CN117165172A - Modified solvent-free polyurethane waterproof coating and preparation method thereof - Google Patents
Modified solvent-free polyurethane waterproof coating and preparation method thereof Download PDFInfo
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- CN117165172A CN117165172A CN202311183582.7A CN202311183582A CN117165172A CN 117165172 A CN117165172 A CN 117165172A CN 202311183582 A CN202311183582 A CN 202311183582A CN 117165172 A CN117165172 A CN 117165172A
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- Prior art keywords
- curing agent
- latent curing
- polyurethane waterproof
- coating
- polyurethane
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Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 84
- 239000004814 polyurethane Substances 0.000 title claims abstract description 84
- 238000000576 coating method Methods 0.000 title claims abstract description 83
- 239000011248 coating agent Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 85
- -1 C 1 ~C 6 Alkyl Chemical group 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000004014 plasticizer Substances 0.000 claims abstract description 31
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 27
- 239000000049 pigment Substances 0.000 claims abstract description 25
- 239000002270 dispersing agent Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 20
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- 239000013530 defoamer Substances 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 125000000732 arylene group Chemical group 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 150000001299 aldehydes Chemical class 0.000 claims description 33
- 239000003973 paint Substances 0.000 claims description 33
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 25
- 229920000570 polyether Polymers 0.000 claims description 25
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 17
- 150000004985 diamines Chemical class 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 3
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 3
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- DMTRWFMFBIMXBX-UHFFFAOYSA-L lead(2+);6-methylheptanoate Chemical compound [Pb+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O DMTRWFMFBIMXBX-UHFFFAOYSA-L 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 23
- 239000011527 polyurethane coating Substances 0.000 abstract description 18
- 238000010276 construction Methods 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 91
- 238000006243 chemical reaction Methods 0.000 description 46
- 238000003756 stirring Methods 0.000 description 17
- 238000006297 dehydration reaction Methods 0.000 description 16
- 229920005862 polyol Polymers 0.000 description 16
- 150000003077 polyols Chemical class 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 150000002466 imines Chemical class 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 229920005646 polycarboxylate Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004849 latent hardener Substances 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 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 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004705 aldimines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The application discloses a modified solvent-free polyurethane waterproof coating and a preparation method thereof, wherein the raw materials of the solvent-free polyurethane waterproof coating comprise: isocyanate-terminated polyurethane prepolymer, latent curing agent and auxiliary agent; the latent curing agent has a structure represented by formula (I):R 1 selected from C 1 ～C 10 Alkylene, optionally substituted C 6 ～C 10 Arylene group, C 3 ～C 8 Any one of cycloalkyl radicals, R 2 Selected from hydrogen atoms, C 1 ～C 6 Alkyl, aryl, C 3 ～C 6 Any one of cycloalkyl radicals, R 3 Any one selected from alkyl, aryl and cycloalkyl; the auxiliary agent comprises one or more of pigment filler, plasticizer, catalyst, dispersant and defoamer.The latent curing agent with the structure is used in the polyurethane coating, so that the volatile organic compounds generated in the coating curing process of the polyurethane coating can be reduced by about half, further, the release of pollutants in the construction process of the polyurethane coating is reduced, and the higher environmental protection requirement is met.
Description
Technical Field
The application relates to the technical field of waterproof coatings, in particular to a modified solvent-free polyurethane waterproof coating and a preparation method thereof.
Background
The polyurethane waterproof paint is prepared by mixing and processing prepolymer containing isocyanate groups, catalyst, auxiliary agent, filler and the like, which are generated by addition polymerization reaction of isocyanate, polyether and the like. The polyurethane waterproof paint is a reaction curing paint and has the characteristics of high strength, large elongation, good water resistance and the like.
Polyurethane waterproof coatings include solvent-based and solvent-free types, and with the increasing demand for environment protection of waterproof coatings, the demand for the content of Volatile Organic Compounds (VOC) in polyurethane waterproof coatings is also increasing. The solvent-free polyurethane waterproof paint is free from adding any volatile organic solvent, so that VOC release caused by solvent volatilization can be reduced, but the latent curing agent used by the solvent-free polyurethane waterproof paint can generate more aldehyde/ketone compounds to volatilize to the atmosphere in the paint curing process, so that the VOC release amount of the waterproof paint is still higher, and the increasingly higher environment-friendly requirement is difficult to meet.
Disclosure of Invention
Aiming at the problems in the prior art, the embodiment of the application provides a modified solvent-free polyurethane waterproof coating and a preparation method thereof, aiming at reducing the release of VOC (volatile organic compounds) in the construction process of the polyurethane waterproof coating so as to meet the higher and higher environmental protection requirements.
In a first aspect, an embodiment of the present application provides a modified solvent-free polyurethane waterproof coating, the raw materials of the coating include: isocyanate-terminated polyurethane prepolymer, latent curing agent and auxiliary agent;
the latent curing agent has a structure shown in formula (I):
R 1 selected from C 1 ～C 10 Alkylene, optionally substituted C 6 ～C 10 Arylene group, C 3 ～C 8 Any one of the cycloalkyl groups, the alkyl groups,
R 2 selected from hydrogen atoms, C 1 ～C 6 Alkyl, C 6 ～C 10 Aryl, C 3 ～C 6 Any one of cycloalkyl radicals, R 3 Any one selected from alkyl, aryl and cycloalkyl;
the auxiliary agent comprises one or more of pigment filler, plasticizer, catalyst, dispersing agent and defoamer.
The latent curing agent used in the embodiment of the application is a semi-closed imine latent curing agent, namely one end of the latent curing agent is reserved with amino, and compared with the fully-closed imine latent curing agent in the prior art, the latent curing agent reduces the amount of volatile organic compounds (mainly aldehyde/ketone compounds) generated in the polyurethane coating film curing process by about half, so that the pollutant release amount in the polyurethane coating construction process is greatly reduced, and further higher environmental protection requirements are met. In addition, the latent curing agent with the structure disclosed by the embodiment of the application has the advantages that as one end of the molecular structure of the latent curing agent is provided with the amino group, the amino group in the molecular structure of the latent curing agent reacts with isocyanate (-NCO) at the end of the polyurethane molecule in the early synthetic reaction process of the polyurethane coating, so that the molecular grafting of the latent curing agent on the polyurethane molecule can lead the regularity of the polyurethane molecular structure to be higher, and the strength and the tensile property of the polyurethane coating can be further improved.
In some embodiments of the application, in formula (I), R 1 Selected from ethylene, propylene, hexylene, and phenylene.
In some embodiments of the application, in formula (I), R 2 Selected from any one of hydrogen atom, methyl, ethyl, propyl, butyl and phenyl.
In some embodiments of the application, in formula (I), R 3 Selected from any one of methyl, ethyl, propyl, butyl, phenyl, hydroxyphenyl and allylphenyl.
In some embodiments of the application, the isocyanate-terminated polyurethane prepolymer comprises a polyether polyurethane prepolymer.
In some embodiments of the application, the auxiliary agent comprises one or more of a pigment filler, a plasticizer, a catalyst, a dispersant, and an antifoaming agent.
In some embodiments of the present application, the coating comprises the following raw materials in parts by weight: 100 parts of isocyanate-terminated polyurethane prepolymer, 7-15 parts of latent curing agent, 70-100 parts of pigment filler, 10-40 parts of plasticizer, 0.1-0.5 part of catalyst, 0.05-0.25 part of dispersing agent and 0.05-0.5 part of defoaming agent.
In some embodiments of the application, the pigment filler comprises one or more combinations of nano calcium carbonate, talc, fumed silica, barium sulfate, heavy calcium, kaolin, carbon black, iron oxide red, titanium dioxide.
In some embodiments of the application, the plasticizer comprises one or more combinations of chlorinated paraffin plasticizers, citrate plasticizers, phthalate plasticizers, trioctyl phosphate plasticizers.
In some embodiments of the application, the catalyst comprises one or more combinations of dibutyltin dilaurate, stannous octoate, lead isooctanoate, bismuth isooctanoate.
In some embodiments of the application, the dispersant comprises one or more combinations of anionic wetting dispersants. For example, the dispersant may be one or more combinations of polycarboxylates, ammonium polycarboxylates, sodium tripolyphosphate, sodium hexametaphosphate, sodium dodecyl sulfate.
In some embodiments of the application, the defoamer comprises one of a silicone-based defoamer, a mineral oil-based defoamer, or a combination thereof.
In some embodiments of the application, the coating has a volatile organic compound content of less than 18g/L.
In a second aspect, the embodiment of the application provides a preparation method of a modified solvent-free polyurethane waterproof coating, which comprises the following steps:
isocyanate-terminated polyurethane prepolymer, latent curing agent of formula (I) and auxiliary agent are provided separately,
wherein R is 1 Selected from C 1 ～C 10 Alkylene, optionally substituted C 6 ～C 10 Arylene group, C 3 ～C 8 Any one of the cycloalkyl groups, the alkyl groups,
R 2 selected from hydrogen atoms, C 1 ～C 6 Alkyl, C 6 ～C 10 Aryl, C 3 ～C 6 Any one of cycloalkyl radicals, R 3 Any one selected from alkyl, aryl and cycloalkyl;
and mixing the isocyanate-terminated polyurethane prepolymer, the latent curing agent and the auxiliary agent to obtain the modified solvent-free polyurethane waterproof coating.
In some embodiments of the application, the providing a latent hardener includes: the corresponding diamine and aldehyde/ketone compound react under the protection of inert atmosphere to obtain the latent curing agent, wherein the molar ratio of the diamine to the aldehyde/ketone compound is 1 (1-1.1).
In some embodiments of the application, the diamine comprises one or more combinations of ethylenediamine, propylenediamine, hexamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine.
In some embodiments of the application, the aldehyde/ketone compound comprises one or more of acetone, butanone, pentanone, cyclohexanone, acetophenone, methyl isobutyl ketone, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, benzaldehyde, salicylaldehyde, cinnamaldehyde.
Detailed Description
Features and exemplary embodiments of various aspects of the application are described in detail below. In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the application. It will be apparent, however, to one skilled in the art that the present application may be practiced without some of these specific details. The following description of the embodiments is merely intended to provide a better understanding of the application by showing examples of the application. In the following description, at least some well-known structures and techniques are not shown in order to avoid unnecessarily obscuring the present application; also, the dimensions of some of the structures may be exaggerated for clarity. Furthermore, the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. In the description of the present application, it is to be noted that the meaning of "plurality" is two or more unless otherwise specified. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of other like elements in a process, method, article or apparatus that comprises the element.
The polyurethane waterproof paint is a single-component polyurethane waterproof paint which is prepared by adding and polymerizing isocyanate, polyether and other prepolymers containing isocyanate groups, and mixing with catalysts, anhydrous auxiliary agents, anhydrous fillers, solvents and the like. The polyurethane waterproof coating is a reaction curing (moisture curing) coating, is a single-component environment-friendly waterproof coating for liquid construction, is cured after being contacted with moisture in air, and forms a layer of firm and tough seamless integral waterproof film on the surface of a base layer.
The polyurethane waterproof paint can be divided into a two-component system and a single-component system, and the polyurethane waterproof paint of the single-component system does not need to be addedOther cross-linking agents and adjuvants can be cured by means of only trace amounts of moisture. The curing mechanism of the single-component polyurethane waterproof coating is as follows: isocyanate groups (-NCO) in polyurethane molecule and water (H 2 O) reacting to form di-or polyamine, and further chain-extending the amine with isocyanate group to cure, wherein the curing method generates CO in the curing process 2 The gas remains in the material, so that pinholes appear on the surface of the material, the glossiness of the material is reduced, the internal bubbles and the strength are reduced, and the performance of the polyurethane material is seriously affected. To eliminate CO 2 The influence of gases, there are currently two main solutions in the industry: firstly, CO is removed by chemical or adsorption method 2 The CO is eliminated from the source by using the latent curing agent 2 And (3) generating gas.
The existing common latent curing agents mainly comprise an imine type substance and an oxazolidine type substance, the latent curing agent is a substance with good water reaction activity, after the latent curing agent is added into the polyurethane coating, the latent curing agent can react with water preferentially, the imine type latent curing agent reacts with water to generate primary amine, the oxazolidine type latent curing agent reacts with water to generate alcohol amine, and the primary amine or the alcohol amine reacts with isocyanate groups on the polyurethane to be cured. Since the isocyanate group does not react directly with water, no CO is present during curing 2 The gas is generated, so that the defects of pinholes, bubbles and the like on the surface of the material can be effectively improved.
The reaction mechanism of the partial imine latent curing agent for curing polyurethane is shown in the following formulas (II) and (III):
in the formula (II), R is an organic functional group such as alkyl, aryl, cycloalkyl, etc., and may contain an atomic group such as ether, ester, tertiary amine, etc., and may be different depending on the ketone, aldehyde, amine structure used. R is R 1 R ' may be a hydrogen atom or other groups, R ' is an aldimine if it is a hydrogen atom, and R ' is a ketimine if it is an organic group such as an alkyl group, an aryl group, or a cycloalkyl group.
According to the reaction process shown in the formulas (II) and (III), aldehyde/ketone compounds are generated in the reaction process of the latent curing agent and water in the curing process of the polyurethane coating, the aldehyde/ketone compounds do not participate in the curing reaction of the polyurethane coating, and in the curing process of a coating film, the aldehyde/ketone compounds volatilize into the environment to generate environmental pollution, which is also a main source of VOC in the construction process of the solvent-free polyurethane waterproof coating. As can be seen from the formula (II), the imine latent curing agent is a totally-enclosed latent curing agent, namely, both ends of one latent curing agent molecule are capped by aldehyde/ketone compounds serving as a sealing agent, and in the polyurethane coating curing process, the latent curing agent with one molecular weight reacts with water to release the aldehyde/ketone compounds with two molecular weights, which is also a main reason for excessively high VOC release in the existing solvent-free polyurethane waterproof coating construction process.
Based on this, the inventors have made a great deal of research aimed at providing a polyurethane waterproof paint capable of reducing the amount of VOC released during construction to meet the increasingly high environmental requirements.
In order to solve the problems in the prior art, the embodiment of the application provides a modified solvent-free polyurethane waterproof coating and a preparation method thereof.
Modified solvent-free polyurethane waterproof paint
An embodiment of the first aspect of the present application provides a modified solvent-free polyurethane waterproof coating, the raw materials of which include an isocyanate-terminated polyurethane prepolymer, a latent curing agent and an auxiliary agent;
the latent curing agent has a structure shown in formula (I):
R 1 selected from C 1 ～C 10 Alkylene, optionally substituted C 6 ～C 10 Arylene group, C 3 ～C 8 Any one of the cycloalkyl groups, the alkyl groups,
R 2 selected from hydrogen atoms, C 1 ～C 6 Alkyl, C 6 ～C 10 Aryl, C 3 ～C 6 Any one of cycloalkyl radicals, R 3 Any one selected from alkyl, aryl and cycloalkyl;
the auxiliary agent comprises one or more of pigment filler, plasticizer, catalyst, dispersant and defoamer.
The latent curing agent provided by the embodiment of the application is a semi-closed latent curing agent, wherein the amino group at one end of the molecule of the latent curing agent reacts with the aldehyde/ketone compound serving as the sealing agent, and the amino group at the other end of the molecule of the latent curing agent is reserved.
In the embodiments of the present application, the isocyanate-terminated polyurethane prepolymer means that the polyurethane prepolymer has a terminal isocyanate group. According to the embodiment of the application, in the curing process of the polyurethane waterproof coating, the semi-closed latent curing agent participates in the pre-curing reaction process of polyurethane, and the reaction mechanism of the semi-closed latent curing agent participating in the curing process of the polyurethane waterproof coating is shown in the following formulas (IV) and (V):
as can be seen from the reaction processes shown in formulas (IV) and (V), in the early preparation process of the polyurethane coating, the amino group at the end of the latent curing agent can react with the isocyanate group in the polyurethane molecule first, and then is grafted onto the polyurethane molecule, so that the structure of the polyurethane molecule is more regular. Compared with the traditional totally-enclosed imine latent curing agent, the latent curing agent participates in the reaction in the polyurethane synthesis process, and the molecular weight and the structure of polyurethane molecules generated by the reaction are more single in the stirring reaction process at a constant temperature, so that the compatibility among the molecules is better because the molecular weight and the structure are similar, and the tensile strength of the prepared coating film is higher.
In addition, as only one end of the latent curing agent can react with water to generate aldehyde/ketone compounds, the latent curing agent with one molecular weight can react with water to generate aldehyde/copper compounds with one molecular weight, compared with the fully-closed latent curing agent in the prior art, the generation amount of the aldehyde/ketone compounds is halved, namely the release amount of VOC is halved, so that the pollutant release amount of the polyurethane waterproof coating in the construction process can be greatly reduced, the environmental protection safety of the polyurethane waterproof coating is further improved, and the higher environmental protection requirement is met.
In the embodiment of the application, the optionally substituted arylene means that a hydrogen atom on the arylene group may be substituted with some substituents, and these substituents may be hydroxyl groups, halogen atoms, and the like.
In some embodiments, in formula (I), R 1 Selected from ethylene, propylene, hexylene, and phenylene.
In some embodiments, in formula (I), R 2 Selected from any one of hydrogen atom, methyl, ethyl, propyl, butyl and phenyl.
In some embodiments, in formula (I), R 3 Selected from any one of methyl, ethyl, propyl, butyl, phenyl, hydroxyphenyl and allylphenyl.
In some embodiments, the isocyanate-terminated polyurethane prepolymer comprises a polyether polyurethane prepolymer.
As will be understood by those skilled in the art, polyether polyurethane prepolymer refers to polyurethane prepolymer synthesized from polyether polyol and isocyanate, wherein the soft segment molecular chain in the prepolymer mainly contains ether bond and has terminal isocyanate group.
In some embodiments, the coating comprises the following raw materials in parts by weight: 100 parts of isocyanate-terminated polyurethane prepolymer, 7-15 parts of latent curing agent, 70-100 parts of pigment filler, 10-40 parts of plasticizer, 0.1-0.5 part of catalyst, 0.05-0.25 part of dispersing agent and 0.05-0.5 part of defoaming agent.
According to the embodiment of the application, the proportion of the raw material components is controlled within the range, so that the prepared coating has better strength and weather resistance, and meanwhile, the processing characteristics of the coating can be effectively improved, the coating is convenient to construct and fast to cure, and the cured coating has good mechanical strength and covering property.
In some embodiments, the pigment and filler comprises one or more combinations of nano calcium carbonate, talc, fumed silica, barium sulfate, heavy calcium, kaolin, carbon black, iron oxide red, titanium dioxide.
According to the embodiment of the application, the addition of the pigment and filler can change the rheological property of the polyurethane waterproof coating, so that the polyurethane waterproof coating has proper viscosity and fluidity, is convenient for construction and coating, can increase the strength and hardness of the coating after the pigment and filler are added, improves the physical property of the coating, improves the coverage rate of the coating, and increases the wear resistance and corrosion resistance; and meanwhile, the pigment and filler can improve the weather resistance and ageing resistance of the coating and increase the oxidation resistance and corrosion resistance of the coating.
In some embodiments, the plasticizer comprises one or more combinations of chlorinated paraffin plasticizers, citrate plasticizers, phthalate plasticizers, trioctyl phosphate plasticizers.
According to the embodiment of the application, the plasticizer can improve the flexibility and the ductility of the coating, so that the polyurethane coating can adapt to the deformation and the expansion of a base material, and the weather resistance and the crack resistance of a coating film are improved.
In some embodiments, the catalyst comprises one or more combinations of dibutyltin dilaurate, stannous octoate, lead iso-octoate, bismuth iso-octoate.
According to the embodiment of the application, the catalyst can accelerate the curing of the polyurethane coating, promote the polymerization reaction of the coating in the curing process of the coating film, and enable the coating to be rapidly cured and dried. Meanwhile, the catalyst can promote more cross-linked structures to be formed in the polyurethane coating, so that the hardness and chemical resistance of the coating are increased, and the wear resistance and corrosion resistance of the coating are improved.
In some embodiments, the dispersant comprises one or more combinations of anionic wetting dispersants. For example, the dispersant may be one or more combinations of polycarboxylates, ammonium polycarboxylates, sodium tripolyphosphate, sodium hexametaphosphate, sodium dodecyl sulfate.
According to the embodiment of the application, the dispersing agent can improve the dispersibility of pigment and filler in polyurethane paint, prevent pigment and filler from agglomerating and depositing, and maintain the stability of the paint, and the pigment and filler can be fully dispersed to increase the contact area between pigment and filler and resin base material, improve the strength and the covering property of the paint, improve the viscosity and the fluidity of the paint, and facilitate construction.
In some embodiments, the defoamer comprises one of a silicone-based defoamer, a mineral oil-based defoamer, or a combination thereof. For example, the defoamer may be one or more combinations of silicone emulsions, polyether-siloxane copolymers, polydimethylsiloxanes, white oils, petroleum ethers.
According to the embodiment of the application, the defoamer can prevent bubbles or foam from being generated in the paint, reduce the surface tension of the paint, reduce the defects of the paint and facilitate the coating construction of the paint.
In some embodiments, the volatile organic compound content of the coating is no more than 18g/L.
According to the embodiment of the application, the VOC release amount in the coating construction process can be further reduced by adjusting the composition ratio of the semi-sealing imine latent curing agent in the coating, and the higher environment-friendly requirement can be met.
Preparation method of modified solvent-free polyurethane waterproof coating
An embodiment of the second aspect of the present application provides a method for preparing a modified solvent-free polyurethane waterproof paint, the method comprising the steps of S10 to S20:
s10, respectively providing isocyanate-terminated polyurethane prepolymer, latent curing agent of formula (1) and auxiliary agent,
wherein R is 1 Selected from C 1 ～C 10 Alkylene, optionally substituted C 6 ～C 10 Arylene group, C 3 ～C 8 Any one of the cycloalkyl groups, the alkyl groups,
R 2 selected from hydrogen atoms, C 1 ～C 6 Alkyl, C 6 ～C 10 Aryl, C 3 ～C 6 Any one of cycloalkyl radicals, R 3 Any one selected from alkyl, aryl and cycloalkyl;
and S20, mixing the isocyanate-terminated polyurethane prepolymer, the latent curing agent and the auxiliary agent to obtain the modified solvent-free polyurethane waterproof coating.
In some embodiments, providing a latent curative comprises: the corresponding diamine and aldehyde/ketone compound react under the protection of inert atmosphere to obtain the latent curing agent, wherein the molar ratio of the diamine to the aldehyde/ketone compound is 1 (1-1.1).
According to the embodiment of the application, when the latent curing agent is prepared, the molar ratio of diamine to aldehyde/ketone compound is controlled within the range of 1 (1-1.1), in the reaction process, the aldehyde/ketone compound reacts with amino groups in diamine molecular bonds, and the reaction activity of amino groups at one end of diamine and aldehyde/ketone compound is reduced after the amino groups at the other end react with aldehyde/ketone compound due to the existence of steric effect, namely, the aldehyde/ketone compound preferentially performs dehydration condensation with unreacted diamine, so that the latent curing agent disclosed by the embodiment of the application can be prepared by controlling the molar ratio of diamine to aldehyde/ketone compound within the range of approximately 1:1, compared with the totally-enclosed imine latent curing agent in the prior art, the dosage of the aldehyde/ketone compound serving as the blocking agent is reduced by approximately half, the unnecessary raw material loss can be reduced, and the cost is lowered. The addition amount of the aldehyde/ketone compound is kept in a slightly excessive state, so that the reaction can be more sufficient.
In some embodiments, the reaction of the diamine with the aldehyde/ketone compound may be as shown in formula (VI) below:
in the formula (VI), R 1 Selected from C 1 ～C 10 Any one of alkyl, aryl, cycloalkyl;
R 2 selected from hydrogen atoms, C 1 ～C 6 Alkyl, C 6 ～C 10 Aryl group,Cycloalkyl, when R is any one of 2 When the hydrogen atom is a hydrogen atom, namely an aldehyde compound, when R 2 When the compound is other groups than hydrogen atoms, the ketone compound is obtained;
R 3 selected from any one of alkyl, aryl and cycloalkyl.
In some embodiments, the diamine comprises one or more combinations of ethylenediamine, propylenediamine, hexamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine.
In some embodiments, the aldehyde/ketone compound comprises one or more combinations of acetone, butanone, pentanone, cyclohexanone, acetophenone, methyl isobutyl ketone, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, benzaldehyde, salicylaldehyde, cinnamaldehyde.
In some embodiments, the reaction temperature of the diamine and the aldehyde/ketone compound is 80 to 120 ℃, e.g., may be 90 ℃,100 ℃,110 ℃, or a range of any two of the foregoing values.
In some embodiments, the diamine and aldehyde/ketone compounds are subjected to a reflux dehydration reaction for 3 to 6 hours, which may be, for example, 4 hours or 5 hours.
In some embodiments, providing a polyurethane prepolymer includes: the corresponding isocyanate and polyether polyol are mixed and reacted to obtain polyurethane prepolymer.
In some embodiments, the isocyanate comprises a diisocyanate, optionally, the diisocyanate comprises one or more combinations of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), toluene Diisocyanate (TDI).
In some embodiments, the polyether polyol comprises one of a polyether diol, a polyether triol, or a combination thereof.
In some embodiments, the polyether polyol has a number average molecular weight of 1000 to 8000.
In some embodiments, the polyether polyol has a functionality of 2 to 4.
In some embodiments, the polyether polyol has a hydroxyl number of 13 to 114mgKOH/g.
In some embodiments, the polyether polyol has an unsaturation of 0.015mol/kg or less.
In some embodiments, mixing the corresponding isocyanate and polyether polyol to react to obtain a polyurethane prepolymer comprises:
s10, mixing polyether polyol, plasticizer, pigment and filler, dispersing agent, defoamer and catalyst, stirring and dehydrating;
and S20, adding isocyanate after dehydration is finished, and reacting to obtain the polyurethane prepolymer.
In some embodiments, the dehydration temperature in step S10 is 100 to 120 ℃.
In some embodiments, the dehydration time in step S10 is 2.5 to 5 hours.
In some embodiments, the dehydration in step S10 is performed under a vacuum environment, with a vacuum level of-0.095 to-0.1 MPa.
In some embodiments, the reaction temperature in step S20 is 70-90 ℃.
In some embodiments, the reaction time in step S20 is 2 to 4 hours.
Examples
The application is illustrated by the following specific examples. It should be noted that the embodiments described below are exemplary only for explaining the present application, and are not to be construed as limiting the present application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following are some sources of the raw materials or their model numbers in the examples.
Polyether polyol: polyether glycol, DL-2000D, shandong Lanxing Dong Co., ltd; trifunctional polyether polyols, EP330N, shandong Lanxing Dong Co., ltd;
pigment and filler, 800 mesh heavy calcium;
plasticizer, 52# chlorinated paraffin;
a catalyst, a T12 organotin catalyst;
dispersing agent Disupers18, guangzhou core New Material technology Co., ltd;
defoamer, BYK-052N.
Example 1
A modified solvent-free polyurethane waterproof coating is prepared by the following steps:
preparation of latent curing agent
S10, mixing ethylenediamine and n-butyraldehyde according to a molar ratio of 1:1, adding the mixture into a reaction container, heating to 100 ℃, charging nitrogen for protection, and carrying out reflux dehydration reaction for 5 hours to obtain a latent curing agent;
preparation of modified solvent-free polyurethane waterproof paint
S20, adding 30 parts by weight of polyether polyol, 40 parts by weight of plasticizer, 85 parts by weight of pigment and filler, 0.15 part by weight of dispersing agent, 0.25 part by weight of defoamer and 0.3 part by weight of catalyst into a reaction container, stirring and heating to 120 ℃, and dehydrating under the vacuum degree of-0.1 Mpa for 4 hours;
s30, cooling to 80 ℃ after the dehydration reaction is finished, adding 70 parts by weight of diisocyanate, and carrying out heat preservation and stirring reaction for 3 hours;
and S40, cooling to 50 ℃ after the reaction is finished, adding 7 parts by weight of latent curing agent, stirring and reacting for 2 hours, vacuum defoaming after the reaction is finished, and discharging to obtain the modified solvent-free polyurethane waterproof coating.
Example 2
A modified solvent-free polyurethane waterproof coating is prepared by the following steps:
preparation of latent curing agent
S10, mixing ethylenediamine and n-butyraldehyde according to a molar ratio of 1:1, adding the mixture into a reaction container, heating to 100 ℃, charging nitrogen for protection, and carrying out reflux dehydration reaction for 5 hours to obtain a latent curing agent;
preparation of modified solvent-free polyurethane waterproof paint
S20, adding 60 parts by weight of polyether polyol, 25 parts by weight of plasticizer, 70 parts by weight of pigment and filler, 0.05 part by weight of dispersing agent, 0.5 part by weight of defoamer and 0.5 part by weight of catalyst into a reaction container, stirring and heating to 120 ℃, and dehydrating and reacting for 4 hours under the vacuum degree of-0.1 Mpa;
s30, cooling to 80 ℃ after the dehydration reaction is finished, adding 40 parts by weight of diisocyanate, and carrying out heat preservation and stirring reaction for 3 hours;
and S40, cooling to 50 ℃ after the reaction is finished, adding 11 parts by weight of latent curing agent, stirring and reacting for 2 hours, vacuum defoaming after the reaction is finished, and discharging to obtain the modified solvent-free polyurethane waterproof coating.
Example 3
A modified solvent-free polyurethane waterproof coating is prepared by the following steps:
preparation of latent curing agent
S10, mixing ethylenediamine and n-butyraldehyde according to a molar ratio of 1:1, adding the mixture into a reaction container, heating to 100 ℃, charging nitrogen for protection, and carrying out reflux dehydration reaction for 5 hours to obtain a latent curing agent;
preparation of modified solvent-free polyurethane waterproof paint
S20, adding 50 parts by weight of polyether polyol, 10 parts by weight of plasticizer, 100 parts by weight of pigment and filler, 0.25 part by weight of dispersing agent, 0.05 part by weight of defoamer and 0.1 part by weight of catalyst into a reaction container, stirring and heating to 120 ℃, and dehydrating under the vacuum degree of-0.1 Mpa for 4 hours;
s30, cooling to 80 ℃ after the dehydration reaction is finished, adding 50 parts by weight of diisocyanate, and carrying out heat preservation and stirring reaction for 3 hours;
and S40, cooling to 50 ℃ after the reaction is finished, adding 15 parts by weight of latent curing agent, stirring and reacting for 2 hours, vacuum defoaming after the reaction is finished, and discharging to obtain the modified solvent-free polyurethane waterproof coating.
Example 4
This example differs from example 3 in that the raw materials for preparing the latent hardener are p-phenylenediamine and cyclohexanone in a molar ratio of 1:1.1, the remainder remaining in accordance with example 3.
Comparative example 1
A modified solvent-free polyurethane waterproof coating is prepared by the following steps:
preparation of latent curing agent
S10, mixing ethylenediamine and n-butyraldehyde according to a molar ratio of 1:2, adding the mixture into a reaction container, heating to 100 ℃, charging nitrogen for protection, and carrying out reflux dehydration reaction for 5 hours to obtain a latent curing agent;
preparation of modified solvent-free polyurethane waterproof paint
S20, adding 50 parts by weight of polyether polyol, 10 parts by weight of plasticizer, 100 parts by weight of pigment and filler, 0.25 part by weight of dispersing agent, 0.05 part by weight of defoamer and 0.1 part by weight of catalyst into a reaction container, stirring and heating to 120 ℃, and dehydrating under the vacuum degree of-0.1 Mpa for 4 hours;
s30, cooling to 80 ℃ after the dehydration reaction is finished, adding 50 parts by weight of diisocyanate, and carrying out heat preservation and stirring reaction for 3 hours;
and S40, cooling to 50 ℃ after the reaction is finished, adding 15 parts by weight of latent curing agent, stirring and reacting for 2 hours, vacuum defoaming after the reaction is finished, and discharging to obtain the modified solvent-free polyurethane waterproof coating.
Comparative example 2
A modified solvent-free polyurethane waterproof coating is prepared by the following steps:
preparation of latent curing agent
S10, taking p-phenylenediamine and cyclohexanone according to a molar ratio of 1:2, mixing and adding the mixture into a reaction container, heating to 100 ℃, charging nitrogen for protection, and carrying out reflux dehydration reaction for 5 hours to obtain a latent curing agent;
preparation of modified solvent-free polyurethane waterproof paint
S20, adding 50 parts by weight of polyether polyol, 10 parts by weight of plasticizer, 100 parts by weight of pigment and filler, 0.25 part by weight of dispersing agent, 0.05 part by weight of defoamer and 0.1 part by weight of catalyst into a reaction container, stirring and heating to 120 ℃, and dehydrating under the vacuum degree of-0.1 Mpa for 4 hours;
s30, cooling to 80 ℃ after the dehydration reaction is finished, adding 50 parts by weight of diisocyanate, and carrying out heat preservation and stirring reaction for 3 hours;
and S40, cooling to 50 ℃ after the reaction is finished, adding 15 parts by weight of latent curing agent, stirring and reacting for 2 hours, vacuum defoaming after the reaction is finished, and discharging to obtain the modified solvent-free polyurethane waterproof coating.
Detection part
The properties of the modified solvent-free polyurethane waterproof coating materials prepared in each example and comparative example were tested according to GB/T19250-2013 standard, and the test results are shown in Table 1 below.
Table 1:
as can be seen from the data in Table 1, the semi-closed latent curing agent is prepared by adjusting the raw material proportion in the preparation process of the latent curing agent, compared with the prior art, the volatile organic compounds generated in the coating film curing process of the polyurethane coating by the latent curing agent are reduced by about half, so that the pollutants of the polyurethane waterproof coating are greatly reduced, the VOC value of the solvent-free polyurethane waterproof coating can be effectively reduced, and the VOC value of the prepared solvent-free polyurethane waterproof coating is not more than 18g/L and is obviously lower than the VOC value of the polyurethane waterproof coating in the prior art, so that the environment-friendly requirement can be met. In the process of preparing the latent curing agent, the dosage of aldehyde/ketone compounds serving as the sealing agent of the latent curing agent is reduced by half, so that unnecessary loss can be effectively reduced, and the cost of the coating is reduced. In addition, as can be seen from the test data of example 3 and comparative examples 1 and 2, the tensile and tear strengths of the polyurethane waterproof coating obtained in comparative example 3 are higher, probably because the latent curing agent participates in the early synthesis reaction of the polyurethane coating, so that the synthesized polyurethane structure is more regular, and the physical strength of the polyurethane coating is further improved.
While the application has been described with reference to a preferred embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the application. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (10)
1. The modified solvent-free polyurethane waterproof paint is characterized by comprising the following raw materials: isocyanate-terminated polyurethane prepolymer, latent curing agent and auxiliary agent;
wherein the latent curing agent has a structure represented by formula (I):
R 1 selected from C 1 ～C 10 Alkylene, optionally substituted C 6 ～C 10 Arylene group, C 3 ～C 8 Any one of the cycloalkyl groups, the alkyl groups,
R 2 selected from hydrogen atoms, C 1 ～C 6 Alkyl, C 6 ～C 10 Aryl, C 3 ～C 6 Any one of the cycloalkyl groups, the alkyl groups,
R 3 any one selected from alkyl, aryl and cycloalkyl;
the auxiliary agent comprises one or more of pigment filler, plasticizer, catalyst, dispersing agent and defoamer.
2. The modified solventless polyurethane water resistant coating material of claim 1 wherein in formula (I), R 1 Selected from any one of ethylene, propylene, hexylene, phenylene, and/or
R 2 Selected from any one of hydrogen atom, methyl, ethyl, propyl, butyl and phenyl, and/or
R 3 Selected from any one of methyl, ethyl, propyl, butyl, phenyl, hydroxyphenyl and allylphenyl.
3. The modified solventless polyurethane waterproof coating of claim 1 wherein the isocyanate-terminated polyurethane prepolymer comprises a polyether polyurethane prepolymer.
4. The modified solvent-free polyurethane waterproof paint as claimed in claim 1, wherein the paint comprises the following raw materials in parts by weight: 100 parts of isocyanate-terminated polyurethane prepolymer, 7-15 parts of latent curing agent, 70-100 parts of pigment filler, 10-40 parts of plasticizer, 0.1-0.5 part of catalyst, 0.05-0.25 part of dispersing agent and 0.05-0.5 part of defoaming agent.
5. The modified solvent-free polyurethane waterproof paint according to claim 4, wherein the pigment and filler comprises one or more of nano calcium carbonate, talcum powder, fumed silica, barium sulfate, heavy calcium, kaolin, carbon black, iron oxide red, titanium dioxide and/or a combination thereof
The plasticizer comprises one or more of chlorinated paraffin plasticizer, citrate plasticizer, phthalic plasticizer, trioctyl phosphate plasticizer, and/or
The catalyst comprises one or more of dibutyl tin dilaurate, stannous octoate, lead isooctanoate, bismuth isooctanoate, and/or
The dispersant comprises one or more combinations of anionic wetting dispersants, and/or
The defoaming agent comprises one or a combination of organic silicon defoaming agents and mineral oil defoaming agents.
6. The modified solventless polyurethane waterproof coating material according to any one of claims 1 to 5, wherein the volatile organic compound content in the coating material is not more than 18g/L.
7. The preparation method of the modified solvent-free polyurethane waterproof coating is characterized by comprising the following steps of:
isocyanate-terminated polyurethane prepolymer, latent curing agent of formula (I) and auxiliary agent are provided separately,
wherein R is 1 Selected from C 1 ～C 10 Alkylene, optionally substituted C 6 ～C 10 Arylene group, C 3 ～C 8 Any one of the cycloalkyl groups, the alkyl groups,
R 2 selected from hydrogen atoms, C 1 ～C 6 Alkyl, C 6 ～C 10 Aryl, C 3 ～C 6 Any one of the cycloalkyl groups, the alkyl groups,
R 3 any one selected from alkyl, aryl and cycloalkyl;
and mixing the isocyanate-terminated polyurethane prepolymer, the latent curing agent and the auxiliary agent to obtain the modified solvent-free polyurethane waterproof coating.
8. The method of preparing a modified solventless polyurethane waterproof coating material according to claim 7, wherein the providing a latent curing agent comprises: the corresponding diamine and aldehyde/ketone compound react under the protection of inert atmosphere to obtain the latent curing agent, wherein the molar ratio of the diamine to the aldehyde/ketone compound is 1 (1-1.1).
9. The method for preparing the modified solvent-free polyurethane waterproof paint according to claim 8, wherein the diamine comprises one or more of ethylenediamine, propylenediamine, hexamethylenediamine, o-phenylenediamine, m-phenylenediamine and p-phenylenediamine.
10. The method for preparing the modified solvent-free polyurethane waterproof paint according to claim 8, wherein the aldehyde/ketone compound comprises one or a combination of more of acetone, butanone, pentanone, cyclohexanone, acetophenone, methyl isobutyl ketone, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, benzaldehyde, salicylaldehyde and cinnamaldehyde.
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