CN116478527A - Flame-retardant polyurethane cable outer sheath material - Google Patents
Flame-retardant polyurethane cable outer sheath material Download PDFInfo
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- CN116478527A CN116478527A CN202310744384.7A CN202310744384A CN116478527A CN 116478527 A CN116478527 A CN 116478527A CN 202310744384 A CN202310744384 A CN 202310744384A CN 116478527 A CN116478527 A CN 116478527A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- outer sheath
- ionic liquid
- cable outer
- zinc borate
- Prior art date
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 76
- 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 70
- 239000000463 material Substances 0.000 title claims abstract description 51
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 42
- 239000004814 polyurethane Substances 0.000 title claims abstract description 42
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 38
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000013329 compounding Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 239000002608 ionic liquid Substances 0.000 claims description 37
- 239000000843 powder Substances 0.000 claims description 35
- 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 claims description 33
- 229920005610 lignin Polymers 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- -1 1-ethyl acetate-3-methylimidazole tetrafluoroborate Chemical compound 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- 229940068041 phytic acid Drugs 0.000 claims description 6
- 239000000467 phytic acid Substances 0.000 claims description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 238000007654 immersion Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 8
- 150000001875 compounds Chemical group 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 229920003225 polyurethane elastomer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- VVRKSAMWBNJDTH-UHFFFAOYSA-N difluorophosphane Chemical compound FPF VVRKSAMWBNJDTH-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The preparation method comprises four steps of preparation of ammonium phytate, compounding of a composite flame retardant, banburying and mixing, and screw extrusion; the flame-retardant polyurethane cable outer sheath material prepared by the invention is extruded to obtain a cable outer sheath finished product, the tensile strength of the cable outer sheath finished product is 46.5-49.2 MPa, the elongation at break is 573-599%, and the cable outer sheath material is heat-aged (75 ℃ for 240 h): -2.6 to-1.9% of tensile strength, 535 to 572% of elongation at break, -6.6 to-4.5% of elongation at break, and hot extension (200 ℃ C., 0.2 MPa): elongation under load of 7.9-8.9%, permanent set after cooling of 0, oil immersion test (100 ℃ for 24 h): the tensile strength change rate is-6.9 to-5.8 percent, the elongation at break change rate is-6.0 to-4.7 percent, and the flame retardant level is V0.
Description
Technical Field
The invention relates to a flame-retardant polyurethane cable outer sheath material, and belongs to the technical field of high polymer materials.
Background
The polyurethane is used for the cable jacket and has the advantages incomparable with other materials, especially the thermoplastic polyurethane elastomer has the remarkable advantages of good mechanical property, good low-temperature flexibility, wear resistance which is 3-5 times that of natural rubber, ozone resistance, radiation resistance, wide chemical resistance, good adhesion with other cable materials (such as aramid fiber, non-woven fabrics, copper wires and the like), and the like, so the polyurethane cable jacket has been widely applied to occasions with higher use requirements, such as mining, oil wells, nuclear power plants and cables for vessels. Polyurethane materials are gradually replacing PVC, various synthetic rubbers and the like as outer jackets of cables, and are used in various severe environments.
Although polyurethane is used for the cable jacket and has the advantages, the biggest defect of the polyurethane material is inflammability, the oxygen index of the polyurethane material without adding any flame retardant is only 16.5-18, and a large amount of dense smoke and toxic gas can be emitted when the polyurethane burns, so that the life and health of human beings are seriously threatened, and how to optimize the flame retardant property of the polyurethane cable jacket material is a key concern in the industry.
Chinese patent CN114031930a discloses a high-strength high-flame-retardant polyurethane cable sheath material and a preparation method thereof. The high-strength high-flame-retardance polyurethane cable sheath material comprises the following raw material components in parts by weight: 40-80 parts of polyurethane resin; 15-40 parts of halogen-free flame retardant; 1-8 parts of glass fiber powder; 0.1 to 1 portion of coupling agent. The high-strength high-flame-retardance polyurethane cable sheath material takes halogen-free flame retardant as a flame retardant and glass fiber powder as a reinforcing agent. In the patent, aluminum hypophosphite and melamine are selected as halogen-free flame retardants, the two flame retardants are inorganic powder, glass fiber powder is also inorganic powder, and the addition amount of the three powder is 16-48 parts, so that the melt viscosity of polyurethane in melt processing can be greatly improved, and a cable outer sheath with good comprehensive performance is difficult to obtain.
Chinese patent CN105860495a discloses a high-toughness flame-retardant polyurethane cable sheath, which comprises the following raw materials in parts by weight: 45-50 parts of high-flexibility hydrophobic flame-retardant polyurethane, 25-30 parts of epoxy resin, 18-22 parts of silicone rubber, 3.2-3.5 parts of dicumyl peroxide, 1-2 parts of ammonium persulfate, 1.3-1.6 parts of cross-linking agent TAC, 0.6-0.9 part of diisodecyl phthalate, 15-18 parts of carbon black, 8-10 parts of zinc oxide, 5-8 parts of quartz powder, 4-6 parts of silane coupling agent KH-550, 0.8-1.2 parts of antioxidant MB and 1.8-2.2 parts of antioxidant RD. The cross-linking agent is added in the patent, so that the process of thermoplastic molding of polyurethane is changed, the molding process of the cable outer sheath material is changed to be abnormal and complicated, and the finally obtained polyurethane material has poor flame retardant property.
The problem that the flame retardance and the comprehensive performance of the existing polyurethane cable outer sheath material are difficult to be simultaneously considered can be seen, and how to prepare the high flame retardance polyurethane cable outer sheath material under the condition that the comprehensive performance is not lost is a problem in the industry that material researchers need to solve.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a flame-retardant polyurethane cable outer sheath material, which realizes the following aims: the polyurethane cable outer sheath material with high flame retardance, good processability and excellent comprehensive performance is prepared by a relatively simple method.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the flame-retardant polyurethane cable outer sheath material comprises a composite flame retardant compounded by ionic liquid, ammonium phytate, lignin and zinc borate as flame-retardant functional components, and the preparation method of the cable outer sheath material comprises four steps of ammonium phytate preparation, compounding of the composite flame retardant, banburying and mixing, and screw extrusion:
the following is a further improvement of the above technical scheme:
step 1, preparation of ammonium phytate
Mixing phytic acid, urea and deionized water according to a mass ratio of 2-5:2-7:15-29, controlling the temperature to be 100-125 ℃, carrying out reflux reaction at a stirring speed of 350-600 r/min for 2-3.5 hours to obtain viscous liquid, and carrying out rotary evaporation for 1-2.5 hours at a temperature of 80-95 ℃ and a vacuum degree of-0.1 to-0.09 MPa to remove water to obtain white solid ammonium phytate.
Step 2, compounding of the composite flame retardant
Mixing the ionic liquid, the ammonium phytate and the lignin according to the mass ratio of 22-35:4-7:4-8, stirring for 2-5 hours at the temperature of 130-170 ℃ at the stirring speed of 600-1000 rpm, placing the obtained liquid on a high-speed dispersing machine after the lignin is completely dissolved, adding zinc borate powder, dispersing for 45-70 minutes at the temperature of 130-170 ℃ at the speed of 75000-95000 rpm, and cooling to room temperature to obtain a viscous composite flame retardant;
the ionic liquid is one of 1-ethyl acetate-3-methylimidazole tetrafluoroborate, 1-allyl-3-methylimidazole tetrafluoroborate and 1-butyl-3-methylimidazole hexafluorophosphate;
the particle size of the zinc borate powder is 1-10 microns;
the adding amount of the zinc borate powder is 15-30% of the mass of the ionic liquid.
Step 3, banburying and mixing
And (3) putting the composite flame retardant and the thermoplastic polyurethane elastomer into an internal mixer according to the mass ratio of 1:9-15, and banburying for 20-40 minutes at the temperature of 150-180 ℃ and the rotating speed of 70-120 r/min to obtain a primary mixed material.
Step 4, screw extrusion
Feeding the primary mixed material into a conical feeding hopper, and melting, extruding, cooling, granulating and drying by a double-screw extruder to obtain the flame-retardant polyurethane cable outer sheath material, wherein the temperature of the double-screw extruder is set as follows in the region 1 to 5: 150-160 ℃, 160-170 ℃, 170-180 ℃, 180-190 ℃ and 190-195 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the phytic acid and urea are used for preparing the ammonium phytate with higher phosphorus and nitrogen contents, and through the process of dissolving the ammonium phytate in the ionic liquid, the ammonium phytate can be fully dispersed into the polyurethane elastomer matrix, so that the synergistic flame-retardant effect of phosphorus and nitrogen can be fully exerted, and the flame-retardant polyurethane cable outer sheath material with the flame retardant property at the V0 level is obtained;
2. the ionic liquid added in the invention contains the combination of boron fluoride or the combination of phosphorus fluoride, the combination of elements with flame retardant effect and the added ammonium phytate, zinc borate, lignin and other compounds form a high flame retardant efficiency cooperative system, wherein the ammonium phytate and the zinc borate can play a role in endothermic cooling and diluting oxygen in air through thermal decomposition at a lower temperature at the initial stage of combustion of the polyurethane elastomer, P element in the ammonium phytate and the zinc borate can form a glassy substance coating layer at the high temperature stage of combustion, the combustion reaction and the heat transfer to the inside of a matrix are prevented, the addition of lignin can improve the carbon residue rate during combustion, so that the combustion surface of the matrix is easier to be carbonized to further prevent the rapid heat transfer to the inside of the matrix, and in addition, the fluorine element in the ionic liquid can generate boron fluoride and zinc fluoride with the elements such as boron and zinc to inhibit and capture free hydroxyl groups, so as to prevent the combustion chain reaction;
3. according to the invention, zinc borate powder is firstly dispersed in the ionic liquid and then is mixed with the polyurethane elastomer in a melting way, so that the difficult problem that the powder is difficult to disperse uniformly when being directly mixed with a high polymer matrix in a melting way is avoided, the flame retardant efficiency of the zinc borate powder is ensured, meanwhile, the reduction of the mechanical and ageing resistance of the polyurethane elastomer caused by uneven mixing is avoided, the viscosity of the ionic liquid is lower, the viscosity of the polyurethane elastomer in the melting way can be reduced, and the tolerance of the technological parameters of the melting mixing and screw extrusion operation is improved;
4. the flame-retardant polyurethane cable outer sheath material prepared by the invention is extruded to obtain a cable outer sheath finished product, the tensile strength of the cable outer sheath finished product is 46.5-49.2 MPa, the elongation at break is 573-599%, and the cable outer sheath material is heat-aged (75 ℃ for 240 h): -2.6 to-1.9% of tensile strength, 535 to 572% of elongation at break, -6.6 to-4.5% of elongation at break, and hot extension (200 ℃ C., 0.2 MPa): elongation under load of 7.9-8.9%, permanent set after cooling of 0, oil immersion test (100 ℃ for 24 h): the tensile strength change rate is-6.9 to-5.8 percent, the elongation at break change rate is-6.0 to-4.7 percent, and the flame retardant level is V0.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
Example 1:
flame-retardant polyurethane cable outer sheath material
Step 1, preparation of ammonium phytate
Mixing phytic acid, urea and deionized water according to the mass ratio of 3:5:20, controlling the temperature to 115 ℃, carrying out reflux reaction at the stirring speed of 450 r/min for 3 hours to obtain viscous liquid, and carrying out rotary evaporation for 2 hours under the conditions of 90 ℃ and the vacuum degree of-0.095 MPa to remove water to obtain white solid ammonium phytate.
Step 2, compounding of the composite flame retardant
Mixing ionic liquid, ammonium phytate and lignin according to a mass ratio of 30:6:7, stirring for 4 hours at 155 ℃ at a stirring rate of 850 r/min, placing the obtained liquid on a high-speed dispersing machine after the lignin is completely dissolved, adding zinc borate powder, dispersing for 60 minutes at 160 ℃ at 85000 r/min, and cooling to room temperature to obtain a viscous compound flame retardant;
the ionic liquid is 1-ethyl acetate-3-methylimidazole tetrafluoroborate;
the particle size of the zinc borate powder is 7 microns;
the adding amount of the zinc borate powder is 20% of the mass of the ionic liquid.
Step 3, banburying and mixing
The composite flame retardant and the thermoplastic polyurethane elastomer are put into an internal mixer according to the mass ratio of 1:11, and are banburying is carried out for 35 minutes at 165 ℃ and the rotating speed of 110 r/min, thus obtaining the primary mixed material.
Step 4, screw extrusion
Feeding the primary mixed material into a conical feeding hopper, and melting, extruding, cooling, granulating and drying by a double-screw extruder to obtain the flame-retardant polyurethane cable outer sheath material, wherein the temperature of the double-screw extruder is set as follows in the region 1 to 5: 156 ℃,167 ℃,174 ℃,186 ℃,193 ℃.
Example 2:
flame-retardant polyurethane cable outer sheath material
Step 1, preparation of ammonium phytate
Mixing phytic acid, urea and deionized water according to a mass ratio of 2:2:15, controlling the temperature to be 100 ℃, carrying out reflux reaction at a stirring rate of 350 r/min for 2 hours to obtain viscous liquid, and carrying out rotary evaporation for 1 hour under the conditions of 80 ℃ and a vacuum degree of-0.1 MPa to remove water to obtain white solid ammonium phytate.
Step 2, compounding of the composite flame retardant
Mixing ionic liquid, ammonium phytate and lignin according to a mass ratio of 22:4:4, stirring for 2 hours at 130 ℃ at a stirring rate of 600 rpm, placing the obtained liquid on a high-speed dispersing machine after the lignin is completely dissolved, adding zinc borate powder, dispersing for 45 minutes at 130 ℃ at 75000 rpm, and cooling to room temperature to obtain a viscous compound flame retardant;
the ionic liquid is 1-allyl-3-methylimidazole tetrafluoroborate;
the particle size of the zinc borate powder is 1 micron;
the adding amount of the zinc borate powder is 15% of the mass of the ionic liquid.
Step 3, banburying and mixing
The composite flame retardant and the thermoplastic polyurethane elastomer are put into an internal mixer according to the mass ratio of 1:9, and are banburying is carried out for 20 minutes at 150 ℃ and the rotating speed of 70 r/min, thus obtaining the primary mixed material.
Step 4, screw extrusion
Feeding the primary mixed material into a conical feeding hopper, and melting, extruding, cooling, granulating and drying by a double-screw extruder to obtain the flame-retardant polyurethane cable outer sheath material, wherein the temperature of the double-screw extruder is set as follows in the region 1 to 5: 150 ℃,160 ℃,170 ℃,180 ℃ and 190 ℃.
Example 3:
flame-retardant polyurethane cable outer sheath material
Step 1, preparation of ammonium phytate
Mixing phytic acid, urea and deionized water according to a mass ratio of 5:7:29, controlling the temperature to 125 ℃, carrying out reflux reaction at a stirring rate of 600 r/min for 3.5 hours to obtain viscous liquid, and carrying out rotary evaporation for 2.5 hours under the conditions of 95 ℃ and a vacuum degree of-0.09 MPa to remove water to obtain white solid ammonium phytate.
Step 2, compounding of the composite flame retardant
Mixing ionic liquid, ammonium phytate and lignin according to a mass ratio of 35:7:8, stirring for 5 hours at 170 ℃ at a stirring rate of 1000 rpm, placing the obtained liquid on a high-speed dispersing machine after the lignin is completely dissolved, adding zinc borate powder, dispersing for 70 minutes at 170 ℃ at a stirring rate of 95000 rpm, and cooling to room temperature to obtain a viscous compound flame retardant;
the ionic liquid is 1-butyl-3-methylimidazole hexafluorophosphate;
the particle size of the zinc borate powder is 10 microns;
the adding amount of the zinc borate powder is 30% of the mass of the ionic liquid.
Step 3, banburying and mixing
Putting the composite flame retardant and the thermoplastic polyurethane elastomer into an internal mixer according to the mass ratio of 1:15, and banburying at 180 ℃ and the rotating speed of 120 r/min for 40 minutes to obtain a primary mixed material.
Step 4, screw extrusion
Feeding the primary mixed material into a conical feeding hopper, and melting, extruding, cooling, granulating and drying by a double-screw extruder to obtain the flame-retardant polyurethane cable outer sheath material, wherein the temperature of the double-screw extruder is set as follows in the region 1 to 5: 160 ℃,170 ℃,180 ℃,190 ℃ and 195 ℃.
Comparative example 1:
based on the embodiment 1, the preparation of the ammonium phytate in the step 1 is not carried out, 6 parts of ammonium phytate is replaced by 6 parts of ionic liquid in the compounding process of the compound flame retardant in the step 2, and the specific operation is as follows:
step 1, preparing ammonium phytate is not carried out;
step 2, compounding of the composite flame retardant
Mixing ionic liquid and lignin according to a mass ratio of 36:7, stirring for 4 hours at 155 ℃ at a stirring speed of 850 r/min, placing the obtained liquid on a high-speed dispersing machine after the lignin is completely dissolved, adding zinc borate powder, dispersing for 60 minutes at 160 ℃ at 85000 r/min, and cooling to room temperature to obtain a viscous compound flame retardant;
the ionic liquid is 1-ethyl acetate-3-methylimidazole tetrafluoroborate;
the particle size of the zinc borate powder is 7 microns;
the adding amount of the zinc borate powder is 20% of the mass of the ionic liquid. The method comprises the steps of carrying out a first treatment on the surface of the
Steps 3 and 4 were performed as in example 1.
Comparative example 2:
based on the embodiment 1, lignin is not added in the compounding process of the step 2 and the composite flame retardant, and 7 parts of lignin is replaced by 7 parts of ionic liquid in an equivalent way, and the specific operation is as follows:
step 1 the procedure is as in example 1;
step 2, compounding of the composite flame retardant
Mixing ionic liquid and ammonium phytate according to a mass ratio of 37:6, stirring for 4 hours at 155 ℃ at a stirring rate of 850 r/min, placing the obtained liquid on a high-speed dispersing machine, adding zinc borate powder, dispersing for 60 minutes at 160 ℃ at 85000 r/min, and cooling to room temperature to obtain a viscous composite flame retardant;
the ionic liquid is 1-ethyl acetate-3-methylimidazole tetrafluoroborate;
the particle size of the zinc borate powder is 7 microns;
the adding amount of the zinc borate powder is 20% of the mass of the ionic liquid;
steps 3 and 4 were performed as in example 1.
Comparative example 3:
based on the embodiment 1, zinc borate powder is not added in the compounding process of the step 2 and the composite flame retardant, and 6 parts of zinc borate powder is replaced by 6 parts of ionic liquid in an equivalent way, and the specific operation is as follows:
step 1 the procedure is as in example 1;
step 2, compounding of the composite flame retardant
Mixing ionic liquid, ammonium phytate and lignin according to a mass ratio of 30:6:7, stirring for 4 hours at 155 ℃ at a stirring rate of 850 r/min, placing the obtained liquid on a high-speed dispersing machine after the lignin is completely dissolved, adding 6 parts of ionic liquid, dispersing for 60 minutes at 160 ℃ at 85000 r/min, and cooling to room temperature to obtain a viscous compound flame retardant;
the ionic liquid is 1-ethyl acetate-3-methylimidazole tetrafluoroborate;
the particle size of the zinc borate powder is 7 microns;
steps 3 and 4 were performed as in example 1.
Performance test:
the flame-retardant polyurethane cable jacket materials obtained in examples 1, 2 and 3 and comparative examples 1, 2 and 3 were extruded into cable jacket on a screw extruder with screw diameter of 120mm and length-diameter ratio of 10:1, extruder temperature distribution of 185 ℃ at die, 190 ℃ at head, 130 ℃ at feeding port, 155 ℃ at first zone of the extruder, 175 ℃ at second zone of the extruder, and 180 ℃ at screw zone. The cable outer sheath obtained after extrusion is subjected to relevant performance test according to GB/T2951-2008, the flame retardant property is subjected to UL94 vertical combustion test according to GB/T2408-2008 'determination of the plastic combustion property horizontal method and vertical method', and specific test results are shown in Table 1:
TABLE 1
As can be seen from the data in table 1, the tensile strength, elongation at break and heat elongation at heat aging performance of the three comparative examples are reduced, and the tensile strength, elongation at break and heat elongation at heat aging performance of the three comparative examples are increased, compared with the examples 1, 2 and 3, because the addition amount of the ionic liquid in the three comparative examples is larger than that of the three examples, the ionic liquid has a relatively strong plasticizing effect, the tensile strength, the heat elongation at aging resistance and the like of the polyurethane cable jacket material are slightly reduced with the increase of the addition amount of the ionic liquid, but the toughness is correspondingly increased, and the elongation at break is increased according to the corresponding physical quantity; the flame retardant performance of comparative example 1 was the worst, and it can be seen that N, P elements contained in ammonium phytate are the most critical for improving the flame retardant performance, and in addition, in comparative example 2 without lignin and comparative example 3 without zinc borate powder, the flame retardant performance is significantly reduced, and lignin and zinc borate have significant synergistic flame retardant effects in the composite flame retardant system.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (4)
1. The utility model provides a fire-retardant polyurethane cable oversheath material which characterized in that:
the preparation method of the flame-retardant polyurethane cable outer sheath material comprises four steps of ammonium phytate preparation, compounding of a composite flame retardant, banburying and mixing and screw extrusion;
the composite flame retardant is formed by compounding ionic liquid, ammonium phytate, lignin and zinc borate;
the ionic liquid is one of 1-ethyl acetate-3-methylimidazole tetrafluoroborate, 1-allyl-3-methylimidazole tetrafluoroborate and 1-butyl-3-methylimidazole hexafluorophosphate;
the preparation method of the ammonium phytate comprises the following steps: mixing phytic acid, urea and deionized water according to a mass ratio of 2-5:2-7:15-29, controlling the temperature to be 100-125 ℃, carrying out reflux reaction at a stirring speed of 350-600 r/min for 2-3.5 hours to obtain viscous liquid, and carrying out rotary evaporation for 1-2.5 hours under the conditions of 80-95 ℃ and a vacuum degree of-0.1 to-0.09 MPa to remove water to obtain white solid ammonium phytate;
the compounding method of the composite flame retardant comprises the following steps: mixing the ionic liquid, the ammonium phytate and the lignin according to the mass ratio of 22-35:4-7:4-8, stirring for 2-5 hours at the temperature of 130-170 ℃ at the stirring speed of 600-1000 rpm, placing the obtained liquid on a high-speed dispersing machine after the lignin is completely dissolved, adding zinc borate powder, dispersing for 45-70 minutes at the temperature of 130-170 ℃ at the speed of 75000-95000 rpm, and cooling to room temperature to obtain the viscous composite flame retardant.
2. The flame retardant polyurethane cable jacket material of claim 1, wherein:
the banburying and mixing method comprises the following steps: and (3) putting the composite flame retardant and the thermoplastic polyurethane elastomer into an internal mixer according to the mass ratio of 1:9-15, and banburying for 20-40 minutes at the temperature of 150-180 ℃ and the rotating speed of 70-120 r/min to obtain a primary mixed material.
3. The flame retardant polyurethane cable jacket material of claim 1, wherein:
the screw extrusion method comprises the following steps: feeding the primary mixed material into a conical feeding hopper, and melting, extruding, cooling, granulating and drying by a double-screw extruder to obtain the flame-retardant polyurethane cable outer sheath material, wherein the temperature of the double-screw extruder is set as follows in the region 1 to 5: 150-160 ℃, 160-170 ℃, 170-180 ℃, 180-190 ℃ and 190-195 ℃.
4. The flame retardant polyurethane cable jacket material of claim 1, wherein:
the particle size of the zinc borate powder is 1-10 microns;
the adding amount of the zinc borate powder is 15-30% of the mass of the ionic liquid.
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