CN110551387A - Antistatic flame-retardant thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
Antistatic flame-retardant thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN110551387A CN110551387A CN201910815070.5A CN201910815070A CN110551387A CN 110551387 A CN110551387 A CN 110551387A CN 201910815070 A CN201910815070 A CN 201910815070A CN 110551387 A CN110551387 A CN 110551387A
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- thermoplastic polyurethane
- polyurethane elastomer
- antistatic
- flame retardant
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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 title claims abstract description 97
- 239000003063 flame retardant Substances 0.000 title claims abstract description 97
- 229920001971 elastomer Polymers 0.000 title claims abstract description 86
- 239000000806 elastomer Substances 0.000 title claims abstract description 84
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 83
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002216 antistatic agent Substances 0.000 claims abstract description 40
- 239000000314 lubricant Substances 0.000 claims abstract description 25
- 239000004014 plasticizer Substances 0.000 claims abstract description 24
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- OHRVBDRGLIWLPA-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(O)=O OHRVBDRGLIWLPA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 10
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 8
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 5
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims abstract description 4
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims abstract description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 14
- 239000012452 mother liquor Substances 0.000 claims description 14
- -1 polyethylene Polymers 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 9
- 239000000347 magnesium hydroxide Substances 0.000 claims description 9
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 9
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 claims description 7
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 claims description 3
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 claims description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 3
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003508 Dilauryl thiodipropionate Substances 0.000 claims description 3
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 3
- 229940100539 dibutyl adipate Drugs 0.000 claims description 3
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- LGOPTUPXVVNJFH-UHFFFAOYSA-N pentadecanethioic s-acid Chemical compound CCCCCCCCCCCCCCC(O)=S LGOPTUPXVVNJFH-UHFFFAOYSA-N 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- QWSZRRAAFHGKCH-UHFFFAOYSA-M sodium;hexane-1-sulfonate Chemical compound [Na+].CCCCCCS([O-])(=O)=O QWSZRRAAFHGKCH-UHFFFAOYSA-M 0.000 description 2
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical group CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical group CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002341 toxic gas 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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 belongs to the technical field of high polymer materials, and particularly relates to an antistatic flame-retardant thermoplastic polyurethane elastomer which comprises the following components in parts by mass: 40-70 parts of thermoplastic polyurethane elastomer, 5-20 parts of flame retardant, 2-10 parts of antistatic agent, 2-5 parts of compatilizer, 2-5 parts of plasticizer, 0.1-2 parts of antioxidant and 0.1-2 parts of lubricant; the flame retardant is melamine salt of pentaerythritol phosphate, graphite and nano metal hydroxide in a mass ratio of 3:2:5, the antistatic agent is a composite antistatic agent consisting of oil monostearate and ethoxylated amine, and the mass ratio of glycerol monostearate to ethoxylated amine is 4-7: 3 to 6. Compared with the prior art, the thermoplastic polyurethane elastomer provided by the invention has the advantages that the flame retardant property and the antistatic property are effectively improved while the mechanical property is not reduced. In addition, the invention also provides a preparation method of the antistatic flame-retardant thermoplastic polyurethane elastomer.
Description
Technical Field
the invention belongs to the technical field of high polymer materials, and particularly relates to an antistatic flame-retardant thermoplastic polyurethane elastomer and a preparation method thereof.
Background
The thermoplastic polyurethane elastomer (TPU) is a special high polymer material between plastic and rubber, has good elasticity, wear resistance, low temperature resistance, oil resistance and tensile strength, is commonly used for manufacturing sheaths, sealing elements, synthetic leather, shock absorption blocks and the like of trundles and electric wires and cables, can replace rubber, can be manufactured by an injection molding machine or an extruder, and has clean, sanitary, environment-friendly and pollution-free manufacturing process.
However, the thermoplastic polyurethane elastomer is similar to most other high polymer materials, is flammable and easy to drip, generates a large amount of smoke, and has a volume resistivity of 10 13 -10 15 Ω. cm 2, so that static electricity is easily accumulated on the surface of the polyurethane elastomer material to generate static electricity, and the accumulation of the static electricity easily causes short circuit and fire, and can explode in severe cases.
However, whether a flame retardant or an antistatic agent is added, the method also brings about some serious problems, which are mainly shown in that: poor compatibility between the flame retardant and the elastomer; the flame retardant emits a large amount of toxic gases (such as HCl, HCN and the like), generates a large amount of smoke and emits a large amount of corrosive substances; the mechanical property of the polyurethane elastomer is reduced due to the addition of the flame retardant and the electrostatic agent; due to these problems, the range of use of polyurethane elastomers is greatly limited.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the antistatic flame-retardant thermoplastic polyurethane elastomer is provided, and the flame retardant property and the antistatic property are effectively improved while the mechanical property of the elastomer is not reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
An antistatic flame-retardant thermoplastic polyurethane elastomer comprises the following components in parts by mass: 40-70 parts of thermoplastic polyurethane elastomer, 5-20 parts of flame retardant, 2-10 parts of antistatic agent, 2-5 parts of compatilizer, 2-5 parts of plasticizer, 0.1-2 parts of antioxidant and 0.1-2 parts of lubricant; the flame retardant is melamine salt of pentaerythritol phosphate, graphite and nano metal hydroxide in a mass ratio of 3:2:5, the antistatic agent is a composite antistatic agent consisting of oil monostearate and ethoxylated amine, and the mass ratio of glycerol monostearate to ethoxylated amine is 4-7: 3 to 6.
the improved antistatic flame-retardant thermoplastic polyurethane elastomer comprises the following components in parts by mass: 50-60 parts of thermoplastic polyurethane elastomer, 10-15 parts of flame retardant, 4-8 parts of antistatic agent, 3-4 parts of compatilizer, 3-4 parts of plasticizer, 0.5-1 part of antioxidant and 0.5-1 part of lubricant.
The improved antistatic flame-retardant thermoplastic polyurethane elastomer comprises the following components in parts by mass: 55 parts of thermoplastic polyurethane elastomer, 12 parts of flame retardant, 6 parts of antistatic agent, 3.5 parts of compatilizer, 3.5 parts of plasticizer, 0.75 part of antioxidant and 0.75 part of lubricant.
as an improvement of the antistatic flame-retardant thermoplastic polyurethane elastomer, the nano metal hydroxide is nano aluminum hydroxide and/or nano magnesium hydroxide.
As an improvement of the antistatic flame-retardant thermoplastic polyurethane elastomer, the compatilizer is any one of polyethylene grafted maleic anhydride, ethylene propylene diene monomer grafted maleic anhydride and polyolefin elastomer grafted maleic anhydride.
As an improvement of the antistatic flame-retardant thermoplastic polyurethane elastomer according to the present invention, the plasticizer is at least one of dipropylene glycol dibenzoate, diethylene glycol dibenzoate, dimethyl adipate, diethyl adipate, dibutyl adipate, and dioctyl adipate.
as an improvement of the antistatic flame-retardant thermoplastic polyurethane elastomer, the antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 4' -thiobis (6-tert-butyl-3-methylphenol), dilauryl thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate) and tris [2, 4-di-tert-butylphenyl ] phosphite.
as an improvement of the antistatic flame-retardant thermoplastic polyurethane elastomer, the lubricant is at least one of zinc stearate, hydroxyl silicone oil, silicone powder and fluorine-containing lubricant.
Another object of the invention is: the preparation method of the antistatic flame-retardant thermoplastic polyurethane elastomer comprises the following steps:
Step one, weighing raw materials in parts by weight;
Step two, adding the thermoplastic polyurethane elastomer into a mixer at the temperature of 60-120 ℃, and stirring for 35-45 min;
Uniformly stirring the flame retardant, the antistatic agent, the plasticizer, the antioxidant and the lubricant at normal temperature to obtain modified mother liquor;
And step four, evenly dividing the modified mother liquor obtained in the step three into 3 equal parts, evenly dividing the compatilizer into 3 equal parts, adding 1 part of modified mother liquor and 1 part of compatilizer into the mixer in the step two every 45min, keeping the mixer in a stirring state during the adding process, and continuing stirring for 3h after all the modified mother liquor and the compatilizer are added, so as to obtain the antistatic flame-retardant thermoplastic polyurethane elastomer.
Compared with the prior art, the invention has the beneficial effects that:
1) The antistatic flame-retardant thermoplastic polyurethane elastomer adopts a composite flame retardant consisting of melamine salt of pentaerythritol phosphate, graphite and nano metal hydroxide in a mass ratio of 3:2:5, wherein the melamine salt of the pentaerythritol phosphate is a compound simultaneously containing two elements of phosphorus and nitrogen, and equivalently, the phosphorus flame retardant and the nitrogen flame retardant are compounded for use and have a synergistic effect, so that the flame-retardant effect of the antistatic flame-retardant thermoplastic polyurethane elastomer is obviously superior to that of a single phosphorus flame retardant or nitrogen flame retardant. In addition, the flame retardant property of the thermoplastic polyurethane elastomer can be improved by adding the graphite and the nano metal hydroxide, so that the using amount of the flame retardant in the whole system can be reduced, and the influence of the flame retardant on the mechanical property of the thermoplastic polyurethane elastomer is reduced.
2) The antistatic flame-retardant thermoplastic polyurethane elastomer adopts the composite antistatic agent consisting of glycerol monostearate and ethoxylated amine, has small addition amount and good effect, can greatly reduce the surface resistivity of the material, and has small influence on the mechanical property of the thermoplastic polyurethane elastomer.
3) The antistatic flame-retardant thermoplastic polyurethane elastomer is added with the plasticizer and the compatilizer, the plasticizer mainly improves the flexibility of the thermoplastic polyurethane elastomer, the compatilizer improves the compatibility between the flame retardant and the antistatic agent and the thermoplastic polyurethane elastomer, and the compatilizer and the modified mother liquor are added into the thermoplastic polyurethane elastomer in batches, so that the components can be well compatible, and the effect of improving the mechanical property is achieved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
The preparation method of the antistatic flame-retardant thermoplastic polyurethane elastomer comprises the following steps:
Weighing 55 parts of thermoplastic polyurethane elastomer, 12 parts of flame retardant, 6 parts of antistatic agent, 3.5 parts of compatilizer, 3.5 parts of plasticizer, 0.75 part of antioxidant and 0.75 part of lubricant; wherein the flame retardant is melamine salt of pentaerythritol phosphate, graphite, nano aluminum hydroxide and nano magnesium hydroxide in a mass ratio of 3:2:2:3, and the antistatic agent is composed of an antistatic agent and a flame retardant in a mass ratio of 6: 4, the compatilizer is polyethylene grafted maleic anhydride, the plasticizer is dipropylene glycol dibenzoate, the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the lubricant is zinc stearate;
Step two, adding the thermoplastic polyurethane elastomer into a mixer at the temperature of 60-120 ℃, and stirring for 35-45 min;
Uniformly stirring the flame retardant, the antistatic agent, the plasticizer, the antioxidant and the lubricant at normal temperature to obtain modified mother liquor;
and step four, evenly dividing the modified mother liquor obtained in the step three into 3 equal parts, evenly dividing the compatilizer into 3 equal parts, adding 1 part of modified mother liquor and 1 part of compatilizer into the mixer in the step two every 45min, keeping the mixer in a stirring state during the adding process, and continuing stirring for 3h after all the modified mother liquor and the compatilizer are added, so as to obtain the antistatic flame-retardant thermoplastic polyurethane elastomer.
Example 2
Different from example 1 is the composition of the antistatic flame retardant thermoplastic polyurethane elastomer: 40 parts of thermoplastic polyurethane elastomer, 5 parts of flame retardant, 2 parts of antistatic agent, 2 parts of compatilizer, 2 parts of plasticizer, 0.1 part of antioxidant and 0.1 part of lubricant; wherein the flame retardant is melamine salt of pentaerythritol phosphate, graphite and nano aluminum hydroxide in a mass ratio of 3:2:5, and the antistatic agent is composed of an antistatic agent and a flame retardant in a mass ratio of 4: 6, the compatilizer is ethylene propylene diene monomer grafted maleic anhydride, the plasticizer is dimethyl adipate, the antioxidant is 4, 4' -thiobis (6-tert-butyl-3-methylphenol), and the lubricant is hydroxyl silicone oil.
The rest is the same as embodiment 1, and the description is omitted here.
example 3
Different from example 1 is the composition of the antistatic flame retardant thermoplastic polyurethane elastomer: 50 parts of thermoplastic polyurethane elastomer, 10 parts of flame retardant, 4 parts of antistatic agent, 3 parts of compatilizer, 3 parts of plasticizer, 0.5 part of antioxidant and 0.5 part of lubricant; wherein the flame retardant is melamine salt of pentaerythritol phosphate, graphite and nano magnesium hydroxide in a mass ratio of 3:2:5, and the antistatic agent is composed of an antistatic agent and a flame retardant in a mass ratio of 5: 5, the compatilizer is polyolefin elastomer grafted maleic anhydride, the plasticizer is diethylene glycol dibenzoate and diethyl adipate, the antioxidant is dilauryl thiodipropionate, and the lubricant is silicone powder.
the rest is the same as embodiment 1, and the description is omitted here.
example 4
Different from example 1 is the composition of the antistatic flame retardant thermoplastic polyurethane elastomer: 60 parts of thermoplastic polyurethane elastomer, 15 parts of flame retardant, 8 parts of antistatic agent, 4 parts of compatilizer, 4 parts of plasticizer, 1 part of antioxidant and 1 part of lubricant; wherein the flame retardant is melamine salt of pentaerythritol phosphate, graphite, nano aluminum hydroxide and nano magnesium hydroxide in a mass ratio of 3:2:3:2, and the antistatic agent is composed of an antistatic agent and a flame retardant in a mass ratio of 7:3, the compatilizer is polyolefin elastomer grafted maleic anhydride, the plasticizer is diethylene glycol dibenzoate and dibutyl adipate, the antioxidant is pentaerythritol tetra (3-lauryl thiopropionate), and the lubricant is a fluorine-containing lubricant.
The rest is the same as embodiment 1, and the description is omitted here.
example 5
different from example 1 is the composition of the antistatic flame retardant thermoplastic polyurethane elastomer: 70 parts of thermoplastic polyurethane elastomer, 20 parts of flame retardant, 10 parts of antistatic agent, 5 parts of compatilizer, 5 parts of plasticizer, 2 parts of antioxidant and 2 parts of lubricant; wherein the flame retardant is melamine salt of pentaerythritol phosphate, graphite, nano aluminum hydroxide and nano magnesium hydroxide in a mass ratio of 3:2:4:1, and the antistatic agent is composed of an antistatic agent and a flame retardant in a mass ratio of 5.5: 4.5 of oil monostearate and ethoxylated amine, a compatilizer of polyethylene grafted maleic anhydride, a plasticizer of dipropylene glycol dibenzoate and dioctyl adipate, an antioxidant of tris [ 2.4-di-tert-butylphenyl ] phosphite, and a lubricant of zinc stearate and hydroxy silicone oil.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
The preparation method of the antistatic flame-retardant thermoplastic polyurethane elastomer comprises the following steps:
Weighing 55 parts of thermoplastic polyurethane elastomer, 20 parts of tricresyl phosphate, 10 parts of sodium hexyl sulfonate, 3.5 parts of polyethylene grafted maleic anhydride, 3.5 parts of dipropylene glycol dibenzoate, 0.75 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.75 part of zinc stearate;
adding the raw materials into a mixer, and stirring for 5 hours; obtaining the antistatic flame-retardant thermoplastic polyurethane elastomer.
comparative example 2
Different from comparative example 1 is the composition of the antistatic flame retardant thermoplastic polyurethane elastomer: 55 parts of thermoplastic polyurethane elastomer, 12 parts of flame retardant (the mass ratio of melamine salt of pentaerythritol phosphate, graphite, nano aluminum hydroxide and nano magnesium hydroxide is 3:2:2:3), 10 parts of sodium hexyl sulfonate, 3.5 parts of polyethylene grafted maleic anhydride, 3.5 parts of dipropylene glycol dibenzoate, 0.75 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.75 part of zinc stearate.
the rest is the same as comparative example 1 and will not be described again.
Comparative example 3
Different from comparative example 1 is the composition of the antistatic flame retardant thermoplastic polyurethane elastomer: 55 parts of thermoplastic polyurethane elastomer, 20 parts of tricresyl phosphate, 6 parts of antistatic agent (the mass ratio of the oil monostearate to the ethoxylated amine is 6: 4), 3.5 parts of polyethylene grafted maleic anhydride, 3.5 parts of dipropylene glycol dibenzoate, 0.75 part of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.75 part of zinc stearate.
The rest is the same as comparative example 1 and will not be described again.
Comparative example 4
The difference from example 1 is: the flame retardant is melamine salt of pentaerythritol phosphate and graphite in a mass ratio of 3: 2.
the rest is the same as embodiment 1, and the description is omitted here.
Comparative example 5
The difference from example 1 is: the flame retardant is graphite, nano aluminum hydroxide and nano magnesium hydroxide in a mass ratio of 2: 5.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 6
The difference from example 1 is: the flame retardant is melamine salt of pentaerythritol phosphate, nano aluminum hydroxide and nano magnesium hydroxide in a mass ratio of 3:2: 3.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 7
The difference from example 1 is: the antistatic agent is prepared from the following components in percentage by mass: 8 and ethoxylated amine and an oil monostearate.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 8
The difference from example 1 is: the antistatic agent is 8: 2 and ethoxylated amine.
the rest is the same as embodiment 1, and the description is omitted here.
Performance testing
The following performance tests were performed on the thermoplastic polyurethane elastomers prepared in examples 1 to 5 and comparative examples 1 to 8, respectively:
Tensile strength (MPa), tested according to GB/T1040.2-2006, tensile specimen size 150mm x 10mm x 4mm, tensile speed 20 mm/min;
The bending strength (MPa) is tested according to GB/T9341-2008, the size of a bending sample strip is 80mm multiplied by 10mm multiplied by 4mm, and the testing speed is 2 mm/min;
The smoke density (kg/m 3) is tested according to GB/T8627-2007, the sample size is 100mm multiplied by 3mm, and the total smoke yield (D4) within 0-4 min is taken.
The oxygen index is tested by referring to GB/T2406-2009, and the size of a sample strip is 80mm multiplied by 10mm multiplied by 4mm by adopting an end face ignition method.
Surface resistivity (Ω) as measured according to ASTM D4496 standard.
The test performance ratios are shown in table 1.
TABLE 1 test results
As can be seen from the test data of table 1:
1) The surface resistivity of the thermoplastic polyurethane elastomer (examples 1-5 and comparative examples 3-6) added with the antistatic agent is 10 7 or 10 8 omega, which is obviously lower than that of the thermoplastic polyurethane elastomer (comparative examples 1-2) not added with the antistatic agent, and the antistatic effect achieved by the thermoplastic polyurethane elastomer is obviously poorer when the mass ratio of any one of the oil monostearate and the ethoxylated amine is too high or too low as shown in examples 1 and 7-8.
2) The oxygen index of the thermoplastic polyurethane elastomer (examples 1-5 and comparative examples 2, 7-8) added with the flame retardant of the invention is higher than that of the thermoplastic polyurethane elastomer (comparative examples 1, 3-6) not added with the flame retardant of the invention, the smoke density of the thermoplastic polyurethane elastomer added with the flame retardant of the invention is lower than that of the thermoplastic polyurethane elastomer not added with the flame retardant of the invention, and it can be seen from examples 1 and comparative examples 4-6 that when any one component is not added in the flame retardant of the invention, the flame retardant effect achieved is obviously poorer, that is, when only melamine salt, graphite and nano metal hydroxide of pentaerythritol phosphate ester with the mass ratio of 3:2:5 in the invention are adopted, the thermoplastic polyurethane elastomer has better flame retardant performance.
3) The tensile strength and the bending strength of the thermoplastic polyurethane elastomers in the examples 1 to 5 are obviously lower than those in the comparative examples 1 to 3, because the examples 1 to 5 and the comparative examples 1 to 3 adopt different preparation methods, the compatilizers and the modified mother liquor are added into the thermoplastic polyurethane elastomers in batches in the examples 1 to 5, and all raw materials are directly mixed and stirred in the comparative examples 1 to 3, so that the preparation method disclosed by the invention is more beneficial to improving the compatibility of the flame retardant and the antistatic agent with the thermoplastic polyurethane elastomers and reducing the influence on the mechanical properties of the thermoplastic polyurethane elastomers.
in conclusion, through the components, the proportion and the preparation method, the flame retardant property and the antistatic property of the thermoplastic polyurethane elastomer can be effectively improved while the mechanical property of the thermoplastic polyurethane elastomer is not reduced.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (9)
1. the antistatic flame-retardant thermoplastic polyurethane elastomer is characterized by comprising the following components in parts by mass: 40-70 parts of thermoplastic polyurethane elastomer, 5-20 parts of flame retardant, 2-10 parts of antistatic agent, 2-5 parts of compatilizer, 2-5 parts of plasticizer, 0.1-2 parts of antioxidant and 0.1-2 parts of lubricant; the flame retardant is melamine salt of pentaerythritol phosphate, graphite and nano metal hydroxide in a mass ratio of 3:2:5, the antistatic agent is a composite antistatic agent consisting of oil monostearate and ethoxylated amine, and the mass ratio of glycerol monostearate to ethoxylated amine is 4-7: 3 to 6.
2. The antistatic flame-retardant thermoplastic polyurethane elastomer according to claim 1, which comprises the following components in parts by mass: 50-60 parts of thermoplastic polyurethane elastomer, 10-15 parts of flame retardant, 4-8 parts of antistatic agent, 3-4 parts of compatilizer, 3-4 parts of plasticizer, 0.5-1 part of antioxidant and 0.5-1 part of lubricant.
3. The antistatic flame-retardant thermoplastic polyurethane elastomer according to claim 1, which comprises the following components in parts by mass: 55 parts of thermoplastic polyurethane elastomer, 12 parts of flame retardant, 6 parts of antistatic agent, 3.5 parts of compatilizer, 3.5 parts of plasticizer, 0.75 part of antioxidant and 0.75 part of lubricant.
4. The antistatic flame retardant thermoplastic polyurethane elastomer according to claim 1, wherein the nano metal hydroxide is nano aluminum hydroxide and/or nano magnesium hydroxide.
5. The antistatic flame retardant thermoplastic polyurethane elastomer according to claim 1, wherein the compatibilizer is any one of polyethylene grafted maleic anhydride, ethylene propylene diene monomer grafted maleic anhydride, and polyolefin elastomer grafted maleic anhydride.
6. The antistatic flame retardant thermoplastic polyurethane elastomer according to claim 1, wherein the plasticizer is at least one of dipropylene glycol dibenzoate, diethylene glycol dibenzoate, dimethyl adipate, diethyl adipate, dibutyl adipate, and dioctyl adipate.
7. The antistatic flame retardant thermoplastic polyurethane elastomer according to claim 1, wherein the antioxidant is at least one of pentaerythrityl tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 4' -thiobis (6-t-butyl-3-methylphenol), dilauryl thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate) and tris [2, 4-di-t-butylphenyl ] phosphite.
8. The antistatic flame retardant thermoplastic polyurethane elastomer according to claim 1, wherein the lubricant is at least one of zinc stearate, hydroxy silicone oil, silicone powder, and fluorine-containing lubricant.
9. A method for preparing the antistatic flame-retardant thermoplastic polyurethane elastomer according to any one of claims 1 to 8, comprising the steps of:
Step one, weighing raw materials in parts by weight;
Step two, adding the thermoplastic polyurethane elastomer into a mixer at the temperature of 60-120 ℃, and stirring for 35-45 min;
Uniformly stirring the flame retardant, the antistatic agent, the plasticizer, the antioxidant and the lubricant at normal temperature to obtain modified mother liquor;
And step four, evenly dividing the modified mother liquor obtained in the step three into 3 equal parts, evenly dividing the compatilizer into 3 equal parts, adding 1 part of modified mother liquor and 1 part of compatilizer into the mixer in the step two every 45min, keeping the mixer in a stirring state during the adding process, and continuing stirring for 3h after all the modified mother liquor and the compatilizer are added, so as to obtain the antistatic flame-retardant thermoplastic polyurethane elastomer.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111454417A (en) * | 2020-05-11 | 2020-07-28 | 江苏绿源新材料有限公司 | Full-water flame-retardant modified spraying polyurethane foam and preparation method thereof |
| CN112745659A (en) * | 2020-01-15 | 2021-05-04 | 昆山科信高分子材料有限公司 | Thermoplastic polyurethane elastomer material containing antistatic master batch and preparation method thereof |
| CN114656885A (en) * | 2022-03-16 | 2022-06-24 | 腕美表现(深圳)科技有限公司 | Watch protective film and manufacturing method thereof |
| CN115612282A (en) * | 2022-08-24 | 2023-01-17 | 南京聚隆科技股份有限公司 | Permanent antistatic halogen-free flame-retardant thermoplastic polyurethane elastomer and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060058455A1 (en) * | 2004-08-31 | 2006-03-16 | Erhard Michels | Polyurethane elastomers having improved antistatic behavior |
| CN102888090A (en) * | 2012-08-31 | 2013-01-23 | 苏州博云塑业有限公司 | Halogen-free flam-retardant thermoplastic polyurethane (TPU) material |
| CN103980695A (en) * | 2014-06-06 | 2014-08-13 | 中煤科工集团重庆研究院有限公司 | halogen-free flame-retardant antistatic TPU material and preparation method thereof |
| US20150203665A1 (en) * | 2012-07-18 | 2015-07-23 | Dow Global Technologies Llc | Fire Retardant and/or Antistatic, Non-Mercury Catalyzed Polyurethane Elastomer |
| CN107936534A (en) * | 2017-12-12 | 2018-04-20 | 厦门本润科技有限公司 | Antistatic flame-retardant thermoplastic polyurethane elastomer |
| CN109796748A (en) * | 2019-02-15 | 2019-05-24 | 美瑞新材料股份有限公司 | A kind of flame-retardant and anti-static thermoplastic polyurethane elastomer and its preparation method and application |
-
2019
- 2019-08-30 CN CN201910815070.5A patent/CN110551387B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060058455A1 (en) * | 2004-08-31 | 2006-03-16 | Erhard Michels | Polyurethane elastomers having improved antistatic behavior |
| US20150203665A1 (en) * | 2012-07-18 | 2015-07-23 | Dow Global Technologies Llc | Fire Retardant and/or Antistatic, Non-Mercury Catalyzed Polyurethane Elastomer |
| CN102888090A (en) * | 2012-08-31 | 2013-01-23 | 苏州博云塑业有限公司 | Halogen-free flam-retardant thermoplastic polyurethane (TPU) material |
| CN103980695A (en) * | 2014-06-06 | 2014-08-13 | 中煤科工集团重庆研究院有限公司 | halogen-free flame-retardant antistatic TPU material and preparation method thereof |
| CN107936534A (en) * | 2017-12-12 | 2018-04-20 | 厦门本润科技有限公司 | Antistatic flame-retardant thermoplastic polyurethane elastomer |
| CN109796748A (en) * | 2019-02-15 | 2019-05-24 | 美瑞新材料股份有限公司 | A kind of flame-retardant and anti-static thermoplastic polyurethane elastomer and its preparation method and application |
Non-Patent Citations (6)
| Title |
|---|
| LI CHANGBING，等: "Preparation and Characterization of Thermoplastic Antistatic Polyurethane Synthesized by In Situ Polymerization", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 宁桂玲主编: "《高等无机合成》", 30 September 2007, 华东理工大学出版社 * |
| 安家驹主编: "《实用精细化工辞典》", 30 September 2000, 中国轻工业出版社 * |
| 李来丙: "季戊四醇磷酸酯三聚氰胺盐的合成及其应用", 《中国塑料》 * |
| 王文广主编: "《聚合物改性原理》", 31 March 2018, 中国轻工业出版社 * |
| 郭腊梅: "《纺织结构成型学3：纺织品染整》", 31 March 2016, 东华大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745659A (en) * | 2020-01-15 | 2021-05-04 | 昆山科信高分子材料有限公司 | Thermoplastic polyurethane elastomer material containing antistatic master batch and preparation method thereof |
| CN111454417A (en) * | 2020-05-11 | 2020-07-28 | 江苏绿源新材料有限公司 | Full-water flame-retardant modified spraying polyurethane foam and preparation method thereof |
| CN114656885A (en) * | 2022-03-16 | 2022-06-24 | 腕美表现(深圳)科技有限公司 | Watch protective film and manufacturing method thereof |
| CN115612282A (en) * | 2022-08-24 | 2023-01-17 | 南京聚隆科技股份有限公司 | Permanent antistatic halogen-free flame-retardant thermoplastic polyurethane elastomer and preparation method thereof |
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