CN114853959B - Preparation method of clean nano organic silicon core-shell toughening powder - Google Patents
Preparation method of clean nano organic silicon core-shell toughening powder Download PDFInfo
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- CN114853959B CN114853959B CN202210514665.9A CN202210514665A CN114853959B CN 114853959 B CN114853959 B CN 114853959B CN 202210514665 A CN202210514665 A CN 202210514665A CN 114853959 B CN114853959 B CN 114853959B
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 63
- 239000000843 powder Substances 0.000 title claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 33
- 239000010703 silicon Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000839 emulsion Substances 0.000 claims abstract description 60
- 238000003756 stirring Methods 0.000 claims abstract description 50
- 239000007787 solid Substances 0.000 claims abstract description 39
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000006228 supernatant Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 20
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract 3
- 239000007788 liquid Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 13
- 239000003377 acid catalyst Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 230000001804 emulsifying effect Effects 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 229920002379 silicone rubber Polymers 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 239000004945 silicone rubber Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000006172 buffering agent Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229960000878 docusate sodium Drugs 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229940083542 sodium Drugs 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- IJRHDFLHUATAOS-DPMBMXLASA-M sodium ricinoleate Chemical compound [Na+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O IJRHDFLHUATAOS-DPMBMXLASA-M 0.000 claims description 2
- ITCAUAYQCALGGV-XTICBAGASA-M sodium;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Na+].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O ITCAUAYQCALGGV-XTICBAGASA-M 0.000 claims description 2
- KQSJSRIUULBTSE-UHFFFAOYSA-M sodium;3-(3-ethylcyclopentyl)propanoate Chemical compound [Na+].CCC1CCC(CCC([O-])=O)C1 KQSJSRIUULBTSE-UHFFFAOYSA-M 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 229940035044 sorbitan monolaurate Drugs 0.000 claims description 2
- 235000011071 sorbitan monopalmitate Nutrition 0.000 claims description 2
- 239000001570 sorbitan monopalmitate Substances 0.000 claims description 2
- 229940031953 sorbitan monopalmitate Drugs 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 229940087291 tridecyl alcohol Drugs 0.000 claims description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 230000003139 buffering effect Effects 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 20
- 239000011347 resin Substances 0.000 abstract description 20
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract description 2
- 238000007639 printing Methods 0.000 abstract description 2
- 238000007865 diluting Methods 0.000 abstract 1
- 238000011085 pressure filtration Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 10
- 229920000515 polycarbonate Polymers 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Images
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a preparation method of clean nano organic silicon core-shell toughening powder. Synthesizing nano organic silicon core-shell emulsion by a pre-emulsified seed emulsion polymerization mode, diluting the emulsion with deionized water, stirring and heating to a certain temperature, slowly dripping demulsifier until demulsification, stirring for a period of time, standing for a period of time at constant temperature, cooling and centrifuging to remove supernatant, adding deionized water, stirring, washing and centrifuging to remove supernatant for several times, stirring with hot water, washing, pressure filtration to remove water, repeating until no foam exists basically, drying the obtained solid, and crushing to obtain the clean nano organic silicon core-shell toughened powder. The clean nano organic silicon core-shell toughening powder prepared by the invention basically has no emulsifying agent, has the characteristics of good toughness, weather resistance, high and low temperature resistance, good compatibility with resin, good electrical property and the like, and has good application value in the fields of electronic appliances, aerospace, automobiles, printing ink and the like.
Description
Technical Field
The invention relates to the field of emulsion breaking, in particular to a preparation method of clean nano organic silicon core-shell toughening powder.
Background
The resin is an organic polymer which has a softening or melting range after being heated, has a flowing tendency under the action of external force during softening, is solid or semi-solid at normal temperature and can be liquid at some time. Any polymer compound that can be used as a raw material for processing plastic products is called a resin.
Resins are classified into two main categories, thermosetting and thermoplastic. The epoxy resin belongs to thermosetting resin, is easy to process and form, has low cost, excellent adhesive property, mechanical property, chemical stability, high and low temperature resistance and low shrinkage rate in the curing process. However, the epoxy resin has poor fatigue resistance and impact resistance due to high crosslinking density and low toughness after being cured, and the basic structure of the cured product determines the low temperature resistance level of the epoxy resin, so that the application of the epoxy resin in the high and new technical fields is limited to a great extent. Polycarbonates (PC) and Polyvinylchlorides (PVC) belong to the group of thermoplastic resins. The main chain of PC molecule contains rigid benzene ring, so that it has tough and rigid mechanical property, but at the same time, the crystallization capability of PC is poor, belonging to non-crystalline polymer. PC is poor in stress cracking resistance in mechanical property, belongs to notch sensitive materials, is low in fatigue strength, poor in chemical resistance and the like, and although ABS and PC are blended, the stress cracking resistance and notch sensitivity of PC can be improved, and the low-temperature impact strength of PC can be improved, but the requirement of products such as impact resistant products and the like on impact toughness still cannot be met in practical application. PVC is widely used as a general plastic with wide application, and is widely applied to the fields of sheets, plates, profiles, pipes and the like due to the excellent mechanical properties and low market price. However, due to the influence of the polar units on the molecular chain, the PVC has the defects of poor processability, poor thermal stability, poor impact strength, very sensitive notch and impurity and the like. Therefore, research on the toughening modification, impact resistance modification, and technological properties of resins has been a research hotspot.
The toughening modification method mainly focuses on toughening of rubber elastomer and thermoplastic resin. Rubber toughening often causes the elastic modulus and glass transition temperature of a modified system to be reduced, and is not suitable for being applied to occasions with higher high-temperature resistance requirements; the thermoplastic resin toughening resin has larger influence on viscosity, the infiltration capacity of the resin on fiber materials is reduced, and the process requirements of the hot-melt prepreg cannot be met. Therefore, resins having a combination of toughness, impact resistance, heat resistance, strength and excellent processability have been the development direction of resin modification.
The core-shell particles are toughening agents which take rubber as a core and polyacrylate as a shell, wherein the rubber core is used for providing impact resistance, and the polyacrylate can be well compatible with resin. When the core-shell particles are used, only the core-shell particles are blended with resin, the core-shell particles and the resin do not have the processes of compatibility and solidification phase separation, and the toughness of the system can be improved to a large extent under the condition of good dispersion. The addition of core-shell particles has less impact on the thermal properties of the epoxy resin because no rubber is dissolved in the resin. In addition, the core-shell particle toughening agent has less influence on the viscosity of the system than the rubber toughening agent.
The organosilicon core-shell powder has a plurality of advantages in the process of toughening the resin. Because the Si-O bond has high bond energy and long bond length, the organic silicon core-shell powder has very obvious advantages in the aspect of high and low temperature resistance, and meanwhile, the soft molecular chain and the lower glass transition temperature enable the organic silicon core-shell powder to obviously improve the low-temperature notch impact resistance and the processing performance of the resin in the process of toughening the resin, which is definitely significant for the use of the resin.
Non-patent literature (Yueyei Li. ACS Applied Materials & Interfaces 2020 12 (4)), 4917-4926 reports that a nano silicon rubber core-shell structure polymer is prepared by taking polysiloxane as a core and methyl methacrylate and glycidyl methacrylate as shells, demulsifies, filter presses at normal temperature, cools and dries, and is used in 3D printing resin, and the fracture toughness is greatly improved on the premise of not losing mechanical strength and thermal performance. However, this method has the following features: (1) After emulsion breaking at normal temperature, the filter pressing time is long and the large-scale production is not easy. (2) The freeze-drying time is long, and the industrial production is impossible. Therefore, how to simply prepare the organic silicon core-shell toughening powder on a large scale and obtain the clean nano organic silicon core-shell toughening powder has great technical challenges.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a preparation method of clean nano organic silicon core-shell toughening powder.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation process of the clean nanometer organosilicon core-shell toughening powder includes the following steps:
(1) 1-30 parts of demulsifier and 50-150 parts of water by weight are mechanically stirred and dissolved to obtain demulsification liquid;
adding 20-200 parts of water into 100 parts of nano organic silicon core-shell emulsion, stirring to obtain diluted emulsion, and heating to 50-100 ℃;
(2) Slowly adding 50-180 parts by weight of demulsification solution into the diluted emulsion to carry out demulsification, continuously stirring for 5-40min after the dropwise addition, standing at a constant temperature for 10-30min, and finally standing and cooling to room temperature;
(3) Centrifuging the cooled liquid for 5-30min by a centrifuge, removing supernatant, adding 20-100 parts of water into the lower layer solid, stirring and washing for 5-30min, centrifuging again to remove supernatant, repeating for 2-10 times, and collecting solid;
(4) Adding 20-100 parts by weight of water into the collected solid, heating to 50-100 ℃, stirring and washing for 5-30min, and then performing filter pressing through a filter press and filter paper, thereby repeating the steps for 2-10 times;
(5) The obtained solid is dried for 1 to 6 hours at 50 to 150 ℃, and crushed for 1 to 20 minutes by a crusher to obtain the clean nano organosilicon core-shell toughening powder.
Preferably, the demulsifier in the step (1) is one or a combination of calcium chloride, magnesium sulfate, aluminum sulfate, sodium chloride and ammonium sulfate.
The synthetic route of the nano organic silicon core-shell emulsion in the step (1) is shown in the attached figure 1, and the preparation method comprises the following steps:
(a) By weight, 500 parts of organosilicon monomer, 2-50 parts of emulsifier, 10-80 parts of silane coupling agent, 10-80 parts of vinyl silane coupling agent and 250-400 parts of deionized water are emulsified for 3-10 min by a high-shear emulsifying machine to obtain organosilicon pre-emulsion; 2-30 parts of acid catalyst and 200-250 parts of deionized water are uniformly mixed to obtain acid catalyst liquid;
(b) 1-25 parts of emulsifying agent and 40-160 parts of deionized water by weight are mechanically stirred and heated to 40-70 ℃, organosilicon pre-emulsion with the preparation amount of 1-20% and acid catalyst with the preparation amount of 5-40% in the step (a) are added, the mixture is heated to 70-95 ℃ and reacts for 15-60 min, after the rest organosilicon pre-emulsion and acid catalyst are added dropwise in 1-4 h, the mixture is reacted for 2-6 h at constant temperature, the PH is adjusted to 5-9 by ammonia water, and nano silicone rubber nuclear emulsion is obtained by filtration;
(c) 5-50 parts by weight of double bond-containing monomer, 0.01-5 parts by weight of emulsifier and 3-30 parts by weight of deionized water are emulsified for 3-10 min by a high shear emulsifying machine to obtain double bond-containing pre-emulsion; stirring and dissolving 0-1 part of buffering agent and 0-10 parts of deionized water to obtain a buffer solution; stirring and dissolving 0.01-5 parts of catalyst and 1-200 parts of deionized water to obtain a catalytic solution;
(d) 100 parts of nano silicone rubber core emulsion, 0.01-5 parts of emulsifying agent, 0-50 parts of deionized water and the buffer solution prepared in the step (c) are stirred and heated to 40-90 ℃, the double bond-containing pre-emulsion and the catalytic liquid prepared in the step (c) are dropwise added in 1-4 h, then the mixture is subjected to constant temperature reaction for 2-6 h, the pH is regulated to 6-9 by ammonia water, and the nano organic silicone core-shell emulsion is prepared by filtering;
wherein the organic silicon monomer in the step (a) is one of hexamethylcyclotrisiloxane, octamethyl cyclotetrasiloxane and low molecular weight hydroxyl silicone oil; the emulsifier in the steps (a) - (d) is one or a combination of docusate sodium, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, dodecyl benzene sulfonic acid, sodium didodecyl phenyl ether disulfonate, sodium abietate, sodium naphthenate, sodium ricinoleate, isomeric tridecyl alcohol ether, polyoxyethylene Zhong Xinfen ether-10, sorbitan monolaurate and sorbitan monopalmitate; the silane coupling agent in the step (a) is one or a combination of methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane and tetraethyl silicate; the vinyl silane coupling agent in the step (a) is one or a combination of gamma- (methacryloxy) propyl trimethoxy silane, vinyl trimethoxy silane and vinyl triethoxy silane; the acid catalyst in the step (a) is one or a combination of benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, hydrochloric acid and sulfuric acid; the monomer containing double bonds in the step (c) is one or a combination of styrene, methyl methacrylate, butyl acrylate, isooctyl acrylate, acrylic acid and lauryl methacrylate; the buffering agent in the step (c) is one or a combination of sodium bicarbonate, sodium formate, sodium acetate, ammonium acetate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium pyrophosphate and sodium phosphate; the catalyst in the step (c) is one of ammonium persulfate and potassium persulfate.
According to the technical scheme, the nano organic silicon core-shell emulsion is synthesized in a pre-emulsified seed emulsion polymerization mode, the emulsion is diluted by deionized water, stirred and heated to a certain temperature, demulsifier is slowly added dropwise until demulsification is performed, stirred for a period of time, kept at a constant temperature for a period of time, cooled and centrifuged to remove supernatant, deionized water is added, stirred, washed and centrifuged to remove supernatant for several times, hot water is added, stirred, washed, pressed and filtered to remove water, the water is removed until no foam is basically generated, and the obtained solid is dried and crushed to obtain the clean nano organic silicon core-shell toughening powder. Compared with the prior art, the invention has the beneficial effects that:
1. under the heating condition, the demulsification liquid can easily demulsify the nano organic silicon core-shell emulsion and can more easily wash out the emulsifier.
2. The invention firstly uses centrifugation to wash out most of the emulsifying agent, has simple and quick operation and is beneficial to mass production.
3. The invention is washed and filter-pressed under heating, which is not only beneficial to the washing of the emulsifier, but also ensures that the nano organic silicon core-shell toughening powder is easy to filter-press.
4. The preparation method is simple to operate and low in cost, and the obtained nano organic silicon core-shell toughening powder is clean and can be produced in a large scale.
5. The clean nano organic silicon core-shell toughening powder prepared by the invention basically has no emulsifying agent, has the characteristics of good toughness, weather resistance, high and low temperature resistance, good compatibility with resin, good electrical property and the like, and has good application value in the fields of electronic appliances, aerospace, automobiles, printing ink and the like.
Drawings
FIG. 1 is a synthetic route diagram of the nano-silicone core-shell emulsion of the present invention.
Fig. 2 is a TEM image of the clean nano silicone core-shell toughening powder prepared in example 1 of the present invention.
FIG. 3 is a diagram of a clean nano silicone core-shell toughening powder prepared according to example 1 of the present invention.
Detailed Description
In order to further explain the technical scheme of the invention, the invention is explained in detail by specific examples.
Example 1
(1) 7.5g of magnesium sulfate and 42.5g of water are added into a beaker, and are mechanically stirred and dissolved to obtain demulsification liquid;
100g of water is added into 100g of nano organic silicon core-shell emulsion (solid content is 45 percent, average grain diameter is 200 nm), diluted emulsion is obtained by stirring, and the temperature is raised to 80 ℃;
(2) Slowly adding 50g of demulsification solution into the diluted emulsion to carry out demulsification, continuously stirring for 5min after the dropwise addition, standing for 30min at constant temperature, and finally standing and cooling to room temperature;
(3) Adding the cooled liquid into a centrifugal cup, centrifuging for 5min, removing supernatant, adding 50g of water into the lower layer solid, stirring and washing for 10min, centrifuging again to remove supernatant, and repeating for 3 times;
(4) Adding 50g of water into the solid after centrifugation, heating to 90 ℃, stirring and washing for 10min, and then performing filter pressing through a filter press and filter paper, thereby repeating the process for 2 times;
(5) The obtained solid is dried for 5 hours at 85 ℃, and crushed for 2 minutes by a crusher to obtain 43.8g of clean nano organic silicon core-shell toughening powder.
Referring to fig. 2, a TEM image of the clean nano-silicone core-shell toughening powder prepared in example 1 of the present invention shows that the powder has a nano-structure and an obvious core-shell structure.
Referring to fig. 3, the powder pattern of the clean nano organic silicon core-shell toughening powder prepared in the embodiment 1 of the invention is white powder, and the particles are uniform.
Example 2
(1) Adding 10g of sodium chloride and 40g of water into a beaker, and mechanically stirring and dissolving to obtain demulsification liquid; adding 150g of water into 100g of nano organic silicon core-shell emulsion (solid content is 45%, average grain diameter is 200 nm), stirring to obtain diluted emulsion, and heating to 80 ℃;
(2) Slowly adding 50g of demulsification solution into the diluted emulsion to carry out demulsification, continuously stirring for 10min after the dropwise addition, standing at constant temperature for 10min, and finally standing and cooling to room temperature;
(3) Adding the cooled liquid into a centrifugal cup, centrifuging for 2min, removing supernatant, adding 100g of water into the lower layer solid, stirring and washing for 5min, centrifuging again to remove supernatant, and repeating for 2 times;
(4) Adding 80g of water into the solid after centrifugation, heating to 90 ℃, stirring and washing for 10min, and then performing filter pressing through a filter press and filter paper, thereby repeating the process for 2 times;
(5) The obtained solid is dried for 5 hours at 85 ℃, and crushed for 2 minutes by a crusher to obtain 43.0g of clean nano organic silicon core-shell toughening powder.
Example 3
(1) Adding 15g of magnesium sulfate and 85g of water into a beaker, and mechanically stirring and dissolving to obtain demulsification liquid; 100g of water is added into 100g of nano organic silicon core-shell emulsion (solid content is 45 percent, average grain diameter is 200 nm), and the mixture is stirred to obtain diluted emulsion, and the temperature is raised to 90 ℃;
(2) Slowly adding 100g of demulsification solution into the diluted emulsion to carry out demulsification, continuously stirring for 5min after the dropwise addition, standing at constant temperature for 10min, and finally standing and cooling to room temperature;
(3) Adding the cooled liquid into a centrifugal cup, centrifuging for 2min, removing supernatant, adding 100g of water into the lower layer solid, stirring and washing for 15min, centrifuging again to remove supernatant, and repeating for 5 times;
(4) Adding 150g of water into the solid after centrifugation, heating to 80 ℃, stirring and washing for 10min, and then performing filter pressing through a filter press and filter paper, thereby repeating the process for 2 times;
(5) The obtained solid is dried for 5 hours at 85 ℃, and crushed for 2 minutes by a crusher to obtain 42.9g of clean nano organosilicon core-shell toughening powder.
Example 4
(1) Adding 5g of aluminum sulfate and 45g of water into a beaker, and mechanically stirring and dissolving to obtain demulsification liquid; adding 150g of water into 100g of nano organic silicon core-shell emulsion (solid content is 45%, average grain diameter is 200 nm), stirring to obtain diluted emulsion, and heating to 80 ℃;
(2) Slowly adding 50g of demulsification solution into the diluted emulsion to carry out demulsification, continuously stirring for 5min after the dropwise addition, standing for 30min at constant temperature, and finally standing and cooling to room temperature;
(3) Adding the cooled liquid into a centrifugal cup, centrifuging for 2min, removing supernatant, adding 25g of water into the lower layer solid, stirring and washing for 5min, centrifuging again to remove supernatant, and repeating for 3 times;
(4) After centrifugation, adding 150g of water into the solid, heating to 75 ℃, stirring and washing for 15min, and then, carrying out filter pressing through a filter press and filter paper, thereby repeating the process for 2 times;
(5) The obtained solid is dried for 3 hours at 95 ℃, and crushed for 3 minutes by a crusher to obtain 43.3g of clean nano organosilicon core-shell toughening powder.
Example 5
(1) Adding 5g of calcium chloride and 95g of water into a beaker, and mechanically stirring and dissolving to obtain demulsification liquid; 100g of water is added into 100g of nano organic silicon core-shell emulsion (solid content is 45 percent, average grain diameter is 200 nm), and the mixture is stirred to obtain diluted emulsion, and the temperature is raised to 90 ℃;
(2) Slowly adding 100g of demulsification solution into the diluted emulsion to carry out demulsification, continuously stirring for 20min after the dropwise addition, standing at constant temperature for 10min, and finally standing and cooling to room temperature;
(3) Adding the cooled liquid into a centrifugal cup, centrifuging for 3min, removing supernatant, adding 100g of water into the lower layer solid, stirring and washing for 15min, centrifuging again to remove supernatant, and repeating for 2 times;
(4) After centrifugation, adding 150g of water into the solid, heating to 100 ℃, stirring and washing for 15min, and then, carrying out filter pressing through a filter press and filter paper, thereby repeating the process for 2 times;
(5) The obtained solid is dried for 6 hours at 80 ℃, and crushed for 2 minutes by a crusher to obtain 43.7g of clean nano organosilicon core-shell toughening powder.
Example 6
(1) Adding 20g of ammonium sulfate and 80g of water into a beaker, and mechanically stirring and dissolving to obtain demulsification liquid; 100g of water is added into 100g of nano organic silicon core-shell emulsion (solid content is 45 percent, average grain diameter is 200 nm), and the mixture is stirred to obtain diluted emulsion, and the temperature is raised to 85 ℃;
(2) Slowly adding 100g of demulsification solution into the diluted emulsion to carry out demulsification, continuously stirring for 20min after the dropwise addition, standing at constant temperature for 10min, and finally standing and cooling to room temperature;
(3) Adding the cooled liquid into a centrifugal cup, centrifuging for 2min, removing supernatant, adding 100g of water into the lower layer solid, stirring and washing for 10min, centrifuging again to remove supernatant, and repeating for 8 times;
(4) Adding 100g of water into the solid after centrifugation, heating to 90 ℃, stirring and washing for 10min, and then performing filter pressing through a filter press and filter paper, thereby repeating the process for 2 times;
(5) The obtained solid is dried for 5 hours at 85 ℃, and crushed for 2 minutes by a crusher to obtain 42g of clean nano organosilicon core-shell toughening powder.
Example 7
In examples 1-6, the preparation method of the nano-silicone core-shell emulsion (solid content 45%, average particle size 200 nm) is as follows:
(1) Sequentially adding 1.3g of sodium dodecyl benzene sulfonate, 50g of deionized water, 100g of octamethyl cyclotetrasiloxane, 4g of methyltriethoxysilane and 2g of gamma-methacryloxypropyl trimethoxysilane into a beaker, and emulsifying for 3min by a high-shear emulsifying machine to obtain an organosilicon pre-emulsion; adding 0.7g of sulfuric acid and 50g of deionized water into a beaker, and stirring and mixing uniformly to obtain an acid catalytic liquid.
(2) Adding 1g of sodium dodecyl benzene sulfonate and 20g of deionized water into a four-necked flask with a constant-temperature water bath jacket provided with a reflux condenser and a mechanical stirrer, stirring and heating to 55 ℃, adding 6% of organosilicon pre-emulsion and 10% of acid catalyst liquid, heating to 75 ℃ for reacting for 60min, dropwise adding the rest of organosilicon pre-emulsion and acid catalyst liquid within 2h, reacting at constant temperature for 5h, adjusting the PH to 8 by ammonia water, and filtering to obtain the nano silicone rubber nuclear emulsion with the solid content of 47% and the average particle size of 150 nm.
(3) Sequentially adding 0.2g of sodium dodecyl benzene sulfonate, 10g of deionized water and 20g of methyl methacrylate into a beaker, and emulsifying for 3min by a high-shear emulsifying machine to obtain methyl methacrylate emulsion; adding 0.2g of sodium bicarbonate and 2g of deionized water into a beaker, and stirring and mixing uniformly to obtain a buffer solution; adding 0.1g of potassium persulfate and 12g of deionized water into a beaker, and stirring and mixing uniformly to obtain a catalytic liquid.
(4) Adding 0.1g of sodium dodecyl benzene sulfonate, 10g of deionized water, nano silicone rubber core-shell emulsion and buffer solution into a four-necked flask with a constant-temperature water bath jacket provided with a reflux condenser and a mechanical stirrer, stirring and heating to 85 ℃, dropwise adding methyl methacrylate pre-emulsion and catalytic liquid within 1.5h, performing constant-temperature reaction for 2h, adjusting the pH to 7 by ammonia water, and filtering to obtain the nano silicone rubber core-shell structure polymer emulsion with the solid content of 45% and the average particle size of 200 nm.
Claims (6)
1. The preparation method of the clean nano organic silicon core-shell toughening powder is characterized by comprising the following steps of:
(1) 1-30 parts of demulsifier and 50-150 parts of water by weight are mechanically stirred and dissolved to obtain demulsification liquid;
adding 20-200 parts of water into 100 parts of nano organic silicon core-shell emulsion, stirring to obtain diluted emulsion, and heating to 50-100 ℃;
the preparation method of the nano organic silicon core-shell emulsion in the step (1) comprises the following steps:
(a) Emulsifying the organosilicon monomer, the emulsifier, the silane coupling agent, the vinyl silane coupling agent and the deionized water by a high-shear emulsifying machine for 3-10 min to obtain organosilicon pre-emulsion;
uniformly mixing an acid catalyst and deionized water to obtain an acid catalyst solution;
the silane coupling agent is one or a combination of methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane and tetraethyl silicate;
(b) Mechanically stirring and heating the emulsifying agent and deionized water to 40-70 ℃, adding the organosilicon pre-emulsion with the preparation amount of 1-20% and the acid catalyst liquid with the preparation amount of 5-40% in the step (a), heating to 70-95 ℃ and reacting for 15-60 min, then dropwise adding the rest organosilicon pre-emulsion and the acid catalyst liquid in 1-4 h, reacting for 2-6 h at constant temperature, adjusting the pH to 5-9 by ammonia water, and filtering to obtain the nano silicone rubber nuclear emulsion;
(c) Emulsifying the double bond-containing monomer, the emulsifier and the deionized water by a high-shear emulsifying machine for 3-10 min to obtain double bond-containing pre-emulsion;
stirring and dissolving a buffering agent and deionized water to obtain a buffering solution;
stirring and dissolving the catalyst and deionized water to obtain a catalytic solution;
the monomer containing double bonds is one or the combination of styrene, methyl methacrylate, butyl acrylate, isooctyl acrylate, acrylic acid and lauryl methacrylate;
(d) Stirring and heating the nano silicone rubber core emulsion, the emulsifier, the deionized water and the buffer solution prepared in the step (c) to 40-90 ℃, dropwise adding the double bond-containing pre-emulsion prepared in the step (c) and the catalytic liquid in 1-4 h, reacting at constant temperature for 2-6 h, adjusting pH to 6-9 by ammonia water, and filtering to obtain the nano organic silicone core-shell emulsion;
(2) Slowly adding 50-180 parts by weight of demulsification solution into the diluted emulsion to carry out demulsification, continuously stirring for 5-40min after the dropwise addition, standing at a constant temperature for 10-30min, and finally standing and cooling to room temperature;
(3) Centrifuging the cooled liquid by a centrifuge to remove supernatant, adding 20-100 parts of water into the lower layer of solid, stirring and washing, centrifuging again to remove supernatant, repeating the process for 2-10 times, and collecting the solid;
(4) Adding 20-100 parts by weight of water into the collected solid, heating to 50-100 ℃, stirring and washing for 5-30min, and then performing filter pressing through a filter press and filter paper, thereby repeating the steps for 2-10 times;
(5) The obtained solid is dried for 1 to 6 hours at the temperature of 50 to 150 ℃ and crushed by a crusher, thus obtaining the clean nano organosilicon core-shell toughening powder.
2. The method for preparing the clean nano-organosilicon core-shell toughening powder according to claim 1, wherein the demulsifier in the step (1) is one or a combination of calcium chloride, magnesium sulfate, aluminum sulfate, sodium chloride and ammonium sulfate.
3. The method for preparing the clean nano-organosilicon core-shell toughening powder according to claim 1, wherein in the preparation process of the preparation method of the nano-organosilicon core-shell emulsion, the organosilicon monomer in the step (a) is one of hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane and low-molecular-weight hydroxyl silicone oil; the emulsifier in the steps (a) - (d) is one or a combination of docusate sodium, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, dodecyl benzene sulfonic acid, sodium didodecyl phenyl ether disulfonate, sodium abietate, sodium naphthenate, sodium ricinoleate, isomeric tridecyl alcohol ether, polyoxyethylene Zhong Xinfen ether-10, sorbitan monolaurate and sorbitan monopalmitate; the vinyl silane coupling agent in the step (a) is one or a combination of gamma- (methacryloxy) propyl trimethoxy silane, vinyl trimethoxy silane and vinyl triethoxy silane; the acid catalyst in the step (a) is one or a combination of benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, hydrochloric acid and sulfuric acid; the buffering agent in the step (c) is one or a combination of sodium bicarbonate, sodium formate, sodium acetate, ammonium acetate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium pyrophosphate and sodium phosphate; the catalyst in the step (c) is one of ammonium persulfate and potassium persulfate.
4. The method for preparing the clean nano-organosilicon core-shell toughening powder according to claim 1, wherein the centrifugation time of the step (3) is 5-30min.
5. The method for preparing the clean nano-organosilicon core-shell toughening powder according to claim 1, wherein the stirring and washing time of the step (4) is 5-30min.
6. The method for preparing the clean nano-organosilicon core-shell toughening powder according to claim 1, wherein the drying temperature in the step (5) is 50-150 ℃, the drying time is 1-6h, and the crushing time is 1-20min.
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