CN109575192B - 一种无乳化剂水性聚氨酯丙烯酸酯疏水乳液及其制备方法 - Google Patents
一种无乳化剂水性聚氨酯丙烯酸酯疏水乳液及其制备方法 Download PDFInfo
- Publication number
- CN109575192B CN109575192B CN201811351538.1A CN201811351538A CN109575192B CN 109575192 B CN109575192 B CN 109575192B CN 201811351538 A CN201811351538 A CN 201811351538A CN 109575192 B CN109575192 B CN 109575192B
- Authority
- CN
- China
- Prior art keywords
- acrylate
- diisocyanate
- polyurethane prepolymer
- total mass
- acrylate monomer
- 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.)
- Expired - Fee Related
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 49
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 44
- 239000004814 polyurethane Substances 0.000 title claims abstract description 44
- 239000000839 emulsion Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 14
- 238000004945 emulsification Methods 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 19
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 17
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 235000019441 ethanol Nutrition 0.000 claims abstract description 8
- 239000012948 isocyanate Substances 0.000 claims abstract description 8
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000005345 coagulation Methods 0.000 claims abstract description 6
- 230000015271 coagulation Effects 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 239000003973 paint Substances 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 150000002009 diols Chemical class 0.000 claims description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-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
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- -1 small molecule diol Chemical class 0.000 claims description 8
- 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 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- STYXVTBFUKQEKM-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F STYXVTBFUKQEKM-UHFFFAOYSA-N 0.000 claims description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- TWLCPLJMACDPFF-UHFFFAOYSA-N cyclohexane;1,2-diisocyanatoethane Chemical compound C1CCCCC1.O=C=NCCN=C=O TWLCPLJMACDPFF-UHFFFAOYSA-N 0.000 claims description 2
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 claims description 2
- 230000032798 delamination Effects 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- XJRAOMZCVTUHFI-UHFFFAOYSA-N isocyanic acid;methane Chemical compound C.N=C=O.N=C=O XJRAOMZCVTUHFI-UHFFFAOYSA-N 0.000 claims description 2
- 125000005609 naphthenate group Chemical group 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 34
- 239000003995 emulsifying agent Substances 0.000 abstract description 14
- 238000003860 storage Methods 0.000 abstract description 9
- 239000003381 stabilizer Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004321 preservation Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000007547 defect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920003009 polyurethane dispersion Polymers 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 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 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 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 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- OVDVGECZCGXFJO-UHFFFAOYSA-N benzene-1,3-diamine;sodium Chemical compound [Na].NC1=CC=CC(N)=C1 OVDVGECZCGXFJO-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
本发明公开了一种无乳化剂水性聚氨酯丙烯酸酯疏水乳液及其制备方法；该制备方法是在将二羟甲基丁酸、小分子二元醇及低聚物二元醇加入到反应器中，脱水，降温，加入异氰酸酯，搅拌均匀，加入催化剂，加入丙烯酸酯单体，反应，再加入甲基丙烯酸羟乙酯，反应，降温，加入无水乙醇进行封端；降温至40℃以下，调节体系PH至6.8～7.0，再加入含氟丙烯酸酯单体，搅拌均匀，加水分散均匀，得到水性聚氨酯预聚体分散液；水性聚氨酯预聚体分散液升温至75～85℃，滴加引发剂1～3h进行丙烯酸酯聚合，再保温，得到PUA乳液；本发明无需加入乳化剂、助稳定剂和丙酮等溶剂，分散效果佳，储存稳定性好，无凝聚沉淀现象，无溶剂残留。
Description
技术领域
本发明涉及一种水性聚氨酯丙烯酸酯(PUA)，具体涉及一种无乳化剂水性聚氨酯丙烯酸酯疏水乳液及其制备方法。
背景技术
随着环保法规的不断加强以及民众环保意识的不断增强，要求降低挥发性有机化合物(VOC)的排放。水性涂料因符合市场和环保需求而得到快速发展，并逐渐取代油性涂料成为市场的主导。水性聚氨酯因其具有耐磨性好、低温柔韧性好、附着力好、弹性好等优点，被广泛应用。目前，水性聚氨酯的制备一般采用丙酮法，即以丙酮为溶剂进行反应。当反应完成后，加水自乳化分散得到水性聚氨酯分散液，再将丙酮抽走，得到少溶剂残留的水性聚氨酯。丙酮法因其在制备过程中使用溶剂，一定程度上增加生产成本，同时会造成环境污染。但是，若不加溶剂，反应体系因黏度太高难以分散、使得反应中断甚至凝胶。
另外，水性聚氨酯还具有耐水性差、耐热性不好等缺点，在一定程度上限制其广泛使用。除此，为提高水性PUA的稳定性，常常在体系中加入乳化剂，但会严重影响漆膜的耐水性。
申请公布号为CN104530370A的中国发明专利申请，通过自乳化细乳液法，制备得到不需外加乳化剂、少加助稳定剂的无溶剂非离子型水性聚氨酯乳液。该发明的优点是提供了一种无溶剂无乳化剂制备非离子水性聚氨酯的方法。然而，该体系中还需加入助稳定剂以维持稳定性。同时，水性聚氨酯自身存在的耐水性差、耐热性不好、机械强度低等缺点并没有得到改善，而非离子链段的引入也会在一定程度上影响漆膜的耐水性。
申请公布号为CN106893041A的中国发明专利申请，通过在体系中加入10～30wt％的丙烯酸酯单体(丙烯酸‐2‐羟乙酯、甲基丙烯酸甲酯、丙烯酸乙酯)取代丙酮制备聚氨酯预聚体，以达到无溶剂制备水性聚氨酯的效果；在体系中加入1.5～3.0wt％的磺酸盐扩链剂(乙二胺基磺酸钠或3，5-二胺基苯磺酸钠)以提供亲水基团；后用0.1～0.5％的二胺类扩链剂对聚氨酯分散液进行扩链；在丙烯酸酯聚合之前，在体系中加入0.3～1.0wt％乳化剂形成乳化液，再在50～70℃加入0.01～0.10wt％的起始剂聚合丙烯酸酯，在75～85℃恒温1-3后，降温至50～70℃后加入0.01～0.08wt％还原剂，得到丙烯酸酯接枝改性水性聚氨酯。该发明专利的优点是提供了一种无溶剂制备水性聚氨酯的方法。然而，在该发明中，水性聚氨酯分散液经后扩链得到的是两端均有双键的聚氨酯预聚体，在丙烯酸酯聚合的过程中易形成互相缠绕的大分子链段而导致乳液不稳定，同时限制丙烯酸酯单体的用量。另外，该发明需要使用乳化剂以维持体系的稳定，乳化剂的使用在一定程度上会影响漆膜的疏水性。
王步华等(王步华等，工程科技，15.3)在《水性丙烯酸酯聚氨酯乳液的合成及性能》中以异佛尔酮二异氰酸酯、聚醚二元醇(N210)、二羟甲基丙酸、三羟甲基丙烷制备得到水性聚氨酯预聚体，以丙烯酸羟乙酯作为封端剂，以三乙胺作为中和剂，加水分散得到水性聚氨酯分散液。而后滴加甲基丙烯酸甲酯和偶氮二异丁腈的混合液反应得到水性丙烯酸酯聚氨酯乳液。在制备水性聚氨酯的过程中，需要加入丙酮调节体系黏度，而且加入的丙酮需要通过加热、抽滤的方法脱除。在该制备方法中，丙酮的使用在一定程度上增加生产成本，同时会造成环境污染。另外，丙酮的脱除大大降低生产效率及增加生产能耗。
发明内容
为了解决上述水性聚氨酯制备过程中存在的使用溶剂、使用乳化剂和助稳定剂等问题以及水性聚氨酯自身存在的耐水性差、耐热性不好等缺点，本发明提供一种具有疏水性，耐水性好，储存稳定性好，耐热性好、机械强度高的无乳化剂水性聚氨酯丙烯酸酯疏水乳液及其制备方法。
本发明以甲基丙烯酸羟乙酯和无水乙醇作为水性聚氨酯的封端剂，得到单个双键封端的聚氨酯链段，避免后续形成互相缠绕的大分子链段影响体系稳定性，同时甲基丙烯酸羟乙酯作为接枝改性水性聚氨酯的单体；以甲基丙烯酸甲酯和丙烯酸丁酯作为合成水性聚氨酯的稀释剂，能在丙酮等溶剂的情况下有效降低水性聚氨酯的黏度以保证反应持续有效进行，同时作为合成PUA的原料；把含氟丙烯酸酯单体接枝到体系中，能在很大程度上提高漆膜的耐水性，得到具有疏水性的漆膜；以DMBA为体系提供亲水基团，无需外加乳化剂和助稳定剂及丙酮等溶剂，得到的PUA无凝聚沉淀等现象，储存稳定性好。
本发明目的通过如下技术方案实现：
一种无乳化剂水性聚氨酯丙烯酸酯疏水乳液的制备方法，包括以下步骤：
1)水性聚氨酯预聚体分散液的制备：将二羟甲基丁酸(DMBA)、小分子二元醇及低聚物二元醇加入到反应器中，脱水，降温至75～90℃，加入异氰酸酯，搅拌均匀，加入催化剂，加入丙烯酸酯单体，反应2.5～4h，再加入甲基丙烯酸羟乙酯(HEMA)，反应0.5～3h，降温至50～70℃，加入无水乙醇进行封端；反应结束后，降温至40℃以下，加入叔胺类中和剂调节体系PH至6.8～7.0，再加入含氟丙烯酸酯单体，搅拌均匀，加水分散均匀，得到水性聚氨酯预聚体分散液；所述的催化剂为有机锡催化剂、有机铋类催化剂、复合铋类催化剂和环烷酸盐类催化剂中的一种或多种；所述的低聚物二元醇的分子量为500～3000；所述的异氰酸酯为二异氰酸酯；所述的丙烯酸酯单体为质量比50：50～95：5的甲基丙烯酸甲酯和丙烯酸丁酯的混合物；
2)水性聚氨酯丙烯酸酯(PUA)的合成：将步骤1)中制得的水性聚氨酯预聚体分散液升温至75～85℃，滴加引发剂1～3h进行丙烯酸酯聚合，再保温1～4h，得到PUA乳液；所述的引发剂为过硫酸铵和/或过硫酸钾，用量为丙烯酸酯单体总质量的0.01～2.5wt％。
为进一步实现本发明目的，优选地，所述的小分子二元醇为1，4-丁二醇、一缩二乙二醇、1，4-环己烷二甲醇、1，5-戊二醇、1，6-己二醇、1，4-环己烷二醇和新戊二醇中的一种或多种。
优选地，，所述的低聚物二元醇为聚醚二元醇、聚酯二元醇和聚碳酸酯二元醇中的一种或多种。
优选地，所述的二异氰酸酯为异佛尔酮二异氰酸酯、1，6-六亚甲基二异氰酸酯、甲苯二异氰酸酯、1，4-环己烷二异氰酸酯、对苯二异氰酸酯、二甲苯基甲烷二异氰酸酯、二甲基联苯二异氰酸酯、环己烷二亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯和4，4-二异氰酸酯二环己基甲烷中的一种或多种。
优选地，所述的含氟丙烯酸酯单体为甲基丙烯酸三氟乙酯、甲基丙烯酸六氟丁酯、全氟己基乙基甲基丙烯酸酯、全氟烷基辛基乙基丙烯酸酯中的一种或多种。
优选地，所述的叔胺类中和剂为三乙胺。
优选地，二羟甲基丁酸、小分子二元醇、异氰酸酯、入甲基丙烯酸羟乙酯和无水乙醇组成聚氨酯预聚体；所述的二羟甲基丁酸用量为聚氨酯预聚体总质量的5～10wt％；所述的小分子二元醇用量为聚氨酯预聚体总质量的0～10wt％；所述的低聚物二元醇的用量为聚氨酯预聚体总质量的20～70wt％；所述的异氰酸酯的质量为聚氨酯预聚体总质量的5～70wt％；所述的甲基丙烯酸羟乙酯的用量为聚氨酯预聚体总质量的2～30wt％；所述催化剂的用量为聚氨酯预聚体总质量的0.05～2.00wt％；所述的无水乙醇的用量为聚氨酯预聚体总质量的0.05～10wt％。
优选地，所述的丙烯酸酯单体和含氟丙烯酸酯的质量和与聚氨酯预聚体的质量比为5：95～40：60；所述的含氟丙烯酸酯单体的用量为甲基丙烯酸甲酯和丙烯酸丁酯总质量的5～60wt％；所述的引发剂的用量为丙烯酸酯单体总质量的0.01～2.5wt％。
优选地，步骤1所述的脱水是在90～110℃真空脱水40～60min；所述加入无水乙醇进行封端的时间为0.5～3h；所述的加水分散均匀是加水在200rmp～4000rmp条件下分散至均匀；
一种无乳化剂水性聚氨酯丙烯酸酯疏水乳液，由上述制备方法制得；该水性聚氨酯丙烯酸酯疏水乳液在50℃储存30天以上不发生凝聚、分层、沉淀和破乳；所得漆膜的水接触角大于90°，漆膜在水中浸泡48小时未见发白现象；漆膜拉伸强度大于6MPa；漆膜断裂伸长率大于100％。
相对于现有技术，本发明的优点和有效效果为：
(1)本发明的无溶剂无乳化剂制备疏水水性PUA的方法，以丙烯酸酯单体代替丙酮等溶剂，达到降低体系黏度，维持体系稳定反应的效果，同时有效降低生产成本；
(2)本发明的无溶剂无乳化剂制备疏水水性PUA的方法，以DMBA为体系提供亲水基团，在无需外加乳化剂和助稳定剂的条件下，制备得到具有优异储存稳定性的水性PUA；
(3)本发明以含氟丙烯酸酯单体对体系进行改性，能有效改善体系耐水性不好等缺点，得到的PUA漆膜具有疏水性；
(4)本发明以丙烯酸酯接枝改性的方法，能有效改善聚氨酯耐热性不好、机械强度低等缺点。
(5)本发明采用甲基丙烯酸羟乙酯和无水乙醇对水性聚氨酯进行封端，得到单个双键封端的聚氨酯链段，避免后续形成互相缠绕的大分子链段影响体系稳定性，避免造成凝胶、凝聚沉淀等现象。
具体实施方式
为更好地理解本发明，下面结合实施例对本发明作进一步的说明，但本发明的实施方式不限如此。
实施例1
取15.10g的二羟甲基丁酸(DMBA)、13.33g的1，4‐丁二醇(BDO)及111.67g的PTMEG1000加入到反应器中，于95℃真空脱水45min，降温至85℃加入100g的异佛尔酮二异氰酸酯(IPDI)，搅拌均匀，加入1.5g的二丁基锡二月桂酸酯，反应1h后，加入43.81g的甲基丙烯酸甲酯(MMA)和43.81g的丙烯酸丁酯(BA)，继续反应2h，再加入11.50g的甲基丙烯酸羟乙酯(HEMA)，反应2h后降温至65℃，加入4.07g的无水乙醇进行封端1h。反应结束后，降至室温，加入9.28g的三乙胺，搅拌10min后，再加入21.90g的全氟烷基辛基乙基丙烯酸酯，搅拌10min后，在转速为1000rpm的条件下加561.51g去离子水高速分散20min，再升温至85℃，滴加引发剂(1.12g的过硫酸铵和311.95g的去离子水)1.5h，再保温2h，即可得到无溶剂无乳化剂的水性PUA。
实施例2
取17.5g的二羟甲基丁酸(DMBA)、16.7g的一缩二乙二醇及102.1g的PEG1000加入到反应器中，于105℃真空脱水40min，降温至85℃加入100g的异佛尔酮二异氰酸酯(IPDI)，搅拌均匀，加入2.3g的辛酸亚锡，反应1h后，加入44g的甲基丙烯酸甲酯(MMA)和24g的丙烯酸丁酯(BA)，继续反应2h，再加入12.3g的甲基丙烯酸羟乙酯(HEMA)，反应2.5h后降温至70℃，加入4.50g的无水乙醇进行封端2h。反应结束后，降至室温，加入10.55g的三乙胺，搅拌10min后，再加入17.04g的全氟己基乙基甲基丙烯酸酯，搅拌10min后，在转速为1000rpm的条件下加525g去离子水高速分散25min，再升温至80℃，滴加引发剂(0.89g的过硫酸钾和291.67g的去离子水)2h，再保温2.5h，即可得到无溶剂无乳化剂的水性PUA。
实施例3
取18g的二羟甲基丁酸(DMBA)、21.36g的1，4-环己烷二甲醇及125.3g的PTMG1000加入到反应器中，于100℃真空脱水60min，降温至85℃加入75.60g的1，6-六亚甲基二异氰酸酯(HDI)，搅拌均匀，加入1.85g的辛酸亚锡，反应1h后，加入31g的甲基丙烯酸甲酯(MMA)和20g的丙烯酸丁酯(BA)，继续反应2h，再加入10.4g的甲基丙烯酸羟乙酯(HEMA)，反应2.5h后降温至70℃，加入4.95g的无水乙醇进行封端2h。反应结束后，降至室温，加入10.45g的三乙胺，搅拌10min后，再加入12.79g的全氟烷基辛基乙基丙烯酸酯，搅拌10min后，在转速为1500rpm的条件下加493.07g去离子水高速分散20min，再升温至85℃，滴加引发剂(0.72g的过硫酸铵和273.93g的去离子水)1.5h，再保温2h，即可得到无溶剂无乳化剂的水性PUA。
对比实施例1：
该实施例采用丙酮法制备水性聚氨酯，以二乙胺作为后扩链剂，说明如下。
取15.1g的二羟甲基丁酸(DMBA)、13.33g的1，4‐丁二醇(BDO)及111.67g的PTMG1000加入到反应器中，于100℃真空脱水60min，降温至85℃加入100g的异佛尔酮二异氰酸酯(IPDI)，搅拌均匀，加入1.50g的二丁基锡二月桂酸酯，反应3h，期间视体系黏度补加丙酮降黏。反应结束后，降至室温，加入9.28g的三乙胺，搅拌10min后，在转速为1000rpm的条件下加入471.01g去离子水高速分散20min，再加入乙二胺溶液(4.24g乙二胺和120.77g去离子水的溶液)进行后扩链30min，得到水性聚氨酯分散液。
结果：
取上述实施例的分散液制成漆膜，经测试，结果如表1所示：
表1：不同实施例性能测试结果
表1中，按照GB/T528-1998标准来评价漆膜的拉伸强度和断裂伸长率。按照申请公布号为CN104449141A的中国发明专利申请方法进行水接触角测试。按照GB1733-79(88)标准评价漆膜的耐水性。按照申请公布号为CN106893041A的中国发明专利申请方法测试漆膜的耐热粘着性能。按照GB-T6753.3-1986标准来评价乳液的储存稳定性。
本发明以丙烯酸酯接枝改性的方法，能有效改善聚氨酯耐热性不好、机械强度低等缺点。本发明以含氟丙烯酸酯单体对体系进行改性，能有效改善体系耐水性不好等缺点，得到的PUA漆膜具有疏水性；本发明采用甲基丙烯酸羟乙酯和无水乙醇对水性聚氨酯进行封端，得到单个双键封端的聚氨酯链段，避免后续形成互相缠绕的大分子链段影响体系稳定性，避免造成凝胶、凝聚沉淀等现象。本发明以丙烯酸酯单体代替丙酮等溶剂，达到降低体系黏度，维持体系稳定反应的效果，同时有效降低生产成本；本发明以DMBA为体系提供亲水基团，在无需外加乳化剂和助稳定剂的条件下，制备得到具有优异储存稳定性的水性PUA；从表1的结果可以发现，随着体系丙烯酸酯含量的增加，漆膜的拉伸强度增加，断裂伸长率降低，水接触角变大，耐水性变好，耐热性也有所提高，说明本发明采用无溶剂无乳化剂制备得到的丙烯酸酯接枝改性水性聚氨酯的方法能提高水性聚氨酯的机械强度、耐热性及疏水性。同时，从乳液储存稳定性测试可以看出，本发明的无溶剂无乳化剂制备得到的水性PUA具有优异的储存稳定性。
本发明提供一种无乳化剂水性聚氨酯丙烯酸酯疏水涂层的制备方法，制备过程无需加入乳化剂、助稳定剂和丙酮等溶剂，分散效果佳，储存稳定性好，无溶剂残留等问题，适合于大规模工业生产和推广应用，同时得到的水性PUA具有优异的机械强度和疏水性，可用于皮革、瓷砖、塑料、玻璃、金属等多种基材，具有很好的应用前景。
对于本领域的技术人员来说，在本发明的原理下，可以对上述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (7)
1.一种无乳化剂水性聚氨酯丙烯酸酯疏水乳液的制备方法，其特征在于由以下步骤组成：
1)水性聚氨酯预聚体分散液的制备：将二羟甲基丁酸、小分子二元醇及低聚物二元醇加入到反应器中，脱水，降温至75～90℃，加入异氰酸酯，搅拌均匀，加入催化剂，加入丙烯酸酯单体，反应2.5～4h，再加入甲基丙烯酸羟乙酯，反应0.5～3h，降温至50～70℃，加入无水乙醇进行封端；反应结束后，降温至40℃以下，加入叔胺类中和剂调节体系pH至6.8～7.0，再加入含氟丙烯酸酯单体，搅拌均匀，加水分散均匀，得到水性聚氨酯预聚体分散液；所述的催化剂为有机锡催化剂、有机铋类催化剂、复合铋类催化剂和环烷酸盐类催化剂中的一种或多种；所述的低聚物二元醇的分子量为500～3000；所述的异氰酸酯为二异氰酸酯；所述的丙烯酸酯单体为质量比50：50～95：5的甲基丙烯酸甲酯和丙烯酸丁酯的混合物；
2)水性聚氨酯丙烯酸酯的合成：将步骤1)中制得的水性聚氨酯预聚体分散液升温至75～85℃，滴加引发剂1～3h进行丙烯酸酯聚合，再保温1～4h，得到PUA乳液；所述的引发剂为过硫酸铵和/或过硫酸钾，用量为丙烯酸酯单体总质量的0.01～2.5wt％；
所述的含氟丙烯酸酯单体为甲基丙烯酸三氟乙酯、甲基丙烯酸六氟丁酯、全氟己基乙基甲基丙烯酸酯、全氟烷基辛基乙基丙烯酸酯中的一种或多种；
所述的二羟甲基丁酸用量为聚氨酯预聚体总质量的5～10wt％；所述的小分子二元醇用量为聚氨酯预聚体总质量的0～10wt％；所述的低聚物二元醇的用量为聚氨酯预聚体总质量的20～70wt％；所述的异氰酸酯的质量为聚氨酯预聚体总质量的5～70wt％；所述的甲基丙烯酸羟乙酯的用量为聚氨酯预聚体总质量的2～30wt％；所述催化剂的用量为聚氨酯预聚体总质量的0.05～2.00wt％；所述的无水乙醇的用量为聚氨酯预聚体总质量的0.05～10wt％；
所述的丙烯酸酯单体和含氟丙烯酸酯的质量和与聚氨酯预聚体的质量比为5：95～40：60；所述的含氟丙烯酸酯单体的用量为甲基丙烯酸甲酯和丙烯酸丁酯总质量的5～60wt％；所述的引发剂的用量为丙烯酸酯单体总质量的0.01～2.5wt％。
2.根据权利要求1所述的制备方法，其特征在于，所述的小分子二元醇为1，4-丁二醇、一缩二乙二醇、1，4-环己烷二甲醇、1，5-戊二醇、1，6-己二醇、1，4-环己烷二醇和新戊二醇中的一种或多种。
3.根据权利要求1所述的制备方法，其特征在于，所述的低聚物二元醇为聚醚二元醇、聚酯二元醇和聚碳酸酯二元醇中的一种或多种。
4.根据权利要求1所述的制备方法，其特征在于，所述的二异氰酸酯为异佛尔酮二异氰酸酯、1，6-六亚甲基二异氰酸酯、甲苯二异氰酸酯、1，4-环己烷二异氰酸酯、对苯二异氰酸酯、二甲苯基甲烷二异氰酸酯、二甲基联苯二异氰酸酯、环己烷二亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯和4，4-二异氰酸酯二环己基甲烷中的一种或多种。
5.根据权利要求1所述的制备方法，其特征在于，所述的叔胺类中和剂为三乙胺。
6.根据权利要求1所述的制备方法，其特征在于，步骤1所述的脱水是在90～110℃真空脱水40～60min；所述加入无水乙醇进行封端的时间为0.5～3h；所述的加水分散均匀是加水在200rmp～4000rmp条件下分散至均匀。
7.一种无乳化剂水性聚氨酯丙烯酸酯疏水乳液，其特征在于，其由权利要求1-6任一项所述制备方法制得；该水性聚氨酯丙烯酸酯疏水乳液在50℃储存30天以上不发生凝聚、分层、沉淀和破乳；所得漆膜的水接触角大于90°，漆膜在水中浸泡48小时未见发白现象；漆膜拉伸强度大于6MPa；漆膜断裂伸长率大于100％。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811351538.1A CN109575192B (zh) | 2018-11-14 | 2018-11-14 | 一种无乳化剂水性聚氨酯丙烯酸酯疏水乳液及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811351538.1A CN109575192B (zh) | 2018-11-14 | 2018-11-14 | 一种无乳化剂水性聚氨酯丙烯酸酯疏水乳液及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109575192A CN109575192A (zh) | 2019-04-05 |
| CN109575192B true CN109575192B (zh) | 2020-09-22 |
Family
ID=65922414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811351538.1A Expired - Fee Related CN109575192B (zh) | 2018-11-14 | 2018-11-14 | 一种无乳化剂水性聚氨酯丙烯酸酯疏水乳液及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109575192B (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110294989A (zh) * | 2019-07-02 | 2019-10-01 | 高碧香 | 一种复合纳米涂料及其制备方法 |
| CN111234124B (zh) * | 2020-03-16 | 2020-12-15 | 中国科学院兰州化学物理研究所 | 一种无溶剂型室温自交联水性聚氨酯-丙烯酸酯乳液及其制备方法 |
| CN114058316B (zh) * | 2020-08-03 | 2023-08-25 | 卫星化学股份有限公司 | 一种具有良好润湿性的水性聚氨酯分散液及其制备方法 |
| CN113072873A (zh) * | 2021-04-30 | 2021-07-06 | 中科院长春应化所黄埔先进材料研究院 | 一种涂料及其制备方法与应用 |
| CN114106650A (zh) * | 2021-12-15 | 2022-03-01 | 中山市中益油墨涂料有限公司 | 一种水性吸塑油及其制备方法 |
| CN115302600A (zh) * | 2022-09-01 | 2022-11-08 | 广东大自然家居科技研究有限公司 | 一种改性实木地板及其制造方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6147722A (ja) * | 1984-08-14 | 1986-03-08 | Sanyo Kokusaku Pulp Co Ltd | ウレタン（メタ）アクリレートプレポリマー含有組成物 |
| US4711929A (en) * | 1985-03-18 | 1987-12-08 | E. I. Du Pont De Nemours And Company | Acrylourethane reaction product |
| JP2011052227A (ja) * | 2004-02-10 | 2011-03-17 | Daicel-Cytec Co Ltd | 活性エネルギー線硬化型樹脂組成物の硬化物 |
| CN106065049A (zh) * | 2016-06-01 | 2016-11-02 | 南雄市瑞晟化学工业有限公司 | 高固含量环保型水性聚氨酯‑丙烯酸酯复合乳液及其制备方法 |
| CN107141419A (zh) * | 2017-05-09 | 2017-09-08 | 佛山市三水协佳化工有限公司 | 一种氟碳型水性聚氨酯‑丙烯酸酯复合乳液及制备方法 |
-
2018
- 2018-11-14 CN CN201811351538.1A patent/CN109575192B/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN109575192A (zh) | 2019-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109575192B (zh) | 一种无乳化剂水性聚氨酯丙烯酸酯疏水乳液及其制备方法 | |
| CN112194772B (zh) | 高固自修复型水性聚氨酯丙烯酸酯及其制备方法 | |
| CN108586667B (zh) | 一种具有弹性交联的耐水浸聚氨酯改性聚丙烯酸酯乳液的制备方法及其产品 | |
| CN109608974B (zh) | 一种氟化水性聚氨酯及其制备方法和用途 | |
| US11053336B2 (en) | High heat resistant and high scratch resistant water-based polyurethane and manufacturing method thereof | |
| CN108467471B (zh) | 一种梳状多支化水性聚氨酯分散体及其制备与应用 | |
| CN110951041A (zh) | 一种水性聚氨酯-丙烯酸酯杂化共聚物及其制备方法 | |
| CN114181605A (zh) | 一种单组分水性聚氨酯防水涂料及其制备方法 | |
| CN109456449A (zh) | 一种彩色共聚型环氧改性水性聚氨酯及其制备方法 | |
| CN114181353B (zh) | 一种改性水性聚氨酯组合物的合成及应用 | |
| CN115449019A (zh) | 一种光响应型自修复含氟聚氨酯丙烯酸酯复合乳液及其制备方法和应用 | |
| CN109575232B (zh) | 一种高抗张强度的无溶剂型水性聚氨酯及其制备方法 | |
| CN114409852A (zh) | 丙烯酸改性水性聚氨酯分散体及其制备方法 | |
| CN112980376A (zh) | 一种水性聚氨酯胶粘剂及其制备方法 | |
| CN114410174B (zh) | 一种高性能水性丙烯酸聚氨酯涂料及其制备方法 | |
| JP3661047B2 (ja) | 重合体水性分散液の製造方法 | |
| US11639414B2 (en) | Water-based polyurethane resin and manufacturing method thereof | |
| CN115851052A (zh) | 一种低污染、低表面能水性无氟涂料及其制备方法 | |
| CN116120801A (zh) | 一种用于金属表面的双组份改性聚氨酯乳液及制备方法 | |
| CN115612029A (zh) | 改性阳离子型水性聚氨酯分散体及其制备方法和应用 | |
| WO2021097659A1 (zh) | 一种环氧改性水性聚氨酯树脂防腐涂料的制备方法 | |
| CN111534215B (zh) | 用于汽车保险杠的水性涂料及其制备方法 | |
| CN111690097A (zh) | 一种核壳型聚酯-丙烯酸乳液及其制备方法和应用 | |
| CN111303349B (zh) | 二氧化碳基阳离子水性聚氨酯接枝聚丙烯酸酯分散体及其制备方法 | |
| CN116041713A (zh) | 一种三嵌段氟硅协同改性水性聚氨酯-丙烯酸酯乳液及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200922 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |