CN117984630B - Modified butyl rubber composite damping material for vibration and noise reduction of new energy automobile and preparation method thereof - Google Patents
Modified butyl rubber composite damping material for vibration and noise reduction of new energy automobile and preparation method thereof Download PDFInfo
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- CN117984630B CN117984630B CN202410405253.0A CN202410405253A CN117984630B CN 117984630 B CN117984630 B CN 117984630B CN 202410405253 A CN202410405253 A CN 202410405253A CN 117984630 B CN117984630 B CN 117984630B
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- butyl rubber
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- 238000013016 damping Methods 0.000 title claims abstract description 159
- 238000002360 preparation method Methods 0.000 title claims abstract description 139
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 121
- 239000000463 material Substances 0.000 title claims abstract description 118
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 title claims abstract description 100
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 230000009467 reduction Effects 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 165
- 239000000945 filler Substances 0.000 claims abstract description 153
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229920002635 polyurethane Polymers 0.000 claims abstract description 38
- 239000004814 polyurethane Substances 0.000 claims abstract description 38
- 239000012745 toughening agent Substances 0.000 claims abstract description 38
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 21
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 21
- 239000010439 graphite Substances 0.000 claims abstract description 21
- 229920005556 chlorobutyl Polymers 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011888 foil Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000011521 glass Substances 0.000 claims description 90
- 239000011324 bead Substances 0.000 claims description 83
- 239000002245 particle Substances 0.000 claims description 56
- 239000000843 powder Substances 0.000 claims description 49
- 229910052799 carbon Inorganic materials 0.000 claims description 46
- 239000002048 multi walled nanotube Substances 0.000 claims description 46
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 43
- 239000000835 fiber Substances 0.000 claims description 43
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 41
- 239000002135 nanosheet Substances 0.000 claims description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 35
- 229910052582 BN Inorganic materials 0.000 claims description 32
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 30
- FKIQSOGFDBALHA-UHFFFAOYSA-L aluminum trimagnesium potassium dioxido(oxo)silane oxygen(2-) difluoride Chemical compound [O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[K+].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O FKIQSOGFDBALHA-UHFFFAOYSA-L 0.000 claims description 28
- 239000004760 aramid Substances 0.000 claims description 22
- 229920003235 aromatic polyamide Polymers 0.000 claims description 22
- 239000002121 nanofiber Substances 0.000 claims description 22
- 238000004513 sizing Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 21
- 239000002071 nanotube Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000011787 zinc oxide Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 229910001152 Bi alloy Inorganic materials 0.000 claims description 20
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 20
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 claims description 20
- 229910052621 halloysite Inorganic materials 0.000 claims description 20
- 238000007731 hot pressing Methods 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 18
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 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 claims description 16
- 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 16
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 13
- 239000005543 nano-size silicon particle Substances 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 238000002386 leaching Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000004005 microsphere Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000001119 stannous chloride Substances 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 4
- 229910020830 Sn-Bi Inorganic materials 0.000 claims description 4
- 229910018728 Sn—Bi Inorganic materials 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims description 4
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 4
- 230000003712 anti-aging effect Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 230000035807 sensation Effects 0.000 claims description 3
- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical compound [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 25
- 229920001971 elastomer Polymers 0.000 abstract description 13
- 239000005060 rubber Substances 0.000 abstract description 13
- 239000010410 layer Substances 0.000 description 64
- 230000000052 comparative effect Effects 0.000 description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 14
- 239000008187 granular material Substances 0.000 description 13
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 229920000909 polytetrahydrofuran Polymers 0.000 description 10
- 229920001169 thermoplastic Polymers 0.000 description 10
- 239000004416 thermosoftening plastic Substances 0.000 description 10
- 239000010426 asphalt Substances 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 9
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 9
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 7
- 229920006231 aramid fiber Polymers 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 3
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- 229920000126 latex Polymers 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229940071536 silver acetate Drugs 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 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 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 description 2
- FDYSSWYQRTVFIS-UHFFFAOYSA-N buta-1,3-diene 3-phenylprop-2-enoic acid Chemical compound C=CC=C.C(=O)(O)C=CC1=CC=CC=C1 FDYSSWYQRTVFIS-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000006235 reinforcing carbon black Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 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 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920003368 Kevlar® 29 Polymers 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
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- FCZCIXQGZOUIDN-UHFFFAOYSA-N ethyl 2-diethoxyphosphinothioyloxyacetate Chemical compound CCOC(=O)COP(=S)(OCC)OCC FCZCIXQGZOUIDN-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the technical field of rubber damping products, in particular to a modified butyl rubber composite damping material for damping and reducing noise of a new energy automobile and a preparation method thereof. The modified butyl rubber composite damping material for new energy automobile vibration and noise reduction comprises a modified butyl rubber damping layer, a special-shaped PP plate layer, an aluminum foil layer and release paper, wherein the modified butyl rubber damping layer is mainly prepared from the following raw materials in parts by weight: 15-20 parts of butyl rubber, 5-10 parts of chlorinated butyl rubber, 8-12 parts of acrylic resin, 3-8 parts of scaly graphite, 4-8 parts of modified polyurethane toughening agent with a shell-core structure, 60-70 parts of filler composition and 0.4-1.2 parts of antioxidant composition. The application not only has good high-frequency damping performance and sound insulation and noise reduction performance, but also has smaller overall density, and can meet the light weight assembly requirement of the new energy automobile.
Description
Technical Field
The application relates to the technical field of rubber damping products, in particular to a modified butyl rubber composite damping material for damping and reducing noise of a new energy automobile and a preparation method thereof.
Background
The damping pad is widely applied to the field of automobile damping, specifically, a damping pad material is attached to the surface of an automobile structural member, and the damping pad material can convert mechanical vibration energy or acoustic energy transferred by the automobile structural member attached to the damping pad material into heat energy or other forms of energy to dissipate, so that the purposes of reducing vibration and noise, improving NVH performance of the whole automobile and improving comfort of passengers are achieved.
The damping mat may be classified into an asphalt-based damping mat and a rubber-based damping mat according to formulation components. Asphalt-based damping pad uses asphalt as main material, and adds in rubber, fiber and other materials to form a mixture. When the asphalt-based damping pad is applied to automobile damping, when a sheet metal structure in an automobile is subjected to external force to vibrate, because fiber substances filled in the asphalt-based damping pad are distributed in a criss-cross mode, the fiber substances can rub due to vibration, and internal friction force is generated, namely mechanical vibration energy is converted into heat energy or other forms of energy is dissipated, so that better vibration damping and damping effects are achieved. However, the main material asphalt contained in the asphalt-based damping pad has great harm to the environment, and the main material asphalt is applied to the automobile damping material and is easy to volatilize gas harmful to human bodies, so that the main material asphalt is gradually replaced by the rubber-based damping pad. The rubber-based damping pad takes rubber as a main material, and is added with a mixture formed by auxiliary materials such as a polymer modified material, an inorganic filler and the like.
The patent number CN115651323A discloses a high-density damping fin which comprises 2 to 3 percent of butyl rubber, 1 to 2 percent of styrene-butadiene rubber, 4 to 10 percent of liquid polyisobutene, 25 to 50 percent of barium sulfate, 25 to 50 percent of reduced iron powder, 10 to 20 percent of barium titanate, 5 to 10 percent of molybdenum disulfide and 0.2 to 1 percent of antioxidant. The problems of low density, weak sound insulation and noise reduction performance and poor high-frequency damping performance of the rubber-based damping pad in the prior art are solved. However, with the protrusion of the new energy automobile, the performance requirement on the rubber-based damping pad is also higher and higher. The whole vehicle light weight of the new energy automobile is a great trend of industry development, and the battery endurance performance of the new energy automobile can be effectively improved through the whole vehicle light weight, so that the new energy automobile market with extremely strong competition in China is preempted in technical high land and market forefront. The requirements of the new energy automobile on the rubber-based damping pad material are not only limited to good high-frequency damping performance and sound insulation and noise reduction performance, but also a new requirement is provided for the overall light weight of the rubber-based damping pad material. Therefore, the applicant provides a modified butyl rubber composite damping material for damping and reducing noise of a new energy automobile and a preparation method thereof.
Disclosure of Invention
In order to solve the technical problems, the application provides a modified butyl rubber composite damping material for vibration and noise reduction of a new energy automobile and a preparation method thereof.
In a first aspect, the modified butyl rubber composite damping material for damping and reducing noise of a new energy automobile is realized by the following technical scheme:
The modified butyl rubber composite damping material for vibration and noise reduction of the new energy automobile comprises a modified butyl rubber damping layer, a special-shaped PP plate layer, an aluminum foil layer and release paper, wherein one surface of the modified butyl rubber damping layer is in composite connection with the release paper, and the other surface of the modified butyl rubber damping layer is in composite connection with the special-shaped PP plate layer; one surface of the special-shaped PP plate layer is in composite connection with the modified butyl rubber damping layer, and the other surface of the special-shaped PP plate layer is in composite connection with the aluminum foil layer; the modified butyl rubber damping layer is mainly prepared from the following raw materials in parts by weight: 15-20 parts of butyl rubber, 5-10 parts of chlorinated butyl rubber, 8-12 parts of acrylic resin, 3-8 parts of scaly graphite, 4-8 parts of modified polyurethane toughening agent with a shell-core structure, 60-70 parts of filler composition and 0.4-1.2 parts of antioxidant composition; the filler composition consists of the following fillers in percentage by mass: 20-40% of hollow glass beads, 10-30% of short fiber mixture, 10-40% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 5-20% of boron nitride hybrid nano-sheet with carbon grafted on the surface, 0.2-2.0% of tetrapod-like zinc oxide whisker, 0.5-4.0% of halloysite nano-tube, and the balance of superfine calcium carbonate or superfine barium sulfate; the synthesized fluorophlogopite hybrid powder with the carbon grafted on the surface is synthesized fluorophlogopite hybrid powder with graphene and/or carbon nano tubes grafted on the surface; the surface-grafted carbon boron nitride hybrid nano-sheet is a surface-grafted graphene and/or carbon nano-tube boron nitride hybrid nano-sheet.
The modified butyl rubber composite damping material prepared by the application not only has good high-frequency damping performance, sound insulation and noise reduction performance and Gao Wentie attachment resistance, but also has smaller overall density, and can meet the light-weight assembly requirement of new energy automobiles.
Preferably, the modified butyl rubber composite damping material for damping and reducing noise of the new energy automobile is mainly prepared from the following raw materials in parts by weight: 15 parts of butyl rubber, 5 parts of chlorinated butyl rubber, 10 parts of acrylic resin, 4 parts of scaly graphite, 5 parts of ABS-g-TPU with a shell-core structure, 60 parts of filler composition and 1 part of antioxidant composition.
By adopting the technical scheme, the performance of the modified butyl rubber composite damping material can be ensured, and the production cost can be reduced.
Preferably, the filler composition consists of the following fillers in mass percent: 20-40% of hollow glass beads, 5-10% of aramid nanofibers, 5-20% of alumina short fibers, 10-40% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 5-20% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.2-2.0% of tetrapod-like zinc oxide whiskers, 0.5-4.0% of halloysite nanotubes and the balance of ultrafine calcium carbonate or ultrafine barium sulfate.
Preferably, the filler composition is composed of the following fillers in percentage by mass: 28-30% of hollow glass beads, 5-6% of aramid nanofibers, 8-10% of alumina short fibers, 28-30% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 14-16% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.4-0.6% of tetrapod-like zinc oxide whiskers, 1.0-2.0% of halloysite nanotubes and the balance of 2000-mesh ultrafine calcium carbonate.
By adopting the technical scheme, the prepared modified butyl rubber composite damping material can be endowed with good high-frequency damping performance, sound insulation and noise reduction performance and Gao Wentie attachment resistance, and meanwhile, the overall quality is effectively reduced, and the light-weight assembly requirement of a new energy automobile is met.
Preferably, the alumina short fiber is formed by mixing alumina short fiber with the length of 0.5-1.0mm, alumina short fiber with the length of 1.0-3.0mm and alumina short fiber with the length of 3.0-5.0mm according to the mass ratio of 2:5:3.
By adopting the technical scheme, the integral high-frequency damping performance, the sound insulation and noise reduction performance and the Gao Wentie attachment resistance can be improved, and the integral mechanical strength can be improved.
Preferably, the hollow glass bead comprises hollow glass beads of which the surfaces are grafted with multi-wall carbon nano tubes and hollow glass beads of which the surfaces are grafted with tin-bismuth alloy particles, and the mass ratio of the hollow glass beads of which the surfaces are grafted with the multi-wall carbon nano tubes to the hollow glass beads of which the surfaces are grafted with the tin-bismuth alloy particles is (2-4): 6-8.
Preferably, the preparation method of the hollow glass microsphere with the surface grafted with the multiwall carbon nanotubes comprises the following steps:
Firstly, preparing Ag (2E 4 MI) 2 Ac complex solution, wherein the Ag (2E 4 MI) 2 Ac complex solution contains 0.7-1.2wt% of Ag (2E 4 MI) 2 Ac complex and the balance of organic solvent;
Adding multi-wall carbon nano tubes and polyvinylpyrrolidone into an Ag (2E 4 MI) 2 Ac complex solution, wherein the mass of the multi-wall carbon nano tubes is 0.08-0.15 times that of the Ag (2E 4 MI) 2 Ac complex, the mass of the polyvinylpyrrolidone is 1.0-1.2 times that of the multi-wall carbon nano tubes, performing ultrasonic dispersion for 4-8 hours after the multi-wall carbon nano tubes and the polyvinylpyrrolidone are added, adding hollow glass beads, the mass of the hollow glass beads is 60-120 times that of the multi-wall carbon nano tubes, continuing ultrasonic dispersion for 1-4 hours, and performing reduced pressure distillation on the obtained dispersion to remove an organic solvent so as to obtain a solid;
Heating the obtained solid at 1-3 ℃/min to 210-220 ℃ and preserving heat for 200-300min, naturally cooling to room temperature in a furnace, and grinding to obtain the hollow glass microsphere with the average particle diameter of 30-120 microns and the surface grafted multi-wall carbon nano tube.
Preferably, the preparation method of the hollow glass microsphere with the surface grafted with the tin-bismuth alloy particles comprises the following steps:
S1, under the conditions of room temperature and inert gas protection, stannous chloride and bismuth chloride are dissolved in ethanol according to a molar ratio of 42:58 to obtain a mixed solution A;
Simultaneously, under the protection of inert gas at room temperature, sodium borohydride is dissolved in water, and then hollow glass beads are added to be stirred and dispersed uniformly to obtain a mixed solution B, wherein the mole number of the sodium borohydride is 0.6 times of the total mole number of stannous chloride and bismuth chloride, and the mass of the hollow glass beads is 5-6 times of that of the sodium borohydride;
S2, dropwise adding the mixed solution A in the step S1 into the mixed solution B in the step S1 under the condition of room temperature and nitrogen protection, continuing to react for 30-40min after the dropwise adding is finished, standing for 30-60min after the reaction is finished, adding distilled water after supernatant liquid is poured out, standing, pouring out supernatant liquid, adding distilled water, and repeating for at least 3 times to obtain a precipitate;
And S3, placing the precipitate obtained in the step S2 at 80 ℃ and under the vacuum degree of 0.1Pa, and performing vacuum heating and drying treatment for 24 hours to obtain the hollow glass microsphere with the surface grafted with the Sn-Bi alloy particles.
Through adopting above-mentioned technical scheme, can improve holistic high frequency damping performance, sound insulation noise reduction performance and resistant Gao Wentie attached performance, can promote holistic mechanical strength and heat conductivility simultaneously, can release the heat of damping fin fast, and then promote holistic life.
Preferably, the preparation method of the modified polyurethane toughening agent with the shell-core structure comprises the following steps:
S1, preparing polyurethane prepolymer: weighing 1mol of aliphatic diisocyanate, 0.2-0.25mol of hydroxyl-terminated polybutadiene or polyoxypropylene glycol, 0.05-0.1mol of (E, E) -2, 4-hexadien-1-ol, 0.60mol of 1, 4-butanediol, 400-500g of acetone and 0.05-0.10g of organic bismuth catalyst, uniformly mixing, heating to 80 ℃, carrying out-NCO content detection on materials in a system after reaction for 4 hours, adding 0.08-0.12mol of hydroxyethyl methacrylate when the-NCO detection value in the system is stable, and continuing to react at 80 ℃ until the-NCO content in the system is lower than 0.1%, thus obtaining the target polyurethane prepolymer after the reaction is finished;
S2, uniformly mixing 0.3-0.4mol of acrylonitrile, 0.5-0.6mol of butadiene, 0.2-0.4mol of styrene, 4-5g of sodium styrene sulfonate and 0.4-0.6g of azodiisobutyronitrile, adding the mixture into the target polyurethane prepolymer prepared in S1, reacting at 80 ℃ for 60-75min, cooling to 55-58 ℃, adding 300-350g of deionized water, performing high-speed shearing and emulsification for 5-15min, and removing acetone in vacuum to obtain the modified polyurethane toughening agent with a shell-core structure, wherein the modified polyurethane toughening agent with the shell-core structure is used for interface modification of a filler composition.
By adopting the technical scheme, the overall high-frequency damping performance and the sound insulation and noise reduction performance can be further improved.
Preferably, the antioxidant composition comprises an antioxidant 1098, an antioxidant 168, an antioxidant 4020 and nano silicon nitride powder in a mass ratio of 5:1:3:1.
By adopting the technical scheme, the whole ageing resistance and mechanical property can be improved, and the market competitiveness of the product is improved.
In a second aspect, the preparation method of the modified butyl rubber composite damping material for damping and reducing noise of the new energy automobile is realized by the following technical scheme:
A preparation method of a modified butyl rubber composite damping material for new energy automobile vibration and noise reduction comprises the following steps:
Firstly, mixing and stirring the prepared filler composition with an aminosilane aqueous solution at 200-500rpm for 30-40min, wherein each liter of aminosilane aqueous solution contains 4-8g of aminosilane, the mass ratio of the filler composition to the aminosilane aqueous solution is (8-12): 100, carrying out ultrasonic dispersion treatment for 20-40min after stirring and mixing, leaching and drying to obtain a primary surface-treated filler composition, mixing and stirring the primary surface-treated filler composition with the prepared modified polyurethane toughening agent with a shell-core structure at 200-500rpm for 30-40min, leaching after uniform mixing, and drying to obtain a finished product surface-modified filler composition; 60-70 parts of the surface of the obtained finished product of the surface modified filler composition is adhered with 4-8 parts of modified polyurethane toughening agent with a shell-core structure;
Secondly, adding the accurately measured butyl rubber, acrylic resin, flake graphite, surface modified filler composition accounting for 60-75wt% of the total mass of the surface modified filler composition in the first step and antioxidant composition accounting for 40-60wt% of the total mass of the antioxidant composition into an open mill for mixing at 40-80 ℃ at 20-40rpm until the sizing material is smooth and has no obvious granular sensation;
Step three, accurately measured chlorinated butyl rubber, the rest surface modified filler composition and the antioxidant composition are put into an open mill for mixing at the temperature of 40-80 ℃ and the rotating speed of 20-40rpm until the sizing material is smooth and has no obvious granular feel;
and fourthly, putting the uniformly mixed sizing material into an extruder, extruding the sizing material into a continuous sheet at the temperature of 60-120 ℃, sequentially compounding a special-shaped PP plate layer and an aluminum foil layer on the upper layer of the obtained continuous sheet after hot pressing by a hot pressing roller, attaching release paper on the lower layer of the sheet, cutting the modified butyl rubber composite damping material into a target size, putting the modified butyl rubber composite damping material into a mould pressing grinding tool with a standard size, carrying out flat hot pressing treatment for 10-20s, and cooling to room temperature to obtain the finished modified butyl rubber composite damping material.
The preparation method provided by the application is relatively simple, has lower embodiment difficulty and is convenient for realizing industrial production and manufacture.
In summary, the application has the following advantages:
1. The modified butyl rubber composite damping material prepared by the application not only has good high-frequency damping performance, sound insulation and noise reduction performance and Gao Wentie attachment resistance, but also has smaller overall density, and can meet the light-weight assembly requirement of new energy automobiles.
2. The preparation method provided by the application is relatively simple, has lower embodiment difficulty and is convenient for realizing industrial production and manufacture.
3. According to the preparation method, the modified butyl rubber composite damping material is subjected to plate hot pressing treatment at 155-165 ℃ for 10-20s, so that tin-bismuth alloy particles in hollow glass beads grafted with tin-bismuth alloy particles on the surface are melted in matrix resin and flow to form a metal network structure, and the overall high-frequency damping performance and sound insulation and noise reduction performance can be further improved.
4. The prepared modified butyl rubber composite damping material is endowed with excellent high-frequency damping performance, sound insulation and noise reduction performance and Gao Wentie attachment resistance by adopting the compounded filler composition and combining a specific preparation process, meanwhile, the overall quality and density are effectively reduced, the light-weight assembly requirement of a new energy automobile is met, and the market core competitiveness of the product is improved.
Drawings
Fig. 1 is a schematic overall structure of embodiment 1 in the present application.
In the figure, 1, a modified butyl rubber damping layer; 2. a special-shaped PP plate layer; 21. a PP substrate; 22. a connection protrusion; 3. an aluminum foil layer; 4. and (5) release paper.
Detailed Description
The following describes the application in further detail in connection with preparation examples, examples and comparative examples.
Preparation example 1: the filler composition comprises the following fillers in percentage by mass: 20% hollow glass beads (U.S. 3M hollow glass beads S15, true density 0.15g/cm 3), 5% self-made aramid nanofibers, 5% alumina short fibers (Fosmann technology (Beijing), monofilament diameter 11-12 μm, custom length 4-5 mm), 40% self-made synthetic fluorophlogopite hybrid powder with surface grafted carbon, 10% self-made boron nitride hybrid nanoplatelets with surface grafted carbon, 0.2% tetrapod-like zinc oxide whiskers (particle size: diameter 0.5-5um, length 10-50um, true density: 5.3+ -0.2 g/cm 3, CAS: 1314-13-2), 0.5% halloysite nanotubes (novel carbon material custom made by Oncomelano), the balance being ultrafine calcium carbonate (nearly spherical nano high purity ultrafine calcium carbonate with average particle size 100-300nm, ultra-Tai metal material in Qinghai county, STOCK: HDYZ).
The preparation method of the aramid nanofiber comprises the following steps: s1, cutting DuPont Kevlar-29 100D aramid fiber into short-fiber aramid fiber with the length of 1.0mm, cleaning the obtained short-fiber aramid fiber for 200min by using acetone ultrasonic waves (the ultrasonic frequency is 44kHz, the ultrasonic power is 800W), then replacing distilled water for ultrasonic waves again (the ultrasonic frequency is 44kHz, the ultrasonic power is 800W) for cleaning for 15min, repeating the ultrasonic cleaning of the distilled water for 3 times, and then placing the short-fiber aramid fiber into a vacuum dryer for vacuum drying at 80 ℃ and under the pressure of <2Pa for 6 h standby; s2, weighing 50g of the short fiber aramid fiber obtained in S1, 50g of potassium hydroxide KOH and 5L of dimethyl sulfoxide DMSO, adding the mixture into a 10L reaction kettle, exhausting air in the reaction kettle by adopting nitrogen, stirring and mixing at 280rpm for 20min, keeping the temperature of the reaction kettle in a 50 ℃ continuous water bath after stirring and mixing uniformly, stirring at a constant speed of 280rpm for 168h under the sealing of the reaction kettle to obtain a reddish brown ANF solution, S3, diluting the prepared ANF solution with the dimethyl sulfoxide DMSO until the concentration of the aramid fiber ANF is 1g/L, adding 4L of deionized water into the 1L of diluted ANF solution, and dispersing 30 min by adopting ultrasonic waves (ultrasonic frequency is 44kHz and ultrasonic power is 800W) to obtain a uniformly dispersed aramid fiber ANF mixed dispersion; s4, performing vacuum-assisted suction filtration washing on the obtained aramid nanofiber ANF mixed dispersion with deionized water for multiple times to remove dimethyl sulfoxide, and obtaining the finished aramid nanofiber.
The preparation method of the synthetic fluorophlogopite hybrid powder with the carbon grafted on the surface comprises the following steps: s1, adding 0.03mol of 2-ethyl-4-methylimidazole 2E4MI (CAS: 931-36-2) and 0.015mol of silver acetate AgAc (CAS: 563-63-3) into 500mL of organic solvent-dichloromethane (CAS: 75-09-2), magnetically stirring at the rotating speed of 240r/min until AgAc particles completely disappear to obtain a clear and transparent Ag (2E 4 MI) 2 Ac complex solution; s2, adding 0.8g of multiwall carbon nanotube (the outer diameter is 10-20nm, the length is 0.5-2um, the national academy of sciences is TNSMH) and 0.8g of polyvinylpyrrolidone PVP (CAS: 84057-81-8) into Ag (2E 4 MI) 2 Ac complex solution, dispersing for 5h by adopting ultrasonic (the ultrasonic frequency is 44kHz, the ultrasonic power is 800W), adding 50g of synthetic fluorophlogopite powder (the average particle size is 0.5-5 mu m) (the 325 mesh synthetic fluorophlogopite is purchased from Hebei Runfang new material science and technology Co., ltd.), performing planetary ball milling treatment on the purchased 325 mesh synthetic fluorophlogopite to obtain finished synthetic fluorophlogopite powder with the average particle size of 0.5-5 mu m, continuing ultrasonic (the ultrasonic frequency is 44kHz, the ultrasonic power is 800W) to disperse for 2h to obtain a dispersion, and performing reduced pressure distillation treatment to remove dichloromethane in the dispersion to obtain a solid; s3, carrying out high-temperature sintering treatment on the solid obtained in the step S2, wherein the high-temperature sintering temperature is 215 ℃, the high-temperature sintering time is 4 hours, then adopting a planetary ball mill to carry out ball milling treatment, the ball milling rotating speed is 60rpm/min, and the ball milling time is 40min, namely the synthesized fluorophlogopite hybrid powder with the surface grafted with the multiwall carbon nano tubes, the average particle size of which is 0.5-3 mu m, and the Zhejiang Rongtai technology is customized.
The preparation method of the boron nitride hybridized nano-sheet with carbon grafted on the surface and the synthetic fluorophlogopite hybridized powder with carbon grafted on the surface is different as follows: s2, adding 0.8g of three-dimensional graphene TN3DRGO (the thickness is 1.3-104nm, the number of layers is 3-4) and 0.8g of polyvinylpyrrolidone PVP (CAS: 84057-81-8) into Ag (2E 4 MI) 2 Ac complex solution, dispersing for 5 hours by adopting ultrasonic waves (ultrasonic frequency is 44kHz, ultrasonic power is 800W), adding 50g of boron nitride nanosheets (hexagonal boron nitride nanosheets with average particle size of 200nm, brand: submicron nanometer), continuing to disperse for 2.5 hours by adopting ultrasonic waves (ultrasonic frequency is 65kHz, ultrasonic power is 1000W) to obtain a dispersion liquid, and removing dichloromethane in the dispersion liquid by reduced pressure distillation treatment to obtain a solid; and S3, carrying out high-temperature sintering treatment on the solid obtained in the step S2, carrying out high-temperature sintering at 220 ℃ for 4 hours, then adopting a planetary ball mill to carry out grinding treatment, wherein the ball milling rotation speed is 100rpm/min, and the ball milling time is 60min, so that the boron nitride hybridized nano-sheet with the surface grafted with the 3D graphene and the average particle size of 200-400nm is obtained, and the Zhejiang Rongtai technology is customized.
Preparation 2 differs from preparation 1 in that: the filler composition comprises the following fillers in percentage by mass: 30% of hollow glass beads, 5% of aramid nanofibers, 10% of alumina short fibers, 30% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 15% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.5% of tetrapod-like zinc oxide whiskers, 1% of halloysite nanotubes and the balance of ultrafine calcium carbonate.
Preparation 3 differs from preparation 1 in that: the filler composition comprises the following fillers in percentage by mass: 30% of hollow glass beads, 5% of aramid nanofibers, 10% of alumina short fibers, 30% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 15% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.5% of tetrapod-like zinc oxide whiskers, 1% of halloysite nanotubes and the balance of ultrafine barium sulfate.
Preparation example 4 differs from preparation example 1 in that: the filler composition comprises the following fillers in percentage by mass: 40% of hollow glass beads, 5% of aramid nanofibers, 10% of alumina short fibers, 20% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 15% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.5% of tetrapod-like zinc oxide whiskers, 2.0% of halloysite nanotubes and the balance of ultrafine calcium carbonate.
Preparation 5 differs from preparation 2 in that: the filler composition comprises the following fillers in percentage by mass: 5% of aramid nanofiber, 10% of alumina short fiber, 30% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 15% of boron nitride hybrid nano-sheet with carbon grafted on the surface, 0.5% of tetrapod-like zinc oxide whisker, 1% of halloysite nanotube and the balance of superfine calcium carbonate.
Preparation example 6 differs from preparation example 2 in that: the filler composition comprises the following fillers in percentage by mass: 10% of hollow glass beads, 5% of aramid nanofibers, 10% of alumina short fibers, 30% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 15% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.5% of tetrapod-like zinc oxide whiskers, 1% of halloysite nanotubes and the balance of ultrafine calcium carbonate.
Preparation 7 differs from preparation 2 in that: the filler composition comprises the following fillers in percentage by mass: 45% of hollow glass beads, 5% of aramid nanofibers, 10% of alumina short fibers, 25% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 10% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.5% of tetrapod-like zinc oxide whiskers, 1% of halloysite nanotubes and the balance of ultrafine calcium carbonate.
Preparation 8 differs from preparation 2 in that: the filler composition comprises the following fillers in percentage by mass: 30% of hollow glass beads, 5% of aramid nanofibers, 10% of alumina short fibers, 30% of synthetic fluorophlogopite powder, 15% of boron nitride nanosheets, 0.5% of tetrapod-like zinc oxide whiskers, 1% of halloysite nanotubes and the balance of ultrafine calcium carbonate.
Preparation 9 differs from preparation 2 in (no aramid nanofibers added): the filler composition comprises the following fillers in percentage by mass: 30% of hollow glass beads, 10% of alumina short fibers, 30% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 15% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.5% of tetrapod-like zinc oxide whiskers, 1% of halloysite nanotubes and the balance of ultrafine calcium carbonate.
Preparation 10 differs from preparation 2 in that (no alumina staple added): the filler composition comprises the following fillers in percentage by mass: 30% of hollow glass beads, 5% of aramid nanofibers, 30% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 15% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.5% of tetrapod-like zinc oxide whiskers, 1% of halloysite nanotubes and the balance of ultrafine calcium carbonate.
Preparation 11 differs from preparation 2 in that (no tetrapod-like zinc oxide whiskers were added): the filler composition comprises the following fillers in percentage by mass: 30% of hollow glass beads, 5% of aramid nanofibers, 10% of alumina short fibers, 30% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 15% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 1% of halloysite nanotubes and the balance of ultrafine calcium carbonate.
Preparation 12 differs from preparation 2 in (unghalloysite nanotubes): the filler composition comprises the following fillers in percentage by mass: 30% of hollow glass beads, 5% of aramid nanofibers, 10% of alumina short fibers, 30% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 15% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.5% of tetrapod-like zinc oxide whiskers and the balance of ultrafine calcium carbonate.
Preparation 13 differs from preparation 2 in that: the alumina short fiber is formed by mixing alumina short fiber with the length of 0.5-1.0mm (manufactured by the Fosmann technology), alumina short fiber with the length of 1.0-3.0mm (manufactured by the Fosmann technology) and alumina short fiber with the length of 3.0-5.0mm (manufactured by the Fosmann technology) according to the mass ratio of 2:5:3.
Preparation 14 differs from preparation 2 in that: the hollow glass beads are replaced by hollow glass beads with the surface grafted with the multiwall carbon nanotubes. The preparation method of the hollow glass bead with the surface grafted with the multiwall carbon nanotube comprises the following steps:
S1, adding 0.03mol of 2-ethyl-4-methylimidazole 2E4MI and 0.015mol of silver acetate AgAc into 500mL of organic solvent-dichloromethane, magnetically stirring at the rotating speed of 240r/min until AgAc particles completely disappear to obtain a clear and transparent Ag (2E 4 MI) 2 Ac complex solution; simultaneously, placing the hollow glass beads (3M hollow glass beads S15 in the United states, the true density of which is 0.15g/cm 3) in 1L of KH550 aqueous solution with the concentration of 5g/L, carrying out ultrasonic (the ultrasonic frequency is 44kHz, the ultrasonic power is 800W) dispersing treatment for 30min, leaching out, and drying for later use;
S2, adding 0.8g of multiwall carbon nanotube (with the outer diameter of 10-20nm and the length of 0.5-2um, which are manufactured by Chinese academy of sciences organic chemistry Co., ltd. TNSMH) and 0.8g of polyvinylpyrrolidone PVP into Ag (2E 4 MI) 2 Ac complex solution, dispersing for 5 hours by adopting ultrasonic (ultrasonic frequency 44kHz and ultrasonic power 800W), adding 50g of hollow glass beads prepared in S1, continuing to disperse for 2 hours by ultrasonic (ultrasonic frequency 44kHz and ultrasonic power 800W) to obtain a dispersion, and removing dichloromethane in the dispersion by reduced pressure distillation treatment to obtain a solid;
S3, carrying out high-temperature sintering treatment on the solid obtained in the step S2, carrying out high-temperature sintering at 220 ℃ for 4 hours, placing the obtained solid in a three-roller machine (the roller spacing of the three-roller machine is adjusted to be 120 mu m), carrying out grinding and crushing for 3 times, dispersing the obtained solid in 500mL of ethanol, pouring the obtained solid into a basket type grinding machine for grinding, grinding for 30 minutes at the rotating speed of 2000r/min, then filtering and drying to obtain hollow glass beads with the surface grafted with the multi-wall carbon nano tubes and the average particle size of 30-120 mu m, and customizing the Zhejiang Thai technology.
Preparation 15 differs from preparation 2 in that: the hollow glass beads are replaced by hollow glass beads with tin-bismuth alloy particles grafted on the surfaces. The preparation method of the hollow glass bead with the tin-bismuth alloy particles grafted on the surface comprises the following steps:
S1, under the condition of room temperature and nitrogen protection, 15.92 g (0.84 mol) of SnCl 2 (CAS: 7772-99-8, analytical grade) and 36.58g (0.116 mol) of BiCl 3 (CAS number: 7787-60-2, analytical grade) are dissolved in 400 ml of ethanol to obtain a mixed solution A;
Simultaneously, under the conditions of room temperature and nitrogen protection, 4.54g (0.12 mol) of sodium borohydride NaBH 4 (CAS: 16940-66-2, chemical purity) is dissolved in 500 ml of deionized water, and then 25 g of hollow glass beads are added to obtain a mixed solution B;
s2, dropwise adding the mixed solution A in the step S1 into the mixed solution B in the step S1 under the condition of room temperature and nitrogen protection, continuing to react for 30min after the dropwise adding is finished, standing for 60min after the reaction is finished, pouring out supernatant, adding 500mL of distilled water, standing, pouring out supernatant, adding distilled water, and repeating the steps for 4 times to obtain a precipitate;
And S3, placing the precipitate obtained in the step S2 at 80 ℃ and under the vacuum degree of 0.1Pa, and performing vacuum heating and drying treatment for 24 hours to obtain the hollow glass beads with the surface grafted with the Sn-Bi alloy particles, wherein the Zhejiang Rongtai technology is customized.
Preparation example 16 differs from preparation example 2 in that: the hollow glass beads are replaced by the hollow glass beads of which the surfaces are grafted with the multiwall carbon nanotubes in preparation example 14 and the hollow glass beads of which the surfaces are grafted with the tin-bismuth alloy particles in preparation example 15, and the mass ratio of the hollow glass beads of which the surfaces are grafted with the multiwall carbon nanotubes to the hollow glass beads of which the surfaces are grafted with the tin-bismuth alloy particles is 1:1.
Preparation 17 differs from preparation 16 in that: the hollow glass beads are replaced by hollow glass beads with the surface grafted with the multiwall carbon nano tube and hollow glass beads with the surface grafted with the tin-bismuth alloy particles, and the mass ratio of the hollow glass beads with the surface grafted with the multiwall carbon nano tube to the hollow glass beads with the surface grafted with the tin-bismuth alloy particles is 2:8.
Preparation 18 differs from preparation 16 in that: the hollow glass beads are replaced by hollow glass beads with the surface grafted with the multiwall carbon nano tube and hollow glass beads with the surface grafted with the tin-bismuth alloy particles, and the mass ratio of the hollow glass beads with the surface grafted with the multiwall carbon nano tube to the hollow glass beads with the surface grafted with the tin-bismuth alloy particles is 4:6.
Preparation example 19A preparation method of the modified polyurethane toughening agent with a shell-core structure comprises the following steps:
S1, preparing polyurethane prepolymer: weighing 1mol of isophorone diisocyanate (IPDI), 0.2mol of hydroxyl-terminated polybutadiene (IV type of Yikou Tianyuan chemical institute, inc., hydroxyl value is 0.71-0.80mmol/g, number average molecular weight is 2700-3300), 0.1mol of (E, E) -2, 4-hexadien-1-ol, 0.60mol of 1, 4-butanediol, 500g of acetone and 0.10g of bismuth neodecanoate (CAS: 25426-20-5), uniformly mixing, heating to 80 ℃, reacting for 4 hours, detecting the-NCO content of the materials in the system, adding 0.12mol of hydroxyethyl methacrylate when the-NCO detection value in the system tends to be stable, and continuously reacting at 80 ℃ until the-NCO content in the system is lower than 0.1%, namely obtaining the target polyurethane prepolymer;
S2, uniformly mixing 0.4mol of acrylonitrile, 0.6mol of butadiene, 0.3mol of styrene, 5g of sodium styrenesulfonate and 0.5g of azodiisobutyronitrile, adding the mixture into the target polyurethane prepolymer prepared in the S1, reacting at 80 ℃ for 70min, cooling to 58 ℃, adding 350g of deionized water, shearing and emulsifying for 10min at a high speed, and removing acetone in vacuum to obtain the modified polyurethane toughening agent with a shell-core structure, wherein the modified polyurethane toughening agent with the shell-core structure is used for interface modification of a filler composition.
Preparation 20 differs from preparation 19 in that: s1, preparing polyurethane prepolymer: 1mol of isophorone diisocyanate (IPDI), 0.2mol of polytetramethylene ether glycol PTMEG (BASF Buff PolyTHF, molecular weight of 2900 PTMEG 3000), 0.1mol of (E, E) -2, 4-hexadien-1-ol, 0.60mol of 1, 4-butanediol, 500g of acetone and 0.10g of bismuth neodecanoate (CAS: 25426-20-5) are weighed, uniformly mixed, heated to 80 ℃, reacted for 4 hours, the materials in the system are subjected to-NCO content detection, when the-NCO detection value in the system tends to be stable, 0.12mol of hydroxyethyl methacrylate is added, and the reaction is continued at 80 ℃ until the-NCO content in the system is lower than 0.1%, namely, the polyurethane prepolymer is prepared after the reaction is finished.
Examples
Referring to fig. 1, a modified butyl rubber composite damping material for vibration and noise reduction of a new energy automobile comprises a modified butyl rubber damping layer 1, a special-shaped PP plate layer 2, an aluminum foil layer 3 and release paper 4, wherein one surface of the modified butyl rubber damping layer 1 is in composite connection with the release paper 4, and the other surface of the modified butyl rubber damping layer is in composite connection with the special-shaped PP plate layer 2; one surface of the special-shaped PP plate layer 2 is in composite connection with the modified butyl rubber damping layer 1, and the other surface of the special-shaped PP plate layer is in composite connection with the aluminum foil layer 3. The special-shaped PP plate layer 2 comprises a PP substrate 21 and a plurality of connecting protrusions 22, wherein the connecting protrusions 22 are integrally formed on one surface of the PP substrate 21 in a lattice mode. The aluminum foil layer 3 is in compound connection with the surface of the PP substrate 21, which is opposite to the connecting protrusion 22, and the connecting protrusion 22 is partially embedded into the modified butyl rubber damping layer 1, so that compound connection between the modified butyl rubber damping layer 1 and the special-shaped PP plate layer 2 is realized.
The modified butyl rubber damping layer 1 is prepared from the following raw materials in parts by weight: 15-20 parts of butyl rubber, 5-10 parts of chlorinated butyl rubber, 8-12 parts of acrylic resin, 3-8 parts of scaly graphite, 4-8 parts of modified polyurethane toughening agent with a shell-core structure, 60-70 parts of filler composition and 0.4-1.2 parts of antioxidant composition.
The preferred formulation is as follows: the modified butyl rubber composite damping material for new energy automobile vibration and noise reduction is prepared from the following raw materials in parts by weight: 15 parts of butyl rubber, 5 parts of chlorinated butyl rubber, 10 parts of acrylic resin, 4 parts of scaly graphite, 5 parts of ABS-g-TPU with a shell-core structure, 60 parts of filler composition and 1 part of antioxidant composition. The antioxidant composition consists of an antioxidant 1098, an antioxidant 168, an anti-aging agent 4020 and nano silicon nitride powder according to the mass ratio of 5:1:3:1.
The preparation method of the modified polyurethane toughening agent with the shell-core structure comprises the following steps:
S1, preparing polyurethane prepolymer: weighing 1mol of aliphatic diisocyanate, 0.2-0.25mol of hydroxyl-terminated polybutadiene or polyoxypropylene glycol, 0.05-0.1mol of (E, E) -2, 4-hexadien-1-ol, 0.60mol of 1, 4-butanediol, 400-500g of acetone and 0.05-0.10g of organic bismuth catalyst, uniformly mixing, heating to 80 ℃, carrying out-NCO content detection on materials in a system after reaction for 4 hours, adding 0.08-0.12mol of hydroxyethyl methacrylate when the-NCO detection value in the system is stable, and continuing to react at 80 ℃ until the-NCO content in the system is lower than 0.1%, thus obtaining the target polyurethane prepolymer after the reaction is finished;
S2, uniformly mixing 0.3-0.4mol of acrylonitrile, 0.5-0.6mol of butadiene, 0.2-0.4mol of styrene, 4-5g of sodium styrene sulfonate and 0.4-0.6g of azodiisobutyronitrile, adding the mixture into the target polyurethane prepolymer prepared in S1, reacting at 80 ℃ for 60-75min, cooling to 55-58 ℃, adding 300-350g of deionized water, performing high-speed shearing and emulsification for 5-15min, and removing acetone in vacuum to obtain the modified polyurethane toughening agent with a shell-core structure, wherein the modified polyurethane toughening agent with the shell-core structure is used for interface modification of a filler composition.
The filler composition comprises the following fillers in percentage by mass: 20-40% of hollow glass beads, 10-30% of short fiber mixture, 10-40% of synthesized fluorophlogopite hybrid powder with carbon grafted on the surface, 5-20% of boron nitride hybrid nano-sheet with carbon grafted on the surface, 0.2-2.0% of tetrapod-like zinc oxide whisker, 0.5-4.0% of halloysite nano-tube, and the balance of superfine calcium carbonate or superfine barium sulfate.
Preferably, the filler composition consists of the following fillers in mass percent: 20-40% of hollow glass beads, 5-10% of aramid nanofibers, 5-20% of alumina short fibers, 10-40% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 5-20% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.2-2.0% of tetrapod-like zinc oxide whiskers, 0.5-4.0% of halloysite nanotubes and the balance of ultrafine calcium carbonate or ultrafine barium sulfate.
The preferred formulation is as follows: the filler composition comprises the following fillers in percentage by mass: 28-30% of hollow glass beads, 5-6% of aramid nanofibers, 8-10% of alumina short fibers, 28-30% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 14-16% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.4-0.6% of tetrapod-like zinc oxide whiskers, 1.0-2.0% of halloysite nanotubes and the balance of 2000-mesh ultrafine calcium carbonate.
The synthetic fluorophlogopite hybrid powder with the surface grafted with carbon in the filler composition is synthetic fluorophlogopite hybrid powder with the surface grafted with graphene and/or carbon nano tubes. The boron nitride hybrid nano-sheet with the carbon grafted on the surface is a boron nitride hybrid nano-sheet with graphene and/or carbon nano-tube grafted on the surface. The alumina short fiber is formed by mixing alumina short fiber with the length of 0.5-1.0mm, alumina short fiber with the length of 1.0-3.0mm and alumina short fiber with the length of 3.0-5.0mm according to the mass ratio of 2:5:3. The hollow glass beads comprise hollow glass beads with the surface grafted with the multiwall carbon nano tube and hollow glass beads with the surface grafted with the tin-bismuth alloy particles, and the mass ratio of the hollow glass beads with the surface grafted with the multiwall carbon nano tube to the hollow glass beads with the surface grafted with the tin-bismuth alloy particles is (2-4) (6-8).
The preparation method of the hollow glass bead with the surface grafted with the multiwall carbon nanotube comprises the following steps: firstly, preparing Ag (2E 4 MI) 2 Ac complex solution, wherein the Ag (2E 4 MI) 2 Ac complex solution contains 0.7-1.2wt% of Ag (2E 4 MI) 2 Ac complex and the balance of organic solvent; adding multi-wall carbon nano tubes and polyvinylpyrrolidone into Ag (2E 4 MI) 2 Ac complex solution, wherein the mass of the multi-wall carbon nano tubes is 0.08-0.15 times that of Ag (2E 4 MI) 2 Ac complex, the mass of the polyvinylpyrrolidone is 1.0-1.2 times that of the multi-wall carbon nano tubes, carrying out ultrasonic dispersion for 4-8h after the addition of the multi-wall carbon nano tubes and the polyvinylpyrrolidone is completed, then adding hollow glass beads, wherein the mass of the hollow glass beads is 60-120 times that of the multi-wall carbon nano tubes, continuing ultrasonic dispersion for 1-4h, distilling the obtained dispersion liquid under reduced pressure to remove an organic solvent to obtain a solid, heating the obtained solid to 210-220 ℃ at 1-3 ℃/min, preserving heat for 200-300min, naturally cooling to room temperature in a furnace, and carrying out grinding treatment to obtain the hollow glass beads with the average particle size of 30-120 mu m.
The preparation method of the hollow glass bead with the surface grafted with the tin-bismuth alloy particles comprises the following steps:
S1, under the conditions of room temperature and inert gas protection, stannous chloride and bismuth chloride are dissolved in ethanol according to a molar ratio of 42:58 to obtain a mixed solution A;
Simultaneously, under the protection of inert gas at room temperature, sodium borohydride is dissolved in water, then hollow glass beads are added, and stirring and dispersing are carried out uniformly to obtain a mixed solution B, wherein the mole number of the sodium borohydride is 0.6 times of the total mole number of stannous chloride and bismuth chloride, and the mass of the hollow glass beads is 5-6 times of the mass of the sodium borohydride;
S2, dropwise adding the mixed solution A in the step S1 into the mixed solution B in the step S1 under the condition of room temperature and nitrogen protection, continuing to react for 30-40min after the dropwise adding is finished, standing for 30-60min after the reaction is finished, adding distilled water after supernatant liquid is poured out, standing, pouring out supernatant liquid, adding distilled water, and repeating for at least 3 times to obtain a precipitate;
And S3, placing the precipitate obtained in the step S2 at 80 ℃ and under the vacuum degree of 0.1Pa, and performing vacuum heating and drying treatment for 24 hours to obtain the hollow glass microsphere with the surface grafted with the Sn-Bi alloy particles.
A preparation method of a modified butyl rubber composite damping material for new energy automobile vibration and noise reduction comprises the following steps:
Firstly, mixing and stirring the prepared filler composition with an aminosilane aqueous solution at 200-500rpm for 30-40min, wherein each liter of aminosilane aqueous solution contains 4-8g of aminosilane, the mass ratio of the filler composition to the aminosilane aqueous solution is (8-12): 100, carrying out ultrasonic dispersion treatment for 20-40min after stirring and mixing, leaching and drying to obtain a primary surface-treated filler composition, mixing and stirring the primary surface-treated filler composition with the prepared modified polyurethane toughening agent with a shell-core structure at 200-500rpm for 30-40min, leaching after uniform mixing, and drying to obtain a finished product surface-modified filler composition; 60-70 parts of the surface of the obtained finished product of the surface modified filler composition is adhered with 4-8 parts of modified polyurethane toughening agent with a shell-core structure;
Secondly, adding the accurately measured butyl rubber, acrylic resin, flake graphite, surface modified filler composition accounting for 60-75wt% of the total mass of the surface modified filler composition in the first step and antioxidant composition accounting for 40-60wt% of the total mass of the antioxidant composition into an open mill for mixing at 40-80 ℃ at 20-40rpm until the sizing material is smooth and has no obvious granular sensation;
Step three, accurately measured chlorinated butyl rubber, the rest surface modified filler composition and the antioxidant composition are put into an open mill for mixing at the temperature of 40-80 ℃ and the rotating speed of 20-40rpm until the sizing material is smooth and has no obvious granular feel;
And fourthly, putting the uniformly mixed sizing material into an extruder, extruding the sizing material into a continuous sheet at the temperature of 60-120 ℃, sequentially compounding a special-shaped PP plate layer 2 and an aluminum foil layer 3 on the upper layer of the obtained continuous sheet after hot pressing by a hot pressing roller, attaching release paper 4 on the lower layer of the sheet, putting the modified butyl rubber composite damping material cut into a target size into a mould pressing grinding tool with a standard size, carrying out plate hot pressing treatment for 10-20s, carrying out hot pressing on the hot pressing plate at the temperature of 80 ℃, and cooling to the room temperature to obtain the finished modified butyl rubber composite damping material.
Example 1: the modified butyl rubber composite damping material for vibration and noise reduction of the new energy automobile comprises a modified butyl rubber damping layer 1, a special-shaped PP plate layer 2, an aluminum foil layer 3 and release paper 4, wherein one surface of the modified butyl rubber damping layer 1 is in composite connection with the release paper 4, and the other surface of the modified butyl rubber damping layer is in composite connection with the special-shaped PP plate layer 2; one surface of the special-shaped PP plate layer 2 is in composite connection with the modified butyl rubber damping layer 1, and the other surface of the special-shaped PP plate layer is in composite connection with the aluminum foil layer 3. The special-shaped PP plate layer 2 comprises a PP substrate 21 and a plurality of connecting protrusions 22, wherein the connecting protrusions 22 are integrally formed on one surface of the PP substrate 21 in a lattice mode. The aluminum foil layer 3 is in compound connection with the surface of the PP substrate 21, which is opposite to the connecting protrusion 22, and the connecting protrusion 22 is partially embedded into the modified butyl rubber damping layer 1, so that compound connection between the modified butyl rubber damping layer 1 and the special-shaped PP plate layer 2 is realized.
The modified butyl rubber damping material in the modified butyl rubber damping layer 1 is prepared from the following raw materials in parts by weight: 15 parts of butyl rubber Yanshan petrochemical product 1751, 5 parts of chlorinated butyl rubber CB1240, 8 parts of acrylic resin (Keding resin MR14890A thermoplastic acrylic resin), 3 parts of flake graphite (superfine 2000 mesh flake graphite, lingshou De Xue mineral product processing factory), 4 parts of modified polyurethane toughening agent with a shell-core structure in preparation example 19, 64 parts of filler composition in preparation example 1, 0.5 part of antioxidant 1098, 0.1 part of antioxidant 168, 0.3 part of antioxidant 4020 and 0.1 part of nano silicon nitride powder with an average particle size of 800nm (Shanghai super-Wired nano technology model CW-Si3N 4-002).
The preparation method of the modified butyl rubber composite damping material for new energy automobile vibration and noise reduction comprises the following steps:
firstly, 640g of the filler composition of preparation example 1 is mixed with 6400mL of an aminosilane aqueous solution at 300rpm for 30min, 5g of aminosilane KH550 is contained in each liter of the aminosilane aqueous solution, after the stirring and mixing are completed, ultrasonic (ultrasonic frequency 44kHz, ultrasonic power 800W) dispersion treatment is carried out for 20min, the obtained filler composition with primary surface treatment is obtained after leaching and drying, the obtained filler composition with primary surface treatment is mixed with 150g of a modified polyurethane toughening agent with a shell-core structure in preparation example 19 at 500rpm for 30min, leaching is carried out after uniform mixing, and 640g of a finished product surface modified filler composition is obtained after drying, namely 640g of the filler composition in the obtained finished product surface modified filler composition is considered to be adhered with 42g of modified polyurethane toughening agent colloidal particles with a shell-core structure in preparation example 19;
Step two, 150g of butyl rubber Yanshan petrochemical 1751, 80g of MR14890A thermoplastic acrylic resin, 30g of superfine 2000-mesh scaly graphite, 477.4g of the surface modified filler composition in the step one, 2.5g of antioxidant 1098, 0.5g of antioxidant 168, 1.5g of antioxidant 4020 and 0.5g of 800nm nanometer silicon nitride powder with average particle size are put into an open mill for mixing, the temperature is 75 ℃, the rotating speed is 35rpm, and the sizing material is smooth and has no obvious granular feel;
Step three, 50g of chlorinated butyl rubber CB1240 and 204.6g of the surface modified filler composition in the step one, 2.5g of antioxidant 1098, 0.5g of antioxidant 168, 1.5g of antioxidant 4020 and 0.5g of nano silicon nitride powder with the average particle size of 800nm are put into an open mill for mixing, the temperature is 70 ℃, the rotating speed is 40rpm, until the sizing material is smooth and no obvious granular feel exists;
And fourthly, putting the uniformly mixed sizing material into an extruder, extruding the sizing material into a continuous sheet at the temperature of 80+/-0.5 ℃, compounding glass fiber cloth on the upper layer of the sheet after hot pressing the continuous sheet by a hot pressing roller, attaching release paper on the lower layer, cutting the modified butyl rubber composite damping material into a target size, putting the modified butyl rubber composite damping material into a mould pressing grinding tool with a standard size, carrying out flat hot pressing treatment for 15s at the temperature of 158 ℃, and cooling the modified butyl rubber composite damping material to room temperature to obtain the finished product.
Example 2 differs from example 1 in that: the modified butyl rubber composite damping material for new energy automobile vibration and noise reduction is prepared from the following raw materials in parts by weight: 15 parts of butyl rubber Yanshan petrochemical 1751 parts of chlorinated butyl rubber CB1240 parts of Keding resin MR14890A thermoplastic acrylic resin, 4 parts of superfine 2000-mesh flake graphite, 5 parts of modified polyurethane toughening agent with a shell-core structure in preparation example 19, 60 parts of filler composition in preparation example 1, 0.5 part of antioxidant 1098, 0.1 part of antioxidant 168, 0.3 part of antioxidant 4020 and 0.1 part of nano silicon nitride powder with the average particle size of 800 nm.
Example 3 differs from example 1 in that: the modified butyl rubber composite damping material for new energy automobile vibration and noise reduction is prepared from the following raw materials in parts by weight: 20 parts of butyl rubber Yanshan petrochemical 1751 parts of chlorinated butyl rubber CB1240 parts of Keding resin MR14890A thermoplastic acrylic resin, 8 parts of superfine 2000-mesh flake graphite, 8 parts of modified polyurethane toughening agent with a shell-core structure in preparation example 19, 70 parts of filler composition in preparation example 1, 0.5 part of antioxidant 1098, 0.1 part of antioxidant 168, 0.3 part of antioxidant 4020 and 0.1 part of nano silicon nitride powder with the average particle size of 800 nm.
Example 4 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 2.
Example 5 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 3.
Example 6 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 4.
Example 7 differs from example 2 in that: 60 parts of the filler composition in preparation example 1 were replaced with 30 parts of the filler composition in preparation example 4 and 30 parts of the filler composition in preparation example 1.
Example 8 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 13.
Example 9 differs from example 2 in that: the filler composition of preparation example 1 was replaced with the filler composition of preparation example 14.
Example 10 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 15.
Example 11 differs from example 2 in that: the filler composition of preparation example 1 was replaced with the filler composition of preparation example 16.
Example 12 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 17.
Example 13 differs from example 2 in that: the filler composition of preparation example 1 was replaced with the filler composition of preparation example 18.
Example 14 differs from example 2 in that: the filler composition comprises the following fillers in percentage by mass: 30% of hollow glass beads, 5% of aramid nanofibers, 10% of alumina short fibers, 20% of synthetic fluorophlogopite hybrid powder with a surface grafted with multi-wall carbon nanotubes, 15% of boron nitride hybrid nano-sheets with a surface grafted with 3D graphene, 10% of molybdenum disulfide hybrid nano-sheets with a surface grafted with multi-wall carbon nanotubes, 0.5% of tetrapod-like zinc oxide whiskers, 1% of halloysite nanotubes and the balance of ultrafine calcium carbonate.
The preparation method of the molybdenum disulfide hybridized nano-sheet grafted with the multiwall carbon nano-tube on the surface comprises the following steps:
s1, adding 0.03mol of 2-ethyl-4-methylimidazole 2E4MI and 0.015mol of silver acetate AgAc into 500mL of organic solvent-dichloromethane, magnetically stirring at the rotating speed of 240r/min until AgAc particles completely disappear to obtain a clear and transparent Ag (2E 4 MI) 2 Ac complex solution;
S2, adding 0.8g of multi-wall carbon nano tube (with the outer diameter of 10-20nm and the length of 0.5-2um and manufactured by Chinese academy of sciences organic chemistry TNSMH) and 0.8g of polyvinylpyrrolidone PVP into Ag (2E 4 MI) 2 Ac complex solution, dispersing for 5 hours by adopting ultrasonic waves (the ultrasonic frequency is 44kHz and the ultrasonic power is 800W), adding 50g of molybdenum disulfide hybrid nano sheet (single-layer molybdenum disulfide nano sheet MoS 2 and the average particle size is 2-3 microns and sub-Mey nano technology), continuing to disperse for 2 hours by adopting ultrasonic waves (the ultrasonic frequency is 44kHz and the ultrasonic power is 800W) to obtain a dispersion liquid, and removing dichloromethane in the dispersion liquid by reduced pressure distillation treatment to obtain a solid;
S3, carrying out high-temperature sintering treatment on the solid obtained in the step S2, carrying out high-temperature sintering at 220 ℃ for 4 hours, then adopting a planetary ball mill to carry out ball milling treatment, wherein the ball milling rotation speed is 100rpm/min, and the ball milling time is 60min, namely the molybdenum disulfide hybridized nano-sheet with the surface grafted with the multi-wall carbon nano-tube and the average particle size of 0.5-3 mu m, and customizing the Zhejiang Rongtai technology.
Example 15 differs from example 2 in that: the modified butyl rubber composite damping material for new energy automobile vibration and noise reduction is prepared from the following raw materials in parts by weight: 15 parts of butyl rubber Yanshan petrochemical 1751, 5 parts of chlorinated butyl rubber CB1240, 5 parts of TPU granules with the self-made average particle size of 50-80 meshes, 10 parts of Keding resin MR14890A thermoplastic acrylic resin, 4 parts of superfine 2000-mesh flake graphite, 5 parts of modified polyurethane toughening agent with a shell-core structure in preparation example 19, 60 parts of filler composition in preparation example 1, 0.5 part of antioxidant 1098, 0.1 part of antioxidant 168, 0.3 part of antioxidant 4020 and 0.1 part of nano silicon nitride powder with the average particle size of 800 nm.
The formulation of the TPU granules is as follows: 0.4mol of MDI diisocyanate, 0.6mol of HDI diisocyanate, 0.5mol of 1, 6-hexanediol, 0.3mol of 1, 4-butanediol, 0.12mol of polytetramethylene ether glycol PTMEG having a molecular weight of 3000, 0.082mol of polycarbonate diol having a molecular weight of 2000, 0.2g of bismuth octodecanoate, 5g of AF 5718 acrylic block polymeric dispersant, 6g of antioxidant 1010, 50g of the filler composition of preparation example 18.
The preparation method of the TPU granules comprises the following steps:
S1, charging accurately metered 1, 6-hexanediol and 1, 4-butanediol into a first trough of a twin-screw extruder, charging accurately metered polytetramethylene ether glycol PTMEG (BASF Pasteff PolyTHF 2900 PTMEG) with a molecular weight of 3000 and polycarbonate diol (PCDL 1012 Polycarbonatediol polycarbonate diol) with a molecular weight of 2000 into a second trough of the twin-screw extruder, simultaneously, the MDI diisocyanate, the HDI diisocyanate, the bismuth octodecanoate, the AF 5718 acrylic acid block high molecular dispersant, the antioxidant 1010 and the filler composition in the preparation example 18 which are accurately metered are evenly stirred and then are put into a third trough of a double-screw extruder, the temperature of a barrel section of the double-screw extruder is 14 sections, 170+ -2deg.C, 175+ -2deg.C, 180+ -2deg.C, 190+ -2deg.C, 170+ -2deg.C, 160+ -2deg.C, 155+ -2deg.C, 150+ -2deg.C, discharging the material from the extruder using a gear pump;
s2, water-cooling granulating, drying in a fluidized bed dryer at 80 ℃ for 10min until the water content is less than 0.05%, transferring the obtained granules to 80 ℃ for 20h of heat adjustment treatment to obtain TPU granules;
S3, crushing and screening the TPU granules obtained in S2 to 50-80 meshes, placing 100g of the TPU granules with the average particle size of 50-80 meshes into 2L of KH550 aqueous solution with the concentration of 10g/L, treating for 30min by ultrasonic (the ultrasonic frequency is 44kHz and the ultrasonic power is 800W), leaching out, and drying to obtain the finished TPU granules.
The preparation method of the modified butyl rubber composite damping material for the vibration and noise reduction of the new energy automobile is characterized in that:
firstly, 640g of the filler composition of preparation example 1 is mixed with 6400mL of an aminosilane aqueous solution at 300rpm for 30min, 5g of aminosilane KH550 is contained in each liter of the aminosilane aqueous solution, after the stirring and mixing are completed, ultrasonic (ultrasonic frequency 44kHz, ultrasonic power 800W) dispersion treatment is carried out for 20min, the obtained filler composition with primary surface treatment is obtained after leaching and drying, the obtained filler composition with primary surface treatment is mixed with 150g of a modified polyurethane toughening agent with a shell-core structure in preparation example 19 at 500rpm for 30min, leaching is carried out after uniform mixing, and 640g of a finished product surface modified filler composition is obtained after drying, namely 640g of the filler composition in the obtained finished product surface modified filler composition is considered to be adhered with 42g of modified polyurethane toughening agent colloidal particles with a shell-core structure in preparation example 19;
Simultaneously preparing TPU granules, placing 500g of prepared finished TPU granules into a reaction kettle, stirring at 200rpm, intermittently spraying the Pasteur 417 carboxylic styrene-butadiene latex into the reaction kettle under stirring, wherein the time of the intermittent spraying is 30s, the total spraying number is 10, the temperature is raised to 65 ℃ after the spraying is finished, and the stirring at 200rpm is maintained for 10min, so that the gel carboxyl styrene-butadiene latex film is attached to the outer wall of the finished TPU granules;
Step two, 150g of butyl rubber Yanshan petrochemical 1751, 80g of MR14890A thermoplastic acrylic resin, 30g of superfine 2000-mesh scaly graphite, 477.4g of the surface modified filler composition in the step one, 2.5g of antioxidant 1098, 0.5g of antioxidant 168, 1.5g of antioxidant 4020 and 0.5g of 800nm nanometer silicon nitride powder with average particle size are put into an open mill for mixing, the temperature is 75 ℃, the rotating speed is 35rpm, and the sizing material is smooth and has no obvious granular feel;
Step three, 50g of chlorinated butyl rubber CB1240, 50g of finished TPU granules with gel carboxyl styrene-butadiene latex films attached to the outer wall, which are prepared in the step one, 204.6g of surface modified filler composition, 2.5g of antioxidant 1098, 0.5g of antioxidant 168, 1.5g of antioxidant 4020 and 0.5g of nano silicon nitride powder with average particle size of 800nm are accurately measured and put into an open mill for mixing, the temperature is 70 ℃, the rotating speed is 40rpm, and the sizing material is smooth and has no obvious granular feel;
And fourthly, putting the uniformly mixed sizing material into an extruder, extruding the sizing material into a continuous sheet at the temperature of 108 ℃, compounding an upper glass fiber cloth on the upper layer of the sheet after hot pressing the continuous sheet by a hot pressing roller, attaching release paper on the lower layer, cutting the modified butyl rubber composite damping material into a target size, putting the modified butyl rubber composite damping material into a mould pressing grinding tool with a standard size, carrying out hot pressing treatment on the modified butyl rubber composite damping material by a 158 ℃ flat plate for 15s, and cooling the modified butyl rubber composite damping material to the room temperature to obtain the finished product.
Example 16 differs from example 15 in that: the filler composition of preparation example 1 was replaced with the filler composition of preparation example 18.
Comparative example 1 differs from example 10 in that: and fourthly, putting the uniformly mixed sizing material into an extruder, extruding the sizing material into a continuous sheet at the temperature of 108 ℃, compounding the upper glass fiber cloth on the upper layer of the sheet after hot pressing the continuous sheet by a hot pressing roller, attaching release paper on the lower layer of the sheet, and cutting the sheet into a target size to obtain the finished product modified butyl rubber composite damping material.
Comparative example 2 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 5.
Comparative example 3 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 6.
Comparative example 4 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 7.
Comparative example 5 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 8.
Comparative example 6 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 9.
Comparative example 7 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 10.
Comparative example 8 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 11.
Comparative example 9 differs from example 2 in that: the filler composition in preparation example 1 was replaced with the filler composition in preparation example 12.
Comparative example 10 differs from example 4 in that: the modified polyurethane toughening agent of the core-shell structure in preparation example 19 was replaced with the modified polyurethane toughening agent of the core-shell structure in preparation example 20.
Comparative example 11 differs from example 4 in that: the modified butyl rubber composite damping material for new energy automobile vibration and noise reduction is prepared from the following raw materials in parts by weight: 15 parts of butyl rubber Yanshan petrochemical 1751, 5 parts of chlorinated butyl rubber CB1240, 10 parts of Keding resin MR14890A thermoplastic acrylic resin, 4 parts of superfine 2000-mesh flake graphite, 5 parts of modified polyurethane toughening agent with a shell-core structure in preparation example 19, 60 parts of filler composition in preparation example 2, 0.8 part of antioxidant 1098 and 0.2 part of antioxidant 168.
Comparative example 12 differs from example 2 in that: the modified butyl rubber composite damping material for new energy automobile vibration and noise reduction is prepared from the following raw materials in parts by weight: 15 parts of butyl rubber Yanshan petrochemical 1751 parts of chlorinated butyl rubber CB1240 parts of Keding resin MR14890A thermoplastic acrylic resin, 4 parts of superfine 2000-mesh flake graphite, 5 parts of modified polyurethane toughening agent with a shell-core structure in preparation example 19, 60 parts of conventional filler composition, 0.5 part of antioxidant 1098, 0.1 part of antioxidant 168, 0.3 part of antioxidant 4020 and 0.1 part of nano silicon nitride powder with the average particle size of 800 nm. 60 parts of conventional filler composition consists of 30 parts of superfine 2000-mesh barium sulfate, 18 parts of 800-mesh reduced iron powder, 6 parts of superfine 2000-mesh barium titanate and 6 parts of 800-mesh molybdenum disulfide.
Comparative example 13 differs from example 4 in that: the modified butyl rubber composite damping material for new energy automobile vibration and noise reduction is prepared from the following raw materials in parts by weight: 20 parts of butyl rubber Yanshan petrochemical product 1751, 5 parts of chlorinated butyl rubber CB1240, 10 parts of Keding resin MR14890A thermoplastic acrylic resin, 4 parts of superfine 2000-mesh flake graphite, 60 parts of filler composition in preparation example 2, 0.5 part of antioxidant 1098, 0.1 part of antioxidant 168, 0.3 part of antioxidant 4020 and 0.1 part of nano silicon nitride powder with average particle size of 800 nm.
Comparative example 14 differs from example 4 in that: the modified butyl rubber composite damping material for new energy automobile vibration and noise reduction is prepared from the following raw materials in parts by weight: 15 parts of butyl rubber Yanshan petrochemical 1751, 5 parts of chlorinated butyl rubber CB1240, 10 parts of Keding resin MR14890A thermoplastic acrylic resin, 4 parts of reinforcing carbon black N550 for rubber, 5 parts of modified polyurethane toughening agent with a shell-core structure in preparation example 19, 60 parts of filler composition in preparation example 2, 0.5 part of antioxidant 1098, 0.1 part of antioxidant 168, 0.3 part of antioxidant 4020 and 0.1 part of nano silicon nitride powder with the average particle size of 800 nm.
Comparative example 15 differs from example 1 in that: the modified butyl rubber composite damping material for new energy automobile vibration and noise reduction is not compounded with special-shaped PP plate layers, and an aluminum foil layer and release paper are respectively compounded on the upper surface and the lower surface of the modified butyl rubber damping layer.
Performance test 1, high frequency damping performance test: the high frequency damping performance of the samples was tested on a VBT-Obest shock Liang Zhuaipan test system according to ASTME 756. The total thickness of the sample was 2.0mm, the width was 12.5mm and the length was 215mm. Specifically, the sample with the cut size is torn off from the release paper and is attached to a steel bar with the thickness of 1.0mm, the width of 12.5mm and the length of 241mm, the steel bar with the sample attached to be tested is vertically clamped at one end, and the steel bar is excited to vibrate at the excitation frequency of 1-1000HZ through a non-contact electromagnetic exciter near the free end; responses of the bars to various frequency excitations are measured by suitably positioned sensors and the vibration amplitude of the test bars is detected. Damping performance is expressed by loss factor, and is considered to meet application requirements when the loss factor of the sample at 1000HZ high frequency excitation is not less than 0.1. 2. The test method for testing the sound insulation performance comprises the following steps: according to GB/T19899.3-2005, the samples were evaluated for sound damping properties at a noise frequency of 2000 Hz. 3. Peel strength test method: according to GB/T2790, a peel force test was performed on a 25mm wide sample attached to a steel plate using a tensile machine at a tensile speed of 100mm/min. 4. Gao Wentie appendage Performance test: and (3) attaching a 10cm multiplied by 10cm sample to a 20cm multiplied by 20cm steel plate, standing for 24 hours, vertically placing the steel plate in a baking oven at 200 ℃ for 1 hour, and judging that the test sample does not slide on the steel plate for qualification, otherwise, judging that the test sample is disqualified.
Table 1 is a table of test parameters for the whole of the modified butyl rubber composite damping materials of examples 1 to 16 and comparative examples 1 to 15
It can be seen from the combination of example 10 and comparative example 1 and the combination of table 1 that the weight reduction performance (preferably the density of the modified butyl rubber composite damping material is 1.2-1.6g cm 3), the high-frequency vibration damping performance, and the sound insulation and noise reduction performance (the sound insulation of the modified butyl rubber composite damping material is >40 dB) of the prepared modified butyl rubber composite damping material can be improved by adopting the preparation method in the application.
It can be seen from the combination of examples 1 to 4 and comparative example 12 and the combination of table 1 that the filler composition provided in the application is used for improving the high-frequency damping performance and the sound insulation and noise reduction performance of the prepared modified butyl rubber composite damping material and simultaneously meeting the requirement of light weight.
It can be seen from the combination of example 4 and comparative example 13 and the combination of table 1 that the modified polyurethane toughening agent with the shell-core structure can improve the high-frequency damping performance and the sound insulation and noise reduction performance of the prepared modified butyl rubber composite damping material.
It can be seen from the combination of example 4 and comparative example 14 and the combination of table 1 that the use of the flake graphite instead of the reinforcing carbon black N550 for rubber has a positive effect on the high-frequency damping performance and the sound insulation and noise reduction performance of the prepared modified butyl rubber composite damping material.
As can be seen by combining example 4 and comparative example 10 and combining table 1, the modified polyurethane toughening agent with the shell-core structure prepared in preparation example 19 has obvious improvement on the high-frequency damping performance and the sound insulation and noise reduction performance of the prepared modified butyl rubber composite damping material.
As can be seen by combining the embodiment 4 and the comparative example 11 and combining the table 1, the high-frequency damping performance and the sound insulation and noise reduction performance of the modified butyl rubber composite damping material prepared by the antioxidant composition consisting of the antioxidant 1098, the antioxidant 168, the anti-aging agent 4020 and the nano silicon nitride powder in the mass ratio of 5:1:3:1 are relatively good, and the modified butyl rubber composite damping material is mainly characterized in that the modified butyl rubber composite damping material can reduce the thermal oxygen degradation rate in the extrusion processing process, has positive effects on the overall mechanical performance and the compact performance, and is assisted in improving the high-frequency damping performance and the sound insulation and noise reduction performance.
It can be seen from the combination of example 4 and example 14 and the combination of table 1 that the filler composition prepared by the molybdenum disulfide hybridized nano-sheet with the surface grafted multiwall carbon nano-tube has a little advantage on the high-frequency damping performance and the sound insulation and noise reduction performance of the prepared modified butyl rubber composite damping material compared with the boron nitride hybridized nano-sheet with the surface grafted carbon, and the filler composition prepared by the molybdenum disulfide hybridized nano-sheet with the surface grafted multiwall carbon nano-tube has a great improvement on the overall flame retardant and fireproof performance.
It can be seen from the combination of examples 4 and 15-16 and the combination of table 1 that the self-made TPU granules with the average particle diameter of 50-80 meshes can improve the high-frequency damping performance, the sound insulation and noise reduction performance of the prepared modified butyl rubber composite damping material, and can further improve the overall strong stripping, thereby further endowing the modified butyl rubber composite damping material with better service life and service stability.
It can be seen from the combination of examples 2, 4 to 13 and comparative examples 2 to 9 and the combination of table 1 that the modified butyl rubber composite damping material prepared by using the filler composition (preparation examples 1 to 4 and preparation examples 13 to 18) provided by the application can effectively meet the requirements of high-frequency damping performance and sound insulation and noise reduction performance of automobiles and simultaneously meet the requirement of light weight of new energy automobiles.
Preferred embodiment of the filler composition: the filler composition comprises the following fillers in percentage by mass: 28-30% of hollow glass beads, 5-6% of aramid nanofibers, 8-10% of alumina short fibers, 28-30% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 14-16% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.4-0.6% of tetrapod-like zinc oxide whiskers, 1.0-2.0% of halloysite nanotubes and the balance of 2000-mesh ultrafine calcium carbonate.
As can be seen by combining examples 2, 4-13 and comparative examples 2-9 and combining table 1, the modified butyl rubber composite damping material prepared by mixing the hollow glass beads of which the surfaces are grafted with the multiwall carbon nanotubes and the hollow glass beads of which the surfaces are grafted with the tin-bismuth alloy particles has better high-frequency damping performance, sound insulation and noise reduction performance requirements and meets the overall light weight requirements.
In conclusion, the modified butyl rubber composite damping material prepared by the method has good high-frequency damping performance, sound insulation and noise reduction performance and Gao Wentie attachment resistance, is low in overall density, and can meet the light-weight assembly requirement of new energy automobiles.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (9)
1. A modified butyl rubber composite damping material for new energy automobile vibration and noise reduction is characterized in that: the modified butyl rubber damping layer (1) is in composite connection with the release paper (4) on one surface and the special-shaped PP plate layer (2) on the other surface; one surface of the special-shaped PP plate layer (2) is in composite connection with the modified butyl rubber damping layer (1) and the other surface of the special-shaped PP plate layer is in composite connection with the aluminum foil layer (3); the modified butyl rubber damping layer (1) is mainly prepared from the following raw materials in parts by weight: 15-20 parts of butyl rubber, 5-10 parts of chlorinated butyl rubber, 8-12 parts of acrylic resin, 3-8 parts of scaly graphite, 4-8 parts of modified polyurethane toughening agent with a shell-core structure, 60-70 parts of filler composition and 0.4-1.2 parts of antioxidant composition;
The filler composition consists of the following fillers in percentage by mass: 28-30% of hollow glass beads, 5-6% of aramid nanofibers, 8-10% of alumina short fibers, 28-30% of synthetic fluorophlogopite hybrid powder with carbon grafted on the surface, 14-16% of boron nitride hybrid nano-sheets with carbon grafted on the surface, 0.4-0.6% of tetrapod-like zinc oxide whiskers, 1.0-2.0% of halloysite nanotubes and the balance of 2000-mesh ultrafine calcium carbonate;
The synthesized fluorophlogopite hybrid powder with the carbon grafted on the surface is synthesized fluorophlogopite hybrid powder with graphene and/or carbon nano tubes grafted on the surface; the surface-grafted carbon boron nitride hybrid nano-sheet is a surface-grafted graphene and/or carbon nano-tube boron nitride hybrid nano-sheet.
2. The modified butyl rubber composite damping material for new energy automobile vibration and noise reduction according to claim 1, which is characterized in that: the material is mainly prepared from the following raw materials in parts by weight: 15 parts of butyl rubber, 5 parts of chlorinated butyl rubber, 10 parts of acrylic resin, 4 parts of scaly graphite, 5 parts of modified polyurethane toughening agent with a shell-core structure, 60 parts of filler composition and 1 part of antioxidant composition.
3. The modified butyl rubber composite damping material for new energy automobile vibration and noise reduction according to claim 1, which is characterized in that: the alumina short fiber is formed by mixing alumina short fiber with the length of 0.5-1.0mm, alumina short fiber with the length of 1.0-3.0mm and alumina short fiber with the length of 3.0-5.0mm according to the mass ratio of 2:5:3.
4. The modified butyl rubber composite damping material for new energy automobile vibration and noise reduction according to claim 1, which is characterized in that: the hollow glass bead comprises a hollow glass bead of which the surface is grafted with the multiwall carbon nano tube and a hollow glass bead of which the surface is grafted with the tin-bismuth alloy particles, and the mass ratio of the hollow glass bead of which the surface is grafted with the multiwall carbon nano tube to the hollow glass bead of which the surface is grafted with the tin-bismuth alloy particles is (2-4): 6-8.
5. The modified butyl rubber composite damping material for new energy automobile vibration and noise reduction according to claim 4, which is characterized in that: the preparation method of the hollow glass microsphere with the surface grafted with the multiwall carbon nanotube comprises the following steps: firstly, preparing an Ag (2E 4 MI) 2Ac complex solution, wherein the Ag (2E 4 MI) 2Ac complex solution contains 0.7-1.2wt% of Ag (2E 4 MI) 2Ac complex and the balance of organic solvent; adding multi-wall carbon nano tubes and polyvinylpyrrolidone into an Ag (2E 4 MI) 2Ac complex solution, wherein the mass of the multi-wall carbon nano tubes is 0.08-0.15 times that of the Ag (2E 4 MI) 2Ac complex, the mass of the polyvinylpyrrolidone is 1.0-1.2 times that of the multi-wall carbon nano tubes, carrying out ultrasonic dispersion for 4-8 hours after the multi-wall carbon nano tubes and the polyvinylpyrrolidone are added, then adding hollow glass beads, the mass of the hollow glass beads is 60-120 times that of the multi-wall carbon nano tubes, continuing ultrasonic dispersion for 1-4 hours to obtain dispersion liquid, carrying out reduced pressure distillation on the obtained dispersion liquid to remove an organic solvent to obtain a solid, heating the obtained solid to 210-220 ℃ at 1-3 ℃/min, carrying out heat preservation for 200-300min, naturally cooling to room temperature in a furnace, and carrying out grinding treatment to obtain the hollow glass beads with the surface grafted with the multi-wall carbon nano tubes, wherein the average particle size of 30-120 micrometers.
6. The modified butyl rubber composite damping material for new energy automobile vibration and noise reduction according to claim 4, which is characterized in that: the preparation method of the hollow glass bead with the tin-bismuth alloy particles grafted on the surface comprises the following steps:
S1, under the conditions of room temperature and inert gas protection, stannous chloride and bismuth chloride are dissolved in ethanol according to a molar ratio of 42:58 to obtain a mixed solution A;
Simultaneously, under the protection of inert gas at room temperature, sodium borohydride is dissolved in water, and then hollow glass beads are added to be stirred and dispersed uniformly to obtain a mixed solution B, wherein the mole number of the sodium borohydride is 0.6 times of the total mole number of stannous chloride and bismuth chloride, and the mass of the hollow glass beads is 5-6 times of that of the sodium borohydride;
S2, dropwise adding the mixed solution A in the step S1 into the mixed solution B in the step S1 under the condition of room temperature and nitrogen protection, continuing to react for 30-40min after the dropwise adding is finished, standing for 30-60min after the reaction is finished, adding distilled water after supernatant liquid is poured out, standing, pouring out supernatant liquid, adding distilled water, and repeating for at least 3 times to obtain a precipitate;
And S3, placing the precipitate obtained in the step S2 at 80 ℃ and under the vacuum degree of 0.1Pa, and performing vacuum heating and drying treatment for 24 hours to obtain the hollow glass microsphere with the surface grafted with the Sn-Bi alloy particles.
7. The modified butyl rubber composite damping material for new energy automobile vibration and noise reduction according to claim 1, which is characterized in that: the preparation method of the modified polyurethane toughening agent with the shell-core structure comprises the following steps:
S1, preparing polyurethane prepolymer: weighing 1mol of aliphatic diisocyanate, 0.2-0.25mol of hydroxyl-terminated polybutadiene or polyoxypropylene glycol, 0.05-0.1mol of (E, E) -2, 4-hexadien-1-ol, 0.60mol of 1, 4-butanediol, 400-500g of acetone and 0.05-0.10g of organic bismuth catalyst, uniformly mixing, heating to 80 ℃, carrying out-NCO content detection on materials in a system after reaction for 4 hours, adding 0.08-0.12mol of hydroxyethyl methacrylate when the-NCO detection value in the system is stable, and continuing to react at 80 ℃ until the-NCO content in the system is lower than 0.1%, thus obtaining the target polyurethane prepolymer after the reaction is finished;
S2, uniformly mixing 0.3-0.4mol of acrylonitrile, 0.5-0.6mol of butadiene, 0.2-0.4mol of styrene, 4-5g of sodium styrene sulfonate and 0.4-0.6g of azodiisobutyronitrile, adding the mixture into the target polyurethane prepolymer prepared in S1, reacting at 80 ℃ for 60-75min, cooling to 55-58 ℃, adding 300-350g of deionized water, performing high-speed shearing and emulsification for 5-15min, and removing acetone in vacuum to obtain the modified polyurethane toughening agent with a shell-core structure, wherein the modified polyurethane toughening agent with the shell-core structure is used for interface modification of a filler composition.
8. The modified butyl rubber composite damping material for new energy automobile vibration and noise reduction according to claim 1, which is characterized in that: the antioxidant composition comprises an antioxidant 1098, an antioxidant 168, an anti-aging agent 4020 and nano silicon nitride powder in a mass ratio of 5:1:3:1.
9. A method for preparing the modified butyl rubber composite damping material for new energy automobile vibration and noise reduction as claimed in any one of claims 1 to 8, which is characterized in that: the method comprises the following steps:
Firstly, mixing and stirring the prepared filler composition with an aminosilane aqueous solution at 200-500rpm for 30-40min, wherein each liter of aminosilane aqueous solution contains 4-8g of aminosilane, the mass ratio of the filler composition to the aminosilane aqueous solution is (8-12): 100, carrying out ultrasonic dispersion treatment for 20-40min after stirring and mixing, leaching and drying to obtain a primary surface-treated filler composition, mixing and stirring the primary surface-treated filler composition with the prepared modified polyurethane toughening agent with a shell-core structure at 200-500rpm for 30-40min, leaching after uniform mixing, and drying to obtain a finished product surface-modified filler composition; 60-70 parts of the surface of the obtained finished product of the surface modified filler composition is adhered with 4-8 parts of modified polyurethane toughening agent with a shell-core structure;
Secondly, adding the accurately measured butyl rubber, acrylic resin, flake graphite, surface modified filler composition accounting for 60-75wt% of the total mass of the surface modified filler composition in the first step and antioxidant composition accounting for 40-60wt% of the total mass of the antioxidant composition into an open mill for mixing at 40-80 ℃ at 20-40rpm until the sizing material is smooth and has no obvious granular sensation;
Step three, accurately measured chlorinated butyl rubber, the rest surface modified filler composition and the antioxidant composition are put into an open mill for mixing at the temperature of 40-80 ℃ and the rotating speed of 20-40rpm until the sizing material is smooth and has no obvious granular feel;
And fourthly, putting the uniformly mixed sizing material into an extruder, extruding the sizing material into a continuous sheet at the temperature of 60-120 ℃, sequentially compounding a special-shaped PP plate layer (2) and an aluminum foil layer (3) on the upper layer of the obtained continuous sheet after hot pressing by a hot pressing roller, attaching release paper (4) on the lower layer of the sheet, putting the modified butyl rubber composite damping material cut into a target size into a standard-size mould pressing grinding tool, carrying out flat hot pressing treatment for 10-20s, and cooling to room temperature to obtain the finished modified butyl rubber composite damping material.
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