CN115926301B - Phase-change temperature-control sheath material for magnetic levitation train cable and manufacturing method thereof - Google Patents
Phase-change temperature-control sheath material for magnetic levitation train cable and manufacturing method thereof Download PDFInfo
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- 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 claims abstract description 57
- 239000003063 flame retardant Substances 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004693 Polybenzimidazole Substances 0.000 claims abstract description 27
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 27
- 239000010433 feldspar Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 23
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 22
- BTXFTCVNWMNXKH-UHFFFAOYSA-N NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC Chemical compound NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC BTXFTCVNWMNXKH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
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- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 10
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 10
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 6
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- 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 4
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- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 2
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- ILXWFJOFKUNZJA-UHFFFAOYSA-N ethyltellanylethane Chemical group CC[Te]CC ILXWFJOFKUNZJA-UHFFFAOYSA-N 0.000 claims description 2
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- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
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- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- VBQRUYIOTHNGOP-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinine 6-oxide Chemical group C1=CC=C2P(=O)OC3=CC=CC=C3C2=C1 VBQRUYIOTHNGOP-UHFFFAOYSA-N 0.000 description 2
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
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- 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
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 239000011258 core-shell material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
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- 239000002071 nanotube Substances 0.000 description 1
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- 238000004321 preservation Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
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- 230000008054 signal transmission Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
Abstract
The invention discloses a high-flame-retardance, high-flexibility and phase-change temperature-control sheath material for a magnetic levitation train cable, and a manufacturing method and application thereof, wherein a polybenzimidazole (DOPO-PBI) phosphorus-nitrogen flame retardant containing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide elements is compounded with a char forming agent containing rich oxygen elements, so that the flame retardant property of the material is improved. The silicon carbide and feldspar powder subjected to surface modification by the aniline methyltriethoxysilane are subjected to a stepwise blending process, a char forming agent, silicon carbide and feldspar powder solid-solid composite controllable phase change system is built in the material, the high motion capability of a molecular chain segment of the material in an operating environment below the glass transition temperature of the material is ensured, the stable service of the material and a cable at an extremely low temperature is realized, and in addition, the material has excellent flame retardant, fire resistance, oil resistance, mechanical and ageing resistance, and can be simultaneously applied to cables for intelligent service equipment in complex environments such as fire extinguishing robots, emergency disposal rescue robots and the like.
Description
Technical Field
The invention belongs to the technical and scientific fields of high polymer materials, and particularly relates to a high-flame-retardance high-flexibility phase-change temperature-control sheath material for a magnetic levitation train cable, and a manufacturing method and application thereof.
Background
The high-frequency fire-resistant communication cable for the magnetic levitation train with the speed of 620 km per hour is in an alternating electromagnetic field space for a long time, and the thermal effect of the electromagnetic field can lead the cable to undergo long-term high-low temperature circulation to influence the signal transmission. Therefore, the development of the sheath material for the phase-change fire-resistant cable with high heat conductivity and high flame retardance and controllable temperature has important significance in ensuring the cable to work in a long-term stable temperature environment.
Patent CN201310442589.6 compounds aluminum hydroxide, magnesium hydroxide and zinc borate to use the flame retardant property of the reinforcing material. The patent CN202011203891.2 is prepared by compounding aluminum hydroxide, magnesium hydroxide and halloysite nanotubes, and forms a honeycomb loose porous structure after high temperature, thereby insulating heat and retarding flame. However, the flame retardant has larger additive content in the research, so that the mechanical property of the material is reduced to a certain extent, the improvement on the material property is single, and the application requirement in a complex environment is difficult to meet.
At present, the types and technologies of cable products adopted by domestic magnetic levitation trains are all mastered by foreign countries, so that the risk of outage of key parts of the domestic high-speed magnetic levitation trains is caused. Therefore, the development of the high-flame-retardance high-flexibility phase-change temperature-control sheath material for the maglev train cable with independent intellectual property has important significance.
Disclosure of Invention
The invention discloses a high-flame-retardance high-flexibility phase-change temperature-control sheath material for a magnetic levitation train cable, and a manufacturing method and application thereof, wherein the high-flame-retardance high-flexibility phase-change temperature-control sheath material comprises the following raw materials in parts by weight: 100-150 parts of EVA; and 40-60 parts of rubber; 30-50 parts of phosphorus-nitrogen flame retardant; 10-15 parts of a charring agent; 40-75 parts of inorganic functional filler; 5-15 parts of macromolecular coupling agent; 5-10 parts of vulcanizing agent; 1-3 parts of vulcanization accelerator; 1-3 parts of an anti-aging agent; 0.5-2 parts of antioxidant; 1-5 parts of color master batch. Wherein the phosphorus-nitrogen flame retardant is polybenzimidazole (DOPO-PBI) containing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide moieties; the char forming agent is substances containing rich oxygen elements such as pentaerythritol, trimethylolethane and the like; the inorganic functional filler is silicon carbide and feldspar powder which are subjected to surface modification by using the aniline methyltriethoxysilane, the controllable migration and dispersion of the filler in the polymer can be realized through a step-by-step blending process, a uniform and compact refractory layer is formed, and a char former/silicon carbide/feldspar powder solid-solid composite controllable phase change system is constructed in the material while the flame retardant property of the material is effectively improved. The phase change system has stronger heat exchange capability, when the operating temperature is too high, the material can quickly absorb heat to realize rapid diffusion and storage of heat in the material, and meanwhile, the heat can be released at low temperature, so that the high motion capability of a molecular chain segment in an operating environment below the glass transition temperature of the material is ensured, the low-temperature brittleness of the material is relieved, the service capability of the material at extremely low temperature is realized, and the service temperature range of the material is increased. The material developed by the patent can be applied to cables for magnetic levitation trains with speed per hour of 620 km or more, cables for intelligent service equipment in complex environments such as fire-fighting and fire-extinguishing robots, emergency disposal and rescue robots and the like. The specific scheme is as follows:
the high-flame-retardance high-flexibility phase-change temperature-control sheath material for the magnetic levitation train cable comprises the following raw materials in parts by weight:
100-150 parts of ethylene-vinyl acetate copolymer EVA;
and 40-60 parts of rubber;
30-50 parts of phosphorus-nitrogen flame retardant;
10-15 parts of a charring agent;
40-75 parts of inorganic functional filler;
5-15 parts of macromolecular coupling agent;
5-10 parts of vulcanizing agent;
1-3 parts of vulcanization accelerator;
1-3 parts of an anti-aging agent;
0.5-2 parts of antioxidant;
1-5 parts of color master batch.
It is characterized in that the phosphorus-nitrogen flame retardant is polybenzimidazole (DOPO-PBI) containing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide element, the structural formula of the phosphorus-nitrogen flame retardant meets the formula I,
(formula I), wherein n is the number of repeating units, n is independently a positive integer between 200 and 500;
wherein the inorganic functional filler is silicon carbide and feldspar powder which are surface modified by aniline methyltriethoxysilane;
wherein the sheath material is prepared by firstly mixing rubber, phosphorus-nitrogen flame retardant, char forming agent and inorganic functional filler in proportion in a melting way to obtain rubber master batch; then adding EVA and a macromolecular coupling agent into an internal mixer according to a proportion, and carrying out melt blending to obtain EVA master batches; adding the EVA master batch and the rubber master batch into an internal mixer, promoting migration and dispersion of filler through shearing action, cooling, drying, placing into a double-screw extruder for melt blending extrusion, cooling and drying to obtain a blending master batch; adding the blending master batch, a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, an antioxidant and a color master batch into a high-speed mixer, mixing, placing into a double-screw extruder for melt blending extrusion, and cooling and drying to obtain the pre-crosslinked master batch. And then placing the pre-crosslinked master batch in a wire and cable extruder for melt extrusion to obtain a pre-crosslinked cable, and finally obtaining a cable finished product through irradiation.
Further, the EVA has a VA mass content of 5-50% and a density of 0.92-1.06g/cm 3 Melting point is 57-85 ℃, and melt flow rate is 0.3-400g/10min under the condition of 190 ℃/2.16 kg;
the combined rubber is one or a mixture of more than one of ethylene propylene diene monomer rubber, nitrile rubber and styrene butadiene rubber, and the density is 0.86-1.51g/cm 3 The Shore hardness (A) is 35-90, and the melt flow rate is 5-23g/10min under the condition of 190 ℃/2.16 kg;
the char forming agent is one or a mixture of more of pentaerythritol, trimethylolethane and ethylene glycol;
the macromolecular coupling agent is one or a mixture of more of ultra-high molecular weight polyethylene, phenolic resin, glycidyl methacrylate grafted ethylene-vinyl acetate (EVA-g-GMA), maleic anhydride grafted ethylene-vinyl acetate (EVA-g-MAH) and glycidyl methacrylate grafted ethylene-octene copolymer (POE-g-GMA);
the vulcanizing agent is one or a mixture of more of 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane, dibenzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide and diisopropyl peroxydicarbonate;
the vulcanization accelerator is one or a mixture of more of tetramethylthiuram disulfide, ethylene thiourea and tellurium diethyl dithiocarbamate;
the anti-aging agent is one or a mixture of more of N-phenyl-2-naphthylamine, 6-ethoxy-2, 4-trimethyl-1, 2-dihydroquinoline and N, N' -di (beta-naphthyl) p-phenylenediamine;
the antioxidant is one or a mixture of more of pentaerythritol tetra [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione.
Further, the method comprises the following steps:
firstly, adding rubber, phosphorus-nitrogen flame retardant, char forming agent and inorganic functional filler into an internal mixer according to a proportion, and carrying out melt blending to obtain rubber master batch;
then adding EVA and a macromolecular coupling agent into an internal mixer according to a proportion, and carrying out melt blending to obtain EVA master batch;
adding the EVA master batch and the rubber master batch into an internal mixer, carrying out melt blending, cooling and drying, and then placing the mixture into a double-screw extruder for melt blending extrusion, cooling and drying to obtain a blending master batch;
adding the blending master batch, a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, an antioxidant and a color master batch into a high-speed mixer, mixing, then placing the mixture into a double-screw extruder for melt blending extrusion, and cooling and drying to obtain a pre-crosslinked master batch;
and placing the pre-crosslinked master batch in a wire and cable extruder for melt extrusion to obtain a pre-crosslinked cable, and finally irradiating the pre-crosslinked cable to obtain a cable finished product.
Further, firstly adding the rubber, the phosphorus-nitrogen flame retardant, the char forming agent and the inorganic functional filler into an internal mixer in proportion, and carrying out melt blending for 10min at 140 ℃ and 50rpm to obtain rubber master batches;
then adding EVA and a macromolecular coupling agent into an internal mixer according to a proportion, and carrying out melt blending for 10min at 140 ℃ and 50rpm to obtain EVA master batch;
adding the EVA master batch and the rubber master batch into an internal mixer, carrying out melt blending for 15min at 140 ℃ and 60rpm, cooling and drying, and then placing the mixture into a double-screw extruder with the temperature of 120-150 ℃ for melt blending extrusion, cooling and drying to obtain a blending master batch;
adding the blending master batch, a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, an antioxidant and a color master batch into a high-speed mixer, mixing for 15min under the condition of 2500-4000r/min, then placing the mixture into a double-screw extruder with the temperature of 120-150 ℃ for melt blending extrusion, cooling and drying to obtain a pre-crosslinked master batch;
and (3) placing the pre-crosslinked master batch in a wire and cable extruder with the temperature of 120-160 ℃ for melt extrusion to obtain a pre-crosslinked cable, and finally irradiating the pre-crosslinked cable for 10min under the conditions of the beam pressure of 1.5-2MeV, the beam current of 40mA and the irradiation dose of 300kGy to obtain a cable finished product.
Further, the preparation method also comprises the preparation of the phosphorus-nitrogen flame retardant, and specifically comprises the following steps:
adding 3,3' -diaminobenzidine and anhydrous phosphorus pentoxide into polyphosphoric acid, stirring and heating under nitrogen atmosphere to completely dissolve the materials, adding isophthalic acid, heating and stirring until the reaction is finished, pouring the reaction mixture into excessive deionized water to precipitate out prepolymer, and washing and drying to obtain polybenzimidazole PBI shown in formula II;
et is added to 3 N, PBI and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide DOPO was dissolved in DMF and CCl was added dropwise 4 Heating and preserving heat until the reaction is finished, filtering, washing, separating and dryingTo obtain the phosphorus-nitrogen flame retardant (DOPO-PBI) shown in the formula I,
wherein n is the number of repeating units, and independently is an integer between 200 and 500.
Further, the preparation of the phosphorus-nitrogen flame retardant specifically comprises the following steps:
3,3' -diamino benzidine and anhydrous phosphorus pentoxide are added into polyphosphoric acid, stirred and heated to 140 ℃ under nitrogen atmosphere, and the temperature is kept for 30min to be completely dissolved. Adding isophthalic acid, heating and stirring to 200 ℃, preserving heat and reacting for 20 hours, pouring the reaction mixture into excessive deionized water after the reaction is finished to precipitate prepolymer, and washing and drying to obtain PBI shown in a formula II;
et is added to 3 N, PBI and DOPO were dissolved in DMF and CCl was added dropwise at 0deg.C 4 Preserving heat for 30min, then heating to 50 ℃, preserving heat for 24h, filtering, washing, separating and drying after the reaction is finished to obtain the phosphorus-nitrogen flame retardant (DOPO-PBI) shown in the formula I,
wherein n is the number of repeating units, and independently is an integer between 200 and 500.
Further, the method also comprises the steps of preparing the inorganic functional filler, and specifically comprises the following steps:
adding silicon carbide or feldspar powder, aniline methyltriethoxysilane and toluene into a flask, stirring and heating under nitrogen flow, preserving heat until the reaction is finished, and performing suction filtration, ultrasonic dispersion, centrifugation and drying to obtain the inorganic functional filler.
Further, the preparation of the inorganic functional filler specifically comprises the following steps:
adding silicon carbide or feldspar powder, aniline methyltriethoxysilane and toluene into a three-neck flask, stirring and heating to 80 ℃ under nitrogen flow, and reacting for 1h. And after the reaction is finished, carrying out suction filtration, carrying out ultrasonic dispersion and centrifugation, and then carrying out vacuum drying at 110 ℃ for 6 hours to obtain the inorganic functional filler.
Further, the material is applied to magnetic levitation train cables with speed per hour of 620 km or more, fire-fighting and fire-fighting robots and emergency disposal and rescue robots and cables for intelligent service equipment in complex environments.
The invention has the following beneficial effects:
1) The phosphorus-nitrogen flame retardant contains DOPO flame retardant elements, a large amount of nitrogen elements and benzene rings, is easy to char, has excellent thermal stability, high flame retardant efficiency, good compatibility with a matrix, small addition content and difficult precipitation, and can improve the comprehensive performance of the material.
2) The inorganic functional filler is silicon carbide and feldspar powder which are subjected to surface modification by the aniline methyltriethoxysilane, a ceramic carbon layer can be formed during combustion, and benzene rings and imino groups on the aniline methyltriethoxysilane can play a role in synergistic flame retardance with a phosphorus-nitrogen flame retardant, so that the flame retardance is improved.
3) The char former is substances containing rich oxygen elements such as pentaerythritol, trimethylolethane and the like, plays a role of promoting char formation, and also cooperates with silicon carbide and feldspar powder, a char former/silicon carbide/feldspar powder solid-solid composite type controllable phase change system is constructed in the sheath material, the phase change system has strong heat exchange capability, when the operation temperature is too high, the material can quickly absorb heat, the rapid diffusion and storage of the heat in the material are realized, meanwhile, the heat can be released at low temperature, the high motion capability of a molecular chain segment in the operation environment below the glass transition temperature of the material is ensured, the low-temperature brittleness of the material is relieved, the service capability of the material at extremely low temperature is realized, the performance degradation caused by uncontrollable heat diffusion process in the operation process of a cable is avoided, and the performance and the service life of the cable are improved.
4) Migration and dispersion of the filler are promoted by stepwise blending. Firstly, mixing a phosphorus-nitrogen flame retardant, a char forming agent, an inorganic functional filler and rubber, and enabling the filler to be melt-coated to form a core-shell structure rubber master batch. And then blending EVA with a macromolecular coupling agent to improve the melt strength of the EVA master batch and form different melt strength gradients. And then the EVA master batch and the rubber master batch are melt blended at a higher rotating speed, and the migration of the coated filler is realized through the shearing action of the EVA master batch with high melt strength, so that the formation of a uniform refractory layer is facilitated, and the controllable phase change process is promoted.
Detailed Description
The present invention will be described in more detail by way of specific examples, but the scope of the present invention is not limited to these examples.
The raw materials used in the following examples were:
EVA: density of 0.955g/cm 3 The melt index is 6g/10min under the test condition of 190 ℃/2.16kg, the VA content is 28%, the tensile strength is 24MPa, the elongation at break is 800-1000%, and EVA260 of the Sanjing Japan is selected.
And rubber: the mass ratio of the ethylene propylene diene monomer rubber to the nitrile rubber is 1:1, wherein the Mooney viscosity of ethylene propylene diene monomer (ML 1+ -4125 ℃ C.) is 45, the ethylene content is 50%, the third monomer is ENB, the content is 8%, and AP241 of Bayer company of Germany is selected; the Mooney viscosity of nitrile rubber (ML 1+ -4100 ℃ C.) is 45, the ACN content is 34%, and 3445 of Bayer company of Germany is selected.
Phosphorus-nitrogen flame retardant: is a polybenzimidazole (DOPO-PBI) containing a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide moiety, which is prepared by the steps of:
107g of 3,3' -diaminobenzidine and 16.34g of anhydrous phosphorus pentoxide were added to 750ml of polyphosphoric acid, and the mixture was stirred and heated to 140℃under nitrogen atmosphere, and the mixture was kept for 30 minutes to dissolve completely. 41.5g of isophthalic acid is then added, heated and stirred to 200 ℃, the reaction is carried out for 20 hours under heat preservation, after the reaction is finished, the reaction mixture is poured into excessive deionized water to precipitate out prepolymer, and 29.7g of PBI shown in the formula II is obtained after washing and drying.
Will 50.95gEt 3 N, 29.7g of PBI and 108g of DOPO are dissolved in 525ml of DMF and 77g of CCl are added dropwise at 0 ℃ 4 And (3) preserving heat for 30min, then heating to 50 ℃, preserving heat for 24h, and filtering, washing, separating and drying after the reaction is finished to obtain the phosphorus-nitrogen flame retardant (DOPO-PBI) shown in the formula I.
Wherein n is the number of repeating units, and independently is an integer between 200 and 500.
Char-forming agent: pentaerythritol and trimethylolethane in a mass ratio of 1:1, all selected from Shanghai Ala Biochemical technologies Co., ltd.
Inorganic functional filler: the preparation of the aniline methyltriethoxysilane surface modified silicon carbide and feldspar powder comprises the following steps:
50g of silicon carbide or feldspar powder, 2ml of aniline methyltriethoxysilane and 350ml of toluene are added into a three-necked flask, and the mixture is stirred and heated to 80 ℃ under nitrogen flow for reaction for 1h. And after the reaction is finished, carrying out suction filtration, carrying out ultrasonic dispersion for many times, centrifuging at 5000r/min, and then carrying out vacuum drying at 110 ℃ for 6 hours to obtain the inorganic functional filler.
Macromolecular coupling agent: glycidyl methacrylate grafted ethylene-vinyl acetate (EVA-g-GMA), maleic anhydride grafted ethylene-vinyl acetate (EVA-g-MAH) and glycidyl methacrylate grafted ethylene-octene copolymer (POE-g-GMA) according to the mass ratio of 1:1:3 mixture. EVA-g-GMA selects Japanese Sumitomo BF-7M, EVA-g-MAH selects French Acomat 9318, and POE-g-GMA selects U.S. DuPont N493.
Vulcanizing agent: 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane was selected for use in Shanghai Ala Biochemical technologies Co., ltd.
Vulcanization accelerators: the tetramethylthiuram disulfide is selected for Shanghai Ala Biochemical technology Co., ltd.
Anti-aging agent: 6-ethoxy-2, 4-trimethyl-1, 2-dihydroquinoline and N-phenyl-N' -cyclohexyl p-phenylenediamine according to a mass ratio of 2:1, all selected from Shanghai Ala Biochemical technologies Co., ltd.
An antioxidant: pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione in a mass ratio of 1:1, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] is 1010,1,3,5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione from Cyanurate, 1790 from Cyanurate.
Color master batch: UN6073 from cabot corporation, U.S. is selected.
Aluminum hydroxide: HT-205 of Jinan Taixing Fine chemical Co., ltd.
Magnesium hydroxide: HT-206 of Jinan Taixing Fine chemical Co., ltd.
Zinc borate: HT-207 of Jinan Taixing Fine chemical Co., ltd.
White carbon black: a200 of Shenyang chemical Co., ltd.
DOPO: selected for Shanghai Ala Biochemical technology Co., ltd.
Silicon carbide: XGR7668 from sigma of America is selected.
Feldspar powder: a-200 from Unimin Canada was selected.
The mass parts of the raw materials in the following examples are shown in Table 1.
Table 1 raw materials and amounts (in parts by mass) of high flame retardant, high flexible, phase change temperature control sheath materials for maglev train cables
Example 1
The raw materials and the formula of the preparation method are shown in Table 1, and the preparation method comprises the following steps:
firstly, adding rubber, phosphorus-nitrogen flame retardant, char forming agent and inorganic functional filler into an internal mixer in proportion, and carrying out melt blending for 10min at 140 ℃ and 50rpm to obtain rubber master batch;
then adding EVA and a macromolecular coupling agent into an internal mixer according to a proportion, and carrying out melt blending for 10min at 140 ℃ and 50rpm to obtain EVA master batch;
adding the EVA master batch and the rubber master batch into an internal mixer, carrying out melt blending for 15min at 140 ℃ and 60rpm, cooling and drying, putting the mixture into a double-screw extruder with the temperature of 120-150 ℃ for melt blending extrusion, and cooling and drying to obtain a blending master batch according to the processing temperature from a feed opening to a die opening of 120 ℃, 130 ℃, 140 ℃, 145 ℃, 150 ℃ and 150 ℃ respectively;
adding the blending master batch, a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, an antioxidant and a color master batch into a high-speed mixer, mixing for 15min under the condition of 2500-4000r/min, then placing the mixture into a 120-150 ℃ twin-screw extruder for melt blending extrusion, and cooling and drying to obtain pre-crosslinked master batch, wherein the processing temperature is 120 ℃ to 130 ℃, 140 ℃, 145 ℃ and 150 ℃ from a blanking port to a die port;
the pre-crosslinked master batch is placed in a wire and cable extruder with the temperature of 120-160 ℃ for melt extrusion, the inlet temperature is 120 ℃, the first section is 120-130 ℃, the second section is 130-140 ℃, the third section is 140-150 ℃, the fourth section is 150-155 ℃, the fifth section is 155-160 ℃, the outlet temperature is 160 ℃, and the surface of a cable conductor core is coated with a sheath; finally, irradiating the coated wire core for 10min under the conditions that the beam pressure is 1.5-2MeV, the beam current is 40mA and the irradiation dose is 300kGy, so as to obtain the cable finished product.
Example 2
The raw materials and the formulation of this example are shown in Table 1, and the preparation process is the same as that of example 1.
Example 3
The raw materials and the formulation of this example are shown in Table 1, and the preparation process is the same as that of example 1.
Comparative example 1
The raw materials and the formulation of this comparative example are shown in Table 1, and the preparation process is the same as in example 1.
Comparative example 2
The raw materials and the formulation of this comparative example are shown in Table 1, and the preparation process is the same as in example 1.
Comparative example 3
The raw materials and the formulation of this comparative example are shown in Table 1, and the preparation process is the same as in example 1.
Comparative example 4
The raw materials and the formulation of this comparative example are shown in Table 1, and the preparation process is the same as in example 1.
Comparative example 5
The raw materials and the formula of the comparative example are the same as those of the example 2, and are shown in the table 1, and the preparation process is carried out according to the following steps:
firstly, adding EVA, rubber, phosphorus-nitrogen flame retardant, char forming agent, inorganic functional filler, macromolecular coupling agent, vulcanizing agent, vulcanization accelerator, anti-aging agent, antioxidant and masterbatch into an internal mixer according to a proportion, melt-blending for 15min at 140 ℃ and 50rpm, cooling and drying, and then placing the mixture into a double-screw extruder for melt-blending extrusion, wherein the processing temperature is 120 ℃ to 130 ℃ to 140 ℃, 145 ℃, 150 ℃ according to a blanking port, cooling and drying to obtain blended masterbatch;
the blending master batch is placed in a wire and cable extruder with the temperature of 120-160 ℃ for melt extrusion, the inlet temperature is 120 ℃, the first section is 120-130 ℃, the second section is 130-140 ℃, the third section is 140-150 ℃, the fourth section is 150-155 ℃, the fifth section is 155-160 ℃, the outlet temperature is 160 ℃, and the surface of a cable conductor core is coated with a sheath; finally, the coated wire core is irradiated for 10min under the conditions that the beam pressure is 1.5-2MeV, the beam current is 40mA and the irradiation dose is 300kGy, and the material is obtained.
The main performance indexes of the cable materials prepared in examples 1-3 and comparative examples 1-5 are shown in Table 2:
table 2 shows the results of the performance tests of the examples and comparative examples
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The test results are shown in Table 2, and the overall performance of example 2 is optimal.
Due to the addition of the phosphorus-nitrogen flame retardant, the char forming capability of the material is improved, combustible gas and heat can be effectively isolated, the separation is difficult, the heat release rate and the smoke generation rate are reduced, the fire performance index is improved, and the efficient flame retardance is realized. The silicon carbide and feldspar powder which are surface modified by the aniline methyl triethoxysilane are introduced, so that a ceramic carbon layer can be formed during combustion, a synergistic flame retardant effect can be achieved with a phosphorus-nitrogen flame retardant and a carbon forming agent rich in oxygen elements, and the flame retardant performance is improved. Meanwhile, the silicon carbide and the feldspar powder are used as nucleating agents, a pentaerythritol/trimethylolethane/silicon carbide and feldspar powder solid-solid composite type controllable phase change system is built in the material, the phase change system has strong heat exchange capability, when the operation temperature is too high, the material can quickly absorb heat, the rapid diffusion and storage of the heat in the material are realized, meanwhile, the heat can be released at low temperature, the high movement capability of a molecular chain segment in the operation environment below the glass transition temperature of the material is ensured, the low-temperature brittleness of the material is relieved, the service capability of the material at extremely low temperature is realized, the performance degradation caused by uncontrollable heat diffusion process of a cable in the operation process is avoided, and the performance and the service life of the cable are improved. The step-by-step blending is adopted, and the migration of the filler is caused by the shearing action among different melt strength gradients, so that the directional regulation and control of the filler dispersion state are realized, the formation of a controllable phase change system is promoted, and the excellent comprehensive performance is finally obtained.
Compared with the comparative example 2, the conventional hydroxide flame retardant is used, and the DOPO and the white carbon black are combined, so that a phase change system is not introduced, the flame retardance, the fire resistance and other performances of the material are poor, the use requirement under a complex environment is difficult to meet, and the use temperature range is narrow. Compared with the embodiment 2, the embodiment 2 uses the traditional hydroxide and DOPO as the flame retardant, and introduces the controllable phase change system, so that the uniform carbon layer is formed, and meanwhile, the rapid diffusion and storage of heat in the material can be realized, thereby being beneficial to improving the flame retardance and the fire resistance of the material, but the flame retardant has larger addition content, weaker interaction with a matrix and difficult to obtain the material with better comprehensive performance. Compared with the embodiment 2, the flame retardant provided by the invention is added in the comparative embodiment 3, so that the flame retardant performance of the material can be improved efficiently, and the flame retardant structure contains a large number of rigid elements, so that the mechanical property of the material can be improved effectively. However, no phase-change system is introduced, so that the comprehensive performance of the material is poor. Comparative example 4 compared to example 2, the incorporation of a large amount of flame retardant, char former, and inorganic functional filler resulted in a filler that was difficult to disperse uniformly, thereby reducing the interaction of the flame retardant and the polymer matrix. In summary, the advantages of the formulation designed in example 2 are demonstrated.
The formula system of the comparative example 5 and the formula system of the example 2 are the same, but the processing technology is different, and the traditional one-step mixing is adopted, so that the filler is poor in dispersion, the refractory layer with uniform quality and density is difficult to construct, and the superiority of the preparation technology is reflected.
According to the analysis of the test data, the performance of the high-flame-retardance high-flexibility phase-change temperature-control sheath material for the magnetic levitation train cable is greatly improved, and the following reasons are included: (1) The synthesized flame retardant contains DOPO flame retardant elements, a large amount of nitrogen elements and benzene rings, is easy to char, has excellent thermal stability, high flame retardant efficiency, good compatibility with a matrix, small addition content and difficult precipitation, and can improve the comprehensive performance of the material. (2) The silicon carbide and feldspar powder which are surface modified by the aniline methyl triethoxy silane are introduced, a ceramic carbon layer can be formed during combustion, and benzene rings and imino groups on the aniline methyl triethoxy silane can play a role in synergistic flame retardance with a phosphorus-nitrogen flame retardant, so that the flame retardance is improved. (3) Pentaerythritol and trimethylolethane are introduced, rich oxygen elements are contained, the carbon forming effect is promoted, the carbon forming effect is achieved, meanwhile, the carbon forming effect is achieved, a pentaerythritol/trimethylolethane/silicon carbide and feldspar powder solid-solid composite type controllable phase change system is built in a sheath material, the phase change system has strong heat exchange capability, when the operation temperature is too high, the material can quickly absorb heat, rapid diffusion and storage of the heat in the material are achieved, meanwhile, the heat can be released at low temperature, high movement capability of a molecular chain segment in an operation environment below the glass transition temperature of the material is guaranteed, the low-temperature brittleness of the material is relieved, the service capability of the material at extremely low temperature is achieved, performance degradation caused by uncontrollable heat diffusion processes in the cable operation process is avoided, and the performance and the service life of the cable are improved. (4) The step-by-step blending is adopted, and the migration of the filler is caused by the shearing action among different melt strength gradients, so that the directional regulation and control of the filler dispersion state are realized, the formation of a uniform refractory layer is facilitated, and the promotion effect on the controllable phase change process is realized.
According to the invention, the phosphorus-nitrogen flame retardant with a specific structure is synthesized, pentaerythritol and trimethylolethane are used as char forming agents, silicon carbide and feldspar powder which are subjected to surface modification by aniline methyl triethoxysilane are introduced, a ceramic carbon layer is formed during combustion, a synergistic flame retardant effect is achieved with the phosphorus-nitrogen flame retardant, and meanwhile, a pentaerythritol/trimethylolethane/silicon carbide and feldspar powder solid-solid composite controllable phase change system is constructed in the sheath material, so that the phase change system has strong heat exchange capability, and when the operating temperature is too high, the material can quickly absorb heat, so that the rapid diffusion and storage of heat in the material are realized, and the fire resistance of the sheath material is improved. Meanwhile, heat can be released at low temperature, so that the molecular chain segment in the operating environment below the glass transition temperature of the material is guaranteed to have higher motion capability, the low-temperature brittleness of the material is relieved, the service capability of the material at extremely low temperature is realized, the performance degradation of the cable caused by uncontrollable heat diffusion in the operating process is avoided, and the performance and the service life of the cable are improved. The material and the related technology are applied to cables for magnetic levitation train with speed of 620 km or more, cables for intelligent service equipment in complex environments such as fire-fighting and fire-extinguishing robots, emergency disposal and rescue robots and the like.
While the invention has been described in detail in connection with the preferred embodiments, it should be understood that the foregoing description is not to be considered as limiting the invention, but is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. The high-flame-retardance high-flexibility phase-change temperature-control sheath material for the magnetic levitation train cable comprises the following raw materials in parts by weight:
100-150 parts of ethylene-vinyl acetate copolymer EVA;
and 40-60 parts of rubber;
30-50 parts of phosphorus-nitrogen flame retardant;
10-15 parts of a charring agent;
40-75 parts of inorganic functional filler;
5-15 parts of macromolecular coupling agent;
5-10 parts of vulcanizing agent;
1-3 parts of vulcanization accelerator;
1-3 parts of an anti-aging agent;
0.5-2 parts of antioxidant;
1-5 parts of color master batch;
it is characterized in that the phosphorus-nitrogen flame retardant is polybenzimidazole (DOPO-PBI) containing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide element, the structural formula of the phosphorus-nitrogen flame retardant meets the formula I,
(formula I), wherein n is the number of repeating units, n is independently a positive integer between 200 and 500;
wherein the inorganic functional filler is silicon carbide and feldspar powder which are surface modified by aniline methyltriethoxysilane; wherein the sheath material is prepared by firstly mixing rubber, phosphorus-nitrogen flame retardant, char forming agent and inorganic functional filler in proportion in a melting way to obtain rubber master batch; then adding EVA and a macromolecular coupling agent into an internal mixer according to a proportion, and carrying out melt blending to obtain EVA master batches; adding the EVA master batch and the rubber master batch into an internal mixer, promoting migration and dispersion of filler through shearing action, cooling, drying, placing into a double-screw extruder for melt blending extrusion, cooling and drying to obtain a blending master batch; adding the blending master batch, a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, an antioxidant and a color master batch into a high-speed mixer, mixing, putting into a double-screw extruder for melt blending extrusion, cooling and drying to obtain a pre-crosslinked master batch, putting the pre-crosslinked master batch into a wire and cable extruder for melt extrusion to obtain a sheath material for a pre-crosslinked cable, and finally irradiating to obtain the sheath material for the cable.
2. The jacket material of claim 1, wherein:
the EVA has VA content of 5-50% and density of 0.92-1.06g/cm 3 Melting point is 57-85 ℃, and melt flow rate is 0.3-400g/10min under the condition of 190 ℃/2.16 kg;
the combined rubber is one or a mixture of more than one of ethylene propylene diene monomer rubber, nitrile rubber and styrene butadiene rubber, and the density is 0.86-1.51g/cm 3 The Shore hardness (A) is 35-90, and the melt flow rate is 5-23g/10min under the condition of 190 ℃/2.16 kg;
the char forming agent is one or a mixture of more of pentaerythritol, trimethylolethane and ethylene glycol;
the macromolecular coupling agent is one or a mixture of more of ultra-high molecular weight polyethylene, phenolic resin, glycidyl methacrylate grafted ethylene-vinyl acetate (EVA-g-GMA), maleic anhydride grafted ethylene-vinyl acetate (EVA-g-MAH) and glycidyl methacrylate grafted ethylene-octene copolymer (POE-g-GMA); the vulcanizing agent is one or a mixture of more of 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane, dibenzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide and diisopropyl peroxydicarbonate;
the vulcanization accelerator is one or a mixture of more of tetramethylthiuram disulfide, ethylene thiourea and tellurium diethyl dithiocarbamate;
the anti-aging agent is one or a mixture of more of N-phenyl-2-naphthylamine, 6-ethoxy-2, 4-trimethyl-1, 2-dihydroquinoline and N, N' -di (beta-naphthyl) p-phenylenediamine;
the antioxidant is one or a mixture of more of pentaerythritol tetra [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 1,3, 5-tri (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione.
3. A method of manufacturing a sheath material according to any one of claims 1-2, comprising the steps of:
firstly, adding rubber, phosphorus-nitrogen flame retardant, char forming agent and inorganic functional filler into an internal mixer according to a proportion, and carrying out melt blending to obtain rubber master batch;
then adding EVA and a macromolecular coupling agent into an internal mixer according to a proportion, and carrying out melt blending to obtain EVA master batch; adding the EVA master batch and the rubber master batch into an internal mixer, carrying out melt blending, cooling and drying, and then placing the mixture into a double-screw extruder for melt blending extrusion, cooling and drying to obtain a blending master batch; adding the blending master batch, a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, an antioxidant and a color master batch into a high-speed mixer for mixing, then placing the mixture into a double-screw extruder for melt blending extrusion, and cooling and drying to obtain a pre-crosslinked master batch;
and (3) placing the pre-crosslinked master batch in a wire and cable extruder for melt extrusion to obtain a sheath material for the pre-crosslinked cable, and finally irradiating the pre-crosslinked cable to obtain the sheath material for the cable.
4. A method of manufacturing a sheath material as claimed in claim 3, comprising the steps of: firstly, adding rubber, phosphorus-nitrogen flame retardant, char forming agent and inorganic functional filler into an internal mixer in proportion, and carrying out melt blending for 10min at 140 ℃ and 50rpm to obtain rubber master batch;
then adding EVA and a macromolecular coupling agent into an internal mixer according to a proportion, and carrying out melt blending for 10min at 140 ℃ and 50rpm to obtain EVA master batch;
adding the EVA master batch and the rubber master batch into an internal mixer, carrying out melt blending for 15min at 140 ℃ and 60rpm, cooling and drying, and then placing the mixture into a double-screw extruder with the temperature of 120-150 ℃ for melt blending extrusion, cooling and drying to obtain a blending master batch;
adding the blending master batch, a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, an antioxidant and a color master batch into a high-speed mixer, mixing for 15min under the condition of 2500-4000r/min, then placing the mixture into a double-screw extruder with the temperature of 120-150 ℃ for melt blending extrusion, cooling and drying to obtain a pre-crosslinked master batch;
and (3) placing the pre-crosslinked master batch in a wire and cable extruder with the temperature of 120-160 ℃ for melt extrusion to obtain a pre-crosslinked cable, and finally irradiating the pre-crosslinked cable for 10min under the conditions of beam pressure of 1.5-2MeV, beam current of 40mA and irradiation dose of 300kGy to obtain the sheath material.
5. The manufacturing method according to claim 3 or 4, further comprising preparing the phosphorus-nitrogen flame retardant, specifically comprising the steps of:
adding 3,3' -diaminobenzidine and anhydrous phosphorus pentoxide into polyphosphoric acid, stirring and heating under nitrogen atmosphere to completely dissolve the materials, adding isophthalic acid, heating and stirring until the reaction is finished, pouring the reaction mixture into excessive deionized water to precipitate out prepolymer, and washing and drying to obtain polybenzimidazole PBI shown in formula II;
et is added to 3 N, PBI and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide DOPO was dissolved in DMF and CCl was added dropwise 4 Heating and preserving heat until the reaction is finished, filtering, washing, separating and drying to obtainThe phosphorus-nitrogen flame retardant (DOPO-PBI) shown in the formula I,
wherein n is the number of repeating units, and independently is an integer between 200 and 500.
6. The method for producing a phosphorus-nitrogen flame retardant according to claim 5, comprising the steps of: adding 3,3' -diaminobenzidine and anhydrous phosphorus pentoxide into polyphosphoric acid, stirring and heating to 140 ℃ under nitrogen atmosphere, preserving heat for 30min to completely dissolve the materials, adding isophthalic acid, heating and stirring to 200 ℃, preserving heat and reacting for 20h, pouring the reaction mixture into excessive deionized water after the reaction is finished to precipitate prepolymer, and washing and drying to obtain PBI shown in formula II;
et is added to 3 N, PBI and DOPO were dissolved in DMF and CCl was added dropwise at 0deg.C 4 Preserving heat for 30min, then heating to 50 ℃, preserving heat for 24h, filtering, washing, separating and drying after the reaction is finished to obtain the phosphorus-nitrogen flame retardant (DOPO-PBI) shown in the formula I,
wherein n is the number of repeating units, and independently is an integer between 200 and 500.
7. The manufacturing method according to claim 3 or 4, further comprising preparing the inorganic functional filler, specifically comprising the steps of:
adding silicon carbide or feldspar powder, aniline methyltriethoxysilane and toluene into a flask, stirring and heating under nitrogen flow, preserving heat until the reaction is finished, and performing suction filtration, ultrasonic dispersion, centrifugation and drying to obtain the inorganic functional filler.
8. The method of claim 7, wherein the preparation of the inorganic functional filler comprises the steps of: adding silicon carbide or feldspar powder, aniline methyltriethoxysilane and toluene into a three-neck flask, stirring and heating to 80 ℃ under nitrogen flow for reaction for 1h, filtering after the reaction, performing ultrasonic dispersion and centrifugation, and then performing vacuum drying at 110 ℃ for 6h to obtain the inorganic functional filler.
9. A method of using the sheathing material of any one of claims 1-2 or the sheathing material obtained by the manufacturing method of any one of claims 3-8, characterized in that:
the material is applied to cables for magnetic levitation trains with speed per hour of 620 km or more, fire-fighting and fire-fighting robots and emergency disposal rescue robots and cables for intelligent service equipment in complex environments.
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| CN104086751A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | DOPO-based symtriazine ring hydrogenated benzimidazole epoxy curing agent and preparation method thereof |
| CN110734462A (en) * | 2019-09-14 | 2020-01-31 | 武汉工程大学 | Synthesis and application of nitrogen-phosphorus efficient flame retardants containing benzimidazole structure |
| CN113402557A (en) * | 2021-06-29 | 2021-09-17 | 福建师范大学 | Phosphorus-containing polynitrogen azole metal complex and preparation method thereof |
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| EP2058321B1 (en) * | 2007-11-02 | 2014-01-08 | Samsung Electronics Co., Ltd. | Phosphorous containing monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086751A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | DOPO-based symtriazine ring hydrogenated benzimidazole epoxy curing agent and preparation method thereof |
| CN110734462A (en) * | 2019-09-14 | 2020-01-31 | 武汉工程大学 | Synthesis and application of nitrogen-phosphorus efficient flame retardants containing benzimidazole structure |
| CN113402557A (en) * | 2021-06-29 | 2021-09-17 | 福建师范大学 | Phosphorus-containing polynitrogen azole metal complex and preparation method thereof |
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