CN113416406A - TPU fuel inhibitor and preparation method thereof - Google Patents
TPU fuel inhibitor and preparation method thereof Download PDFInfo
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- CN113416406A CN113416406A CN202110852560.XA CN202110852560A CN113416406A CN 113416406 A CN113416406 A CN 113416406A CN 202110852560 A CN202110852560 A CN 202110852560A CN 113416406 A CN113416406 A CN 113416406A
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- 239000000446 fuel Substances 0.000 title claims description 13
- 239000003112 inhibitor Substances 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003063 flame retardant Substances 0.000 claims abstract description 63
- 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 58
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 33
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 33
- 239000000779 smoke Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000005469 granulation Methods 0.000 claims abstract description 11
- 230000003179 granulation Effects 0.000 claims abstract description 11
- 239000013013 elastic material Substances 0.000 claims abstract description 5
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 76
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 150000008301 phosphite esters Chemical group 0.000 claims description 10
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 9
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 9
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical group [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- 229910001376 inorganic hypophosphite Inorganic materials 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 3
- DECPGQLXYYCNEZ-UHFFFAOYSA-N tris(6-methylheptyl) phosphite Chemical compound CC(C)CCCCCOP(OCCCCCC(C)C)OCCCCCC(C)C DECPGQLXYYCNEZ-UHFFFAOYSA-N 0.000 claims description 3
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 10
- 238000005303 weighing Methods 0.000 abstract description 9
- 230000001629 suppression Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 57
- 238000001816 cooling Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a TPU flame retardant and a preparation method thereof, and relates to the technical field of polymer material synthesis. Weighing thermoplastic elastic material, flame retardant, novel hyperbranched macromolecular flame-retardant char forming agent, perovskite smoke suppressant and antioxidant, and then adding into a high-speed mixer for mixing; and introducing the mixture into a conical feeding hopper, and performing melt extrusion granulation at the processing temperature of 140-200 ℃ of a double-screw extruder to obtain the product. The TPU material prepared by the invention has the characteristics of low smoke, no halogen, high flame retardance, flexibility and elasticity, effectively improves the flame retardance, smoke suppression and mechanical properties, can be widely applied to the related fields of rail transit, automobiles and the like, and meets the requirement of the application standard EN45545 of the fireproof element of the railway vehicle.
Description
Technical Field
The invention relates to the technical field of polymer material synthesis, in particular to a TPU flame retardant and a preparation method thereof.
Background
The study of smoke suppression properties of thermoplastic polyurethane elastomer rubbers (TPU) has been one of the most important issues in the field of flame retardancy of polyurethanes. Because of its abundance in C, H, TPU is extremely flammable, with significant melt dripping and toxic smoke emissions, necessitating flame retardant modification. All the time, foreign TPU synthesis manufacturers such as Luoborun, Hensman and Basff have halogen-free TPU flame retardant materials with respective brands meeting the flame retardant requirement of UL electric wires, and many domestic manufacturers have developed corresponding environment-friendly flame retardant TPU and halogen-free flame retardant TPU.
At present, the most common flame retardant in domestic halogen-free flame retardant TPU materials is a phosphorus-nitrogen flame retardant, and the flame retardant is favored by researchers due to the high flame retardant property, the addition amount is small when the flame retardant is applied to the TPU materials, and the mechanical property of the materials is weakened, but the release of toxic smoke can not be reduced by the flame retardant, so that the development of halogen-free TPU flame retardant with higher cost performance is urgent in the domestic polyurethane manufacturing industry at present. In addition, along with the promotion of the application standard EN45545 of the fireproof element of the railway vehicle, stricter standards are provided for the smoke density and the toxic gas emission of the fireproof element of the railway electrical appliance. Therefore, the development of the high-efficiency low-smoke halogen-free TPU fuel-resistant material becomes an inevitable choice for the development of times.
Patent CN103665829B discloses a high flame retardant environment-friendly thermoplastic polyurethane elastomer and a preparation method thereof. The halogen-free flame-retardant thermoplastic polyurethane material described in the patent takes phosphorus-containing products such as dimethyl methylphosphonate or triphenyl phosphate and the like as flame retardants, so that the flame retardant property is excellent, but the mechanical property is greatly weakened; although the smoke suppression performance is improved, a small amount of black smoke is generated, and the smoke suppression requirement of railway electrical appliance elements cannot be met.
Disclosure of Invention
The invention aims to provide a low-smoke halogen-free, high-flame-retardant, strong-thermoplasticity, flexible and elastic TPU flame retardant used in the related fields of rail transit, automobiles and the like and a preparation method thereof.
According to the technical scheme of the invention, the TPU flame retardant is prepared from the following raw materials in parts by weight: thermoplastic elastomer material: 60-90 parts; flame retardant: 10-40 parts; a char-forming agent: 5-30 parts of a solvent; smoke suppressant: 1-10 parts; antioxidant: 0.3 to 1.0 portion.
Preferably, the char-forming agent is a novel hyperbranched macromolecular flame-retardant char-forming agent (UHPCA).
Specifically, the molecular formula of the novel hyperbranched macromolecular flame-retardant charring agent is C27H33P2O8N15Molecular weight of756.79, theoretical carbon content 42.81%; the molecule contains phosphorus element and nitrogen element, and has P/N synergistic effect.
Preferably, the smoke suppressant is a perovskite.
In particular, the perovskite has a molecular general formula of ABO3The metal ions are cubic or octahedral crystal forms, the A site is generally rare earth or alkaline earth element ions, the B site is transition metal element ions, the metal ions have good capacity of capturing free radicals, the free radical reaction generated by toxic smoke in the combustion process can be blocked, the smoke release amount is greatly reduced, and meanwhile, the metal ions have strong catalytic carbonization effect and can form good compound synergistic effect with a flame retardant and a carbonizing agent.
It is further noted that the perovskite is synthesized by a high-energy ball milling method, and the method can obtain various composite oxides with perovskite structures without high-temperature sintering, and can also greatly improve the dispersion degree of products, so that the material can achieve high performance under the condition of small addition amount.
Preferably, the thermoplastic elastic material is a polyether type TPU resin or a polyester type TPU resin.
Preferably, the polyether type TPU resin is selected from one or more of TPU 590A resin, TPU 580A resin, TPU585A resin, TPU 590A resin, TPU C890A resin, TPU 8380 resin, and TPU 890A resin.
Preferably, the flame retardant is a phosphorus nitrogen flame retardant.
Preferably, the phosphorus-nitrogen flame retardant is selected from one or more of ammonium polyphosphate, melamine polyphosphate, red phosphorus, inorganic hypophosphite and organic hypophosphite.
Preferably, the antioxidant consists of a main antioxidant and an auxiliary antioxidant, and the mass ratio of the main antioxidant to the auxiliary antioxidant is 1-3: 0.3 to 1.
Preferably, the primary antioxidant is selected from one or more of antioxidant 1010, antioxidant 1035, antioxidant 1024, and antioxidant 1174.
Preferably, the secondary antioxidant is a phosphite ester selected from one or more of phosphite, triphenyl phosphite, diphenyl phosphite, triisooctyl phosphite, diisooctyl diphenyl phosphite and polyphenyl phosphite.
The invention also provides a preparation method of the TPU flame retardant, which comprises the following steps:
(1) mixing a thermoplastic elastic material, a flame retardant, a char forming agent, a smoke suppressant and an antioxidant to obtain a mixture;
(2) and granulating the mixture to obtain the TPU fuel inhibitor.
Preferably, the processing temperature of the granulation is 140-220 ℃.
Specifically, the preparation method of the TPU flame retardant comprises the following steps: weighing 60-90 parts of thermoplastic elastic material, 10-40 parts of flame retardant, 10-30 parts of char forming agent, 1-10 parts of smoke suppressant and 0.3-1.0 part of antioxidant, placing the weighed materials in a high-speed mixer, and stirring at room temperature and low speed for 3-5 min to obtain a mixture; and introducing the mixture into a conical feeding hopper, performing melt extrusion, cooling, granulating and drying at the processing temperature of 140-220 ℃ by using a double-screw extruder to obtain the TPU fuel inhibitor.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1) the novel hyperbranched macromolecular flame-retardant char forming agent adopted by the invention has a flame-retardant effect, can be used as a flame retardant alone, and can also be compounded with the flame retardant to form a compound Intumescent Flame Retardant (IFR) system, so that a more effective flame-retardant effect is achieved;
2) according to the invention, the perovskite prepared by a ball milling method is used as a smoke suppressant for the first time, and is compounded with the flame retardant, so that the char formation and flame retardance of the material are further improved; the introduction of perovskite metal can capture free radicals generated in the combustion process, block the generation of toxic smoke and greatly reduce the smoke release amount; in addition, the ball milling method can obtain various composite oxides with perovskite structures without high-temperature sintering, greatly improves the dispersion degree of products, and enables the materials to achieve high performance under the condition of small addition amount;
3) the TPU material prepared by the invention has the advantages of low smoke, no halogen, high flame retardance, strong thermoplasticity, flexibility and elasticity, and meets the requirements of the application standard EN45545 of the railway vehicle fireproof element that the oxygen index is more than or equal to 28%, the smoke density is less than or equal to 300, and the discharge amount of thermally degraded gas at 600 ℃ is less than or equal to 1.5;
4) the TPU flame retardant prepared by the invention effectively improves the flame retardant property, smoke suppression property and mechanical property, and can be widely applied to fireproof elements in the related fields of rail transit, automobiles and the like.
Detailed Description
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.
Example 1:
77 parts of TPU 590A resin, 15 parts of ammonium polyphosphate, 5 parts of UHPCA and GaTiO31 part, antioxidant 10101 part and phosphite ester 1 part. Weighing, placing in a high-speed mixer, and stirring at low speed for 5min at room temperature to obtain a mixture. And introducing the mixture into a conical feeding hopper, and performing melt extrusion, cooling, granulation and drying by using a double-screw extruder to obtain the halogen-free flame-retardant thermoplastic polyurethane cable sheath. The temperature of the 1-10 zones of the double-screw extruder is set as follows: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃ and 195 ℃.
Example 2:
77 parts of TPU 590A resin, 15 parts of diethyl aluminum hypophosphite, 5 parts of UHPCA and NiTiO31 part, antioxidant 10101 part and phosphite ester 1 part. Weighing, placing in a high-speed mixer, and stirring at low speed for 5min at room temperature to obtain a mixture. And introducing the mixture into a conical feeding hopper, and performing melt extrusion, cooling, granulation and drying by using a double-screw extruder to obtain the halogen-free flame-retardant thermoplastic polyurethane cable sheath. The temperature of the 1-10 zones of the double-screw extruder is set as follows: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃ and 195 ℃.
Example 3
60 parts of TPU 590A resin, 10 parts of ammonium polyphosphate, 5 parts of UHPCA and GaTiO31 part, 10100.3 parts of antioxidant and 0.03 part of phosphite ester. The height is higher than the speed after weighingStirring at low speed for 5min at room temperature in a mixer to obtain a mixture. And introducing the mixture into a conical feeding hopper, and performing melt extrusion, cooling, granulation and drying by using a double-screw extruder to obtain the halogen-free flame-retardant thermoplastic polyurethane cable sheath. The temperature of the 1-10 zones of the double-screw extruder is set as follows: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃ and 195 ℃.
Example 4
90 parts of TPU 590A resin, 40 parts of ammonium polyphosphate, 30 parts of UHPCA and GaTiO310 parts of antioxidant 10101 parts and 1 part of phosphite ester. Weighing, placing in a high-speed mixer, and stirring at low speed for 5min at room temperature to obtain a mixture. And introducing the mixture into a conical feeding hopper, and performing melt extrusion, cooling, granulation and drying by using a double-screw extruder to obtain the halogen-free flame-retardant thermoplastic polyurethane cable sheath. The temperature of the 1-10 zones of the double-screw extruder is set as follows: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃ and 195 ℃.
Example 5
90 parts of TPU 590A resin, 40 parts of ammonium polyphosphate, 30 parts of UHPCA and GaTiO310 parts of antioxidant 10101 parts and 0.3 part of phosphite ester. Weighing, placing in a high-speed mixer, and stirring at low speed for 5min at room temperature to obtain a mixture. And introducing the mixture into a conical feeding hopper, and performing melt extrusion, cooling, granulation and drying by using a double-screw extruder to obtain the halogen-free flame-retardant thermoplastic polyurethane cable sheath. The temperature of the 1-10 zones of the double-screw extruder is set as follows: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃ and 195 ℃.
Example 6
90 parts of TPU 590A resin, 40 parts of ammonium polyphosphate, 30 parts of UHPCA and GaTiO310 parts of antioxidant 10101 parts and 1 part of phosphite ester. Weighing, placing in a high-speed mixer, and stirring at low speed for 5min at room temperature to obtain a mixture. And introducing the mixture into a conical feeding hopper, and performing melt extrusion, cooling, granulation and drying by using a double-screw extruder to obtain the halogen-free flame-retardant thermoplastic polyurethane cable sheath. The temperature of the 1-10 zones of the double-screw extruder is set as follows: 160 ℃, 170 ℃, 180 ℃, 190℃，195℃，195℃，195℃，195℃，195℃，195℃。
Examples 7 to 12
The TPU 590A resin is replaced by TPU 580A resin, TPU585A resin, TPU 590A resin, TPU C890A resin, TPU 8380 resin or TPU 890A resin on the basis of the embodiment 1.
Examples 13 to 20
Ammonium polyphosphate was replaced with melamine polyphosphate, red phosphorus, inorganic hypophosphite or organic hypophosphite on the basis of example 1.
Examples 21 to 25
The phosphites were replaced on the basis of example 1 by triphenyl phosphite, diphenyl phosphite, triisooctyl phosphite, diisooctyl diphenyl phosphite or polyphenyl phosphites.
Comparative example 1:
77 parts of TPU 590A resin, 15 parts of ammonium polyphosphate, 10101 parts of antioxidant and 1 part of phosphite ester. Weighing, placing in a high-speed mixer, and stirring at low speed for 5min at room temperature to obtain a mixture. And introducing the mixture into a conical feeding hopper, and performing melt extrusion, cooling, granulation and drying by using a double-screw extruder to obtain the halogen-free flame-retardant thermoplastic polyurethane cable sheath. The temperature of the 1-10 zones of the double-screw extruder is set as follows: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃ and 195 ℃.
Comparative example 2:
77 parts of TPU 590A resin, 15 parts of diethyl aluminum hypophosphite, 10101 parts of antioxidant and 1 part of phosphite ester. Weighing, placing in a high-speed mixer, and stirring at low speed for 5min at room temperature to obtain a mixture. And introducing the mixture into a conical feeding hopper, and performing melt extrusion, cooling, granulation and drying by using a double-screw extruder to obtain the halogen-free flame-retardant thermoplastic polyurethane cable sheath. The temperature of the 1-10 zones of the double-screw extruder is set as follows: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃, 195 ℃ and 195 ℃.
The extruded granulated material was tested for its smoke suppression properties according to the requirements of standard EN 45545; the oxygen index test was carried out according to the requirements of GB/T2406.2-2009 Combustion behavior for plastics by oxygen index method, and the results are shown in Table 1.
TABLE 1
| Name of test | Unit of | Require that | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 |
| Tensile strength | MPa | 20 | 34.17 | 37.25 | 34.92 | 37.05 |
| Elongation at break | ％ | 300 | 503 | 590 | 518 | 576 |
| Oxygen index | ％ | ≥28 | 32 | 33 | 26 | 27 |
| Density of smoke | ≤300 | 195 | 170 | 328 | 356 | |
| Emission of thermal degradation gas | ≤1.5 | 1.1 | 1.0 | 2.0 | 2.2 |
The TPU flame retardant with low smoke, no halogen, high flame retardance, flexibility and elasticity is finally prepared through the synergistic effect of the flame retardant, the char forming agent, the smoke suppressant and the antioxidant. As can be seen from Table 1, the TPU flame retardants prepared in examples 1 and 2 meet the requirements of the application standard EN45545 for the fireproof elements of railway vehicles, such as an oxygen index of not less than 28%, a smoke density of not more than 300, and a thermal degradation gas emission at 600 ℃ of not more than 1.5, are obviously superior to the TPU materials prepared in comparative examples 1 and 2, and have excellent mechanical properties.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The TPU flame retardant is characterized by being prepared from the following raw materials in parts by weight: thermoplastic elastomer material: 60-90 parts; flame retardant: 10-40 parts; a char-forming agent: 5-30 parts of a solvent; smoke suppressant: 1-10 parts; antioxidant: 0.3-1.0 part;
the charring agent is a novel hyperbranched macromolecular flame-retardant charring agent;
the smoke suppressant is perovskite.
2. The TPU fuel barrier of claim 1, wherein the thermoplastic elastomer is a polyether TPU resin or a polyester TPU resin.
3. The TPU fuel barrier of claim 2, wherein the polyether TPU resin is selected from one or more of TPU 590A resin, TPU 580A resin, TPU585A resin, TPU 590A resin, TPU C890A resin, TPU 8380 resin, and TPU 890A resin.
4. The TPU fuel barrier of claim 1, wherein the flame retardant is a phosphorus nitrogen flame retardant.
5. The TPU fuel barrier of claim 4, wherein the phosphorus nitrogen flame retardant is selected from one or more of the group consisting of ammonium polyphosphate, melamine polyphosphate, red phosphorus, inorganic hypophosphites, and organic hypophosphites.
6. The TPU flame retardant of claim 1, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant, and the mass ratio of the primary antioxidant to the secondary antioxidant is 1-3: 0.3 to 1.
7. The TPU fuel blocker of claim 6, wherein the primary antioxidant is selected from one or more of antioxidant 1010, antioxidant 1035, antioxidant 1024, and antioxidant 1174.
8. The TPU fuel blocker of claim 6, wherein the secondary antioxidant is a phosphite ester selected from one or more of phosphite, triphenyl phosphite, diphenyl phosphite, triisooctyl phosphite, diisooctyl diphenyl phosphite, and polyphenyl phosphite.
9. A method for preparing the TPU fuel inhibitor as set forth in any one of claims 1 to 8, comprising the steps of:
(1) mixing a thermoplastic elastic material, a flame retardant, a char forming agent, a smoke suppressant and an antioxidant to obtain a mixture;
(2) and granulating the mixture to obtain the TPU fuel inhibitor.
10. The method according to claim 9, wherein the granulation is carried out at a processing temperature of 140 to 220 ℃.
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