CN110551356A - 一种超高压电缆用阻燃护套料及其制备方法 - Google Patents
一种超高压电缆用阻燃护套料及其制备方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 87
- 239000003063 flame retardant Substances 0.000 title claims abstract description 57
- 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 claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 235000010410 calcium alginate Nutrition 0.000 claims abstract description 20
- 239000000648 calcium alginate Substances 0.000 claims abstract description 20
- 229960002681 calcium alginate Drugs 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims abstract description 13
- 229920001744 Polyaldehyde Polymers 0.000 claims abstract description 12
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229920001971 elastomer Polymers 0.000 claims abstract description 3
- 239000000314 lubricant Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000005060 rubber Substances 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 11
- 235000010413 sodium alginate Nutrition 0.000 claims description 11
- 239000000661 sodium alginate Substances 0.000 claims description 11
- 229940005550 sodium alginate Drugs 0.000 claims description 11
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 229920002943 EPDM rubber Polymers 0.000 claims description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 8
- 235000013539 calcium stearate Nutrition 0.000 claims description 8
- 239000008116 calcium stearate Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- IWICDTXLJDCAMR-UHFFFAOYSA-N trihydroxy(propan-2-yloxy)silane Chemical compound CC(C)O[Si](O)(O)O IWICDTXLJDCAMR-UHFFFAOYSA-N 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 18
- 239000011347 resin Substances 0.000 abstract description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 9
- 229910000464 lead oxide Inorganic materials 0.000 abstract description 8
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 abstract description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000012796 inorganic flame retardant Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- -1 silicate ester Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 27
- 229910052760 oxygen Inorganic materials 0.000 description 27
- 239000001301 oxygen Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 24
- 238000004080 punching Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- HDRTWMBOUSPQON-ODZAUARKSA-L calcium;(z)-but-2-enedioate Chemical compound [Ca+2].[O-]C(=O)\C=C/C([O-])=O HDRTWMBOUSPQON-ODZAUARKSA-L 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2234—Oxides; Hydroxides of metals of lead
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/262—Alkali metal carbonates
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种超高压电缆用阻燃护套料及其制备方法,属于复合高分子材料技术领域。本发明研制的产品包括:马来酸酐接枝改性EVA树脂、橡胶、多醛基海藻酸钙、硅酸酯、氟化钙、金属碳酸、纳米氧化铅、硫化剂、防老剂、抗氧剂和润滑剂,在产品制备过程中,先按原料组成称量各组分;再将各组分原料混合后,依次经塑炼、混炼后,挤出造粒,即得超高压电缆用阻燃护套料。本发明通过提升无机阻燃成分在体系中的分散和相容性,使产品护套料力学性能和阻燃性能得到显著提升。
Description
技术领域
本发明公开了一种超高压电缆用阻燃护套料及其制备方法,属于复合高分子材料技术领域。
背景技术
绝大多数塑料都是可燃的,当温度达到一定程度之后,会产生挥发性的可燃气体,促使其进一步燃烧。塑料聚合物是电缆基材的主要来源,赋予塑料聚合物一定的阻燃性能是亟待解决的技术问题。
目前行业内普遍采用的阻燃剂的种类主要包括如下:
(1)卤素阻燃体系,其阻燃机理是卤素阻燃剂可分解产生HX,HX降解产生自由基,终止并延缓了燃烧过程中的链式反应;
(2)膨胀型阻燃剂体系,化学膨胀型阻燃剂(IFR)是以磷、氮为主要成分的无卤阻燃剂,燃烧过程中产生的氨气、氮气和水等能够起到气相稀释的作用,降低可燃气体的浓度,从而有效防止了火焰的传播;
(3)磷系阻燃体系,燃烧时的高温促使含磷阻燃剂经一系列的反应生成有很强脱水性的聚磷酸。产生的聚磷酸可以促使有氧有机物快速脱水而碳化,碳化后所形成的物质是一种难以燃烧的结构致密的物质;
(4)氮系阻燃剂,氮系阻燃剂受热放出二氧化碳、氨气、氮气和水,上述气体均属于难燃气体,从而阻止燃烧;
(5)水合金属化合物阻燃体系,水合金属化合物阻燃由于其分解产生大量的水,一方面吸收了大量的热,从而使材料表面的温度降低,另一方面分解出来的水蒸气又可稀释可燃气体,因此具有良好的阻燃效果;
其中,日本住友电气工业株式会社申请的专利JPS59117549A公开了,以醋酸乙烯含量在50~85%的EVA为基材,阻燃抑烟剂使用的是二价或三价金属的碳酸盐或氢氧化物和硼酸锌,两者的重量比在0.25~0.75之间,基于基材100份,阻燃抑烟剂总量100份,氧指数在30以上,烟密度低于100.其中,该申请提及了二价或三价的金属碳酸盐或氢氧化物大量使用产生的弊端,即降低了材料的力学性能。
为了克服上述碳酸盐或氢氧化物阻燃剂大量填充带来的力学性能下降的缺陷,就需要开发填充量小,阻燃效果好的阻燃剂。
发明内容
针对现有电缆护套料采用大量添加碳酸盐以及金属氢氧化物后,引起护套料力学性能下降,且无机阻燃添加料和有机基体树脂之间的界面相容性较差,进一步恶化产品力学性能的弊端,提供了一种超高压电缆用阻燃护套料及其制备方法。
为了解决上述技术问题,本发明所采用的技术方案为:
一种超高压电缆用阻燃护套料,包括以下重量份数的原料组成:
所述橡胶为天然橡胶、三元乙丙橡胶、丁基橡胶、丁苯橡胶或丁腈橡胶中的任意一种。
所述多醛基海藻酸钙的制备过程为:将海藻酸钠和水按质量比为1:20~1:50混合,再加入海藻酸钠质量0.3~0.4倍的高碘酸钠,加热搅拌反应后,浓缩,再经加热烘干,得干燥料,随后将干燥料浸渍于氯化钙溶液中,再经过滤,洗涤和干燥,即得多醛基海藻酸钙。
所述硅酸酯为正硅酸甲酯、正硅酸乙酯或正硅酸异丙酯中的任意一种。
所述金属碳酸盐为碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、碳酸铵、碳酸氢铵、碳酸氢钙、碳酸钙中的任意一种。
所述硫化剂为硫磺,一氯化硫或过氧化苯甲酰中任意一种。
所述防老剂为防老剂4020、防老剂RD或防老剂NBC中的任意一种。
所述抗氧剂为抗氧剂1010,抗氧剂1076或抗氧剂168中任意一种。
所述润滑剂为硬脂酸镁、硬脂酸钙或硬脂酸锌中的任意一种。
所述超高压电缆用阻燃护套料的制备步骤为:
(1)按原料组成称量各组分;
(2)将各组分原料混合后,依次经塑炼、混炼后,挤出造粒,即得超高压电缆用阻燃护套料。
与现有技术相比,本发明的有益效果为:
(1)本发明技术方案通过利用马来酸酐对EVA基体树脂进行接枝改性,利用马来酸酐提高EVA大分子链的极性,从而提升基体树脂对体系中无机颗粒的界面相容性,有效提升了产品力学性能;另外,通过利用马来酸酐对EVA基体树脂进行改性,降低了EVA树脂原本的热解温度,使EVA树脂在受热时,在低于体系着火点温度下就发生热解,从而转变为相对难燃的炭质包覆层,提升了产品的阻燃性能;
(2)本发明技术方案在马来酸钙改性的EVA基体树脂基础上,引入多醛基海藻酸钙以及硅酸酯,在产品加工过程中,受热后,多醛基海藻酸钙分子结构中的醛基可与体系存在的羧基逐渐发生羟醛缩合反应而脱水,一旦形成水分子,即可和硅酸酯分子接触,从而使硅酸酯水解,该水解反应的发生,由于水分子和硅酸酯分子的接触处于分子级别,保障了水解反应缓慢均匀进行,避免了水解产物二氧化硅晶体的快速生长,且一旦有二氧化硅晶核形成,即可被极性的马来酸钙改性EVA树脂大分子链吸附固定,从而在树脂基体中形成了大量均匀分布的二氧化硅晶核,二氧化硅晶核在EVA树脂大分子链空间填充后,不仅可有效提升产品的力学性能,且在高温受热后,可在纳米氧化铅作用下发生快速熔融,该熔融速率相比于颗粒较大的二氧化硅晶体而言更快,因此可快速熔融并迁移至体系表面,在护套表面形成熔融的无机玻璃包覆层,有效隔绝了氧气,避免护套料的进一步燃烧,起到良好的阻燃作用;而海藻酸钙和体系中羟基脱水缩合后,共价结构增多,热解需要消耗更多的热量,提高了护套料整体的热稳定性和残炭率,且经过钙离子的处理后,钙离子可催化体系活性中心的脱水反应,从而使护套料初始降解温度降低,使护套料在较低温度发生裂解,裂解产生的可燃性气体由于达不到着火点而直接溢出,减少其燃烧反馈给产品的热量,从而有利于进一步阻止剩余产品继续裂解,而在较低温度下,EVA树脂和表面保护层(海藻酸钙)生成焦炭的反应占据主导地位,生成的焦炭可与其他无机组分覆盖于产品表面,阻燃氧气的进入和热量的扩散,起到良好的阻燃屏障作用。
具体实施方式
以下对本发明的实施例进行详细说明,但是本发明可以根据权利要求限定和覆盖的多种不同方式实施。
实施例1
多醛基海藻酸钙:
将海藻酸钠和水按质量比为1:20混合后,再加入海藻酸钠质量0.3倍的高碘酸钠,随后于温度为65℃,搅拌转速为200r/min条件下,加热搅拌反应3h,待反应结束,于温度为75℃,压力为400mmHg条件下,减压浓缩至物料原体积的1/2,得浓缩物,再将所得浓缩物转入真空干燥箱中,于温度为105℃,压力为60Pa条件下真空干燥至恒重,得干燥料,再将所得干燥料浸渍于质量分数为3%的氯化钙溶液中,于超声频率为55kHz条件下,浸渍10min后,过滤,得滤饼,并用去离子水洗涤滤饼3次,再将洗涤后的滤饼转入真空干燥箱中,于温度为105℃,压力为60Pa条件下,真空干燥至恒重,得多醛基海藻酸钙;
护套料的制备:
按重量份数计,依次取80份接枝率为0.3的马来酸酐接枝改性EVA树脂,30份三元乙丙橡胶,4份多醛基海藻酸钙,10份正硅酸乙酯,2份氟化钙,4份碳酸钠,0.1份纳米氧化铅,1份过氧化苯甲酰,1份防老剂RD,1份抗氧剂1010,1份硬脂酸钙;将上述原料加入混料机中,用搅拌器以300r/min转速搅拌混合30min后,将混料机中物料转入密炼机中,于温度为80℃条件下塑炼5min后,转入混练机中,于温度为68℃条件下混炼10min,随后经双螺杆熔融挤出机挤出造粒,即得超高压电缆用阻燃护套料。
测试试样的制作:
将本发明所得产品超高压电缆用阻燃护套料加入模具中,再将模具移至平板硫化机,于温度为160℃,压力为15MPa条件下,热压硫化15min后,冷却,出料,即得测试试样;
力学性能测试:
使用CREE-6040型冲片机将1mm厚的待测样件进行冲样,裁剪出5个以上的Ⅱ型哑铃片,试样宽度为6mm,中间的标距选定为2.5cm,参照GB/T1040-92标准,使用万能拉力机进行测试,设定拉伸速率为200mm/min,最大拉力为500N,测量得到样件的拉伸强度为18MPa,断裂伸长率为340%。
氧指数测试:
本测试采用氧指数测定仪测试产品氧指数,测试参照GB/T2406.2-2009标准,测试得到产品样件的氧指数为:32%。
实施例2
多醛基海藻酸钙:
将海藻酸钠和水按质量比为1:30混合后,再加入海藻酸钠质量0.3倍的高碘酸钠,随后于温度为70℃,搅拌转速为300r/min条件下,加热搅拌反应4h,待反应结束,于温度为80℃,压力为410mmHg条件下,减压浓缩至物料原体积的1/2,得浓缩物,再将所得浓缩物转入真空干燥箱中,于温度为108℃,压力为70Pa条件下真空干燥至恒重,得干燥料,再将所得干燥料浸渍于质量分数为5%的氯化钙溶液中,于超声频率为70kHz条件下,浸渍50min后,过滤,得滤饼,并用去离子水洗涤滤饼4次,再将洗涤后的滤饼转入真空干燥箱中,于温度为108℃,压力为70Pa条件下,真空干燥至恒重,得多醛基海藻酸钙;
护套料的制备:
按重量份数计,依次取90份接枝率为0.4的马来酸酐接枝改性EVA树脂,35份三元乙丙橡胶,6份多醛基海藻酸钙,12份正硅酸乙酯,2份氟化钙,5份碳酸钠,0.2份纳米氧化铅,1份过氧化苯甲酰,1份防老剂RD,1份抗氧剂1010,1份硬脂酸钙;将上述原料加入混料机中,用搅拌器以400r/min转速搅拌混合40min后,将混料机中物料转入密炼机中,于温度为82℃条件下塑炼8min后,转入混练机中,于温度为69℃条件下混炼12min,随后经双螺杆熔融挤出机挤出造粒,即得超高压电缆用阻燃护套料。
测试试样的制作:
将本发明所得产品超高压电缆用阻燃护套料加入模具中,再将模具移至平板硫化机,于温度为160℃,压力为15MPa条件下,热压硫化15min后,冷却,出料,即得测试试样;
力学性能测试:
使用CREE-6040型冲片机将1mm厚的待测样件进行冲样,裁剪出5个以上的Ⅱ型哑铃片,试样宽度为6mm,中间的标距选定为2.5cm,参照GB/T1040-92标准,使用万能拉力机进行测试,设定拉伸速率为200mm/min,最大拉力为500N,测量得到样件的拉伸强度为19MPa,断裂伸长率为350%。
氧指数测试:
本测试采用氧指数测定仪测试产品氧指数,测试参照GB/T2406.2-2009标准,测试得到产品样件的氧指数为:34%。
实施例3
多醛基海藻酸钙:
将海藻酸钠和水按质量比为1:50混合后,再加入海藻酸钠质量0.4倍的高碘酸钠,随后于温度为75℃,搅拌转速为500r/min条件下,加热搅拌反应5h,待反应结束,于温度为85℃,压力为420mmHg条件下,减压浓缩至物料原体积的1/2,得浓缩物,再将所得浓缩物转入真空干燥箱中,于温度为110℃,压力为80Pa条件下真空干燥至恒重,得干燥料,再将所得干燥料浸渍于质量分数为8%的氯化钙溶液中,于超声频率为80kHz条件下,浸渍100min后,过滤,得滤饼,并用去离子水洗涤滤饼5次,再将洗涤后的滤饼转入真空干燥箱中,于温度为110℃,压力为80Pa条件下,真空干燥至恒重,得多醛基海藻酸钙;
护套料的制备:
按重量份数计,依次取100份接枝率为0.5的马来酸酐接枝改性EVA树脂,40份三元乙丙橡胶,8份多醛基海藻酸钙,15份正硅酸乙酯,3份氟化钙,8份碳酸钠,0.3份纳米氧化铅,2份过氧化苯甲酰,2份防老剂RD,2份抗氧剂1010,2份硬脂酸钙;将上述原料加入混料机中,用搅拌器以500r/min转速搅拌混合60min后,将混料机中物料转入密炼机中,于温度为85℃条件下塑炼10min后,转入混练机中,于温度为70℃条件下混炼15min,随后经双螺杆熔融挤出机挤出造粒,即得超高压电缆用阻燃护套料。
测试试样的制作:
将本发明所得产品超高压电缆用阻燃护套料加入模具中,再将模具移至平板硫化机,于温度为160℃,压力为15MPa条件下,热压硫化15min后,冷却,出料,即得测试试样;
力学性能测试:
使用CREE-6040型冲片机将1mm厚的待测样件进行冲样,裁剪出5个以上的Ⅱ型哑铃片,试样宽度为6mm,中间的标距选定为2.5cm,参照GB/T1040-92标准,使用万能拉力机进行测试,设定拉伸速率为200mm/min,最大拉力为500N,测量得到样件的拉伸强度为21MPa,断裂伸长率为360%。
氧指数测试:
本测试采用氧指数测定仪测试产品氧指数,测试参照GB/T2406.2-2009标准,测试得到产品样件的氧指数为36%。
实施例4
本实施例和实施例1相比,区别之处在于:
护套料的制备:按重量份数计,依次取80份接枝率为0.3的马来酸酐接枝改性EVA树脂,30份三元乙丙橡胶,4份多醛基海藻酸钠,10份正硅酸乙酯,2份氟化钙,4份碳酸钠,0.1份纳米氧化铅,1份过氧化苯甲酰,1份防老剂RD,1份抗氧剂1010,1份硬脂酸钙;将上述原料加入混料机中,用搅拌器以300r/min转速搅拌混合30min后,将混料机中物料转入密炼机中,于温度为80℃条件下塑炼5min后,转入混练机中,于温度为68℃条件下混炼10min,随后经双螺杆熔融挤出机挤出造粒,即得超高压电缆用阻燃护套料。
测试试样的制作:
将本发明所得产品超高压电缆用阻燃护套料加入模具中,再将模具移至平板硫化机,于温度为160℃,压力为15MPa条件下,热压硫化15min后,冷却,出料,即得测试试样;
力学性能测试:
使用CREE-6040型冲片机将1mm厚的待测样件进行冲样,裁剪出5个以上的Ⅱ型哑铃片,试样宽度为6mm,中间的标距选定为2.5cm,参照GB/T1040-92标准,使用万能拉力机进行测试,设定拉伸速率为200mm/min,最大拉力为500N,测量得到样件的拉伸强度为17.9MPa,断裂伸长率为335%。
氧指数测试:
本测试采用氧指数测定仪测试产品氧指数,测试参照GB/T2406.2-2009标准,测试得到产品样件的氧指数为:22%。
实施例5
本实施例和实施例1相比,区别指出在于:
护套料的制备:
按重量份数计,依次取80份接枝率为0.3的马来酸酐接枝改性EVA树脂,30份三元乙丙橡胶,4份多醛基海藻酸钙,2份平均粒径为2μm的二氧化硅粉体,2份氟化钙,4份碳酸钠,0.1份纳米氧化铅,1份过氧化苯甲酰,1份防老剂RD,1份抗氧剂1010,1份硬脂酸钙;将上述原料加入混料机中,用搅拌器以300r/min转速搅拌混合30min后,将混料机中物料转入密炼机中,于温度为80℃条件下塑炼5min后,转入混练机中,于温度为68℃条件下混炼10min,随后经双螺杆熔融挤出机挤出造粒,即得超高压电缆用阻燃护套料。
测试试样的制作:
将本发明所得产品超高压电缆用阻燃护套料加入模具中,再将模具移至平板硫化机,于温度为160℃,压力为15MPa条件下,热压硫化15min后,冷却,出料,即得测试试样;
力学性能测试:
使用CREE-6040型冲片机将1mm厚的待测样件进行冲样,裁剪出5个以上的Ⅱ型哑铃片,试样宽度为6mm,中间的标距选定为2.5cm,参照GB/T1040-92标准,使用万能拉力机进行测试,设定拉伸速率为200mm/min,最大拉力为500N,测量得到样件的拉伸强度为12MPa,断裂伸长率为220%。
氧指数测试:
本测试采用氧指数测定仪测试产品氧指数,测试参照GB/T2406.2-2009标准,测试得到产品样件的氧指数为:28%。
实施例6
本实施例和实施例1相比,区别之处在于:
护套料的制备:
按重量份数计,依次取80份EVA树脂,30份三元乙丙橡胶,4份多醛基海藻酸钙,10份正硅酸乙酯,2份氟化钙,4份碳酸钠,0.1份纳米氧化铅,1份过氧化苯甲酰,1份防老剂RD,1份抗氧剂1010,1份硬脂酸钙;将上述原料加入混料机中,用搅拌器以300r/min转速搅拌混合30min后,将混料机中物料转入密炼机中,于温度为80℃条件下塑炼5min后,转入混练机中,于温度为68℃条件下混炼10min,随后经双螺杆熔融挤出机挤出造粒,即得超高压电缆用阻燃护套料。
测试试样的制作:
将本发明所得产品超高压电缆用阻燃护套料加入模具中,再将模具移至平板硫化机,于温度为160℃,压力为15MPa条件下,热压硫化15min后,冷却,出料,即得测试试样;
力学性能测试:
使用CREE-6040型冲片机将1mm厚的待测样件进行冲样,裁剪出5个以上的Ⅱ型哑铃片,试样宽度为6mm,中间的标距选定为2.5cm,参照GB/T1040-92标准,使用万能拉力机进行测试,设定拉伸速率为200mm/min,最大拉力为500N,测量得到样件的拉伸强度为16.5MPa,断裂伸长率为310%。
氧指数测试:
本测试采用氧指数测定仪测试产品氧指数,测试参照GB/T2406.2-2009标准,测试得到产品样件的氧指数为:30%。
以上所述仅为本发明的较佳方式,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种超高压电缆用阻燃护套料,其特征在于,包括以下重量份数的原料组成:
2.根据权利要求1所述的一种超高压电缆用阻燃护套料,其特征在于:所述橡胶为天然橡胶、三元乙丙橡胶、丁基橡胶、丁苯橡胶或丁腈橡胶中的任意一种。
3.根据权利要求1所述的一种超高压电缆用阻燃护套料,其特征在于:所述多醛基海藻酸钙的制备过程为:将海藻酸钠和水按质量比为1:20~1:50混合,再加入海藻酸钠质量0.3~0.4倍的高碘酸钠,加热搅拌反应后,浓缩,再经加热烘干,得干燥料,随后将干燥料浸渍于氯化钙溶液中,再经过滤,洗涤和干燥,即得多醛基海藻酸钙。
4.根据权利要求1所述的一种超高压电缆用阻燃护套料,其特征在于:所述硅酸酯为正硅酸甲酯、正硅酸乙酯或正硅酸异丙酯中的任意一种。
5.根据权利要求1所述的一种超高压电缆用阻燃护套料,其特征在于:所述金属碳酸盐为碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、碳酸铵、碳酸氢铵、碳酸氢钙、碳酸钙中的任意一种。
6.根据权利要求1所述的一种超高压电缆用阻燃护套料,其特征在于:所述硫化剂为硫磺,一氯化硫或过氧化苯甲酰中任意一种。
7.根据权利要求1所述的一种超高压电缆用阻燃护套料,其特征在于:所述防老剂为防老剂4020、防老剂RD或防老剂NBC中的任意一种。
8.根据权利要求1所述的一种超高压电缆用阻燃护套料,其特征在于:所述抗氧剂为抗氧剂1010,抗氧剂1076或抗氧剂168中任意一种。
9.根据权利要求1所述的一种超高压电缆用阻燃护套料,其特征在于:所述润滑剂为硬脂酸镁、硬脂酸钙或硬脂酸锌中的任意一种。
10.一种如权利要求1-9任一项所述的超高压电缆用阻燃护套料,其特征在于:所述超高压电缆用阻燃护套料的制备步骤为:
(1)按原料组成称量各组分;
(2)将各组分原料混合后,依次经塑炼、混炼后,挤出造粒,即得超高压电缆用阻燃护套料。
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