CN106243314A - A kind of composite modified aqueous polyurethane and preparation method and application - Google Patents
A kind of composite modified aqueous polyurethane and preparation method and application Download PDFInfo
- Publication number
- CN106243314A CN106243314A CN201610754969.7A CN201610754969A CN106243314A CN 106243314 A CN106243314 A CN 106243314A CN 201610754969 A CN201610754969 A CN 201610754969A CN 106243314 A CN106243314 A CN 106243314A
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- CN
- China
- Prior art keywords
- aqueous polyurethane
- preparation
- modified aqueous
- modified
- composite modified
- 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.)
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 55
- 239000004814 polyurethane Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 38
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910000077 silane Inorganic materials 0.000 claims abstract description 35
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004970 Chain extender Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 229920005862 polyol Polymers 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 150000003077 polyols Chemical class 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- -1 poly- Ester polyol Chemical class 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims description 7
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims description 7
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000006837 decompression Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 230000033228 biological regulation Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 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 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005488 sandblasting Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical group [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
- C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- 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
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- 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
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- 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
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Abstract
The present invention discloses a kind of composite modified aqueous polyurethane and preparation method and application, comprises the following steps: 1) during preparing performed polymer, add small molecule alcohol chain extender and small carboxylic acid molecules's chain extender；2) acidic silicasol is modified with silane coupler；3) acidic silicasol after modifying reacts with Waterborne Polyurethane Prepolymer, obtains silica sol modified aqueous urethane；4) grapheme modified with silane coupler；5) composite modified: the Graphene after modifying mixes with silica sol modified aqueous urethane, and reaction obtains composite modified aqueous polyurethane.The method can make Ludox, being dispersed in aqueous polyurethane of Graphene stable and uniform, it is to avoid the agglomeration between particle；The method is simple, convenient, be prone to industrialization；This composite modified aqueous polyurethane has the hardness of excellence, pliability, compactness, resistance to impact, corrosion resistance, resistance to water etc. after film forming.
Description
Technical field
The present invention relates to new material the field of chemical synthesis, particularly to preparation and the application technology neck of functional high molecule material
Territory, more particularly, it relates to a kind of composite modified aqueous polyurethane and preparation method and application.
Background technology
Aqueous polyurethane is to replace organic solvent as the polyurethane system of disperse medium using water, gathers with traditional solvent-borne type
Urethane is compared, and aqueous polyurethane has features such as nontoxic, nonflammable, environmentally friendly, and aqueous polyurethane structure-performance
Controllability makes it have elastomer and the character of plastics and excellent wearability and adhesive force etc. simultaneously, is widely used in skin
Leather/synthetic leather finishing agent, fabric coating and finishing agent, coating, adhesive, sheet surface treating agent and Fiber strength agent etc.
Field, has wide market prospect.But the resistance to water of aqueous polyurethane, solvent resistance, thermostability, physical and mechanical properties are relatively
Difference, limits the application of aqueous polyurethane to a certain extent.Meanwhile, along with the development of science and technology, people are to material
The requirement of physical and mechanical properties more and more higher, in order to improve the combination property of aqueous polyurethane, expand range, need
It is modified.
Ludox is nano level silica dioxide granule dispersion liquid in water or in solvent.Due to the SiO in Ludox2
Containing substantial amounts of water and hydroxyl, therefore Ludox can also be expressed as SiO2·nH2O.Nano-silica surface hydroxy radical content is relatively
Height, can carry out chemical bond with NCO, and the active Hydrogen Energy of carbamate groups and nanometer two on polyurethane molecular
The oxygen atom of silicon oxide surface forms hydrogen bond so that nano material and the aqueous polyurethane being modified are carried out effectively on interface
In conjunction with.But nano silicon itself has stronger hydrophilic and autohemagglutination, very difficult high uniformity is dispersed in aqueous polyurethane
In system, prepare nano silicon dioxide modifying water polyurethane the most frequently used for blending method, first blending method prepares various shape
The nanoparticle of state, then by various modes, it is mixed with aqueous polyurethane；For preventing nanoparticle from reuniting, right before being blended
Nanoparticle carries out surface modification, improves its dispersion stabilization.
Graphene is by carbon atom sp2The two-dimensional layer material that hydridization is constituted, its thickness is only monolayer carbon atomic thickness.Cause
Have for Graphene and be better than the electric conductivity of conventional carbon material and strong mechanicalness etc., and add a small amount of Graphene in the polymer and just may be used
To significantly improve the performance of each side such as the mechanical performance of composite, electric conductivity and heat stability.But, this excellence
The performance of performance by Graphene in the polymer can dispersed premised on.Owing to Graphene is the most hydrophilic the closeest
Oil, and reactivity is relatively low, adds and is easily generated strong stacking trend between its adjacent sheets, causes it to hold in the polymer
Easily reunite so that the performance of polymer composites is affected.By Graphene being carried out functional modification, improve stone
Ink alkene dispersibility in aqueous polyurethane so that optical, electrical, sound, the magnetic characteristic of Graphene and the performance such as hydrophobicity, thermostability exist
Aqueous polyurethane is played well.
Summary of the invention
In order to overcome the deficiencies in the prior art, first purpose of the present invention is to provide a kind of inorganic particulate to be difficult to group
The preparation method of the composite modified aqueous polyurethane of poly-, good dispersion.
Second object of the present invention is to provide for the composite modified aqueous polyurethane prepared by said method.
The composite modified aqueous polyurethane that third object of the present invention is to provide for being prepared by said method exists
The application of sheet metal surface.
Realize the purpose of the present invention to reach by adopting the following technical scheme that:
The preparation method of a kind of composite modified aqueous polyurethane, comprises the following steps:
1) prepare performed polymer: macromolecular polyol, polyisocyanates are added catalyst prepolymerization, add small molecule alcohol and expand
Chain agent and small carboxylic acid molecules's chain extender, add salt forming agent, obtain Waterborne Polyurethane Prepolymer after dilution；
2) Ludox is modified: reacted with silane coupler by acidic silicasol；
3) emulsifying: by step 1) Waterborne Polyurethane Prepolymer that obtains adds to through step 2) process after acid silicon molten
Glue, adds deionized water and obtains silica sol modified aqueous urethane through high speed shear emulsion dispersion；
4) grapheme modified: Graphene is reacted with silane coupler；
5) composite modified: by step 3) silica sol modified aqueous urethane that obtains joins through step 4) graphite that processes
Alkene, mixing reaction obtains composite modified aqueous polyurethane.
As preferably, step 1) in, described macromolecular polyol is PEPA or polyether polyol；Described many
Isocyanates is selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate, isophorone two
Isocyanates；Described catalyst is selected from dibutyl tin laurate, stannous octoate；Described catalyst is selected from tin dilaurate two
Butyl tin, stannous octoate.
As preferably, step 1) in, the relative molecular weight of described PEPA or polyether polyol is 1000 or 2000；
Described PEPA is 10PE27, poly adipate succinic acid ester, polyadipate hexanediol ester or Merlon；
Described polyether polyol is polypropylene glycol or polytetrahydrofuran diol.
As preferably, step 1) in, described small molecule alcohol chain extender is BDO, ethylene glycol, hexanediol, a contracting
One or more in diethylene glycol, neopentyl glycol, trimethylolpropane；Described small carboxylic acid molecules's chain extender is 2,2-bis-
Hydroxymethyl propionic acid or 2,2-dimethylolpropionic acid.
As preferably, step 1) in, adding solvent and be diluted, described solvent is acetone, butanone or oxolane；Described
Salt forming agent is triethylamine, triethanolamine or ammonia.
As preferably, step 1) in, during preparing performed polymer, each component proportioning by weight is as follows: 40-60 part
Macromolecular polyol, 20-40 part polyisocyanates, 0.2-0.5 part catalyst, 2-5 part small molecule alcohol chain extender, 2-8 part are little
Carboxylic acids chain extender, 10-20 part solvent, 2-5 part salt forming agent.
As preferably, step 2) and/or step 4) in, described silane coupler is selected from MTMS, methyl
Triethoxysilane, KH560 or KH570.
As preferably, step 2) in, acidic silicasol and silane coupler react in isopropanol, described acidic silicasol
PH value=4.
The method design principle of the present invention is as follows:
The preparation method of the composite modified aqueous polyurethane that the present invention provides, first, by aqueous polyurethane pre-polymerization
Cheng Zhong, utilizes small molecular alcohol chain extender and small carboxylic acid molecules's chain extender, to increase the degree of cross linking of Waterborne Polyurethane Prepolymer；Its
Secondary, it is utilized respectively silane coupler and Ludox and Graphene are carried out structural modification, to improve Ludox and Graphene and aqueous
The affinity of base polyurethane prepolymer for use as；Finally, more successively it is pre-that Ludox after modifying and Graphene add to aqueous polyurethane successively
In aggressiveness, thus the composite modified aqueous polyurethane obtained.
Compared to existing technology, the beneficial effects of the present invention is:
The present invention modified by silane coupler after Ludox, Graphene can be dispersed in the poly-ammonia of aqueous with stable and uniform
In ester, it is to avoid the agglomeration between particle；
The preparation method that the present invention provides, Ludox and Graphene after utilizing silane coupler to modify are more branched to having
The aqueous polyurethane of chain structure is composite modified to composite modified aqueous polyurethane have after film forming excellence hard
Degree, pliability, compactness, resistance to impact, corrosion resistance, resistance to water etc.；
The preparation method that the present invention provides is simple, convenient, be prone to industrialization；The composite modified aqueous obtained by the present invention is gathered
Weatherability, resistance to water after urethane film forming, acidproof and resistance to salt water is good, good with coating substrate adhesive force, and impact resistance is good, it is possible to
Use in sheet metal kinds of surface.
Detailed description of the invention
In detailed description below, such as non-specified otherwise, the reagent used or raw material all can be by commercially available approach
Or the laboratory facilities of routine obtain.
The present invention provides the preparation method of a kind of composite modified aqueous polyurethane, comprises the following steps:
1) prepare performed polymer: macromolecular polyol, polyisocyanates are added catalyst prepolymerization, add small molecule alcohol and expand
Chain agent and small carboxylic acid molecules's chain extender, add salt forming agent, obtain Waterborne Polyurethane Prepolymer after dilution；
In this step, aqueous polyurethane is made to have relatively highly branched chain by small molecular alcohol chain extender and small carboxylic acid molecules's chain extender
Structure, improves the degree of cross linking of aqueous polyurethane, thus is that aqueous polyurethane is in physical property sides such as hardness, pliability, compactness
The raising in face provides the foundation；
In this step, macromolecular polyol is PEPA or polyether polyol, its relative molecular weight be 1000 or
2000, wherein, PEPA is 10PE27, poly adipate succinic acid ester, polyadipate hexanediol ester and gathers
One or more in carbonic ester；Polyether polyol is polypropylene glycol or polytetrahydrofuran diol；
In this step, polyisocyanates is that toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexa-methylene two are different
One in cyanate and isophorone diisocyanate；Catalyst is selected from dibutyl tin laurate or stannous octoate；
In this step, small molecule alcohol chain extender be BDO, ethylene glycol, hexanediol, diglycol, new penta
One or more in glycol or trimethylolpropane；Small carboxylic acid molecules's chain extender is 2,2-dihydromethyl propionic acid or 2,2-
Dimethylolpropionic acid, small carboxylic acid molecules's chain extender has good hydrophilic, can improve performed polymer and Ludox or Graphene
Affinity；
In this step, by solvent dilution, solvent selected from acetone, butanone or oxolane；Salt forming agent is triethylamine, three second
Hydramine or ammonia.
In this step, specifically, macromolecular polyol is added in reaction vessel, at 95-105 DEG C of decompression distillation 40-60
Minute, until water content is less than 0.5%, it is cooled to 70-80 DEG C, adds polyisocyanates, catalyst, react 1-3 hour；Cooling
To 50-60 DEG C, add small molecule alcohol chain extender and small carboxylic acid molecules's chain extender, react 2-4 hour；It is cooled to 40-50 DEG C, and
After adding solvent viscosity reduction, add salt forming agent, react 15-30 minute, obtain the performed polymer of aqueous polyurethane.
In this step, it is preferable that each component proportioning by weight is as follows: 40-60 part macromolecular polyol, 20-40
Part polyisocyanates, 0.2-0.5 part catalyst, 2-5 part small molecule alcohol chain extender, 2-8 part small carboxylic acid molecules's chain extender, 10-
20 parts of solvents, 2-5 part salt forming agents.
2) Ludox is modified: reacted with silane coupler by acidic silicasol；
In this step, the pH value of Ludox is 4, and in Ludox, silicon dioxide grain size specification is 20nm, Gu containing being
30%；Silane coupler is selected from MTMS, MTES, KH560 and KH570；
In this step, KH560 or KH570 refers to the silane coupler that model is KH560 or KH570；
3) emulsifying: by step 1) Waterborne Polyurethane Prepolymer that obtains adds to through step 2) process after acid silicon molten
Glue, adds deionized water and obtains silica sol modified aqueous urethane through high speed shear emulsion dispersion；
In this step, the consumption of acidic silicasol is the 20-80% of Waterborne Polyurethane Prepolymer weight；The use of deionized water
Amount is the 20-80% of Waterborne Polyurethane Prepolymer weight；
Specifically, by step 1) Waterborne Polyurethane Prepolymer that obtains adds to through step 2) process after acid silicon molten
Glue, adds deionized water and obtains with the rotating speed high speed shear emulsion dispersion of 1000-3000rpm silica sol modified aqueous poly-at normal temperatures
Urethane；
4) grapheme modified: Graphene is reacted with silane coupler；
In this step, silane coupler consumption is the 10-40% of Graphene weight；
5) composite modified: by step 3) silica sol modified aqueous urethane that obtains joins through step 4) graphite that processes
Alkene, mixing reaction obtains composite modified aqueous polyurethane.
In this step, the consumption of Graphene is the 1-10% of Waterborne Polyurethane Prepolymer mass fraction.
In the present embodiment, Graphene can use the reinforced graphite alkene of Changzhou No.6 Element Material Technology Co., Ltd.
SE1430, conductive and heat-conductive type Graphene SE1231 or the graphene powder G-Powder of Ningbo Mo Xi Science and Technology Ltd..
Below in conjunction with embodiment, the present invention is described further, but embodiments of the present invention are not only in this.
Embodiment 1
1) performed polymer is prepared: being added in reaction bulb by the 10PE27 that 40g molecular weight is 1000,100 DEG C subtract
Pressure distillation 30 minutes, is cooled to 70 DEG C, adds 20g toluene di-isocyanate(TDI), 0.2g dibutyl tin laurate, reacts 2 hours；
It is cooled to 50 DEG C, adds 2g BDO, 2g 2,2-dihydromethyl propionic acid, 2g trimethylolpropane, react 4
Hour, until NCO content reaches theoretical value；
It is cooled to 40 DEG C, and with after 10g acetone viscosity reduction, adds 2g triethylamine, react 30 minutes, obtain aqueous polyurethane
Performed polymer；
2) Ludox is modified: by 20g acidic silicasol 10g isopropanol, then with 10g MTMS
Mix, stirring at normal temperature reaction 4h, obtain the Ludox that silane coupler is modified；
3) emulsifying: by step 1) Waterborne Polyurethane Prepolymer that obtains joins step 2) silane coupler that obtains modifies
Ludox in, and add 40g deionized water, with the rotating speed high speed shear emulsion dispersion 15 minutes of 2000rpm, decompression under room temperature
Acetone and isopropanol are distilled off, i.e. obtain silica sol modified aqueous urethane；
4) grapheme modified: by 5g Graphene SE1430 10g isopropanol, then with 10g methyl trimethoxy epoxide silicon
Alkane mixes, stirring at normal temperature reaction 4h, obtains the Graphene that silane coupler is modified；
5) composite modified: the silica sol modified aqueous urethane that step 3 is obtained join step 4) silane that obtains
In the Graphene that coupling agent is modified, with the rotating speed high speed shear emulsion dispersion 15 minutes of 2000rpm under room temperature, decompression is distilled off
Solvent, i.e. obtains composite modified aqueous polyurethane.
Embodiment 2
1) performed polymer is prepared: add in reaction bulb by the polytetrahydrofuran diol that 60g molecular weight is 2000,100 DEG C of decompressions
Distill 30 minutes, be cooled to 70 DEG C, add 40g hexamethylene diisocyanate, 0.5g stannous octoate, react 2 hours；
It is cooled to 55 DEG C, addition 5g diglycol, 8g 2,2-dimethylolpropionic acid and 3g trimethylolpropane, instead
Answer 4 hours, until NCO content reaches theoretical value；
It is cooled to 45 DEG C, and with after 20g butanone viscosity reduction, adds 5g ammonia, react 15 minutes, obtain the pre-of aqueous polyurethane
Aggressiveness；
2) Ludox is modified: by 80g acidic silicasol 20g isopropanol, then mix with 40gKH560, often
Temperature stirring reaction 4h, obtains the Ludox that silane coupler is modified；
3) emulsifying: by step 1) Waterborne Polyurethane Prepolymer that obtains joins step 2) silane coupler that obtains modifies
Ludox in, and add 80g deionized water, with the rotating speed high speed shear emulsion dispersion 30 minutes of 1500rpm, decompression under room temperature
Butanone and isopropanol are distilled off, i.e. obtain silica sol modified aqueous urethane；
It is 4) grapheme modified: by 20g Graphene SE1231 20g isopropanol, then to mix with 40gKH560,
Stirring at normal temperature reaction 4h, obtains the Graphene that silane coupler is modified；
5) composite modified: by step 3) silica sol modified aqueous urethane that obtains join step 4) silane that obtains
In the Graphene that coupling agent is modified, with the rotating speed high speed shear emulsion dispersion 30 minutes of 1500rpm under room temperature, decompression is distilled off
Solvent, i.e. obtains composite modified aqueous polyurethane.
Embodiment 3
1) performed polymer is prepared: add in reaction bulb by the polypropylene glycol that 40g molecular weight is 2000,100 DEG C of decompression distillations 60
Minute, it is cooled to 70 DEG C, adds 30g isophorone diisocyanate, 0.3g dibutyl tin laurate, react 2 hours；
Being cooled to 60 DEG C, add 3g neopentyl glycol, 4g 2,2-dihydromethyl propionic acid and 2g trimethylolpropane, reaction 4 is little
Time, until NCO content reaches theoretical value；
It is cooled to 40 DEG C, and with after 10g oxolane viscosity reduction, adds 3g triethanolamine, react 15 minutes, obtain aqueous and gather
The performed polymer of urethane；
2) Ludox is modified: by 40g acidic silicasol 15g isopropanol, then mix with 20gKH570, often
Temperature stirring reaction 4h, obtains the Ludox that silane coupler is modified；
3) emulsifying: by step 1) Waterborne Polyurethane Prepolymer that obtains joins step 2) silane coupler that obtains modifies
Ludox in, and add 40g deionized water, with the rotating speed high speed shear emulsion dispersion 30 minutes of 2500rpm, decompression under room temperature
Oxolane and isopropanol are distilled off, i.e. obtain silica sol modified aqueous urethane；
4) grapheme modified: by 10g Graphene G-Powder 15g isopropanol, then to mix with 20gKH570
Close, stirring at normal temperature reaction 4h, obtain the Graphene that silane coupler is modified；
5) composite modified: by step 3) silica sol modified aqueous urethane that obtains join step 4) silane that obtains
In the Graphene that coupling agent is modified, with the rotating speed high speed shear emulsion dispersion 15 minutes of 2500rpm under room temperature, decompression is distilled off
Solvent, i.e. obtains composite modified aqueous polyurethane.
Embodiment 4
1) preparing performed polymer: added by 50g polyadipate hexanediol ester in reaction bulb, 100 DEG C of decompressions are distilled 60 minutes, fall
Temperature, to 70 DEG C, adds 30g methyl diphenylene diisocyanate, 0.5g stannous octoate, reacts 2 hours；
Be cooled to 60 DEG C, add hexanediol, 2,2-dihydromethyl propionic acid and trimethylolpropane, react 4 hours, until
NCO content reaches theoretical value；
It is cooled to 40 DEG C, and with after 10g acetone viscosity reduction, adds 5g triethanolamine, react 30 minutes, obtain aqueous polyurethane
Performed polymer；
2) Ludox is modified: by 60g acidic silicasol 10g isopropanol, then with 20g MTES
Mix, stirring at normal temperature reaction 4h, obtain the Ludox that silane coupler is modified；
3) emulsifying: by step 1) Waterborne Polyurethane Prepolymer that obtains joins step 2) silane coupler that obtains modifies
Ludox in, and add 60g deionized water, with the rotating speed high speed shear emulsion dispersion 15 minutes of 3000rpm, decompression under room temperature
Acetone and isopropanol are distilled off, i.e. obtain silica sol modified aqueous urethane；
4) grapheme modified: by 15g Graphene SE1231 10g isopropanol, then with 20g methyltriethoxy silane
Alkane mixes, stirring at normal temperature reaction 4h, obtains the Graphene that silane coupler is modified；
5) composite modified: by step 3) silica sol modified aqueous urethane that obtains join step 4) silane that obtains
In the Graphene that coupling agent is modified, with the rotating speed high speed shear emulsion dispersion 15 minutes of 3000rpm under room temperature, decompression is distilled off
Solvent, i.e. obtains composite modified aqueous polyurethane.
Detection embodiment
With the aqueous polyurethane of commercially available non-modified as comparative example, and compound changing of preparing of embodiment of the present invention 1-4
Property aqueous polyurethane is respectively coated on the aluminium sheet after sandblasting and iron plate, then to its hardness, thermostability, resistance to impact, resistance to molten
The performances such as agent scrubbing character, acid resistance, resistance to salt water and wearability detect, wherein hardness test by GB/T 6739 specify into
OK, result evaluation: paint film abrades；Thermostability test is evaluated with initial pyrolyzation temperature, obtains according to thermogravimetric analysis；Impact resistance
Property test carry out by GB/T 1732 regulation, result evaluation: 4 times of magnifieres are observed, paint film flawless, wrinkle and peeling phenomenon；Resistance to
Solvent scouring test is carried out by GB/T 23989 Instrumental wipe method regulation, and solvent is butanone；GB/T is pressed in acid resistance test
In 9274 infusion method regulation carry out, medium be mass fraction be the hydrochloric acid solution of 3%；Resistance to salt water test is pressed in GB/T 9274
Infusion method regulation carry out, medium be mass fraction be the NaCl solution of 5%；Wearability test is carried out by GB/T 1768 regulation, sand
Wheel model: CS-10；), shown in testing result table 1 below and table 2.
Table 1 comparative example and embodiment 1-4 properties of product (sandblasting aluminium flake) test result
Table 2 comparative example and embodiment 1-4 properties of product (sandblasting iron plate) test result
Through inspection, the compound modified aqueous polyurethane that changes of this embodiment 1-4, for comparative example, has the hard of excellence
Degree, thermostability, resistance to impact, solvent resistant scrubbing character, acid resistance, resistance to salt water and wearability, illustrate to be repaiied by silane coupler
Ludox after decorations, Graphene can being dispersed in aqueous polyurethane with stable and uniform, it is to avoid the agglomeration between particle,
And make to increase between Ludox, Graphene particle and polyurethane macromolecular chain to hand over by adding side chain small molecule chain extender
Connection, makes combination between the two the tightst.This composite modified aqueous polyurethane has the hardness, pliable and tough of excellence after film forming
Property, compactness, resistance to impact, corrosion resistance, resistance to water etc..
For a person skilled in the art, can technical scheme as described above and design, make other each
Plant corresponding change and deformation, and all these changes and deforms the protection model that all should belong to the claims in the present invention
Within enclosing.
Claims (10)
1. a preparation method for composite modified aqueous polyurethane, comprises the following steps:
1) performed polymer is prepared: macromolecular polyol, polyisocyanates are added catalyst prepolymerization, adds small molecule alcohol chain extender
With small carboxylic acid molecules's chain extender, add salt forming agent after dilution, obtain Waterborne Polyurethane Prepolymer；
2) Ludox is modified: reacted with silane coupler by acidic silicasol；
3) emulsifying: by step 1) Waterborne Polyurethane Prepolymer that obtains adds to through step 2) process after acidic silicasol, add
Deionized water obtains silica sol modified aqueous urethane through high speed shear emulsion dispersion；
4) grapheme modified: Graphene is reacted with silane coupler；
5) composite modified: by step 3) silica sol modified aqueous urethane that obtains joins through step 4) Graphene that processes,
Mixing reaction obtains composite modified aqueous polyurethane.
Preparation method the most according to claim 1, it is characterised in that step 1) in, described macromolecular polyol is poly-
Ester polyol or polyether polyol；Described polyisocyanates selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate；Described catalyst is sub-selected from dibutyl tin laurate, octanoic acid
Stannum.
Preparation method the most according to claim 2, it is characterised in that step 1) in, described PEPA or polyethers are many
The relative molecular weight of unit's alcohol is 1000 or 2000；Described PEPA is 10PE27, polybutyleneadipate
Ester, polyadipate hexanediol ester or Merlon；Described polyether polyol is polypropylene glycol or polytetrahydrofuran diol.
Preparation method the most according to claim 1, it is characterised in that step 1) in, described small molecule alcohol chain extender is
In 1,4-butanediol, ethylene glycol, hexanediol, diglycol, neopentyl glycol, trimethylolpropane one or both with
On；Described small carboxylic acid molecules's chain extender is 2,2-dihydromethyl propionic acid or 2,2-dimethylolpropionic acid.
Preparation method the most according to claim 1, it is characterised in that step 1) in, add solvent and be diluted, described molten
Agent is acetone, butanone or oxolane；Described salt forming agent is triethylamine, triethanolamine or ammonia.
Preparation method the most according to claim 1, it is characterised in that step 1) in, during preparing performed polymer, each component
Proportioning by weight is as follows: 40-60 part macromolecular polyol, 20-40 part polyisocyanates, 0.2-0.5 part catalyst, 2-
5 parts of small molecule alcohol chain extenders, 2-8 part small carboxylic acid molecules's chain extender, 10-20 part solvent, 2-5 part salt forming agents.
Preparation method the most according to claim 1, it is characterised in that step 2) and/or step 4) in, described silane coupled
Agent is selected from MTMS, MTES, KH560 or KH570.
Preparation method the most according to claim 1, it is characterised in that step 2) in, acidic silicasol and silane coupler
Isopropanol reacts, described acidic silicasol pH value=4.
9. the composite modified aqueous polyurethane prepared according to claim 1-8 any one method.
10. the composite modified aqueous polyurethane prepared according to claim 1-8 any one method is at sheet metal surface
Application.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110540801A (en) * | 2019-09-21 | 2019-12-06 | 盐城增材科技有限公司 | Environment-friendly flame-retardant heat-insulating conductive water-based paint and application thereof |
| CN111117467A (en) * | 2019-12-30 | 2020-05-08 | 烟台大学 | Preparation method of graphene-modified flame-retardant water-based polyurethane coating and adhesive |
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| CN111234167A (en) * | 2020-04-03 | 2020-06-05 | 胡黎明 | Preparation method of high-stability organic silicon modified waterborne polyurethane |
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| CN118667424A (en) * | 2024-07-29 | 2024-09-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of anti-erosion nano coating for protecting front edge of wind power blade, product and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540801A (en) * | 2019-09-21 | 2019-12-06 | 盐城增材科技有限公司 | Environment-friendly flame-retardant heat-insulating conductive water-based paint and application thereof |
| CN111117467A (en) * | 2019-12-30 | 2020-05-08 | 烟台大学 | Preparation method of graphene-modified flame-retardant water-based polyurethane coating and adhesive |
| CN111117467B (en) * | 2019-12-30 | 2021-07-09 | 烟台大学 | Preparation method of graphene modified flame retardant waterborne polyurethane coating |
| CN111171374A (en) * | 2020-01-22 | 2020-05-19 | 黎明化工研究设计院有限责任公司 | A kind of modified silica sol, its preparation method and application in all-water-based foaming polyurethane spray foam |
| CN111171374B (en) * | 2020-01-22 | 2022-05-24 | 黎明化工研究设计院有限责任公司 | Modified silica sol, preparation method thereof and application of modified silica sol in all-water-based foaming polyurethane spraying foam |
| CN111234167A (en) * | 2020-04-03 | 2020-06-05 | 胡黎明 | Preparation method of high-stability organic silicon modified waterborne polyurethane |
| CN112679695A (en) * | 2020-04-03 | 2021-04-20 | 胡黎明 | Preparation method of high-stability organic silicon modified waterborne polyurethane |
| CN112679696A (en) * | 2020-04-03 | 2021-04-20 | 胡黎明 | Preparation method of high-stability organosilicon modified waterborne polyurethane |
| CN113831830A (en) * | 2021-09-28 | 2021-12-24 | 江苏图研新材料科技有限公司 | A kind of high-barrier polyurethane self-healing composition and preparation method thereof |
| CN118667424A (en) * | 2024-07-29 | 2024-09-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of anti-erosion nano coating for protecting front edge of wind power blade, product and application thereof |
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