CN106433098B - 一种石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备方法 - Google Patents
一种石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备方法 Download PDFInfo
- Publication number
- CN106433098B CN106433098B CN201610861193.9A CN201610861193A CN106433098B CN 106433098 B CN106433098 B CN 106433098B CN 201610861193 A CN201610861193 A CN 201610861193A CN 106433098 B CN106433098 B CN 106433098B
- Authority
- CN
- China
- Prior art keywords
- graphene
- silicon
- polyurethane
- polyacrylate
- hyperbranched
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 75
- 239000004814 polyurethane Substances 0.000 title claims abstract description 68
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 38
- 239000010703 silicon Substances 0.000 title claims abstract description 38
- 239000000839 emulsion Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 239000004970 Chain extender Substances 0.000 claims abstract description 16
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229920002545 silicone oil Polymers 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000006185 dispersion Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 229920000058 polyacrylate Polymers 0.000 claims description 18
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 butyl acrylate compound Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 150000002009 diols Chemical class 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 230000001804 emulsifying effect Effects 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 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 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000004317 sodium nitrate Substances 0.000 claims description 8
- 235000010344 sodium nitrate Nutrition 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 claims description 6
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 claims description 2
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 claims description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229940117969 neopentyl glycol Drugs 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 229920000587 hyperbranched polymer Polymers 0.000 abstract description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000011219 quaternary composite Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 11
- 238000000576 coating method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 239000013035 waterborne resin Substances 0.000 description 2
- 229920006313 waterborne resin Polymers 0.000 description 2
- DBXBTMSZEOQQDU-UHFFFAOYSA-N 3-hydroxyisobutyric acid Chemical compound OCC(C)C(O)=O DBXBTMSZEOQQDU-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/10—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种石墨烯/聚丙烯酸酯‑含硅超支化水性聚氨酯多元复合乳液制备方法,首先采用改进Hummers法制备氧化石墨烯,用乙二胺对GO改性后与丙烯酸丁酯反应引入双键(MGO),然后与丙烯酸酯类单体在DMF中进行溶液聚合制备MGO/PA溶液;同时以二异氰酸酯、低聚物二元醇以及扩链剂,通过超支化聚合物扩链法,在多羟基亲水性超支化聚氨酯核外围接枝原位聚合制备的部分双键封端的羟基硅油改性的线性聚氨酯预聚体,与MGO/PA混合后缩聚并交联,获得氨基化氧化石墨烯/聚丙烯酸酯‑含硅超支化聚氨酯四元复合乳液。
Description
技术领域
本发明属高分子材料技术领域,尤其涉及一种石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备方法。
背景技术
聚氨酯(PU)材料的综合性能优良,在塑料、橡胶、涂料、粘合剂、织物整理剂以及生物医用材料等领域均有广泛应用。鉴于涂料工业发展方向日益趋向于依照“三前提”(资源、能源、无污染)和遵从“四E原则”(经济economy、效率efficiency、生态ecology、能源energy),更多聚氨酯材料的开发逐渐转变为产品的水性化、组分的复合化以及应用的功能化。相应于环保日益强化的时代要求,水性聚氨酯涂料取代传统溶剂型材料,凭借其无污染、运输安全、中毒和着火的几率低等特点脱颖而出。相对于传统线性水性聚氨酯材料,超支化聚氨酯不但具有聚氨酯材料的优异性能,还拥有超支化聚合物所具有的共同特点,如低黏度、良好的溶解性、较高的反应活性、优良的成膜性能等。然而水性聚氨酯材料强度不高,且耐水性、耐热性、光泽性较差,因此限制了其进一步的应用。
聚丙烯酸酯(PA)具有优异的耐光性、耐候性和优良的力学性能。有机硅结构中含有硅元素,属于半有机半无机结构的高分子物质,因此兼有有机、无机两种化合物的特性,比如耐低温,耐气候老化,憎水等。另外,近年来发展起来的石墨烯作为一种新型的“至薄、至坚”炭质晶体材料,具有极强的抗形变能力(模量可达1012Pa)和抵抗破坏能力(强度可达109Pa),且石墨烯片层的共轭结构能够形成致密的绝缘层,阻止水分浸润或渗透到涂膜中,且又因表面疏水特性,材料受到物理防腐和电化学双重防腐保障,因此石墨烯与聚氨酯材料的复合,很大程度上使石墨烯聚合物复合涂层的很多方面的性能得到有效的改善和提高,获得性能更加优异的高分子纳米复合材料,两者的复合不仅拓宽了各自的应用领域,还使得它们的研究和开发具有更大的应用价值。石墨烯层与层之间的范德华力很强,其本身非亲油、亲水,且在高分子基体中自身易团聚,导致GE在复合基材料中的相容性和分散性很差,很大程度上限制了其与聚合物材料之间的复合。因此,在实际应用中,研究者们往往首先利用在制备石墨烯过程中产生的缺陷和活性基团进行改性,以增强其与高分子聚合物的亲和性,减少自身团聚等负影响,从而使石墨烯更好地同聚合物基体进行复合。
虽然很多研究者在近几年以多种方法合成了石墨烯/聚氨酯复合材料,仍存在一定的不足。中国专利CN104059395A提供了一种以苝酐为原料制备苝酰亚胺聚氨酷液晶,然后采取非共价方式修饰石墨烯,能后实现在树脂基体中的均匀分散,但非共价方式的作用力往往低于采用接枝改性等共价方式获得复合物的相互作用。中国专利CN104761882A将制备的氧化石墨烯的水分散液与水溶性聚氨酯进行物理共混获得石墨烯/聚氨酯复合材料,也是采用非共价方式键和,作用力不强。中国专利CN105176067A制备出单层氧化石墨烯,低温条件下在水性聚氨酯预聚体成盐乳化阶段与其共混制备了单层氧化石墨烯改性水性聚氨酯复合材料,实际应用中,单层的氧化石墨烯很难制备,且温度稍高,其自身就易发生团聚。
本发明先采用小分子二元胺对氧化石墨烯进行接枝共价改性,增加片层间的间距,使氧化石墨烯片层剥离得更完全些,然后与丙烯酸酯反应引入双键,可与多种丙烯酸酯类单体共聚,功能化石墨烯的羟基等反应官能团将与剩余-NCO继续反应,且体积庞大的超支化分子共价接枝在石墨烯边缘和表面,使石墨烯片层之间的间距逐步增大的同时,分子量较小的支链聚合物将填充在石墨烯片层间,形成部分插层结构,同时功能化的石墨烯与聚氨酯之间也通过氢键作用使乳液分散更均匀、稳定。
发明内容
本发明目的在于制备一种与高分子基体具有很好相容性的改性氧化石墨烯分散液,然后与丙烯酸酯聚合,与含硅超支化聚氨酯预聚体复合,提供了一种制备石墨烯/聚丙烯酸酯-含硅超支化聚氨酯多元复合材料得方法。
本发明具体技术方案如下:
一种石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备方法,
其特征在于,包括以下具体步骤:
(1)冰水浴冷却下,将一定计量比的石墨粉、硝酸钠、质量分数为98%浓硫酸混合并搅拌1~5min,缓慢分步加入高锰酸钾,约1.5h完成后,继续搅拌1-1.2h,30~40℃保温1~2d,缓慢滴加少量去离子水进行稀释,加入大量水继续搅拌,随后缓慢滴加30%左右的过氧化氢溶液,充分搅拌后加入稀盐酸溶液进行洗涤,静置,沉淀,除去上层清液后,使用大量去离子水进行反复洗涤、离心、沉淀至溶液呈弱酸性,经超声和高速离心后,上层清液即GO分散液;
(2)将步骤(1)所得GO分散液冷冻干燥或30~50℃真空干燥,取一定量干燥后的GO重新分散在溶剂N,N-二甲基甲酰胺中,超声剥离2h以上得到GO的DMF分散液,常温快速搅拌下滴加乙二胺,惰性气体保护反应24-26h,加入与乙二胺等摩尔比的丙烯酸丁酯反应48-50h,获得进一步乙二胺化氧化石墨烯MGO的DMF分散液;
(3)惰性气体保护下,将二异氰酸酯与二元醇亲水扩链剂于60~90℃反应1~4h,冰盐浴冷却至0℃左右,缓慢滴加二羟基仲胺的DMF溶液,约1~2.5h完成后继续反应0.5~2h,升温至60~90℃,反应2~4h,获得多羟基超支化聚氨酯HBPU-0;
惰性气体保护下,将二异氰酸酯,低聚物二元醇和小分子羟硅于70~90℃保温1~4h,加入小分子扩链剂,于70~90℃反应0.5~5h,反应过程中加入1~3滴催化剂,加入适量丙酮降低体系粘度使得搅拌器顺利搅拌即可,按计量比加入所制多羟基超支化聚氨酯HBPU-0作为核,于60~100℃反应1~5h,获得含硅超支化聚氨酯预聚体,保温备用;上述低聚物二元醇、小分子扩链剂与二异氰酸酯基摩尔比为1:1~3:3~7,小分子羟硅为超支化聚氨酯总质量的1~7%;
(4)取一定量步骤(2)所制乙二胺化氧化石墨烯MGO的DMF分散液,与按照质量比约1:1混合的甲基丙烯酸甲酯、丙烯酸丁酯复配单体混合,于60~80℃反应2~4h,加入混有引发剂的含羟基丙烯酸酯单体,引发剂量为上述含羟基丙烯酸酯单体总量的0.1~0.5%,继续反应1~3h,获得含有羟基的乙二胺化氧化石墨烯/聚丙烯酸酯溶液MGO/PA;步骤(3)的含硅超支化聚氨酯预聚体降温至30~40℃,与MGO/PA溶液混合均匀后,与体系中含亲水基团二元醇等摩尔中和,高速均质乳化机作用下,加入混有乙二胺的蒸馏水,乳化3~5min,减压蒸馏除去丙酮,获得超支化多元复合乳液;其中,上述乳化机转速800~1300r/min,蒸馏水量使乳液固含约30~40%之间,乙二胺量与剩余异氰酸酯基等摩尔。
所述石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液,其特征在于:步骤(1)制备GO所用的硝酸钠、浓硫酸、高锰酸钾、首次稀释用去离子水和石墨粉质量比为0.5~1:40~85:3~6:30~50:1。
所述石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液,其特征在于:步骤(2)所用乙二胺、丙烯酸丁酯与氧化石墨质量比为0.3~1:0.15~0.5:0.1。
所述石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液,其特征在于:所述的小分子扩链剂指的是亲水基团二元醇、简单二元醇中的一种或两种。
所述石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液,其特征在于:步骤(3)所用二异氰酸酯为异佛尔酮二异氰酸酯IPDI、甲苯二异氰酸酯TDI、二苯甲烷二异氰酸酯MDI、1,6-己二异氰酸酯HDI中的一种或几种的混合物;
步骤(3)所用低聚物二元醇为聚氧化丙烯二醇、聚四氢呋喃二醇、聚碳酸酯二醇、聚己内酯二醇、聚丙二醇中的至少一种。
步骤(3)所用小分子扩链剂亲水基团二元醇,简单二元醇,二羟基仲胺与二异氰酸酯摩尔比为1:1:4~9:3~6;
步骤(3)所用亲水基团二元醇为而羟甲基丙酸DMPA、二羟甲基丁酸DMBA中的至少一种;
步骤(3)所用简单二元醇为乙二醇、1,4-丁二醇BDO、一缩二乙二醇、甲基丙二醇、1,2-丙二醇、新戊二醇中的一种。
步骤(3)所用催化剂为二月桂酸二丁基锡DBTDL、辛酸亚锡T9的至少一种;
步骤(3)所用羟基硅油占聚氨酯总质量的2~7%;
所述石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液,其特征在于:
步骤(4)所用引发剂为偶氮二异丁腈AIBN、过氧化二苯甲酰BPO的至少一种;
步骤(4)所用乙二胺化氧化石墨烯MGO占终聚氨酯总含量的0.2%~0.6%
步骤(4)所用含羟基丙烯酸酯单体为甲基丙烯酸酯羟乙酯HEMA、丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酸羟丙酯中的一种,且与小分子扩链剂等摩尔。
步骤(4)所用中和剂为三乙胺TEA、氨水中的至少一种。
所述石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液,其特征在于:步骤(1)所述的弱酸性指的是pH为5~7,步骤(1)所述的稀盐酸溶液的浓度约为1mol/L。
本发明制备方法如下:
(1)冰水浴冷却下,将一定计量比的石墨粉、硝酸钠、浓硫酸混合并搅拌1~5min,缓慢分步加入高锰酸钾,约1.5h完成,继续搅拌1h,30~40℃保温1~2d。缓慢滴加少量去离子水进行稀释,加入大量水继续搅拌,随后缓慢滴加30%过氧化氢溶液,充分搅拌后加入稀盐酸溶液进行洗涤,静置,沉淀。除去上层清液后,使用大量去离子水进行反复洗涤、离心、沉淀至溶液呈弱酸性,经超声和高速离心后,上层清液即GO分散液;其中,上述所用硝酸钠、浓硫酸、高锰酸钾、去离子水(首次稀释)同石墨粉质量比为0.5~1:40~85:3~6:30~50:1。
(2)将步骤(1)所得GO分散液冷冻或30~50℃真空干燥,取一定量干燥后的GO重新分散在溶剂N,N-二甲基甲酰胺中,超声剥离2h以上得到GO的DMF分散液,常温快速搅拌下滴加乙二胺,惰性气体保护反应24h,加入丙烯酸丁酯(与乙二胺等摩尔比)反应48h,获得进一步乙二胺化氧化石墨烯(MGO)的DMF分散液;其中,上述所用乙二胺、丙烯酸丁酯与氧化石墨质量比为0.3~1:0.15~0.5:0.1。
(3)惰性气体保护下,将二异氰酸酯与二元醇亲水扩链剂于60~90℃反应1~4h,冰盐浴冷却至0℃左右,缓慢滴加二羟基仲胺的DMF溶液,约1~2.5h完成后继续反应0.5~2h,升温至60~90℃,反应2~4h,获得多羟基超支化聚氨酯(HBPU-0);其中,上述所用扩链剂,二羟基仲胺与二异氰酸酯摩尔比为1:4~9:3~6;
惰性气体保护,将二异氰酸酯,低聚物二元醇和小分子羟硅于70~90℃保温1~4h,加入小分子扩链剂(如含亲水基团二元醇、简单二元醇等),于70~90℃反应0.5~5h(反应过程中加入1~3滴催化剂,加入适量丙酮降低体系粘度),按计量比加入所制HBPU-0作为“核”,于60~100℃反应1~5h,获得含硅超支化聚氨酯预聚体;其中,上述低聚物二元醇、小分子扩链剂与二异氰酸酯基摩尔比为1:1~3:3~7,小分子羟硅为聚氨酯总质量的1~7%;
(4)取一定量步骤(2)所制MGO得DMF分散液,与甲基丙烯酸甲酯、丙烯酸丁酯单体混合(质量比1:1),引发剂量为单体总量的0.1~0.5%,于60~80℃反应2~4h,加入混有引发剂的含羟基丙烯酸酯单体,继续反应1~3h,获得含有羟基的乙二胺化氧化石墨烯/聚丙烯酸酯溶液(MGO/PA);其中,所用改性石墨烯占聚氨酯总含量的0.2%~0.6%。
步骤(3)降温至30~40℃,与MGO/PA溶液混合均匀后,中和(与体系中含亲水基团二元醇等摩尔),高速均质乳化剂作用下,加入混有乙二胺的蒸馏水,乳化3~5min,减压蒸馏除去丙酮,获得超支化多元复合乳液;其中,上述乳化剂转速约800~1300r/min,蒸馏水量使乳液固含约30~40%之间,乙二胺量与剩余异氰酸酯基等摩尔,获得乙二胺化GO/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液。
文中提到的所有聚氨酯总质量均指乳化前,除溶剂外,合成最终超支化聚氨酯所有原料总和。
本发明具有以下优点:
(1)本发明制备氧化石墨烯周期较短,不仅具有低成本、操作简单等优点,而且产量高、易于加工成型,更易进行改性获得氨基化石墨烯,提高其与聚氨酯复合材料的相容性。对氧化石墨烯进行两步改性,由于双键的引入,能够更好地实现丙烯酸酯类单体进行共聚。
(2)本发明采用共聚的方式对超支化聚氨酯进行改性,由于强共价作用、范德华力以及π-π作用,复合材料的耐热性、力学性能均显著提高。采用的羟基硅油使超支化聚氨酯链上引入了有机硅氧烷链段,和石墨烯两者均有一定耐水性,因此多元复合材料膜疏水性显著性增加。
(3)本发明分别制得带有官能团的PU预聚体与PA溶液,混合后缩聚并同时交联,该制备方法获得的胶乳性能优良,避免了由于各种单体相容性差而难以制备互穿网络的PUA结构。超支化水性聚氨酯和氨基化石墨烯可单独或与其他水性树脂配合,应用于环保型水性涂料等领域,具有广泛的应用前景。
附图说明
图1是实施例1所得氧化石墨烯改性前后的TEM图:图中可以很明显的看出经改性后,石墨烯褶皱结构趋于平面化,剥离更完全。
图2是实施例2氨基化石墨烯/聚丙烯酸酯-含硅超支化聚氨酯复合材料的TEM图,图中可观察到,少量石墨烯能够均匀分散在聚氨酯基质中,相容性较好。
图3是实施例1氨基化石墨烯/聚丙烯酸酯-含硅超支化聚氨酯复合材料的TG图,图中可以看到经复合改性的材料比单一改性与未经改性材料的耐热性能得到了不同程度的提高。
具体实施方式
下面列举具体实施例对本发明作进一步地说明。
实施例1
1、氧化石墨烯GO的制备:冰水浴冷却下,将石墨粉(3g)、硝酸钠(1g)、浓硫酸(75mL)混合并搅拌1min,缓慢分步加入高锰酸钾(9g),约1.5h完成,继续搅拌1h,30~40℃保温2d。缓慢滴加150mL去离子水进行稀释,加入450mL水继续搅拌,随后缓慢滴加20mL30%过氧化氢溶液,充分搅拌后加入200mL 1mol/L稀盐酸溶液进行洗涤,静置,沉淀。除去上层清液后,使用大量去离子水进行反复洗涤、离心、沉淀至溶液呈弱酸性(pH≈5~7),使用大功率超声波洗涤器超声剥离4h以上,以12000r/min转速高速离心后,取上层清液即GO分散液。为进一步纯化,使用透析袋透析7d,最后冷冻干燥或40~50℃低温干燥后待用。
2、氨基改性氧化石墨烯的合成:取100mg步骤2所制GO重新分散在20mL溶剂N,N-二甲基甲酰胺中,超声剥离2h得到GO的DMF分散液,常温快速搅拌下滴加0.3g乙二胺,N2气体保护反应24h,加入0.67g丙烯酸丁酯反应48h,获得进一步乙二胺化氧化石墨烯(MGO)的DMF分散液;
图1是本实施例所得氧化石墨烯改性前后的TEM图:图中可以很明显的看出经改性后,石墨烯褶皱结构趋于平面化,剥离更完全。
3、含硅超支化聚氨酯预聚体的合成:N2气体保护下,将IPDI(46g)与DMPA(4.7g)的DMF(20g)溶液于85℃反应1.5h,冰盐浴冷却至0℃左右,缓慢滴加DEOA(20g)的DMF(50g)溶液,约2h完成后继续反应0.5h,升温至60℃,反应2h,获得多羟基超支化聚氨酯(HBPU-0);
N2气体保护,将IPDI(11g),聚醚N220(20g)和羟硅(1.2g)于90℃保温2h,加入DMPA(1.34g)与BDO(1.6g),于85℃反应2h,加入2滴T9反应1.5h,(反应过程中加入适量丙酮降低体系粘度),加入HBPU-0(2.4g,固含量50%)作为“核”,于80℃反应3h,获得含硅超支化聚氨酯预聚体。
4、改性石墨烯含量为0.23%的乙二胺化GO/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备:取5mL步骤2所制MGO得DMF分散液,与甲基丙烯酸甲酯(2g)、丙烯酸丁酯(2.56g)单体混合,0.04gAIBN,于70℃反应3h,加入含有0.002g的甲基丙烯酸羟乙酯(1g),继续反应1h,获得含有羟基的乙二胺化氧化石墨烯/聚丙烯酸酯溶液(MGO/PA);
步骤3降温至30~40℃,与MGO/PA混合均匀后,加入1.2g三乙胺中和10min,高速均质乳化剂1200r/min作用下,加入混有0.5g乙二胺的蒸馏水(150g),乳化3~5min,减压蒸馏除去丙酮,获得超支化多元复合乳液。
图3是本实施例氨基化石墨烯/聚丙烯酸酯-含硅超支化聚氨酯复合材料的TG图,图中可以看到经复合改性的材料比单一改性与未经改性材料的耐热性能得到了不同程度的提高。
将得到的复合乳液倒在聚四氟乙烯板上流延成膜,常温干燥5天,60℃真空干燥箱中干燥即得到复合材料胶膜。表1为复合涂膜的24h吸水率、表面接触角与材料的拉伸强度、断裂伸长率测试分析结果,从表中可以观察到与纯超支化聚氨酯材料(HBPU)、羟基硅油单一改性超支化聚氨酯复合材料(HBPUS)相比,石墨烯羟基硅油复合改性超支化聚氨酯复合材料(HBPUS-0.23与HBPUS-0.46)的耐水性与力学性能均得到了明显的改善,获得了疏水柔软的功能复合产品。
表1
实施例2
1、氧化石墨烯GO的制备:冰水浴冷却下,将石墨粉(3g)、硝酸钠(1g)、浓硫酸(75mL)混合并搅拌1min,缓慢分步加入高锰酸钾(9g),约1.5h完成,继续搅拌1h,30~40℃保温2d。缓慢滴加150mL去离子水进行稀释,加入450mL水继续搅拌,随后缓慢滴加20mL30%过氧化氢溶液,充分搅拌后加入200mL 1mol/L稀盐酸溶液进行洗涤,静置,沉淀。除去上层清液后,使用大量去离子水进行反复洗涤、离心、沉淀至溶液呈弱酸性(pH≈5~7),使用大功率超声波洗涤器超声剥离4h以上,以12000r/min转速高速离心后,取上层清液即GO分散液。为进一步纯化,使用透析袋透析7d,最后冷冻干燥或40~50℃低温干燥后待用。
2、氨基改性氧化石墨烯的合成:取100mg步骤2所制GO重新分散在20mL溶剂N,N-二甲基甲酰胺中,超声剥离2h得到GO的DMF分散液,常温快速搅拌下滴加0.3g乙二胺,N2气体保护反应24h,加入0.67g丙烯酸丁酯反应48h,获得进一步乙二胺化氧化石墨烯(MGO)的DMF分散液;
3、含硅超支化聚氨酯预聚体的合成:N2气体保护下,将IPDI(46g)与DMPA(4.7g)的DMF(20g)溶液于85℃反应1.5h,冰盐浴冷却至0℃左右,缓慢滴加DEOA(20g)的DMF(50g)溶液,约2h完成后继续反应0.5h,升温至60℃,反应2h,获得多羟基超支化聚氨酯(HBPU-0);
N2气体保护,将IPDI(11g),聚醚N220(20g)和羟硅(1.2g)于90℃保温2h,加入DMPA(1.34g)与BDO(1.6g),于85℃反应2h,加入2滴T9反应1.5h,(反应过程中加入适量丙酮降低体系粘度),加入HBPU-0(2.4g,固含量50%)作为“核”,于80℃反应3h,获得含硅超支化聚氨酯预聚体。
4、改性石墨烯含量为0.46%的乙二胺化GO/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备:取10mL步骤2所制MGO得DMF分散液,与甲基丙烯酸甲酯(2g)、丙烯酸丁酯(2.56g)单体混合,0.04gAIBN,于70℃反应3h,加入含有0.002g的甲基丙烯酸羟乙酯(1g),继续反应1h,获得含有羟基的乙二胺化氧化石墨烯/聚丙烯酸酯溶液(MGO/PA);
步骤3降温至30~40℃,与MGO/PA混合均匀后,加入1.2g三乙胺中和10min,高速均质乳化剂1200r/min作用下,加入混有0.5g乙二胺的蒸馏水(150g),乳化3~5min,减压蒸馏除去丙酮,获得超支化多元复合乳液。
图2是本实施例氨基化石墨烯/聚丙烯酸酯-含硅超支化聚氨酯复合乳液的TEM图,图中可观察到,少量石墨烯能够均匀分散在聚氨酯基质中,相容性较好。
将得到的复合乳液倒在聚四氟乙烯板上流延成膜,常温干燥5天,60℃真空干燥箱中干燥即得到复合材料胶膜。其复合涂膜的24h吸水率、表面接触角与材料的拉伸强度、断裂伸长率测试分析见表1。
Claims (4)
1.一种石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备方法,其特征在于,包括以下具体步骤:
(1)冰水浴冷却下,将一定计量比的石墨粉、硝酸钠、质量分数为98%浓硫酸混合并搅拌1~5min,缓慢分步加入高锰酸钾,1.5h完成后,继续搅拌1-1.2h,30~40℃保温1~2d,缓慢滴加少量去离子水进行稀释,加入大量水继续搅拌,随后缓慢滴加30%的过氧化氢溶液,充分搅拌后加入稀盐酸溶液进行洗涤,静置,沉淀,除去上层清液后,使用大量去离子水进行反复洗涤、离心、沉淀至溶液呈弱酸性,经超声和高速离心后,上层清液即氧化石墨烯GO分散液;
(2)将步骤(1)所得氧化石墨烯GO分散液冷冻干燥或30~50℃真空干燥,取一定量干燥后的氧化石墨烯GO重新分散在溶剂N,N-二甲基甲酰胺中,超声剥离2h以上得到氧化石墨烯GO的DMF分散液,常温快速搅拌下滴加乙二胺,惰性气体保护反应24-26h,加入与乙二胺等摩尔比的丙烯酸丁酯反应48-50h,获得进一步乙二胺化氧化石墨烯MGO的DMF分散液;
(3)惰性气体保护下,将二异氰酸酯与二元醇亲水扩链剂于60~90℃反应1~4h,冰盐浴冷却至0℃,缓慢滴加二羟基仲胺的DMF溶液,1~2.5h完成后继续反应0.5~2h,升温至60~90℃,反应2~4h,获得多羟基超支化聚氨酯HBPU-0;惰性气体保护下,将二异氰酸酯,低聚物二元醇和小分子羟硅于70~90℃保温1~4h,加入小分子扩链剂,于70~90℃反应0.5~5h,反应过程中加入1~3滴催化剂,加入适量丙酮降低体系粘度使得搅拌器顺利搅拌即可,按计量比加入所制多羟基超支化聚氨酯HBPU-0作为核,于60~100℃反应1~5h,获得含硅超支化聚氨酯预聚体,保温备用;上述低聚物二元醇、小分子扩链剂与二异氰酸酯基摩尔比为1:1~3:3~7,小分子羟硅为超支化聚氨酯总质量的1~7%;
(4)取一定量步骤(2)所制乙二胺化氧化石墨烯MGO的DMF分散液,与按照质量比1:1混合的甲基丙烯酸甲酯、丙烯酸丁酯复配单体混合,于60~80℃反应2~4h,加入混有引发剂的含羟基丙烯酸酯单体,引发剂量为上述含羟基丙烯酸酯单体总量的0.1~0.5%,继续反应1~3h,获得含有羟基的乙二胺化氧化石墨烯/聚丙烯酸酯溶液MGO/PA;步骤(3)的含硅超支化聚氨酯预聚体降温至30~40℃,与含有羟基的乙二胺化氧化石墨烯/聚丙烯酸酯溶液MGO/PA溶液混合均匀后,与体系中含亲水基团二元醇等摩尔中和,高速均质乳化机作用下,加入混有乙二胺的蒸馏水,乳化3~5min,减压蒸馏除去丙酮,获得超支化多元复合乳液;其中,上述乳化机转速800~1300r/min,蒸馏水量使乳液固含量30~40%之间,乙二胺量与剩余异氰酸酯基等摩尔;
所述的小分子扩链剂指的是亲水基团二元醇、简单二元醇中的一种或两种;
步骤(3)所用二异氰酸酯为异佛尔酮二异氰酸酯IPDI、甲苯二异氰酸酯TDI、二苯甲烷二异氰酸酯MDI、1,6-己二异氰酸酯HDI中的一种或几种的混合物;步骤(3)所用低聚物二元醇为聚氧化丙烯二醇、聚四氢呋喃二醇、聚碳酸酯二醇、聚己内酯二醇、聚丙二醇中的至少一种;步骤(3)所用小分子扩链剂亲水基团二元醇,简单二元醇,二羟基仲胺与二异氰酸酯摩尔比为1:1:4~9:3~6;步骤(3)所用亲水基团二元醇为二羟甲基丙酸DMPA、二羟甲基丁酸DMBA中的至少一种;步骤(3)所用简单二元醇为乙二醇、1,4-丁二醇BDO、一缩二乙二醇、甲基丙二醇、1,2-丙二醇、新戊二醇中的一种;步骤(3)所用催化剂为二月桂酸二丁基锡DBTDL、辛酸亚锡T9的至少一种;步骤(3)所用羟基硅油占多羟基超支化聚氨酯HBPU-0总质量的2~7%;
步骤(4)所用引发剂为偶氮二异丁腈AIBN、过氧化二苯甲酰BPO的至少一种;步骤(4)所用乙二胺化氧化石墨烯MGO占聚氨酯总含量的0.2%~0.6%步骤(4)所用含羟基丙烯酸酯单体为甲基丙烯酸酯羟乙酯HEMA、丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酸羟丙酯中的一种,且与小分子扩链剂等摩尔。
2.据权利要求1所述石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备方法,其特征在于:步骤(1)制备氧化石墨烯GO所用的硝酸钠、浓硫酸、高锰酸钾、首次稀释用去离子水和石墨粉质量比为0.5~1:40~85:3~6:30~50:1。
3.据权利要求1所述石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备方法,其特征在于:步骤(2)所用乙二胺、丙烯酸丁酯与氧化石墨烯GO质量比为0.3~1:0.15~0.5:0.1。
4.据权利要求1所述石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备方法,其特征在于:步骤(1)所述的弱酸性指的是pH为5~7,步骤(1)所述的稀盐酸溶液的浓度为1mol/L。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610861193.9A CN106433098B (zh) | 2016-09-28 | 2016-09-28 | 一种石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610861193.9A CN106433098B (zh) | 2016-09-28 | 2016-09-28 | 一种石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106433098A CN106433098A (zh) | 2017-02-22 |
CN106433098B true CN106433098B (zh) | 2021-02-19 |
Family
ID=58170232
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610861193.9A Active CN106433098B (zh) | 2016-09-28 | 2016-09-28 | 一种石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106433098B (zh) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107141680B (zh) * | 2017-06-12 | 2019-07-09 | 常州大学 | 一种改性氧化石墨烯/pmma复合材料的制备方法 |
CN109575623A (zh) * | 2017-09-29 | 2019-04-05 | 中科众创(重庆)秸秆产业研究院有限公司 | 基于超支化聚合物改性石墨烯的秸秆阻燃材料及其制备方法 |
CN107586399B (zh) * | 2017-10-18 | 2019-04-23 | 桂林电子科技大学 | 一种功能化氧化石墨烯、其制备方法及其水分散体 |
CN107737530B (zh) * | 2017-11-15 | 2020-11-06 | 北京工业大学 | 一种改性氧化石墨烯/超支化聚合物复合膜、制备方法及应用 |
CN108752563B (zh) * | 2018-05-24 | 2020-12-15 | 哈尔滨工业大学无锡新材料研究院 | 一种水性超支化结构改性聚氨酯聚合物及其制备方法、及自修复漫反射涂料组合物 |
CN108864875A (zh) * | 2018-06-05 | 2018-11-23 | 朱东洋 | 一种高强度高热稳定水性光油的制备方法 |
CN109705398B (zh) * | 2018-12-17 | 2020-08-07 | 汕头市贝斯特科技有限公司 | 一种聚烯烃薄膜用非迁移性亲水防雾母料及其制备 |
CN109880014B (zh) * | 2019-01-28 | 2021-08-03 | 济南大学 | 一种超支化型有机硅-丙烯酸酯乳液的制备及在人造板中的应用 |
CN110229369B (zh) * | 2019-06-11 | 2020-05-08 | 江苏盈泰新材料科技有限公司 | 一种疏水疏油抗静电pvc复合薄膜及其制备方法 |
CN110982316B (zh) * | 2019-12-26 | 2021-08-24 | 杭州高烯科技有限公司 | 一种石墨烯改性的丙烯酸酯水泥防水涂料 |
CN111691233B (zh) * | 2020-05-28 | 2022-02-15 | 仙鹤股份有限公司 | 一种低平滑度医用包装原纸的制备方法 |
CN112920678B (zh) * | 2021-01-28 | 2022-03-01 | 山东世纪联合新材料科技有限公司 | 一种超支化聚合物接枝石墨烯改性环氧树脂涂料及其制备方法 |
CN114752035B (zh) * | 2022-05-30 | 2024-07-05 | 浙江大学衢州研究院 | 一种高固含量的水性聚氨酯分散体及其制备方法和应用 |
CN115304963B (zh) * | 2022-08-26 | 2023-06-30 | 河北昊泽化工有限公司 | 一种初期高附着力耐水环保金属涂料 |
CN115926624B (zh) * | 2022-12-27 | 2023-09-12 | 黄山中邦孚而道涂料有限公司 | 一种耐腐蚀膨胀型水性钢结构防火涂料及其制备方法和应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104861643A (zh) * | 2015-05-29 | 2015-08-26 | 安徽大学 | 一种石墨烯/水性聚氨酯复合材料的制备方法 |
-
2016
- 2016-09-28 CN CN201610861193.9A patent/CN106433098B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104861643A (zh) * | 2015-05-29 | 2015-08-26 | 安徽大学 | 一种石墨烯/水性聚氨酯复合材料的制备方法 |
Non-Patent Citations (2)
Title |
---|
水性聚氨酯丙烯酸酯/氧化石墨烯防腐涂层的制备与性能;费贵强等;《高分子材料科学与工程》;20160430;第32卷(第4期);第173-178页 * |
羟丙基硅油改性超支化水性聚氨酯的合成与性能;刘棚滔等;《化学新型材料》;20160229;第44卷(第2期);第67-69页 * |
Also Published As
Publication number | Publication date |
---|---|
CN106433098A (zh) | 2017-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106433098B (zh) | 一种石墨烯/聚丙烯酸酯-含硅超支化水性聚氨酯多元复合乳液的制备方法 | |
CN101225226B (zh) | 水分散蒙脱土/有机硅嵌段聚氨酯纳米复合材料的制备方法及用途 | |
CN101225150B (zh) | 水分散有机硅-聚氨酯嵌段共聚物的合成方法及应用 | |
CN104877099B (zh) | 一种有机氟改性超支化水性聚氨酯的制备方法 | |
Qiu et al. | Preparation, characterization and properties of UV-curable waterborne polyurethane acrylate/SiO 2 coating | |
Lee et al. | Waterborne polyurethane nanocomposites having shape memory effects | |
CN113248755A (zh) | 一种纳米二氧化硅/羟基硅烷偶联剂复合改性聚氨酯超疏水膜的制备方法 | |
CN107163217B (zh) | 一种纳米金刚石改性水性聚氨酯的制备方法 | |
CN109694684A (zh) | 一种水性单组份耐热胶粘剂及其制备方法和应用 | |
CN1854165A (zh) | 有机硅改性水性聚氨酯 | |
Park et al. | Hyperbranched waterborne polyurethanes | |
CN102093517A (zh) | 用于合成革面料的水性聚氨酯-丙烯酸酯树脂及其制备方法 | |
CN109749048A (zh) | 端氟烷基和侧链氟烷基双改性聚氨酯乳液及其制备方法 | |
CN109072040B (zh) | 粘接剂组合物、固化体、电子部件和组装部件 | |
CN105418853A (zh) | 一种羟基型水性阳离子聚氨酯-丙烯酸树脂及其制备方法 | |
CN111019076A (zh) | 快速uv固化的超支化聚氨酯丙烯酸酯及其制备方法 | |
Zhang et al. | Hydrophobic, transparent waterborne UV-curable polyurethane nanocomposites based on polycarbonate and PCL-PDMS-PCL reinforced with colloidal silica | |
CN114276519B (zh) | 一种自消光水性聚氨酯及其制备方法 | |
CN113801271A (zh) | 一种硅溶胶改性水性聚氨酯丙烯酸酯复合乳液及其制备 | |
KR101102867B1 (ko) | 수분산 재유화형 폴리우레탄/아크릴공중합체 하이브리드 수지 조성물 및 그의 제조방법 | |
CN109021250B (zh) | 一种水性聚氨酯改性蒙脱土纳米复合乳液的制备 | |
Li et al. | Synthesis and characterization of self-crosslinked polyurethane/polyacrylate composite emulsion based on carbonyl–hydrazide reaction | |
Zhang et al. | Effect of polyether soft segments on structure and properties of waterborne UV-curable polyurethane nanocomposites | |
Honarkar | The effect of different acrylic monomers contents on the properties of waterborne polyurethane/acrylate hybrids | |
CN116656229B (zh) | 一种耐污型改性水性聚氨酯涂层的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |