CN116855160A - Preparation method of aliphatic polyurethane coating with high weather resistance, high performance and high cost performance - Google Patents
Preparation method of aliphatic polyurethane coating with high weather resistance, high performance and high cost performance Download PDFInfo
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- CN116855160A CN116855160A CN202310623873.7A CN202310623873A CN116855160A CN 116855160 A CN116855160 A CN 116855160A CN 202310623873 A CN202310623873 A CN 202310623873A CN 116855160 A CN116855160 A CN 116855160A
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- polyurethane coating
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- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000011527 polyurethane coating Substances 0.000 title claims description 67
- 229920000642 polymer Polymers 0.000 claims abstract description 108
- 239000003973 paint Substances 0.000 claims abstract description 41
- 239000004814 polyurethane Substances 0.000 claims abstract description 18
- 229920002635 polyurethane Polymers 0.000 claims abstract description 18
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims description 80
- 239000000178 monomer Substances 0.000 claims description 79
- -1 acrylic ester Chemical class 0.000 claims description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 34
- 239000003999 initiator Substances 0.000 claims description 29
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 29
- 238000007865 diluting Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000000049 pigment Substances 0.000 claims description 13
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 12
- 239000012024 dehydrating agents Substances 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 12
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 12
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 6
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- 239000006254 rheological additive Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 3
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 claims description 3
- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical class CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 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 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-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
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 3
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 22
- 239000000126 substance Substances 0.000 abstract description 16
- 238000001035 drying Methods 0.000 abstract description 14
- 230000032683 aging Effects 0.000 abstract description 11
- 230000008859 change Effects 0.000 abstract description 11
- 238000005187 foaming Methods 0.000 abstract description 4
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 238000003847 radiation curing Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 35
- 239000011248 coating agent Substances 0.000 description 34
- 239000004615 ingredient Substances 0.000 description 18
- 239000004925 Acrylic resin Substances 0.000 description 11
- 229920000178 Acrylic resin Polymers 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 10
- 238000013461 design Methods 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000009396 hybridization Methods 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 229920001225 polyester resin Polymers 0.000 description 6
- 239000004645 polyester resin Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 229940124543 ultraviolet light absorber Drugs 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- 229920002396 Polyurea Polymers 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of polyurethane paint, in particular to a preparation method of aliphatic polyurethane paint with high weather resistance, high performance and high cost performance, which is characterized in that A.B two economic low weather-resistant polymers are hybridized and crosslinked with HDI trimer to prepare the aliphatic polyurethane paint with high weather resistance and high performance, and the aliphatic polyurethane paint prepared by the method has the following characteristics: the UV accelerated artificial aging is carried out for 1200 hours (initial gloss is more than 92/60 DEG and the light loss rate is less than 10 percent, the light loss level is 1, the color difference is less than 2, the color change level is 1, the pulverization is 0, no foaming, no crack and no peeling are generated), the ultraviolet radiation curing agent is high in performance (high in solid content, low in VOC, high in gloss, high in fullness, high in brightness, excellent in mechanical performance and chemical resistance, good in drying performance) and the cost performance (economical and excellent in performance).
Description
Technical Field
The invention relates to the technical field of polyurethane paint, in particular to a preparation method of aliphatic polyurethane paint with high weather resistance, high performance and high cost performance.
Background
The coating is a material which can be coated on the surface of an object to form a continuous film and has the special functions of protection, decoration or the like, and the coating can prevent the surface of the object from being corroded by weather, chemical corrosion and changes caused by sunlight irradiation, prevent or lighten the surface of the object from being directly rubbed and impacted, and can increase the beauty of the surface of the object. In the use process of the coating, the coating film is oxidized and damaged under the action of ultraviolet rays, water and oxygen, and light loss, color change, chalking, cracking and the like are caused, so that outdoor weather resistance is very important for various coatings, and particularly, the coating with excellent weather resistance is required for automobiles, airplanes, bridges, building outer walls and the like.
Polyurethane is taken as an organic high polymer material, is known as a fifth large plastic, is prepared by reacting polyisocyanate with polyhydroxy compound, and is prepared by taking resin and isocyanate as cores, so that the best, most economical and flexible solution can be provided, and the baking paint performance can be achieved without baking. The coating film is tough, wear-resistant, chemical corrosion-resistant, oil-resistant, solvent-resistant, outstanding in stability and bright, and is widely applied to the fields of national economy such as wood coating, automobile repair coating, anti-corrosion coating, floor coating, electronic coating, special coating, polyurethane waterproof coating and the like due to the excellent performance of the coating film, and particularly the aliphatic polyurethane coating is widely applied to the decoration and protection of high-grade cars, automobile repair, large buses, airplanes, wind power blades, airports, bridges, large buildings, high-grade woodware and the like which are required to have better weather resistance.
The widely used aliphatic polyurethane coating at present has the advantages of heat resistance, good color retention, chemical corrosion resistance and the like, has better weather resistance, is easy to age under the action of short-wave ultraviolet rays, can not meet the requirement of long-term weather resistance, has poor fullness and definition of a coating film, has low construction solid content and needs to be further improved in other mechanical properties. Therefore, the aging mechanism of the aliphatic polyurethane coating is researched, the weather resistance is improved, the performance of a coating film is improved, the application value of the aliphatic polyurethane coating is greatly improved, and the aliphatic polyurethane coating plays an increasingly important role in China along with the importance of China on the coating.
The invention discloses a preparation method of quick-drying weather-proof high-solid acrylic resin, which comprises the following steps that step 1) a solvent and tertiary glycidyl ester are sequentially added into a reactor, nitrogen is simultaneously introduced for protection, and the temperature is gradually increased to the reaction temperature; step 2), uniformly dripping a comonomer, an initiator and a solvent into the reactor, wherein the comonomer comprises an unsaturated monomer accounting for 70-95% of the total monomer amount and a macromolecular monomer accounting for 5-30% of the total monomer amount; and 3) after the dripping is finished, adding an initiator and a solvent, preserving heat for 2 hours, cooling to 100 ℃, filtering and discharging. Compared with the prior art, the obtained high-solid acrylic resin has the characteristics of low viscosity and high solid content, and the coating prepared by the high-solid acrylic resin has the advantages of high drying speed and good weather resistance, and the main bright point is that the high-solid acrylic resin is prepared by using a catalytic chain transfer free radical (CCPT) technology and a special monomer grafting modification technology to prepare a large monomer, and then the large monomer is subjected to free radical polymerization to prepare a polymer with 70 percent of solid content, so that the aliphatic acrylic polyurethane coating prepared by the polymer has good weather resistance, high brightness and quick drying property, and the catalytic chain transfer free radical (CCPT) technology needs high monomer refining purity and has limited mass production. The price of the special (methyl) acrylic ester monomer is higher, and the economical efficiency is poor. Meanwhile, 70% of the solid content is slightly lower, and the fullness is required to be further improved. In addition, the ultraviolet light absorber capable of increasing weather resistance is added into the paint, which is a part of the resin for evaluating the weather resistance.
The invention relates to a preparation method of resin for coating, in particular to a preparation method of acrylic acid graft modified saturated polyester resin, which is characterized in that saturated polyester, maleic anhydride and an organic solvent are heated to a certain temperature, after a certain period of reaction, a (methyl) acrylic ester monomer and a mixture of a special vinyl monomer and an initiator are slowly added, and the mixture is kept for a certain period of time, so that the acrylic acid graft modified saturated polyester resin can be obtained. The invention has the advantages that the acrylic acid grafting modified saturated polyester resin obtains excellent fullness of the polyester resin and weather resistance and quick drying property of the acrylic acid resin through maleic anhydride, and the defects that the synthesis process of a grafting copolymerization method is difficult to control, the gel phenomenon is easy to appear, the high solid content is difficult to obtain, a large number of ungrafted acrylic acid and polyester macromolecules exist in a system, and the improvement on the system compatibility is limited. Defects such as light loss and shrinkage cavity are easy to occur, and meanwhile, the weather resistance of the paint is influenced and reduced.
In summary, the aliphatic polyurethane coating is classified into an aliphatic acrylic polyurethane coating, an aliphatic polyester polyurethane coating, an aliphatic fluorocarbon polyurethane coating, an aliphatic polyurea polyurethane coating and an aliphatic polyurethane coating modified with each other according to the difference of hydroxyl-containing components. The aliphatic acrylic polyurethane coating can be prepared by optimizing common (methyl) acrylic ester monomers and initiator, and introducing special (methyl) acrylic ester monomers, special initiator (such as initiator for GTP synthesis) and special process (such as CCPT or ATRP or GTP), wherein the two can meet the high weather-proof requirement, the solid content, the fullness and the distinctness of image are limited, but the economic quick-drying market has more application, the cost of the latter is expensive, the cost performance is very low and the mass production has certain limitation. The aliphatic polyester polyurethane paint can be prepared by synthesizing preferably polyhydric alcohol and polybasic acid, meets the requirements of high weather resistance, high solid content, high fullness and high brightness, but has relatively high cost and great limitation on normal-temperature drying property. The aliphatic fluorocarbon polyurethane coating has super weather resistance and excellent chemical resistance and mechanical properties, but has solid content, luster, plumpness and fresh-mapping property which are less than the high-performance requirement, and has higher price. The modified polypropylene is widely used in occasions with high weather resistance and low gloss and fullness. The aliphatic polyurea polyurethane coating not only has super weather-proof property, but also has high solid content, high fullness, high brightness, excellent mechanical property, excellent acid rain resistance, chemical resistance and other high performance properties, but also has high price and limited construction property, and is limited to be used in special occasions such as wind power blades and the like.
The four types of mutually modified aliphatic polyurethane coatings such as aliphatic fluorocarbon polyurethane coating or aliphatic polyurea polyurethane coating modified acrylic polyurethane coating or aliphatic polyester polyurethane coating have the defects that the amount of fluorocarbon or polyurea is less than the modification purpose, the cost is higher due to more amount, the cost performance is still lower, the economical efficiency is poor, and certain high performance still has limitations. The research reports of the aliphatic polyurethane coating of the polyester modified acrylic resin are relatively more, but the polyester modified acrylic resin has a plurality of limitations in balancing high weather resistance, high fullness, drying performance, economy and the like.
Therefore, we propose a preparation method of aliphatic polyurethane coating with high weather resistance, high performance and high cost performance to solve the above problems.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a preparation method of aliphatic polyurethane coating with high weather resistance, high performance and high cost performance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the aliphatic polyurethane coating with high weather resistance, high performance and high cost performance provided by the invention comprises the following steps:
s1 preparation of a polymer A: adding monoacid, dibasic acid, triol and catalyst into a reaction kettle, reacting for 2-4 hours at 170-190 ℃, adding an antioxidant and a modified monomer 1, heating to 220-230 ℃ for reacting for 4-6 hours until the acid value is less than 10-12, reducing the temperature to 140 ℃, diluting the solvent 1, adding a modified monomer 2, heating to 150-160 ℃, dropwise adding a mixture of a (methyl) acrylic ester monomer 1, an initiator and a molecular weight regulator for 3-5 hours, preserving the heat for 0.5-2 hours, adding, preserving the heat for 2-3 hours, and diluting the solvent 1 to obtain a polymer A;
s2 preparation of a polymer B: heating part of the solvent 2 and the modified monomer 1 to 150-160 ℃, dropwise adding a mixture of the (methyl) acrylic ester monomer 2, styrene, an initiator and a molecular weight regulator for 3-5 hours, preserving heat for 1-2 hours, adding, preserving heat for 2-3 hours, and diluting the solvent 2 to obtain a polymer B;
s3 preparation of a polymer C: the polymer A and the polymer B are mixed according to 1/1 ratio;
s4, preparation of aliphatic polyurethane paint: dispersing part of polymer C, pigment, filler, dispersing agent, rheological agent and part of solvent 3 at high speed, grinding to below 20um, adding the rest of polymer C, leveling aid and rest of solvent 3 to prepare a polyurethane coating component A, stirring HDI trimer, dehydrating agent and solvent 4 at high speed to prepare a component B, and preparing the aliphatic polyurethane coating according to the ratio of component A/component B=5/1.
Preferably, the polymer A comprises the following components in percentage by weight: 5 to 10 percent of monoacid, 12 to 18 percent of dibasic acid, 10 to 18 percent of triol, 0.02 to 0.08 percent of catalyst, 0.05 to 1.0 percent of antioxidant, 12 to 5 percent of modified monomer, 23 to 5 percent of modified monomer, 120 percent of solvent, 110 to 20 percent of (methyl) acrylic ester monomer, 15 to 25 percent of styrene, 3 to 5 percent of initiator and 0.5 to 2 percent of molecular weight regulator.
Preferably, the polymer B comprises the following components in percentage by weight: 230 percent of solvent, (methyl) acrylic ester monomer 225 percent to 35 percent, 25 percent to 35 percent of styrene, 8 percent to 12 percent of modified monomer 1, 3 percent to 4 percent of initiator and 0.5 percent to 2 percent of molecular weight regulator.
Preferably, the polymer C comprises the following components in percentage by weight: 50% of polymer A and 50% of polymer B.
Preferably, the polyurethane coating A comprises the following components in percentage by weight: 40-60% of polymer C, 20-30% of pigment, 5-10% of filler, 0.2-1.0% of rheological additive, 0.5-1.5% of dispersing additive, 0.3-1% of leveling additive and 310-15% of solvent.
Preferably, the polyurethane coating B comprises the following components in percentage by weight: 85-95% of HDI trimer, 0.5-1% of dehydrating agent and 45-15% of solvent.
Preferably, the monoacid is one or more of lauric acid, benzoic acid, isooctanoic acid and nonylic acid, the dibasic acid is one or more of phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, sebacic acid and hexahydrophthalic anhydride, and the triol is one or more of glycerol and trimethylolpropane.
Preferably, the catalyst is one or more of monobutyl tin oxide, dibutyl tin oxide, stannous octoate and dibutyl tin dilaurate; the antioxidant is one or more of phosphoric acid and triphenyl phosphite; the modified monomer 1 is one of tertiary glycidyl ester of carbonic acid and glycidyl methacrylate; the modified monomer 2 is one or more of vinyl versatate, glycidyl methacrylate and dibutyl maleate.
Preferably, the solvent 1 is one of propylene glycol methyl ether acetate and butyl acetate; the solvent 2 is one of propylene glycol methyl ether acetate and butyl acetate; the solvent 3 is one or more of propylene glycol methyl ether acetate, butyl acetate, dimethylbenzene and trimethylbenzene; the solvent 4 is propylene glycol methyl ether acetate.
Preferably, the (meth) acrylic monomer 1 is one or more of butyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; the (methyl) acrylic ester monomer 2 is one or more of acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; the initiator is one or more of tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, di-tert-amyl peroxide and tert-butyl peroxy3, 5-trimethylhexanoate; the molecular weight regulator is AMSD (methyl styrene dimer).
Compared with the prior art, the invention has the beneficial effects that:
1. the aliphatic polyurethane paint of the present invention is subjected to ultraviolet ray and heat to produce free radical in the polymer to degrade, and has oxygen and water to promote oxidation, and pigment to catalyze photooxidation. The physical and chemical changes interact. The presence of oxygen greatly affects the aging of the coating film, and in practice, in the case of an oxygen-free weather, the aging of the coating film hardly occurs, and the influence of moisture on the aging of the coating film is great, but tends to be neglected, and in chemical terms, moisture participates in the hydrolysis of the rupture of the secondary bond of hydrogen bond and the primary bond of ester bond.
2. The invention designs and synthesizes A.B two polymer resins, wherein, polymer A is prepared by synthesizing polyester and modifying twice, and polymer B is prepared by synthesizing modified acrylic resin and modifying A and B. Not only the side chain has a hydrophobic structure of soft alkyl and a uniformly dispersed group-like inert alkyl high steric hindrance structure (alpha-carbon has no active wave hydrogen atom), but also the A.B has good compatibility, the A, B side chains in an interpenetrating network formed by hybridization crosslinking of A, B polymer and HDI trimer are ensured to be mutually stretched and penetrated, the group-like inert alkyl structure in the A side chain protects the functional group in the B polymer from being attacked by ultraviolet rays like an umbrella, the group-like inert alkyl structure in the B side chain protects the functional group in the A polymer from being attacked by ultraviolet rays like an umbrella, meanwhile, the soft alkyl resists and absorbs ultraviolet energy to be converted into thermal motion energy to be absorbed, the paint film is prevented from cracking caused by expansion and contraction of a paint film or a substrate due to temperature and humidity change, the structures of the hydrophobic parts of the two polymer side chains mutually reduce the hydrolysis tendency of various groups, and the hydrolysis resistance is enhanced. Greatly reduces the ageing of the paint film caused by chemical change. Through the design of the A.B polymer, the A has low TG glass transition temperature, the B has high TG glass transition temperature, the difference of the surface tension of the A and the B is small, the compatibility is good, the intermolecular cohesion, entanglement and internal stress in an interpenetrating network structure formed by hybridization and cross-linking of the HDI trimer are small, and the coating film is adhered and compact, so that the water-proof permeability is good, the moisture is prevented from transporting oxygen into the coating film, and the small internal stress among the polymer molecules prevents the paint film from expanding and contracting due to the change of temperature and humidity to cause the paint film to crack, thereby greatly reducing the ageing of the paint film caused by physical change. Thereby ensuring the high weather resistance of the subject paint film: the UV accelerated artificial aging is carried out for 1200 hours (initial gloss is more than 92/60 degrees, the light loss rate is less than 10 percent, the light loss level is 1, the color difference is less than 2, the color change level is 1, the pulverization is 0, and the foaming, the cracking and the peeling are avoided).
3. The structural design of the polymer A and the polymer B has the advantages of high solid content, plumpness, fresh mapping property, good leveling property, quick drying of acrylic resin, good color and light retention and the like of the polyester resin, counteracts the defects and adverse factors, mutually compensates the defects, and the prepared high solid content coating has VOC less than 420g/L, greatly improves the construction solid content, and has excellent leveling property, sagging resistance and other construction properties. The small surface tension difference between A and B, good compatibility and moderate TG gradient ensure the good drying process of the paint film, the paint film is bright and plump after cross-linking hybridization, the definition is high, the high cross-linking density ensures the chemical resistance of the paint film, and the soft and hard chains and side chain structures of different TG between A and B and the compact interpenetrating network structure formed after cross-linking ensure the excellent mechanical property and chemical resistance of the paint film. Thus ensuring the high performance (high solid content, low VOC, high gloss, high fullness, high brightness, excellent mechanical properties and chemical resistance, good drying property) of the subject paint film.
4. In the invention, the raw materials in the design synthesis of A and B are economical and cheap, the mixed content of phthalic anhydride and styrene in the polymer A accounts for 35% -40% of the monomer, the content of styrene in the polymer B accounts for 40% of the monomer, so that the coating is ensured to have the characteristics of high economy, high weather resistance and high performance, the cost performance and the economy of the aliphatic polyurethane coating are highlighted, and the cost performance (economy and excellent performance) of the subject coating is ensured.
5. The high weather resistance mentioned in the invention means that the prepared coating does not contain the evaluation result of the light stabilizer and the ultraviolet light absorber which can increase weather resistance, and the weather resistance can be further improved by adding the light stabilizer and the ultraviolet light absorber according to the requirements of practical application occasions.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, definitions, will control. When an "amount, concentration, temperature, time, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1-50 should be understood to include any number, combination of numbers, or subranges of numbers selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, and all fractional values between the foregoing integers, such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. Regarding sub-ranges, specifically considered are "nested sub-ranges" that extend from any end point within the range. For example, the nested subranges of exemplary ranges 1-50 can include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction. "
The invention is further illustrated below in connection with specific examples in which various processes and methods, not described in detail, are conventional methods well known in the art. Materials, reagents, devices, instruments, equipment and the like used in the examples described below are commercially available unless otherwise specified.
Wherein the pigment is Bailey-associated rutile type titanium dioxide 699, the filler is Yongan Weiton superfine precipitated barium sulfate AW15, the dispersing agent is BYK-163, the rheological additive is gram Lei Weili thixotropic agent CRAYVALLAC ULTRA, the leveling additive is BYK-310, the HDI trimer is Bayer (Korea) N3300, and the dehydrating agent is Zusatzmittel TI of OMG company in the United states.
In the following examples:
the polymer A comprises the following components in percentage by weight: 5 to 10 percent of monoacid, 12 to 18 percent of dibasic acid, 10 to 18 percent of triol, 0.02 to 0.08 percent of catalyst, 0.05 to 1.0 percent of antioxidant, 12 to 5 percent of modified monomer, 23 to 5 percent of modified monomer, 120 percent of solvent, 110 to 20 percent of (methyl) acrylic ester monomer, 15 to 25 percent of styrene, 3 to 5 percent of initiator and 0.5 to 2 percent of molecular weight regulator;
the polymer B comprises the following components in percentage by weight: 230 percent of solvent, (methyl) acrylic ester monomer 225 percent to 35 percent, 25 percent to 35 percent of styrene, 8 percent to 12 percent of modified monomer 1, 3 percent to 4 percent of initiator and 0.5 percent to 2 percent of molecular weight regulator.
Specifically, the polymer C comprises the following components in percentage by weight: 50% of polymer A and 50% of polymer B.
Specifically, the polyurethane coating A comprises the following components in percentage by weight: 40-60% of polymer C, 20-30% of pigment, 5-10% of filler, 0.2-1.0% of rheological additive, 0.5-1.5% of dispersing additive, 0.3-1% of leveling additive and 310-15% of solvent.
Specifically, the polyurethane coating B comprises the following components in percentage by weight: 85-95% of HDI trimer, 0.5-1% of dehydrating agent and 45-15% of solvent.
Concretely, the monoacid is one or more of lauric acid, benzoic acid, isooctanoic acid and nonylic acid, the dibasic acid is one or more of phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, sebacic acid and hexahydrophthalic anhydride, and the triol is one or more of glycerol and trimethylolpropane.
Specifically, the catalyst is one or more of monobutyl tin oxide, dibutyl tin oxide, stannous octoate and dibutyl tin dilaurate; the antioxidant is one or more of phosphoric acid and triphenyl phosphite; the modified monomer 1 is one of tertiary glycidyl ester and glycidyl methacrylate; the modified monomer 2 is one or more of vinyl versatate, glycidyl methacrylate and dibutyl maleate.
Specifically, the solvent 1 is one of propylene glycol methyl ether acetate and butyl acetate; the solvent 2 is one of propylene glycol methyl ether acetate and butyl acetate; the solvent 3 is one or more of propylene glycol methyl ether acetate, butyl acetate, dimethylbenzene and trimethylbenzene; the solvent 4 is propylene glycol methyl ether acetate.
Specifically, the (methyl) acrylic ester monomer 1 is one or more of butyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; the (methyl) acrylic ester monomer 2 is one or more of acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; the initiator is one or more of tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, di-tert-amyl peroxide and tert-butyl peroxy3, 5-trimethylhexanoate; the molecular weight regulator is AMSD (methyl styrene dimer).
Example 1
The preparation method of the aliphatic polyurethane coating comprises the following steps:
polymer a preparation: 1. adding monoacid, dibasic acid, triol and catalyst into a reaction kettle, reacting for 2 hours at 180 ℃, adding an antioxidant and a modified monomer 1, heating to 220 ℃ for reacting for 5 hours until the acid value is less than 12, reducing to 140 ℃, diluting a solvent 1, adding a modified monomer 2, heating to 150 ℃, dropwise adding a mixture of a (methyl) acrylic ester monomer 1, an initiator and a molecular weight regulator for 3 hours, preserving heat for 0.5 hour, adding, preserving heat for 3 hours, and diluting the solvent 1 to obtain a polymer A;
preparation of polymer B: heating part of the solvent 2 and the modified monomer 1 to 160 ℃, dropwise adding a mixture of the (methyl) acrylic ester monomer 2, styrene, an initiator and a molecular weight regulator for 4.5 hours, preserving heat for 2 hours, adding, preserving heat for 2 hours, and diluting the solvent 2 to obtain a polymer B;
the polymer C is prepared by mixing the polymer A and the polymer B according to 1/1 ratio;
preparation of aliphatic polyurethane paint: dispersing part of the polymer C, pigment, filler, dispersing agent, rheological agent and part of the solvent 3 at high speed, grinding to below 20um, adding the rest of the polymer C, leveling auxiliary agent and the rest of the solvent 3, and preparing the polyurethane coating component A. The HDI trimer, the dehydrating agent and the solvent 4 are stirred at high speed to prepare an ingredient B, and the aliphatic polyurethane coating is prepared according to the formula of ingredient A/ingredient B=5/1.
Example 2
The preparation method of the aliphatic polyurethane coating comprises the following steps:
polymer a preparation: 1. adding monoacid, dibasic acid, triol and catalyst into a reaction kettle, reacting for 3 hours at 170 ℃, adding an antioxidant and a modified monomer 1, heating to 230 ℃ for reacting for 4 hours until the acid value is less than 12, reducing to 140 ℃, diluting a solvent 1, adding a modified monomer 2, heating to 160 ℃, dropwise adding a mixture of a (methyl) acrylic ester monomer 1, an initiator and a molecular weight regulator for 3.5 hours, preserving heat for 1 hour, adding, preserving heat for 3 hours, and diluting the solvent 1 to obtain a polymer A;
preparation of polymer B: heating part of the solvent 2 and the modified monomer 1 to 150 ℃, dropwise adding a mixture of the (methyl) acrylic ester monomer 2, styrene, an initiator and a molecular weight regulator for 5 hours, preserving heat for 0.5 hour, adding, preserving heat for 2 hours, and diluting the solvent 2 to obtain a polymer B;
the polymer C is prepared by mixing the polymer A and the polymer B according to 1/1 ratio;
preparation of aliphatic polyurethane paint: dispersing part of the polymer C, pigment, filler, dispersing agent, rheological agent and part of the solvent 3 at high speed, grinding to below 20um, adding the rest of the polymer C, leveling auxiliary agent and the rest of the solvent 3, and preparing the polyurethane coating component A. The HDI trimer, the dehydrating agent and the solvent 4 are stirred at high speed to prepare an ingredient B, and the aliphatic polyurethane coating is prepared according to the formula of ingredient A/ingredient B=5/1.
Example 3
The preparation method of the aliphatic polyurethane coating comprises the following steps:
polymer a preparation: 1. adding monoacid, dibasic acid, triol and catalyst into a reaction kettle, reacting for 2 hours at 190 ℃, adding an antioxidant and a modified monomer 1, heating to 230 ℃ for reacting for 4 hours until the acid value is less than 10, reducing to 140 ℃, diluting with a solvent 1, adding a modified monomer 2, heating to 160 ℃, dropwise adding a mixture of a (methyl) acrylic ester monomer 1, an initiator and a molecular weight regulator for 4.5 hours, preserving heat for 0.5 hour, adding, preserving heat for 3 hours, and diluting with the solvent 1 to obtain a polymer A;
preparation of polymer B: heating part of the solvent 2 and the modified monomer 1 to 155 ℃, dropwise adding a mixture of the (methyl) acrylic ester monomer 2, styrene, an initiator and a molecular weight regulator for 4 hours, preserving heat for 1 hour, adding, preserving heat for 2 hours, and diluting the solvent 2 to obtain a polymer B;
the polymer C is prepared by mixing the polymer A and the polymer B according to 1/1 ratio;
preparation of aliphatic polyurethane paint: dispersing part of the polymer C, pigment, filler, dispersing agent, rheological agent and part of the solvent 3 at high speed, grinding to below 20um, adding the rest of the polymer C, leveling auxiliary agent and the rest of the solvent 3, and preparing the polyurethane coating component A. The HDI trimer, the dehydrating agent and the solvent 4 are stirred at high speed to prepare an ingredient B, and the aliphatic polyurethane coating is prepared according to the formula of ingredient A/ingredient B=5/1.
Example 4
The preparation method of the aliphatic polyurethane coating comprises the following steps:
polymer a preparation: 1. adding monoacid, dibasic acid, triol and catalyst into a reaction kettle, reacting for 3 hours at 170 ℃, adding an antioxidant and a modified monomer 1, heating to 230 ℃ for reacting for 5 hours until the acid value is less than 10, reducing to 140 ℃, diluting with a solvent 1, adding a modified monomer 2, heating to 160 ℃, dropwise adding a mixture of a (methyl) acrylic ester monomer 1, an initiator and a molecular weight regulator for 3 hours, preserving heat for 2 hours, adding, preserving heat for 2 hours, and diluting with the solvent 1 to obtain a polymer A;
preparation of polymer B: heating part of the solvent 2 and the modified monomer 1 to 160 ℃, dropwise adding a mixture of the (methyl) acrylic ester monomer 2, styrene, an initiator and a molecular weight regulator for 4.5 hours, preserving heat for 1 hour, adding, preserving heat for 3 hours, and diluting the solvent 2 to obtain a polymer B;
the polymer C is prepared by mixing the polymer A and the polymer B according to 1/1 ratio;
preparation of aliphatic polyurethane paint: dispersing part of the polymer C, pigment, filler, dispersing agent, rheological agent and part of the solvent 3 at high speed, grinding to below 20um, adding the rest of the polymer C, leveling auxiliary agent and the rest of the solvent 3, and preparing the polyurethane coating component A. The HDI trimer, the dehydrating agent and the solvent 4 are stirred at high speed to prepare an ingredient B, and the aliphatic polyurethane coating is prepared according to the formula of ingredient A/ingredient B=5/1.
Comparative example one
Polymer a preparation: 1. adding monoacid, dibasic acid, triol and catalyst into a reaction kettle, reacting for 3 hours at 170 ℃, adding an antioxidant and a modified monomer 1, heating to 230 ℃ for reacting for 5 hours until the acid value is less than 10, reducing to 140 ℃, diluting with a solvent 1, adding a modified monomer 2, heating to 160 ℃, dropwise adding a mixture of a (methyl) acrylic ester monomer 1, an initiator and a molecular weight regulator for 3 hours, preserving heat for 2 hours, adding, preserving heat for 2 hours, and diluting with the solvent 1 to obtain a polymer A;
preparation of aliphatic polyurethane paint: dispersing part of the polymer A, pigment, filler, dispersing agent, rheological agent and part of the solvent 3 at high speed, grinding to below 20um, and adding the rest of the polymer A, leveling auxiliary agent and the rest of the solvent 3 to prepare the polyurethane coating component A. The HDI trimer, the dehydrating agent and the solvent 4 are stirred at high speed to prepare an ingredient B, and the aliphatic polyurethane coating is prepared according to the formula of ingredient A/ingredient B=5/1.
Comparative example two
Preparation of polymer B: heating part of the solvent 2 and the modified monomer 1 to 160 ℃, dropwise adding a mixture of the (methyl) acrylic ester monomer 2, styrene, an initiator and a molecular weight regulator for 4.5 hours, preserving heat for 1 hour, adding, preserving heat for 3 hours, and diluting the solvent 2 to obtain a polymer B;
preparation of aliphatic polyurethane paint: and dispersing part of the polymer B, pigment, filler, dispersing agent, rheological agent and part of the solvent 3 at high speed, grinding to below 20 mu m, and adding the rest of the polymer B, leveling auxiliary agent and the rest of the solvent 3 to prepare the polyurethane coating component A. The HDI trimer, the dehydrating agent and the solvent 4 are stirred at high speed to prepare an ingredient B, and the aliphatic polyurethane coating is prepared according to the formula of ingredient A/ingredient B=5/1.
The aliphatic polyurethane coatings prepared in examples one to four above were tested and the results were as follows:
the aliphatic polyurethane coating prepared in the first to fourth examples is artificially aged under UV acceleration for 1200 hours (initial gloss > 92/60 DEG light loss rate < 10%,. Sup. Light loss level 1, color difference < 2, color change level 1, powdering level 0, no foaming, no cracking, no flaking);
the aliphatic polyurethane coatings prepared in the first and second comparative examples have initial gloss 78/60 degree gloss loss = 15%, color difference 4, chalking grade 2, foaming, cracking, flaking after UV accelerated artificial aging for 1200 hours;
thus, in summary, the present invention relates to the synthesis of two polymer resins A.B, polymer A is prepared by first synthesizing polyester and modifying it twice, and polymer B is prepared by synthesizing modified acrylic resin and modifying it. The side chains are provided with hydrophobic structures of soft alkyl groups and uniformly dispersed group-like inert alkyl high steric hindrance structures (alpha-carbon does not have active wave hydrogen atoms), the A.B is good in compatibility, A, B side chains in an interpenetrating network formed by hybridization and cross-linking of the A, B polymer and the HDI trimer are ensured to be mutually stretched and penetrated, the group-like inert alkyl structures in the A side chains are used for protecting functional groups in the B polymer from being attacked by ultraviolet rays like an umbrella, the group-like inert alkyl structures in the B side chains are used for protecting the functional groups in the A polymer from being attacked by ultraviolet rays like an umbrella, meanwhile, soft alkyl groups resist and absorb ultraviolet energy to be converted into thermal motion energy to be absorbed, paint films or substrates are prevented from being expanded and contracted due to temperature and humidity changes, the structures of hydrophobic parts of the two polymer side chains are mutually reduced in hydrolysis tendency of various groups, and the anti-hydrolysis capability is enhanced. Greatly reduces the ageing of the paint film caused by chemical change. Through the design of the A.B polymer, the A has low TG glass transition temperature, the B has high TG glass transition temperature, the difference of the surface tension of the A and the B is small, the compatibility is good, the intermolecular cohesion, entanglement and internal stress in an interpenetrating network structure formed by the hybridization and crosslinking of the HDI trimer are small, and the coating film is adhered and compact, so that the water-proof permeability is good, the moisture is prevented from transporting oxygen into the coating film, and the paint film cracks caused by the expansion and contraction of the paint film due to the change of temperature and humidity are avoided by the small internal stress among the polymer molecules, and the ageing of the paint film caused by physical change is greatly reduced.
The structural design of different characteristics of the polymer A and the polymer B takes the advantages of high solid content, plumpness, good brightness, good leveling property, quick drying of acrylic resin, good color and light retention and the like of the polyester resin, counteracts the disadvantages and adverse factors, mutually compensates the disadvantages, and the prepared high solid content coating has VOC less than 420g/L, greatly improves the construction solid content, and has excellent leveling property, sagging resistance and other construction properties. The small surface tension difference between A and B, good compatibility and moderate TG gradient ensure the good drying process of the paint film, the paint film is bright and plump after cross-linking hybridization, the definition is high, the high cross-linking density ensures the chemical resistance of the paint film, and the soft and hard chains and side chain structures of different TG between A and B and the compact interpenetrating network structure formed after cross-linking ensure the excellent mechanical property and chemical resistance of the paint film. Thus ensuring the high performance (high solid content, low VOC, high gloss, high fullness, high brightness, excellent mechanical properties and chemical resistance, good drying property) of the subject paint film.
The raw materials in the design synthesis of A and B are economical and cheap, the mixed content of phthalic anhydride and styrene in the polymer A accounts for 35% -40% of the monomer, and the content of styrene in the polymer B accounts for 40% of the monomer. The high economical efficiency of the coating is ensured, the characteristics of high weather resistance and high performance are highlighted, and the cost performance and the economical efficiency of the aliphatic polyurethane coating are highlighted, so that the high cost performance (economy and excellent performance) of the subject coating is ensured.
The high weather resistance in the invention means that the prepared coating does not contain a light stabilizer capable of increasing weather resistance and an evaluation result of an ultraviolet light absorber. The weather resistance can be further improved by adding the light stabilizer and the ultraviolet light absorber according to the requirements of practical application occasions.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The preparation method of the aliphatic polyurethane coating with high weather resistance, high performance and high cost performance is characterized by comprising the following steps:
s1 preparation of a polymer A: adding monoacid, dibasic acid, triol and catalyst into a reaction kettle, reacting for 2-4 hours at 170-190 ℃, adding an antioxidant and a modified monomer 1, heating to 220-230 ℃ for reacting for 4-6 hours until the acid value is less than 10-12, reducing the temperature to 140 ℃, diluting the solvent 1, adding a modified monomer 2, heating to 150-160 ℃, dropwise adding a mixture of a (methyl) acrylic ester monomer 1, an initiator and a molecular weight regulator for 3-5 hours, preserving the heat for 0.5-2 hours, adding, preserving the heat for 2-3 hours, and diluting the solvent 1 to obtain a polymer A;
s2 preparation of a polymer B: heating part of the solvent 2 and the modified monomer 1 to 150-160 ℃, dropwise adding a mixture of the (methyl) acrylic ester monomer 2, styrene, an initiator and a molecular weight regulator for 3-5 hours, preserving heat for 1-2 hours, adding, preserving heat for 2-3 hours, and diluting the solvent 2 to obtain a polymer B;
s3 preparation of a polymer C: the polymer A and the polymer B are mixed according to 1/1 ratio;
s4, preparation of aliphatic polyurethane paint: dispersing part of polymer C, pigment, filler, dispersing agent, rheological agent and part of solvent 3 at high speed, grinding to below 20um, adding the rest of polymer C, leveling aid and rest of solvent 3 to prepare a polyurethane coating component A, stirring HDI trimer, dehydrating agent and solvent 4 at high speed to prepare a component B, and preparing the aliphatic polyurethane coating according to the ratio of component A/component B=5/1.
2. The method for preparing the high weather-resistant, high-performance and high-cost-performance aliphatic polyurethane coating according to claim 1, wherein the polymer A comprises the following components in percentage by weight: 5 to 10 percent of monoacid, 12 to 18 percent of dibasic acid, 10 to 18 percent of triol, 0.02 to 0.08 percent of catalyst, 0.05 to 1.0 percent of antioxidant, 12 to 5 percent of modified monomer, 23 to 5 percent of modified monomer, 120 percent of solvent, 110 to 20 percent of (methyl) acrylic ester monomer, 15 to 25 percent of styrene, 3 to 5 percent of initiator and 0.5 to 2 percent of molecular weight regulator.
3. The method for preparing the high weather-resistant, high-performance and high-cost-performance aliphatic polyurethane coating according to claim 1, wherein the polymer B comprises the following components in percentage by weight: 230 percent of solvent, (methyl) acrylic ester monomer 225 percent to 35 percent, 25 percent to 35 percent of styrene, 8 percent to 12 percent of modified monomer 1, 3 percent to 4 percent of initiator and 0.5 percent to 2 percent of molecular weight regulator.
4. The method for preparing the high weather-resistant, high-performance and high-cost-performance aliphatic polyurethane coating according to claim 1, wherein the polymer C comprises the following components in percentage by weight: 50% of polymer A and 50% of polymer B.
5. The method for preparing the high weather-resistant, high-performance and high-cost-performance aliphatic polyurethane coating according to claim 1, wherein the polyurethane coating A comprises the following components in percentage by weight: 40-60% of polymer C, 20-30% of pigment, 5-10% of filler, 0.2-1.0% of rheological additive, 0.5-1.5% of dispersing additive, 0.3-1% of leveling additive and 310-15% of solvent.
6. The preparation method of the high weather-resistant, high-performance and high-cost-performance aliphatic polyurethane coating according to claim 1, wherein the polyurethane coating comprises the following components in percentage by weight: 85-95% of HDI trimer, 0.5-1% of dehydrating agent and 45-15% of solvent.
7. The method for preparing the high weather-resistant, high-performance and high-cost-performance aliphatic polyurethane coating according to any one of claims 1 to 6, wherein the monoacid is one or more of lauric acid, benzoic acid, isooctanoic acid and nonylic acid, the dibasic acid is one or more of phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, sebacic acid and hexahydrophthalic anhydride, and the triol is one or more of glycerol and trimethylolpropane.
8. The method for preparing the high weather-resistant, high-performance and high-cost-performance aliphatic polyurethane coating according to any one of claims 1 to 6, wherein the catalyst is one or more of monobutyl tin oxide, dibutyl tin oxide, stannous octoate and dibutyl tin dilaurate; the antioxidant is one or more of phosphoric acid and triphenyl phosphite; the modified monomer 1 is one of tertiary glycidyl ester of carbonic acid and glycidyl methacrylate; the modified monomer 2 is one or more of vinyl versatate, glycidyl methacrylate and dibutyl maleate.
9. The method for preparing the high weather-resistant, high-performance and high-cost-performance aliphatic polyurethane coating according to any one of claims 1 to 6, wherein the solvent 1 is one of propylene glycol methyl ether acetate and butyl acetate; the solvent 2 is one of propylene glycol methyl ether acetate and butyl acetate; the solvent 3 is one or more of propylene glycol methyl ether acetate, butyl acetate, dimethylbenzene and trimethylbenzene; the solvent 4 is propylene glycol methyl ether acetate.
10. The method for preparing the high weather-resistant, high-performance and high-cost-performance aliphatic polyurethane coating according to any one of claims 1 to 6, wherein the (methyl) acrylic ester monomer 1 is one or more of butyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; the (methyl) acrylic ester monomer 2 is one or more of acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; the initiator is one or more of tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, di-tert-amyl peroxide and tert-butyl peroxy3, 5-trimethylhexanoate; the molecular weight regulator is AMSD (methyl styrene dimer).
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