669A (en) * | 2017-02-28 | 2017-08-25 | 华东师范大学 | A kind of perovskite solar cell light absorption layer |
| CN109133180A (en) * | 2018-05-31 | 2019-01-04 | 青岛科技大学 | A kind of semiconductive composite material and preparation method of modification |
| CN115157735A (en) * | 2022-08-12 | 2022-10-11 | 华中科技大学鄂州工业技术研究院 | A kind of preparation method of composite thick film |
| CN116500738A (en) * | 2023-06-27 | 2023-07-28 | 西安西古光通信有限公司 | Environment-friendly optical cable and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101133743A (en) * | 2007-10-12 | 2008-03-05 | 厦门大学 | A kind of preparation method of photocatalytic bactericidal antibacterial agent under visible light |
| CN101269839A (en) * | 2007-03-22 | 2008-09-24 | 天津市环科机动车尾气催化净化技术有限公司 | Preparation technique for perovskite type rare earth manganate with lemon acid method |
| CN101791575A (en) * | 2010-03-23 | 2010-08-04 | 上海师范大学 | Preparation method of heterogeneous catalyst of organic coordination compounds of mesoporous structure metals |
| CN102532649A (en) * | 2010-12-24 | 2012-07-04 | 江苏亨通电力电缆有限公司 | Novel low-smoke halogen-free flame-retardant cable sheath material |
| CN104437645A (en) * | 2014-11-19 | 2015-03-25 | 河南工业大学 | Metal-organic framework supported heteropoly acid catalyst for synthesizing glutaraldehyde and production method of metal-organic framework supported heteropoly acid catalyst |
| CN105017605A (en) * | 2015-06-25 | 2015-11-04 | 合肥蓝科新材料有限公司 | Cracking-resistant silane crosslinked polyethylene insulation composite material and preparation method thereof |
-
2016
- 2016-06-23 CN CN201610458518.9A patent/CN105949581A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269839A (en) * | 2007-03-22 | 2008-09-24 | 天津市环科机动车尾气催化净化技术有限公司 | Preparation technique for perovskite type rare earth manganate with lemon acid method |
| CN101133743A (en) * | 2007-10-12 | 2008-03-05 | 厦门大学 | A kind of preparation method of photocatalytic bactericidal antibacterial agent under visible light |
| CN101791575A (en) * | 2010-03-23 | 2010-08-04 | 上海师范大学 | Preparation method of heterogeneous catalyst of organic coordination compounds of mesoporous structure metals |
| CN102532649A (en) * | 2010-12-24 | 2012-07-04 | 江苏亨通电力电缆有限公司 | Novel low-smoke halogen-free flame-retardant cable sheath material |
| CN104437645A (en) * | 2014-11-19 | 2015-03-25 | 河南工业大学 | Metal-organic framework supported heteropoly acid catalyst for synthesizing glutaraldehyde and production method of metal-organic framework supported heteropoly acid catalyst |
| CN105017605A (en) * | 2015-06-25 | 2015-11-04 | 合肥蓝科新材料有限公司 | Cracking-resistant silane crosslinked polyethylene insulation composite material and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 于辰等: "CNFs取向对CNFs/LDPE复合材料空间电荷的影响", 《湖北大学学报（自然科学版）》 * |
| 杨中文: "《塑料用树脂与助剂》", 31 December 2009 * |
| 王永强: "《阻燃材料及应用技术》", 30 April 2003 * |
| 苏家齐: "《塑料工业辞典》", 31 December 1989 * |
| 赵巍巍: "UiO-66类MOFs在高效液相色谱分离中的应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107093669A (en) * | 2017-02-28 | 2017-08-25 | 华东师范大学 | A kind of perovskite solar cell light absorption layer |
| CN107093669B (en) * | 2017-02-28 | 2019-06-14 | 华东师范大学 | A perovskite solar cell light absorbing layer |
| CN109133180A (en) * | 2018-05-31 | 2019-01-04 | 青岛科技大学 | A kind of semiconductive composite material and preparation method of modification |
| WO2019227466A1 (en) * | 2018-05-31 | 2019-12-05 | 青岛科技大学 | Modified semi-conductive composite and preparation method therefor |
| CN109133180B (en) * | 2018-05-31 | 2021-07-20 | 青岛科技大学 | A kind of modified semiconductive composite material and preparation method thereof |
| CN115157735A (en) * | 2022-08-12 | 2022-10-11 | 华中科技大学鄂州工业技术研究院 | A kind of preparation method of composite thick film |
| CN116500738A (en) * | 2023-06-27 | 2023-07-28 | 西安西古光通信有限公司 | Environment-friendly optical cable and preparation method thereof |
| CN116500738B (en) * | 2023-06-27 | 2023-09-01 | 西安西古光通信有限公司 | Environment-friendly optical cable and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103756121B (en) | A kind of heatproof oil-resistant low-smoke halogen-free flame-retardant cross-linking radiation composite polyolefine material and preparation method thereof | |
| CN110878155B (en) | Halogen-free flame-retardant external insulation material for nuclear power station cable and preparation method thereof | |
| CN101885873B (en) | Semi-conductive ethylene vinyl acetate (EVA) plastic for shielding and production method thereof | |
| CN110862604B (en) | A kind of halogen-free flame-retardant sheath material for nuclear power plant and preparation method thereof | |
| CN105949581A (en) | Preparation method and application of flame-retardant cable insulating material comprising nano perovskite oxide LaxSr[1-x]CoO3 | |
| CN106117699A (en) | A kind of preparation method of the Fire retardation electric cable insulation material containing magnesium aluminate spinel | |
| CN105860426A (en) | Method for preparing cable insulating materials with nanometer magnesium oxide/low-density polyethylene/modified bentonite and application of cable insulating materials | |
| CN105837907A (en) | Flame-retardant cable insulating material containing NCNFS/ZIF-90 and application | |
| CN105968491A (en) | Cable insulation material containing flame retardant compound agent LDHS/SBA-15 and application of cable insulation material | |
| CN110862620A (en) | Halogen-free flame retardant filling material for nuclear power plant cables and preparation method thereof | |
| CN105968492A (en) | Preparation method and application of cable insulating material containing composite flame retardant LDHS/ZIF-8 | |
| CN110862599A (en) | Internal insulation material for nuclear power station cable and preparation method thereof | |
| CN105330943B (en) | A kind of fire retardant insulating CABLE MATERIALS and preparation method thereof | |
| CN110172178A (en) | A kind of fire-retardant polyolefine polymer composite and preparation method thereof | |
| CN105802122B (en) | A kind of cable insulation material comprising nano magnesia/low density polyethylene (LDPE)/modified alta-mud and its application | |
| CN117534897A (en) | A high-toughness, low-smoke, halogen-free, flame-retardant wire and cable sheathing material | |
| CN112194835A (en) | Low-smoke halogen-free silane cross-linked flame-retardant cable material and production process thereof | |
| CN104961967B (en) | Pyrocondensation insulating materials and preparation process in the shell of generation Ⅲ nuclear power station | |
| CN104262875B (en) | Intumescent flame-retardant cable material taking plant-based active carbon as synergist and preparation method thereof | |
| CN113563829B (en) | A kind of flame-retardant EVA adhesive film and its preparation method and application | |
| CN114479385A (en) | A conductive flame retardant biodegradable PBAT composite material and its preparation method and application | |
| CN112961431A (en) | High-temperature-resistant flame-retardant insulating material and preparation method thereof | |
| CN109485989A (en) | A kind of photovoltaic cable CABLE MATERIALS and preparation method thereof | |
| CN106117700A (en) | A kind of Fire retardation electric cable insulation material comprising nano-perovskite oxide and purposes | |
| CN105924725A (en) | Preparation method and application of flame-retardant cable insulation material containing Ag-CNFS/ZIF-90 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160921 |