CN114316194A - Polyurethane composite material for motor shell and preparation method thereof - Google Patents
Polyurethane composite material for motor shell and preparation method thereof Download PDFInfo
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- CN114316194A CN114316194A CN202111504267.0A CN202111504267A CN114316194A CN 114316194 A CN114316194 A CN 114316194A CN 202111504267 A CN202111504267 A CN 202111504267A CN 114316194 A CN114316194 A CN 114316194A
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- Prior art keywords
- composite material
- polyurethane composite
- diisocyanate
- acid
- motor housing
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000004814 polyurethane Substances 0.000 title claims abstract description 45
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 60
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 60
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 47
- 239000004917 carbon fiber Substances 0.000 claims abstract description 47
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 22
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 20
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 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 6
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims abstract description 6
- 239000003063 flame retardant Substances 0.000 claims abstract description 6
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000001694 spray drying Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 35
- -1 1, 6-hexanediol adipate diol Chemical class 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 20
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000010306 acid treatment Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- MWCADZVQNIHFGT-UHFFFAOYSA-N 1-anilinopropan-2-ol Chemical compound CC(O)CNC1=CC=CC=C1 MWCADZVQNIHFGT-UHFFFAOYSA-N 0.000 claims description 3
- RVCHQYCXJDVJQF-UHFFFAOYSA-N (3,5-diethylphenyl)methanediamine Chemical compound CCC1=CC(CC)=CC(C(N)N)=C1 RVCHQYCXJDVJQF-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- 229940043237 diethanolamine Drugs 0.000 description 15
- 238000007792 addition Methods 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 12
- WPEOOEIAIFABQP-UHFFFAOYSA-N hexanedioic acid;hexane-1,6-diol Chemical compound OCCCCCCO.OC(=O)CCCCC(O)=O WPEOOEIAIFABQP-UHFFFAOYSA-N 0.000 description 9
- 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 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- FKOMNQCOHKHUCP-UHFFFAOYSA-N 1-[n-(2-hydroxypropyl)anilino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)C1=CC=CC=C1 FKOMNQCOHKHUCP-UHFFFAOYSA-N 0.000 description 7
- 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 description 7
- 229920000877 Melamine resin Polymers 0.000 description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 5
- 239000008116 calcium stearate Substances 0.000 description 5
- 235000013539 calcium stearate Nutrition 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 5
- 229920000388 Polyphosphate Polymers 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000001205 polyphosphate Substances 0.000 description 4
- 235000011176 polyphosphates Nutrition 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920005586 poly(adipic acid) Polymers 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- KTLIMPGQZDZPSB-UHFFFAOYSA-M diethylphosphinate Chemical compound CCP([O-])(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 2
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 2
- NCEGJIHRQBRVJQ-UHFFFAOYSA-N 2-amino-3-[3-[2-(phosphonomethyl)phenyl]phenyl]propanoic acid Chemical compound OC(=O)C(N)CC1=CC=CC(C=2C(=CC=CC=2)CP(O)(O)=O)=C1 NCEGJIHRQBRVJQ-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a preparation method of a polyurethane composite material for a motor shell, which comprises the following steps: s1, dissolving polyester polyol and diisocyanate in an organic solvent to form a mixed solution; s2, adding the carbon nano tube and the carbon fiber into the mixed solution, stirring and dispersing, and then spray drying to obtain powder; and S3, uniformly mixing the powder, the chain extender, the flame retardant, the antioxidant and the lubricant, feeding the mixture into a double-screw extruder, and performing extrusion reaction to obtain the polyurethane composite material for the motor shell. The polyurethane composite material prepared by the invention has excellent thermal conductivity and mechanical property.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a polyurethane composite material for a motor shell and a preparation method thereof.
Background
The motor is used for converting electric energy into mechanical energy, and the motor shell provides a positioning supporting effect for the motor, protects a rotor and an electronic coil in the motor, and dissipates heat for the motor during operation. Therefore, the material of the motor shell has great influence on the function of the motor shell, the common motor shell is mostly cast by metal materials such as cast iron, aluminum alloy and the like, but the use of the metal motor shell increases the cost of the motor, increases the weight of the motor and also has the problem of environmental pollution.
With the development of light weight, thinness, refinement and multi-functionalization of electronic and electrical equipment, people put their eyes on plastics, and it is a research trend to replace metal housings of motors with plastics to reduce the weight and cost of electrical equipment. Although plastics substitute metal has many advantages, the heat conductivity and the mechanical strength of plastics are lower, and being applied to motor housing can lead to the heat that the motor operation produced can't in time discharge, and cause motor trouble, and suffer to collide with the collision in-process at the motor, because of the mechanical strength of plastics is lower, lead to adverse effect such as motor housing fracture.
At present, the thermal conductivity and mechanical strength of plastics are improved by adding fillers, for example, a high thermal conductivity acrylonitrile-styrene-polyphenylene sulfide copolymer for motor housings disclosed in chinese patent CN109929205A, in which a thermal conductive agent such as KH-560 modified alumina, glass fiber, aluminum nitride, boron nitride is added to the polymer to improve the thermal conductivity of the polymer; for another example, chinese patent CN103396612A discloses a modified polypropylene material for a micromotor housing, which is prepared by adding 25-35% of glass fiber into a composite material to improve the mechanical properties of the polypropylene composite material.
The filler/plastic compound is prepared by a melt blending method, and when the filling amount of the filler is low, the improvement range of the thermal conductivity and the mechanical strength is small; when the filling amount of the filler is high, the viscosity of the plastic melt is high, the filling of the filler is difficult, the filler is not uniformly dispersed, and the heat-conducting property and the mechanical property of the compound are difficult to improve.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the preparation method of the polyurethane composite material for the motor shell, which improves the dispersion uniformity of the filler in the polyurethane, realizes the high-content addition of the filler in the polyurethane and improves the thermal conductivity and the mechanical property of the composite material.
The first purpose of the invention is to provide a preparation method of a polyurethane composite material for a motor shell, which comprises the following steps:
s1, dissolving polyester polyol and diisocyanate in an organic solvent to form a mixed solution;
s2, adding the carbon nano tube and the carbon fiber into the mixed solution, stirring and dispersing, and then spray drying to obtain powder;
and S3, uniformly mixing the powder, the chain extender, the flame retardant, the antioxidant and the lubricant, feeding the mixture into a double-screw extruder, and performing extrusion reaction to obtain the polyurethane composite material for the motor shell.
The carbon nano tube and the carbon fiber are soaked in an organic solution formed by polyester polyol and diisocyanate, the polyester polyol and the diisocyanate are combined on the surfaces of the carbon nano tube and the carbon fiber, and then the carbon nano tube and the carbon fiber are uniformly dispersed in a polyurethane matrix after the heating reaction of a double-screw extruder, so that the heat conduction performance and the mechanical performance of the polyurethane composite material are improved.
Preferably, the polyester polyol is selected from one or more of 1, 6-hexanediol adipate diol (PHA), 1, 4-butanediol adipate diol (PBA), neopentyl glycol adipate diol (PNA), 1, 4-butanediol neopentyl glycol adipate diol (PBNA), methyl-1, 3-propanediol adipate diol (PMA), and methyl-1, 3-propanediol adipate 1, 4-butanediol diol (PMBA).
Preferably, the diisocyanate is one or more of toluene diisocyanate, 4-diphenylmethane diisocyanate, hexamethylene diisocyanate and 1, 5-naphthalene diisocyanate. The Toluene Diisocyanate (TDI) is 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate.
Preferably, the organic solvent is one or more of ethyl acetate, toluene, xylene and acetone. The polyester polyol is dissolved in an organic solvent to form a polyester polyol solution preferably having a concentration of 20 to 100 g/L.
Preferably, the chain extender is one or more of ethanolamine, diethanolamine, N-bis (2-hydroxypropyl) aniline, 1, 4-cyclohexanediol, 3, 5-diethyltoluenediamine, 3-dichloro-4, 4-diaminodiphenylmethane.
Preferably, the molar ratio of the polyester polyol, the diisocyanate and the chain extender is (1-2): (4-10): 1.
preferably, the mass of the carbon nano tube is 10-50% of the total mass of the polyester polyol, the diisocyanate and the chain extender. The invention can realize high filling amount of the carbon nano tube, and the polyurethane composite material can be filled with up to 50 percent of the carbon nano tube, thereby greatly improving the heat-conducting property of the composite material.
Preferably, the mass of the carbon fiber is 5 to 10% of the total mass of the polyester polyol, the diisocyanate and the chain extender.
Preferably, the stirring dispersion time of step S2 is 30-60min, and the stirring rotation speed is 200-1000 rpm.
Preferably, the carbon nanotubes are carbon nanotubes after acid treatment, the carbon fibers are carbon fibers after acid treatment, and the acid treatment of the carbon nanotubes comprises the following steps: and (3) placing the carbon nano tube in a 0.2-1mol/L sulfuric acid solution, soaking for 20-40min, cleaning and drying to obtain the acid-treated carbon nano tube. The acid-treated carbon fiber comprises the following steps: and (3) placing the carbon fiber in a 0.2-1mol/L sulfuric acid solution, soaking for 20-40min, cleaning and drying to obtain the acid-treated carbon fiber.
Or, the carbon nano tube and the carbon fiber are proportioned in advance according to the mass ratio, then the proportioned carbon nano tube and the carbon fiber are placed in a 0.2-1mol/L sulfuric acid solution together to be soaked for 20-40min, and then the mixture of the acid-treated carbon nano tube and the carbon fiber is obtained after cleaning and drying.
The surface roughness of the carbon nanotubes and the carbon fibers is increased by treating the carbon nanotubes and the carbon fibers with sulfuric acid with a certain concentration, and the depressions and the micropores formed in the way are beneficial to improving the binding property of the carbon nanotubes and the carbon fibers with polyester polyol and diisocyanate through the so-called latch effect; in addition, the sulfuric acid treatment can also generate hydroxyl on the surfaces of the carbon nano tubes and the carbon fibers, so that the bonding property of the carbon nano tubes and the carbon fibers with polyester polyol and diisocyanate is further improved. In general, the carbon nanotubes and carbon fibers treated by the acid can effectively improve the dispersion uniformity of the carbon nanotubes and carbon fibers in the polyurethane matrix.
The polyurethane composite material for the motor shell can also comprise a flame retardant, an antioxidant, a lubricant and the like, wherein the addition amount of the flame retardant is 0.5-5% of the total mass of the polyester polyol, the diisocyanate and the chain extender, the addition amount of the antioxidant is 0.1-0.5% of the total mass of the polyester polyol, the diisocyanate and the chain extender, and the addition amount of the lubricant is 0.1-0.5% of the total mass of the polyester polyol, the diisocyanate and the chain extender. The flame retardant can be one or more of melamine, melamine cyanurate, melamine polyphosphate (MPP), tris (2-chloropropyl) phosphate (TCPP), melamine polyphosphate (MPP), ammonium polyphosphate, diethyl hypophosphite and the like; examples of the antioxidant include one or more compounds of tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (antioxidant 1098), 2, 6-di-tert-butyl-4-methylphenol (BHT, antioxidant 264), pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate (antioxidant 1010), N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), and tris (nonylphenyl) phosphite (TNPP); the lubricant can be one or more of calcium stearate, zinc stearate, stearic acid, paraffin, ethylene double-fatty acid amide, erucamide and the like; the above specific components are merely illustrative and are not intended to limit the present invention.
The second purpose of the invention is to provide a polyurethane composite material for a motor shell, which is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the carbon nano tubes and the carbon fibers are firstly soaked in an organic solution formed by polyester polyol and diisocyanate, and are uniformly dispersed in a polyurethane matrix after being heated and reacted by a double-screw extruder, so that the heat conduction performance and the mechanical performance of the polyurethane composite material are improved;
(2) according to the invention, the adopted carbon nano tube is the carbon nano tube after acid treatment, the carbon fiber is the carbon fiber after acid treatment, and through acid treatment, the binding property of the carbon nano tube and the carbon fiber with polyester polyol and diisocyanate is improved, and the dispersion uniformity of the carbon nano tube and the carbon fiber in a polyurethane matrix is effectively improved;
(3) the preparation method of the polyurethane composite material realizes high-content filling of the carbon nano tube, thereby greatly improving the heat-conducting property of the composite material;
(4) the polyurethane composite material prepared by the invention can replace metal materials such as cast iron, aluminum alloy and the like to be applied to the motor shell, and the motor shell is light in weight and low in cost.
Detailed Description
The technical solutions of the present invention will be further described and illustrated by the following specific examples, which are not intended to limit the present invention. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
The poly adipic acid 1, 6-hexanediol glycol ester diol and the poly adipic acid-1, 4-butanediol glycol ester diol are purchased from the chemical industry Co., Ltd in Tangshan; 2, 4-toluene diisocyanate, 4-diphenylmethane diisocyanate available from Vanhua chemical group, Inc.;
carbon fiber: dongli MLD-30 in Japan (30 μm in length);
carbon nanotube: FT9000 powder of Tiannei science and technology of Jiangsu, average tube diameter 20nm, and average length 10 μm.
Example 1
The polyurethane composite material for the motor housing of the embodiment is obtained by the following preparation method:
s1, dissolving poly adipic acid 1, 6-hexanediol ester diol and 2, 4-toluene diisocyanate in ethyl acetate to form a mixed solution;
s2, adding the acid-treated carbon nano-tubes and the acid-treated carbon fibers into the mixed solution, stirring and dispersing for 40min at the rotating speed of 500rpm, and then spray-drying to obtain powder;
s3, uniformly mixing the powder, diethanolamine, melamine cyanurate, diethyl hypophosphite, an antioxidant 168, an antioxidant 1010 and calcium stearate, feeding the mixture into a double-screw extruder, wherein the diameter of a screw of the double-screw extruder is 30mm, the rotating speed of the screw is 100r/min, the length-diameter ratio of the screw is 44, 11 sections are heated, the temperature of each section from a feeding port to a neck mold is 130 ℃, 150 ℃, 170 ℃, 190 ℃, 210 ℃, 220 ℃, 230 ℃, 220 ℃, 210 ℃ and 210 ℃ in sequence, and the polyurethane composite material for the motor shell is prepared by extrusion reaction.
Poly (1, 6-hexanediol adipate) glycol was dissolved in ethyl acetate at a concentration of 50 g/L.
Wherein the molar ratio of the poly adipic acid 1, 6-hexanediol glycol, the 2, 4-toluene diisocyanate and the diethanol amine is 2: 8: 1, the mass of the acid-treated carbon nano tube is 30 percent of the total mass of the 1, 6-hexanediol adipate, the 2, 4-toluene diisocyanate and the diethanolamine, the mass of the acid-treated carbon fiber is 5 percent of the total mass of the 1, 6-hexanediol adipate, the 2, 4-toluene diisocyanate and the diethanolamine, the addition amount of the melamine cyanurate is 2 percent of the total mass of the 1, 6-hexanediol adipate, the 2, 4-toluene diisocyanate and the diethanolamine, the addition amount of the diethylphosphinate is 3 percent of the total mass of the 1, 6-hexanediol adipate, the 2, 4-toluene diisocyanate and the diethanolamine, the addition amount of the antioxidant 168 is 0.1 percent of the total mass of the 1, 6-hexanediol adipate, the 2, 4-toluene diisocyanate and the diethanolamine, and the addition amount of the antioxidant 1010 is 1 percent of the adipic acid, the total mass of the 6-hexanediol glycol, the 2, 4-toluene diisocyanate and the diethanolamine is 0.1 percent, and the addition amount of the calcium stearate is 0.2 percent of the total mass of the 1, 6-hexanediol adipate glycol, the 2, 4-toluene diisocyanate and the diethanolamine.
The acid-treated carbon nanotube is prepared by the following steps: and (3) placing the carbon nano tube in a 0.5mol/L sulfuric acid solution, soaking for 30min, cleaning and drying to obtain the acid-treated carbon nano tube. The acid-treated carbon fiber is prepared by the following steps: and (3) placing the carbon nano tube in a 0.6mol/L sulfuric acid solution, soaking for 35min, cleaning and drying to obtain the acid-treated carbon fiber.
Example 2
The polyurethane composite material for the motor housing of the embodiment is obtained by the following preparation method:
s1, dissolving poly adipic acid-1, 4-butanediol ester diol and 4, 4-diphenylmethane diisocyanate in toluene to form a mixed solution;
s2, adding the acid-treated carbon nano-tubes and the acid-treated carbon fibers into the mixed solution, stirring and dispersing for 30min at the rotating speed of 700rpm, and then spray-drying to obtain powder;
s3, uniformly mixing the powder, N-bis (2-hydroxypropyl) aniline, melamine polyphosphate, an antioxidant 168, an antioxidant 1010 and zinc stearate, feeding the mixture into a double-screw extruder, wherein the diameter of a screw of the double-screw extruder is 30mm, the length-diameter ratio of the screw is 44, the rotating speed of the screw is 120r/min, 11 sections of the extruder are heated, the temperature of each section from a feeding port to a neck die is 130 ℃, 160 ℃, 180 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 230 ℃, 220 ℃, 210 ℃ in sequence, and the polyurethane composite material for the motor shell is prepared through extrusion reaction.
The 1, 4-butanediol adipate diol was dissolved in toluene at a concentration of 80 g/L.
Wherein the molar ratio of the poly adipic acid-1, 4-butanediol ester diol, the 4, 4-diphenylmethane diisocyanate and the N, N-bis (2-hydroxypropyl) aniline is 1: 6: 1, the mass of the acid-treated carbon nano tube is 20 percent of poly-1, 4-butanediol adipate glycol, 4-diphenylmethane diisocyanate and N, N-bis (2-hydroxypropyl) aniline, the mass of the acid-treated carbon fiber is 6 percent of the poly-1, 4-butanediol adipate glycol, 4-diphenylmethane diisocyanate and N, N-bis (2-hydroxypropyl) aniline, the addition amount of melamine polyphosphate is 4 percent of the total mass of the poly-1, 4-butanediol adipate glycol, 4-diphenylmethane diisocyanate and N, N-bis (2-hydroxypropyl) aniline, and the addition amount of the antioxidant 168 is 4 percent of the total mass of the poly-1, 4-butanediol adipate glycol, 4-diphenylmethane diisocyanate, 0.1 percent of the total mass of the N, N-bis (2-hydroxypropyl) aniline, 0.1 percent of the antioxidant 1010 accounting for the total mass of the poly (1, 4-butanediol adipate) glycol, the 4, 4-diphenylmethane diisocyanate and the N, N-bis (2-hydroxypropyl) aniline, and 0.3 percent of the zinc stearate accounting for the total mass of the poly (1, 4-butanediol adipate) glycol, the 4, 4-diphenylmethane diisocyanate and the N, N-bis (2-hydroxypropyl) aniline.
The acid-treated carbon nanotube is prepared by the following steps: and (3) placing the carbon nano tube in a 0.7mol/L sulfuric acid solution, soaking for 20min, cleaning and drying to obtain the acid-treated carbon nano tube. The acid-treated carbon fiber is prepared by the following steps: and (3) placing the carbon nano tube in a 0.5mol/L sulfuric acid solution, soaking for 40min, cleaning and drying to obtain the acid-treated carbon fiber.
Example 3
Example 3 differs from example 1 only in that the mass of the acid-treated carbon nanotubes of example 3 was 10% of the total mass of 1, 6-hexanediol adipate diol, 2, 4-toluene diisocyanate and diethanolamine, and a polyurethane composite for a motor housing was prepared in the same manner as in example 1.
Example 4
Example 4 differs from example 1 only in that the mass of the acid-treated carbon nanotubes of example 4 was 40% of the total mass of 1, 6-hexanediol adipate diol, 2, 4-toluene diisocyanate and diethanolamine, and a polyurethane composite for a motor housing was prepared in the same manner as in example 1.
Example 5
Example 5 differs from example 1 only in that the mass of the acid-treated carbon nanotubes of example 5 was 50% of the total mass of 1, 6-hexanediol adipate diol, 2, 4-toluene diisocyanate and diethanolamine, and a polyurethane composite for a motor housing was prepared in the same manner as in example 1.
Example 6
Example 6 differs from example 5 only in that the carbon nanotubes and carbon fibers of example 6 were not subjected to acid treatment, and a polyurethane composite for a motor housing was prepared in the same manner as in example 5.
Comparative example 1
Comparative example 1 is different from example 1 only in that comparative example 1 does not add carbon nanotubes and a polyurethane composite for a motor housing is prepared in the same manner as in example 1.
Comparative example 2
The polyurethane composite for the motor case of comparative example 2 was obtained by the following preparation method:
uniformly mixing poly (1, 6-hexanediol adipate) diol, 2, 4-toluene diisocyanate, an acid-treated carbon nano tube, acid-treated carbon fiber, diethanolamine, melamine cyanurate, diethyl hypophosphite, an antioxidant 168, an antioxidant 1010 and calcium stearate, and feeding the mixture into a double-screw extruder, wherein the diameter of a screw of the double-screw extruder is 30mm, the length-diameter ratio is 44, the rotating speed of the screw is 100r/min, 11 sections are heated, and the temperatures of all the sections from a feeding port to a neck die are 130 ℃, 150 ℃, 170 ℃, 190 ℃, 210 ℃, 220 ℃, 230 ℃, 220 ℃, 210 ℃ and 210 ℃ in sequence, and carrying out extrusion reaction to obtain the polyurethane composite material for the motor shell.
The added mass of 1, 6-hexanediol polyadipate, 2, 4-toluene diisocyanate, acid-treated carbon nanotubes, acid-treated carbon fibers, diethanolamine, melamine cyanurate, diethylphosphinate, antioxidant 168, antioxidant 1010 and calcium stearate, and the preparation methods of the acid-treated carbon nanotubes and the acid-treated carbon fibers were the same as those of example 5.
The polyurethane composite materials for the motor housings of examples 1-6 and comparative examples 1-2 were made into test strips, and the tensile strength, impact strength and thermal conductivity of the composite materials were measured according to GB/T1040-.
TABLE 1 polyurethane composite Performance data for examples 1-6 and comparative examples 1-2
As shown in table 1, as the content of the carbon nanotubes increases, the thermal conductivity, tensile strength and impact strength of the composite material all increase, and when the content of the carbon nanotubes is increased up to 50%, the thermal conductivity and tensile strength are excellent, and only the impact strength is reduced to a small extent. The carbon nanotubes and carbon fibers of example 6 were not acid-treated, and the thermal conductivity, tensile strength and impact strength of the composite material were reduced as compared to example 5. Comparative example 2 the raw materials were extruded together by twin screw, and the carbon nanotubes and carbon fibers were not uniformly dispersed in the composite material, resulting in a significant decrease in the thermal conductivity, tensile strength and impact strength of the composite material.
The specific embodiments described herein are merely illustrative of the spirit of the invention and do not limit the scope of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a polyurethane composite material for a motor shell is characterized by comprising the following steps:
s1, dissolving polyester polyol and diisocyanate in an organic solvent to form a mixed solution;
s2, adding the carbon nano tube and the carbon fiber into the mixed solution, stirring and dispersing, and then spray drying to obtain powder;
and S3, uniformly mixing the powder, the chain extender, the flame retardant, the antioxidant and the lubricant, feeding the mixture into a double-screw extruder, and performing extrusion reaction to obtain the polyurethane composite material for the motor shell.
2. The method of claim 1, wherein the polyester polyol is selected from one or more of 1, 6-hexanediol adipate diol, 1, 4-butanediol adipate diol, neopentyl glycol adipate diol, 1, 4-butanediol neopentyl glycol adipate diol, methyl-1, 3-propanediol adipate diol, and 1, 4-butanediol adipate diol.
3. The method for preparing a polyurethane composite material for a motor housing according to claim 1, wherein the diisocyanate is one or more of toluene diisocyanate, 4-diphenylmethane diisocyanate, hexamethylene diisocyanate, and 1, 5-naphthalene diisocyanate.
4. The method of preparing a polyurethane composite material for a motor housing as set forth in claim 1, wherein the organic solvent is one or more of ethyl acetate, toluene, xylene and acetone.
5. The method of preparing a polyurethane composite material for a motor housing as set forth in claim 1, wherein the chain extender is one or more of ethanolamine, diethanolamine, N-bis (2-hydroxypropyl) aniline, 1, 4-cyclohexanediol, 3, 5-diethyltoluenediamine, 3-dichloro-4, 4-diaminodiphenylmethane.
6. The method for preparing the polyurethane composite material for the motor housing as claimed in claim 1, wherein the molar ratio of the polyester polyol, the diisocyanate and the chain extender is (1-2): (4-10): 1.
7. the preparation method of the polyurethane composite material for the motor housing according to claim 1, wherein the mass of the carbon nanotube is 10-50% of the total mass of the polyester polyol, the diisocyanate and the chain extender; the mass of the carbon fiber is 5-10% of the total mass of the polyester polyol, the diisocyanate and the chain extender.
8. The method as claimed in claim 1, wherein the stirring dispersion time of step S2 is 30-60min, and the stirring rotation speed is 200-1000 rpm.
9. The method of preparing the polyurethane composite material for the motor housing as set forth in claim 1, wherein the carbon nanotubes are acid-treated carbon nanotubes, and the carbon fibers are acid-treated carbon fibers, the acid treatment comprising the steps of: and (2) placing the carbon nano tube and/or the carbon fiber in a 0.2-1mol/L sulfuric acid solution, soaking for 20-40min, cleaning and drying to obtain the acid-treated carbon nano tube and/or the acid-treated carbon fiber.
10. A polyurethane composite material for a motor housing, characterized in that the polyurethane composite material for a motor housing is prepared by the preparation method of claim 1.
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