EP4267641A1 - Polyaspartic acid ester-containing composition - Google Patents
Polyaspartic acid ester-containing compositionInfo
- Publication number
- EP4267641A1 EP4267641A1 EP21839529.1A EP21839529A EP4267641A1 EP 4267641 A1 EP4267641 A1 EP 4267641A1 EP 21839529 A EP21839529 A EP 21839529A EP 4267641 A1 EP4267641 A1 EP 4267641A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- acid ester
- polyaspartic acid
- composition
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 229920000805 Polyaspartic acid Polymers 0.000 title claims abstract description 76
- 108010064470 polyaspartate Proteins 0.000 title claims abstract description 76
- 150000002148 esters Chemical class 0.000 title claims abstract description 75
- 239000008199 coating composition Substances 0.000 claims abstract description 44
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 19
- 125000003277 amino group Chemical group 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 150000003573 thiols Chemical class 0.000 claims description 34
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 15
- -1 2 -mercaptoethyl Chemical group 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 8
- 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 8
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 6
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 4
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 claims description 4
- CEUQYYYUSUCFKP-UHFFFAOYSA-N 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol Chemical compound SCCSCC(CS)SCCS CEUQYYYUSUCFKP-UHFFFAOYSA-N 0.000 claims description 3
- CFKONAWMNQERAG-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis[2-(3-sulfanylpropanoyloxy)ethyl]-1,3,5-triazinan-1-yl]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCN1C(=O)N(CCOC(=O)CCS)C(=O)N(CCOC(=O)CCS)C1=O CFKONAWMNQERAG-UHFFFAOYSA-N 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001718 carbodiimides Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- FLVFPAIGVBQGET-UHFFFAOYSA-N 1-methylpyrrolidin-3-ol Chemical compound CN1CCC(O)C1 FLVFPAIGVBQGET-UHFFFAOYSA-N 0.000 claims description 2
- RFMXKZGZSGFZES-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS.OC(=O)CS.CCC(CO)(CO)CO RFMXKZGZSGFZES-UHFFFAOYSA-N 0.000 claims description 2
- XSRJBLNNOOTBTM-UHFFFAOYSA-N 6-methylheptyl 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)CCCCCOC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XSRJBLNNOOTBTM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 238000004383 yellowing Methods 0.000 abstract description 16
- 230000000052 comparative effect Effects 0.000 description 20
- 229920001228 polyisocyanate Polymers 0.000 description 12
- 239000005056 polyisocyanate Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 5
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 3
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- DLYLVPHSKJVGLG-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexane-1,1-diamine Chemical compound C1CC(N)(N)CCC1CC1CCCCC1 DLYLVPHSKJVGLG-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JWTVQZQPKHXGFM-UHFFFAOYSA-N 2,5-dimethylhexane-2,5-diamine Chemical compound CC(C)(N)CCC(C)(C)N JWTVQZQPKHXGFM-UHFFFAOYSA-N 0.000 description 1
- AAAWJUMVTPNRDT-UHFFFAOYSA-N 2-methylpentane-1,5-diol Chemical compound OCC(C)CCCO AAAWJUMVTPNRDT-UHFFFAOYSA-N 0.000 description 1
- SYMNXYZGEQDEPK-UHFFFAOYSA-N 3-(hydroxymethyl)-3,5,5-trimethylcyclohexan-1-ol Chemical compound CC1(C)CC(O)CC(C)(CO)C1 SYMNXYZGEQDEPK-UHFFFAOYSA-N 0.000 description 1
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- 150000007945 N-acyl ureas Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WTSXICLFTPPDTL-UHFFFAOYSA-N pentane-1,3-diamine Chemical compound CCC(N)CCN WTSXICLFTPPDTL-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3851—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
- C08G18/3853—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring containing cyanurate and/or isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
Definitions
- the invention relates to a polyaspartic acid ester-containing composition, a two-component coating composition containing the composition, a coating method and application of the coating composition, and a product obtained by applying the coating composition.
- Polyaspartic acid ester-containing coating compositions and elastomers can be widely used in a variety of substrates to protect them and to improve their performance.
- polyaspartic acid ester-containing coating compositions are widely used in industrial coating compositions due to their excellent corrosion resistance, wear resistance, chemical resistance and weather resistance.
- the general disadvantage of polyaspartic acid ester-based coating compositions and elastomers is that polyaspartic acid ester has an obvious yellowing tendency during storage, which is undesirable during formulation design, storage and use.
- sterically hindered phenol antioxidants such as 3, 5 -di -tert-butyl -4- hydroxytoluene
- organic phosphite antioxidants such as trinonylphenyl phosphite, triphenyl phosphite, diphenyl isodecyl phosphite, diphenyl isooctyl phosphite, tridodecyl phophite and tris(2,4-di-tert-butyl-phenyl) phosphite are added to increase the color stability of polyaspartic acid ester-containing coating compositions or elastomers.
- CN104449303B discloses that at least two antioxidants (TPP, BHT, TNPP, TEPA, Irganoxl 135 and triisodecyl phosphite) are used together to significantly improve the color stability of polyaspartic acid ester-containing coating compositions and the transparent coatings formed therefrom.
- US2002132965A discloses that a thiol can be used as a co-reactant in the reaction of a primary amine and diethyl maleate for the synthesis of polyaspartic acid esters to increase the conversion in the synthesis of polyaspartic acid esters.
- US2010311890A discloses that the thiol contained in low modulus polyaspartic acid ester- containing coating compositions can be used as a component that provides active hydrogen for other reaction resins (including polyethers, polyols, thiol ethers, polycarbonates and polyesters) in the reaction to generate polyurea coating compositions. It is desired to develop a polyaspartic acid ester-containing coating composition with high color stability and low yellowing tendency.
- the objects of the present invention are to provide a polyaspartic acid ester-containing composition, a two-component coating composition containing the composition, a coating method and use of the coating composition, and a product obtained by applying the coating composition.
- the polyaspartic acid ester-containing composition according to the present invention comprises: a. a polyaspartic acid ester; b. a thiol with an active hydrogen group; and c. optionally an antioxidant in an amount of not more than 3% by weight, relative to the total weight of the composition; wherein the molar ratio of mercapto groups of the thiol of component b) to amino groups of the polyaspartic acid ester of component a) is of 0.060-0.720.
- a coating composition, an adhesive or a sealant comprising the polyaspartic acid ester-containing composition according to the present invention is provided .
- a two-component coating composition comprising component A and component B is provided, wherein said component A is the polyaspartic acid ester-containing composition according to the present invention, and said component B is a crosslinking agent.
- a coating method comprising applying the two-component coating composition according to the present invention to a surface of a substrate and then curing and drying is provided.
- a product comprising a substrate and a coating formed by applying the two-component coating composition of the present invention to the substrate and then curing and drying is provided.
- a method for preparing the polyaspartic acid ester-containing composition according to the present invention comprises mixing the polyaspartic acid ester of component a), the thiol with an active hydrogen group of component b) and optionally an antioxidant of component c) in any desired manner.
- the thiol and optionally the antioxidant in the polyaspartic acid ester-containing composition of the present invention can effectively inhibit the yellowing of the composition, and thus the composition has high color stability.
- a coating composition comprising the composition of the present invention, especially a transparent coating composition, can still have color stability and show unobvious yellowing after being stored for 20 weeks at the temperature of 50°C.
- the present invention provides a polyaspartic acid ester-containing composition
- a polyaspartic acid ester-containing composition comprising a. a polyaspartic acid ester; b. a thiol with an active hydrogen group; and c. optionally an antioxidant in an amount of not more than 3% by weight, relative to the total weight of the composition; wherein the molar ratio of mercapto groups of the thiol of component b) to amino groups of the polyaspartic acid ester of component a) is of 0.060-0.720.
- the present invention also provides a method for preparing the composition, a two-component coating composition comprising the composition, a coating method and use of the coating composition, and a product obtained by applying the coating composition.
- primary thiol refers to a thiol with a mercapto group attached to the primary position of the end group.
- thiol used herein refers to an organic sulfur compound corresponding to the general formula R-SH, where R represents an alkyl group or other organic substituent, the sulfur atom being connected to a carbon atom.
- two-component coating composition used herein refers to a coating composition comprising at least two components, which have to be stored in separate containers due to their reactivity with each other. When these two separate components are mixed and applied to a substrate, the reactive compounds in the two components react with each other to crosslink and form a cured coating.
- coating composition refers to a chemical composition that can be applied to a surface of an object by a variety of application processes to form a continuous solid coating with firm adhesion and certain strength.
- curing and drying refers to a process from a liquid state to a cured state of a coating composition.
- each independently used herein means that the groups may be identical or different.
- organic group non-reactive toward isocyanate refers to an organic group that is inert to isocyanate groups at a temperature of 100°C or lower.
- Amino herein refers to -NR2, -NHR, R-NH2, where R is an alkyl group.
- the polyaspartic acid ester-containing composition is preferably transparent.
- the molar ratio of mercapto groups of the thiol of component b) to amino groups of the polyaspartic acid ester of component a) refers to the ratio of the mercapto group moles of the thiol of component b) to the amino group moles of the polyaspartic acid ester of component a).
- the molar ratio of mercapto groups of the thiol of component b) to amino groups of the polyaspartic acid ester of component a) is preferably of 0.070-0.72, more preferably of 0.070-0.240, and most preferably of 0.070-0.200.
- the calculation method is as follows:
- the amount of the polyaspartic acid ester is preferably of 40% to 95% by weight, relative to the total weight of the composition.
- the polyaspartic acid ester has preferably the structure of formula I:
- R 1 and R 2 are each independently an organic group, which is non-reactive toward isocyanate groups under normal pressure and at a temperature of less than or equal to 100°C, n is an integer of not less than 2.
- the aliphatic residue is preferably one or more of linear alkyl residues, branched alkyl residues and cycloalkyl residues, and most preferably cycloalkyl residues.
- the aliphatic residue herein is preferably derived from an alcohol compound which is preferably one or more of ethylene glycol, 1,2-dihydroxypropane, 1,4-dihydroxybutane, 1,6- dihydroxyhexane, 2,2,4-and/or 2,4,4-trimethyl-l,6-dihydroxyhexane, 1 -hydroxy-3, 3,5- trimethyl-5-hydroxymethylcyclohexane, 4, 4'-dihydroxy di cyclohexylmethane, 3,3'- dimethyl-4',4'-dihydroxydicyclohexylmethane, 1,5 -dihydroxy -2 -methylpentane, 1,1,1- trimethylolpropane and 2,2-bis(hydroxymethyl)-l,3-propanediol (pentaerythritol).
- an alcohol compound which is preferably one or more of ethylene glycol, 1,2-dihydroxypropane, 1,4-dihydroxybutane, 1,6- dihydroxyhexan
- R 1 and R 2 are each independently preferably an alkyl residue having 1 to 10 carbon atoms, and most preferably one or more of methyl, ethyl and butyl.
- n is preferably an integer of 2 to 4, and most preferably 2.
- the polyaspartic acid ester is most preferably one or more of Desm ophen NH 1420, Desmophen 1520, Desmophen 1220, Desmophen 2872, Desmophen 2850, Desmophen 1422 and Desmophen 1521, all available from Covestro Polymers (China) Co., Ltd.
- the amino equivalent of the polyaspartic acid ester is preferably of 200-500.
- the viscosity of the polyaspartic acid ester is preferably of 500 to 4000 mPa s.
- n of the polyaspartic acid ester is 2, it is obtained by the reaction of a polyamine of the following formula and a maleate and/or fumarate of the following formula:
- the polyamine is preferably one or more of ethylenediamine, 1,2-diaminopropane, 1,4- diaminobutane, 1,3 -diaminopentane, 1,6-diaminohexane, 2,5-diamino-2,5-dimethylhexane,
- the maleate and/or fumarate is preferably one or more of dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate and dibutyl fumarate.
- the reaction temperature is preferably of 0°C to 100°C.
- the weight ratio of the maleate and/or fumarate to the polyamine is preferably 2:1.
- the weight ratio of the olefinic double bonds of the maleate and/or fumarate to the primary amino groups of the polyamine is preferably 1 : 1.
- the product obtained from the reaction is preferably purified by rectification.
- the components of the reaction may or may not comprise a solvent, and preferably comprises a solvent.
- the solvent is preferably one or more of methanol, ethanol, propanol and dioxane.
- the amount of the thiol with an active hydrogen group of component b) is preferably of 3% by weight to 8% by weight, relative to the total weight of the composition.
- the thiol of component b) is one or more of tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate, pentaerythritol tetra(3 -mercaptopropionate), bi s(2 -mercaptoethyl) sulfide, 2,3- bis[(2-mercaptoethyl)thio]-l-propanethiol, trimethylolpropane tri(2-mercaptoacetate), and pentaerythritol tetra(mercaptoacetate) .
- the amount of the antioxidant is preferably of not more than 2% by weight, relative to the total weight of the composition.
- composition does not comprise an antioxidant.
- the antioxidant is preferably one or more of sterically hindered phenolic antioxidants and organic phosphite antioxidants; and most preferably one or more of triphenyl phosphite, trinonylphenyl phosphite, 3,5-di-tert-butyl-4-hydroxytoluene and isooctyl 3, 5 -di -tert-butyl - 4-hydroxyphenylpropionate.
- the two-component coating composition is preferably transparent.
- component A and component B of the two-component coating composition are preferably stored separately, and mixed prior to use to give the two-component coating composition.
- Crosslinking agent of component B is preferably stored separately, and mixed prior to use to give the two-component coating composition.
- the crosslinking agent is preferably one or more of isocyanate group-containing compounds and carbodiimides.
- Isocyanate groups of the isocyanate group-containing compounds of the present invention include free and/or potentially free isocyanate groups.
- the potentially free isocyanate groups can be released by a method well known to those skilled in the art, such as heating.
- the isocyanate group-containing compound is preferably liquid at room temperature or becomes liquid by adding an organic solvent.
- the isocyanate group-containing compound may comprise a blocked isocyanate group.
- the blocked isocyanate group is blocked by reacting with a low molecular weight compound containing active hydrogen.
- the low molecular weight compound containing active hydrogen may be a aliphatic alcohol, an alicyclic alcohol, a dialkylamino alcohol, oxime, lactam, imide, hydroxyalkyl ester, malonate or acetoacetate.
- the isocyanate group-containing compound may have hydrophilic groups.
- the isocyanate group-containing compound is preferably one or more of aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates and aromatic polyisocyanates, most preferably one or more of aliphatic polyisocyanates and alicyclic polyisocyanates.
- the isocyanate group-containing compound may be a prepolymer or an adduct of diisocyanate, for example, a trimer of diisocyanate.
- the isocyanate group-containing compound may also be an isocyanurate, a biuret group-containing polyisocyanate, a urethane group-containing polyisocyanate, an allophanate group-containing polyisocyanate, an isocyanurate group- and allophanate group-containing polyisocyanate, a carbodiimide group-containing polyisocyanate, and a ureide group-containing polyisocyanate.
- the equivalent ratio of the isocyanate groups of the isocyanate group-containing compound to the isocyanate-reactive groups of component A is preferably of 0.5: 1-10: 1.
- the two-component coating composition may further comprise an additive.
- the additive is selected from one or more of pigments such as organic pigments, inorganic pigments, metallic pigments or pearlescent pigments, wetting agents, matting agents, defoamers, film formers, thickeners, elastic agents, catalysts, UV absorbers, and other additives that can be added to the two-component coating composition as well known to those skilled in the art.
- the additive may be added in an amount which is well known to those skilled in the art.
- the two-component coating composition may further comprise a solvent.
- the solvent may be one that can be added to the two-component coating composition as well known to those skilled in the art, most preferably one or more of n-butyl acetate, xylene and propylene glycol methyl ether acetate.
- the solvent may be added in an amount which is well known to those skilled in the art.
- the substrate may be artificial stone, wood, artificial wood, marble, terrazzo, ceramic, felt, metal, plastic, rubber, concrete, composite board, paper, leather or glass, most preferably metal or glass.
- the substrate may be pre-treated.
- the pre-treatment may be polishing or coating.
- the application may be a method well known to those skilled in the art, such as knife coating, brush coating, roller coating, spray coating or curtain coating.
- the product can be windows, mirrors, furniture, bicycles, cars, road signs, bridges, books or boxes, most preferably cars.
- the isocyanate group (NCO) content is determined by volume in accordance with DIN-EN ISO 11909.
- the measured data include free and potentially free NCO contents.
- Hazen value is measured by using Hazen tester of Hash LICO 690 equipment according to ASTMD1209 standard.
- Hazen tester of Hash LICO 690 equipment according to ASTMD1209 standard.
- Desmophen NH1520 polyaspartic acid ester having a solid content of 100% by weight with amino functionality of 2.0 and amino equivalent of 290, available from Covestro Co., Ltd., Germany.
- TEMPIC tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate, thiol, from Bruno Bock-DE.
- PETMP pentaerythritol tetra(3 -mercaptopropionate), thiol, from Bruno Bock-DE.
- GST 2,3-bis[(2-mercaptoethyl)thio]-l-propanethiol, thiol, from Bruno Bock-DE.
- DMDS bi s(2 -mercaptoethyl) sulfide, thiol, from Bruno Bock-DE.
- TPP Triphenyl phosphite, antioxidant, from Shanghai Macklin Biochemical Co., Ltd.
- BHT 3,5-di-tert-butyl-4-hydroxytoluene, antioxidant, from Sigma-Aldrich (Shanghai), n-butyl acetate: solvent, from Shanghai Ling Feng Chemical reagent Co. Ltd.
- BYK-333 Surface active agent, from BYK.
- BYK-141 Defoamer, from BYK.
- BYK-358N Wetting agent, from BYK.
- Table 1 shows the TEMPIC content, the initial color value and the color value after several weeks of storage at 50°C of the polyaspartic acid ester-containing compositions from Examples 1-2 and Comparative Examples 1-4.
- Table 2 shows the PETMP content, the initial color value and the color value after several weeks of storage at 50°C of the polyaspartic acid ester-containing compositions from Examples 3-5 and Comparative Examples 1, 5 and 6.
- Table 3 shows the GST content, the initial color value and the color value after several weeks of storage at 50°C of the polyaspartic acid ester-containing compositions from Examples 6- 9 and Comparative Examples 1 and 7.
- Table 4 shows the DMDS content, the initial color value and the color value after several weeks of storage at 50°C of the polyaspartic acid ester-containing compositions from Examples 10-14 and Comparative Example 1.
- Table 5 shows the composition, the initial color value and the color value after several weeks of storage at 50°C of the polyaspartic acid ester-containing compositions from Examples 14- 15 and Comparative Examples 1, and 8-9.
- Table 6 shows the composition, the initial color value and the color value after several weeks of storage at 50°C of the polyaspartic acid ester-containing compositions from Examples 14 and 16 and Comparative Examples 1 and 10.
- the initial Hazen values in the table below refer to the Hazen values obtained by the color value test within 60 minutes after the compositions have been prepared.
- 6 weeks, 8 weeks, 15 weeks and 20 weeks indicate respectively that the Hazen values were obtained by the color value test after the compositions have been prepared and stored at 50°C for 6 weeks, 8 weeks, 15 weeks and 20 weeks.
- Table 1 polyaspartic acid ester-containing compositions of Examples 1 to 2 and Comparative Examples 1 to 4 and color values thereof It can be seen from the comparation between Comparative Examples 1-4 with Examples 1- 2 that the color value of the composition after being stored at 50°C for 15 weeks was less than 150, that is, the composition was color stable and not prone to yellowing, when the molar ratio of mercapto groups of the thiol TEMPIC to amino groups of the polyaspartic acid ester in the transparent composition containing polyaspartic acid ester was greater than 0.060.
- Comparative Examples 1 and 8 It can be seen from Comparative Examples 1 and 8 that the color value of the composition after being stored at 50°C for 15 weeks was much higher than 150, that is, the composition had poor color stability and was prone to yellowing, when the composition comprised no thiol.
- the 5% by weight of antioxidant in the composition of Comparative Example 8 could not improve the color stability of the composition.
- Comparative Examples 1 and 10 that the color value of the composition after being stored at 50°C for 15 weeks was much higher than 150, that is, the composition had poor color stability and was prone to yellowing, when the composition comprised no thiol.
- the 5% by weight of antioxidant in the composition of Comparative Example 10 could not improve the color stability of the composition.
- the color value of the transparent composition containing polyaspartic acid ester after being stored at 50°C for 15 weeks was much less than 150, that is, the composition was color stable and not prone to yellowing, when the molar ratio of mercapto groups of DMDS to amino groups of the polyaspartic acid ester in the composition was greater than 0.060 and the antioxidant content of the composition was 1.67 % by weight and 0 % by weight.
Abstract
The invention relates to a polyaspartic acid ester-containing composition, a two-component coating composition containing said composition, a coating method and use of the coating composition, and a product obtained by applying the coating composition. The polyaspartic acid ester-containing composition comprises a. a Polyaspartic acid ester; b. a thiol with an active hydrogen group; and c. optionally an antioxidant in an amount of not more than 3% by weight, relative to the total weight of the composition; wherein the molar ratio of mercapto groups of the thiol of component b) to amino groups of the polyaspartic acid ester of component a) is of 0.060-0.720. The composition of the present invention has high color stability and is not prone to yellowing.
Description
Polyaspartic acid ester-containing composition
Technical Field
The invention relates to a polyaspartic acid ester-containing composition, a two-component coating composition containing the composition, a coating method and application of the coating composition, and a product obtained by applying the coating composition.
Prior Art
Polyaspartic acid ester-containing coating compositions and elastomers can be widely used in a variety of substrates to protect them and to improve their performance. Nowadays, polyaspartic acid ester-containing coating compositions are widely used in industrial coating compositions due to their excellent corrosion resistance, wear resistance, chemical resistance and weather resistance. However, the general disadvantage of polyaspartic acid ester-based coating compositions and elastomers is that polyaspartic acid ester has an obvious yellowing tendency during storage, which is undesirable during formulation design, storage and use.
In the prior art, sterically hindered phenol antioxidants such as 3, 5 -di -tert-butyl -4- hydroxytoluene, and organic phosphite antioxidants such as trinonylphenyl phosphite, triphenyl phosphite, diphenyl isodecyl phosphite, diphenyl isooctyl phosphite, tridodecyl phophite and tris(2,4-di-tert-butyl-phenyl) phosphite are added to increase the color stability of polyaspartic acid ester-containing coating compositions or elastomers.
CN104449303B discloses that at least two antioxidants (TPP, BHT, TNPP, TEPA, Irganoxl 135 and triisodecyl phosphite) are used together to significantly improve the color stability of polyaspartic acid ester-containing coating compositions and the transparent coatings formed therefrom.
US2002132965A discloses that a thiol can be used as a co-reactant in the reaction of a primary amine and diethyl maleate for the synthesis of polyaspartic acid esters to increase the conversion in the synthesis of polyaspartic acid esters.
US2010311890A discloses that the thiol contained in low modulus polyaspartic acid ester- containing coating compositions can be used as a component that provides active hydrogen for other reaction resins (including polyethers, polyols, thiol ethers, polycarbonates and polyesters) in the reaction to generate polyurea coating compositions.
It is desired to develop a polyaspartic acid ester-containing coating composition with high color stability and low yellowing tendency.
Summary of the invention
The objects of the present invention are to provide a polyaspartic acid ester-containing composition, a two-component coating composition containing the composition, a coating method and use of the coating composition, and a product obtained by applying the coating composition.
The polyaspartic acid ester-containing composition according to the present invention comprises: a. a polyaspartic acid ester; b. a thiol with an active hydrogen group; and c. optionally an antioxidant in an amount of not more than 3% by weight, relative to the total weight of the composition; wherein the molar ratio of mercapto groups of the thiol of component b) to amino groups of the polyaspartic acid ester of component a) is of 0.060-0.720.
According to an aspect of the present invention, a coating composition, an adhesive or a sealant comprising the polyaspartic acid ester-containing composition according to the present invention is provided .
According to another aspect of the present invention, a two-component coating composition comprising component A and component B is provided, wherein said component A is the polyaspartic acid ester-containing composition according to the present invention, and said component B is a crosslinking agent.
According to still another aspect of the present invention, use of the two-component coating composition according to the present invention for protecting a surface of a substrate or a coating on the surface of a substrate is provided .
According to yet another aspect of the present invention, a coating method comprising applying the two-component coating composition according to the present invention to a surface of a substrate and then curing and drying is provided.
According to yet another aspect of the present invention, a product comprising a substrate and a coating formed by applying the two-component coating composition of the present invention to the substrate and then curing and drying is provided.
According to yet another aspect of the present invention, a method for preparing the polyaspartic acid ester-containing composition according to the present invention is provided, which comprises mixing the polyaspartic acid ester of component a), the thiol with an active hydrogen group of component b) and optionally an antioxidant of component c) in any desired manner.
The thiol and optionally the antioxidant in the polyaspartic acid ester-containing composition of the present invention can effectively inhibit the yellowing of the composition, and thus the composition has high color stability. A coating composition comprising the composition of the present invention, especially a transparent coating composition, can still have color stability and show unobvious yellowing after being stored for 20 weeks at the temperature of 50°C.
Embodiments
The present invention provides a polyaspartic acid ester-containing composition comprising a. a polyaspartic acid ester; b. a thiol with an active hydrogen group; and c. optionally an antioxidant in an amount of not more than 3% by weight, relative to the total weight of the composition; wherein the molar ratio of mercapto groups of the thiol of component b) to amino groups of the polyaspartic acid ester of component a) is of 0.060-0.720. The present invention also provides a method for preparing the composition, a two-component coating composition comprising the composition, a coating method and use of the coating composition, and a product obtained by applying the coating composition.
The term "primary thiol" used herein refers to a thiol with a mercapto group attached to the primary position of the end group.
The term "thiol" used herein refers to an organic sulfur compound corresponding to the general formula R-SH, where R represents an alkyl group or other organic substituent, the sulfur atom being connected to a carbon atom.
The term "two-component coating composition" used herein refers to a coating composition comprising at least two components, which have to be stored in separate containers due to their reactivity with each other. When these two separate components are mixed and applied to a substrate, the reactive compounds in the two components react with each other to crosslink and form a cured coating.
The term "coating composition" used herein refers to a chemical composition that can be applied to a surface of an object by a variety of application processes to form a continuous solid coating with firm adhesion and certain strength.
The term "curing and drying" used herein refers to a process from a liquid state to a cured state of a coating composition.
The term "each independently" used herein means that the groups may be identical or different.
The term "organic group non-reactive toward isocyanate" used herein refers to an organic group that is inert to isocyanate groups at a temperature of 100°C or lower.
"Amino" herein refers to -NR2, -NHR, R-NH2, where R is an alkyl group.
Polyaspartic acid ester-containing composition
The polyaspartic acid ester-containing composition is preferably transparent.
The molar ratio of mercapto groups of the thiol of component b) to amino groups of the polyaspartic acid ester of component a) refers to the ratio of the mercapto group moles of the thiol of component b) to the amino group moles of the polyaspartic acid ester of component a).
The molar ratio of mercapto groups of the thiol of component b) to amino groups of the polyaspartic acid ester of component a) is preferably of 0.070-0.72, more preferably of 0.070-0.240, and most preferably of 0.070-0.200. The calculation method is as follows:
Molar ratio of mercapto groups of the thiol of component b) to amino groups of the polyaspartic acid ester of component a) Mass of the thiol of component b) / mercapto equivalent of the thiol of component b)
Mass of polyaspartic acid ester of component a) / amino equivalent of the polyaspartic acid ester of component a)
Polyaspartic acid ester of component a)
The amount of the polyaspartic acid ester is preferably of 40% to 95% by weight, relative to the total weight of the composition.
The polyaspartic acid ester has preferably the structure of formula I:
I wherein X is an aliphatic residue,
R1 and R2 are each independently an organic group, which is non-reactive toward isocyanate groups under normal pressure and at a temperature of less than or equal to 100°C, n is an integer of not less than 2.
The aliphatic residue is preferably one or more of linear alkyl residues, branched alkyl residues and cycloalkyl residues, and most preferably cycloalkyl residues.
The aliphatic residue herein is preferably derived from an alcohol compound which is preferably one or more of ethylene glycol, 1,2-dihydroxypropane, 1,4-dihydroxybutane, 1,6- dihydroxyhexane, 2,2,4-and/or 2,4,4-trimethyl-l,6-dihydroxyhexane, 1 -hydroxy-3, 3,5- trimethyl-5-hydroxymethylcyclohexane, 4, 4'-dihydroxy di cyclohexylmethane, 3,3'- dimethyl-4',4'-dihydroxydicyclohexylmethane, 1,5 -dihydroxy -2 -methylpentane, 1,1,1- trimethylolpropane and 2,2-bis(hydroxymethyl)-l,3-propanediol (pentaerythritol).
R1 and R2 are each independently preferably an alkyl residue having 1 to 10 carbon atoms, and most preferably one or more of methyl, ethyl and butyl. n is preferably an integer of 2 to 4, and most preferably 2.
The polyaspartic acid ester is most preferably one or more of Desm ophen NH 1420, Desmophen 1520, Desmophen 1220, Desmophen 2872, Desmophen 2850, Desmophen 1422 and Desmophen 1521, all available from Covestro Polymers (China) Co., Ltd.
The amino equivalent of the polyaspartic acid ester is preferably of 200-500.
The viscosity of the polyaspartic acid ester is preferably of 500 to 4000 mPa s.
When n of the polyaspartic acid ester is 2, it is obtained by the reaction of a polyamine of the following formula and a maleate and/or fumarate of the following formula:
The polyamine is preferably one or more of ethylenediamine, 1,2-diaminopropane, 1,4- diaminobutane, 1,3 -diaminopentane, 1,6-diaminohexane, 2,5-diamino-2,5-dimethylhexane,
2.2.4-trimethyl-l,6-diaminohexane, 2,4,4-trimethyl-l,6-diaminohexane, 1,11- diaminoundecane, 1,12-diaminododecane, 1,3-cyclohexanediamine, and 1,4- cyclohexanediamine, amino-3, 3, 5-trimethyl-5-aminomethyl -cyclohexane, 2,4- hexahydrotoluenediamine, 2,6-hexahydrotoluenediamine, 2,4'- diaminodi cyclohexylmethane, 4, 4'-diaminodi cyclohexylmethane, 3,3'-dialkyl-4,4'-diamino- di cyclohexylmethane, 2, 4, 4'-triamino-5-methyldi cyclohexylmethane, 2-methyl-l,5- pentanediamine, 1,3 -xylenediamine and 1,4-xylenediamine, more preferably one or more of
1.4-diaminobutane, 1,6-diaminohexane, 2,2,4-trimethyl-l,6-diaminohexane, 2,4,4- trimethyl-l,6-diaminohexane, amino-3, 3, 5-trimethyl-5-aminomethylcyclohexane, 4,4'- diamino-dicyclohexylmethane, 3,3'-dialkyl-4,4'-diaminodicyclohexylmethane and 2- methyl-l,5-pentanediamine, and most preferably one or more of 2-methyl-l,5- pentanediamine, amino-3, 3, 5 -tris methyl-5-aminomethylcyclohexane, 2,4'-diamino- dicyclohexylmethane, 4,4'-diamino-dicyclohexylmethane and 3,3'-dialkyl-4,4'- diaminodi cyclohexylmethane.
The maleate and/or fumarate is preferably one or more of dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate and dibutyl fumarate.
The reaction temperature is preferably of 0°C to 100°C.
The weight ratio of the maleate and/or fumarate to the polyamine is preferably 2:1.
The weight ratio of the olefinic double bonds of the maleate and/or fumarate to the primary amino groups of the polyamine is preferably 1 : 1.
The product obtained from the reaction is preferably purified by rectification.
The components of the reaction may or may not comprise a solvent, and preferably comprises a solvent.
The solvent is preferably one or more of methanol, ethanol, propanol and dioxane.
Thiol with an active hydrogen group of component b)
The amount of the thiol with an active hydrogen group of component b) is preferably of 3% by weight to 8% by weight, relative to the total weight of the composition.
The thiol of component b) is one or more of tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate, pentaerythritol tetra(3 -mercaptopropionate), bi s(2 -mercaptoethyl) sulfide, 2,3- bis[(2-mercaptoethyl)thio]-l-propanethiol, trimethylolpropane tri(2-mercaptoacetate), and pentaerythritol tetra(mercaptoacetate) .
Antioxidant of component c)
The amount of the antioxidant is preferably of not more than 2% by weight, relative to the total weight of the composition.
Most preferably, the composition does not comprise an antioxidant.
The antioxidant is preferably one or more of sterically hindered phenolic antioxidants and organic phosphite antioxidants; and most preferably one or more of triphenyl phosphite, trinonylphenyl phosphite, 3,5-di-tert-butyl-4-hydroxytoluene and isooctyl 3, 5 -di -tert-butyl - 4-hydroxyphenylpropionate.
Two-component coating composition
The two-component coating composition is preferably transparent.
The component A and component B of the two-component coating composition are preferably stored separately, and mixed prior to use to give the two-component coating composition.
Crosslinking agent of component B
The crosslinking agent is preferably one or more of isocyanate group-containing compounds and carbodiimides.
Isocyanate groups of the isocyanate group-containing compounds of the present invention include free and/or potentially free isocyanate groups.
The potentially free isocyanate groups can be released by a method well known to those skilled in the art, such as heating.
The isocyanate group-containing compound is preferably liquid at room temperature or becomes liquid by adding an organic solvent.
The isocyanate group-containing compound may comprise a blocked isocyanate group. The blocked isocyanate group is blocked by reacting with a low molecular weight compound containing active hydrogen. The low molecular weight compound containing active hydrogen may be a aliphatic alcohol, an alicyclic alcohol, a dialkylamino alcohol, oxime, lactam, imide, hydroxyalkyl ester, malonate or acetoacetate.
The isocyanate group-containing compound may have hydrophilic groups.
The isocyanate group-containing compound is preferably one or more of aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates and aromatic polyisocyanates, most preferably one or more of aliphatic polyisocyanates and alicyclic polyisocyanates.
The isocyanate group-containing compound may be a prepolymer or an adduct of diisocyanate, for example, a trimer of diisocyanate. The isocyanate group-containing compound may also be an isocyanurate, a biuret group-containing polyisocyanate, a urethane group-containing polyisocyanate, an allophanate group-containing polyisocyanate, an isocyanurate group- and allophanate group-containing polyisocyanate, a carbodiimide group-containing polyisocyanate, and a ureide group-containing polyisocyanate.
The equivalent ratio of the isocyanate groups of the isocyanate group-containing compound to the isocyanate-reactive groups of component A is preferably of 0.5: 1-10: 1.
The equivalent ratio of the N=C=N groups of the carbodiimide to the isocyanate-reactive groups of component A is preferably of 0.5: 1-10: 1.
Additive
The two-component coating composition may further comprise an additive. The additive is selected from one or more of pigments such as organic pigments, inorganic pigments, metallic pigments or pearlescent pigments, wetting agents, matting agents, defoamers, film formers, thickeners, elastic agents, catalysts, UV absorbers, and other additives that can be added to the two-component coating composition as well known to those skilled in the art.
The additive may be added in an amount which is well known to those skilled in the art.
The two-component coating composition may further comprise a solvent. The solvent may be one that can be added to the two-component coating composition as well known to those skilled in the art, most preferably one or more of n-butyl acetate, xylene and propylene glycol methyl ether acetate.
The solvent may be added in an amount which is well known to those skilled in the art.
Substrate
The substrate may be artificial stone, wood, artificial wood, marble, terrazzo, ceramic, felt, metal, plastic, rubber, concrete, composite board, paper, leather or glass, most preferably metal or glass.
The substrate may be pre-treated. The pre-treatment may be polishing or coating.
Application
The application may be a method well known to those skilled in the art, such as knife coating, brush coating, roller coating, spray coating or curtain coating.
Product
The product can be windows, mirrors, furniture, bicycles, cars, road signs, bridges, books or boxes, most preferably cars.
Examples
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. When the definition of a term in this specification conflicts with the meanings commonly understood by those skilled in the art, the definition described herein shall prevail.
Unless indicated otherwise, all numbers expressing quantities of ingredients, reaction conditions and the like used in the specification and claims are to be understood as being modified by the wording "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties to be obtained.
The wording "and/or" used herein refers to one or all of the cited elements.
The wording "include" and "comprise" used herein cover the presence of the mentioned elements alone and the presence of other unmentioned elements in addition to the mentioned elements.
All percentages in the present invention are weight percentages, unless otherwise stated.
The analysis and measurement in the present invention are performed at 23±2°C, unless otherwise stated.
The isocyanate group (NCO) content is determined by volume in accordance with DIN-EN ISO 11909. The measured data include free and potentially free NCO contents.
Color value (Hazen value) is measured by using Hazen tester of Hash LICO 690 equipment according to ASTMD1209 standard. When the measured Hazen values of the composition at the beginning, after 6 weeks of storage, after 8 weeks of storage, and after 15 weeks of storage are all less than 150, the color of the composition is considered to be stable and not prone to yellowing.
Raw materials and agents
Desmophen NH1520: polyaspartic acid ester having a solid content of 100% by weight with amino functionality of 2.0 and amino equivalent of 290, available from Covestro Co., Ltd., Germany.
TEMPIC: tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate, thiol, from Bruno Bock-DE.
PETMP: pentaerythritol tetra(3 -mercaptopropionate), thiol, from Bruno Bock-DE.
GST: 2,3-bis[(2-mercaptoethyl)thio]-l-propanethiol, thiol, from Bruno Bock-DE.
DMDS: bi s(2 -mercaptoethyl) sulfide, thiol, from Bruno Bock-DE.
TPP: Triphenyl phosphite, antioxidant, from Shanghai Macklin Biochemical Co., Ltd.
BHT: 3,5-di-tert-butyl-4-hydroxytoluene, antioxidant, from Sigma-Aldrich (Shanghai), n-butyl acetate: solvent, from Shanghai Ling Feng Chemical reagent Co. Ltd.
Xylene: solvent, from Shanghai Ling Feng Chemical reagent Co. Ltd.
Propylene glycol methyl ether acetate: solvent, from Shanghai Macklin Biochemical Co., Ltd.
BYK-333: Surface active agent, from BYK.
BYK-141 : Defoamer, from BYK.
BYK-358N: Wetting agent, from BYK.
Table 1 shows the TEMPIC content, the initial color value and the color value after several weeks of storage at 50°C of the polyaspartic acid ester-containing compositions from Examples 1-2 and Comparative Examples 1-4.
Table 2 shows the PETMP content, the initial color value and the color value after several weeks of storage at 50°C of the polyaspartic acid ester-containing compositions from Examples 3-5 and Comparative Examples 1, 5 and 6.
Table 3 shows the GST content, the initial color value and the color value after several weeks of storage at 50°C of the polyaspartic acid ester-containing compositions from Examples 6- 9 and Comparative Examples 1 and 7.
Table 4 shows the DMDS content, the initial color value and the color value after several weeks of storage at 50°C of the polyaspartic acid ester-containing compositions from Examples 10-14 and Comparative Example 1.
Table 5 shows the composition, the initial color value and the color value after several weeks of storage at 50°C of the polyaspartic acid ester-containing compositions from Examples 14- 15 and Comparative Examples 1, and 8-9.
Table 6 shows the composition, the initial color value and the color value after several weeks of storage at 50°C of the polyaspartic acid ester-containing compositions from Examples 14 and 16 and Comparative Examples 1 and 10.
Preparation of curable transparent composition containing polyaspartic acid ester
According to the thiol and antioxidant and the contents thereof shown in Tables 1-6, 60 g of Desmophen NH1520, a thiol, an antioxidant and a solvent mixture (wherein the ratio of each component of the solvent mixture was n-butyl acetate: xylene: propylene glycol methyl ether acetate: BYK 358N: BYK 333: BYK 141 = 15: 15: 7: 0.08: 0.01 : 0.03, and the amount of the solvent mixture in the composition was adjusted according to the amount of other components in the composition so that the weight of the composition was 100g) were put into a vessel, stirred and mixed to obtain 100g of the composition, in which the content of Desmophen NH1520 was 60% by weight.
The initial Hazen values in the table below refer to the Hazen values obtained by the color value test within 60 minutes after the compositions have been prepared.
6 weeks, 8 weeks, 15 weeks and 20 weeks indicate respectively that the Hazen values were obtained by the color value test after the compositions have been prepared and stored at 50°C for 6 weeks, 8 weeks, 15 weeks and 20 weeks.
Table 1 polyaspartic acid ester-containing compositions of Examples 1 to 2 and Comparative Examples 1 to 4 and color values thereof
It can be seen from the comparation between Comparative Examples 1-4 with Examples 1- 2 that the color value of the composition after being stored at 50°C for 15 weeks was less than 150, that is, the composition was color stable and not prone to yellowing, when the molar ratio of mercapto groups of the thiol TEMPIC to amino groups of the polyaspartic acid ester in the transparent composition containing polyaspartic acid ester was greater than 0.060.
Table 2 polyaspartic acid esters-containing compositions of Examples 3 to 5 and
Comparative Examples 1, 5 to 6 and color values thereof
It can be seen from the comparation between Comparative Examples 1, 5-6 with Examples 3-5 that the color value of the composition after being stored at 50°C for 15 weeks was less than 150, that is, the composition was color stable and not prone to yellowing and not prone to yellowing, when the molar ratio of mercapto groups of PETMP to amino groups of the polyaspartic acid ester in the transparent composition containing polyaspartic acid ester was greater than 0.060.
Table 3 polyaspartic acid ester-containing compositions of Examples 6 to 9 and
Comparative Examples 1 and 7 and color values thereof
It can be seen from the comparation between Comparative Examples 1 and 7 with Examples 6-9 that the color value of the composition after being stored at 50°C for 15 weeks was less than 150, that is, the composition was color stable and not prone to yellowing, when the molar ratio of mercapto groups of GST to amino groups of the polyaspartic acid ester in the transparent composition containing polyaspartic acid ester was greater than 0.060. Table 4 polyaspartic acid esters-containing compositions of Examples 10 to 14 and Comparative Example 1 and color values thereof
It can be seen from Examples 10-14 that the color value of the composition after being stored at 50°C for 15 weeks was less than 150, that is, the composition was color stable and not prone to yellowing, when the molar ratio of mercapto groups of DMDS to amino groups of the polyaspartic acid ester in the transparent composition containing polyaspartic acid ester was greater than 0.060.
Table 5 polyaspartic acid ester-containing compositions of Examples 14 to 15 and
Comparative Examples 1, 8 to 9 and color values thereof
It can be seen from Comparative Examples 1 and 8 that the color value of the composition after being stored at 50°C for 15 weeks was much higher than 150, that is, the composition had poor color stability and was prone to yellowing, when the composition comprised no thiol. The 5% by weight of antioxidant in the composition of Comparative Example 8 could not improve the color stability of the composition.
It can be seen from Comparative Example 9 that the color value of the composition after being stored at 50°C for 15 weeks is much higher than 150, that is, the composition had poor color stability and was prone to yellowing, when the composition comprised a suitable amount of the thiol and 3.33% by weight of the antioxidant.
It can be seen from Examples 14-15 that the color value of the transparent composition containing polyaspartic acid ester after being stored at 50°C for 15 weeks was much less than 150, that is, the composition was color stable and not prone to yellowing, when the molar ratio of mercapto groups of DMDS to amino groups of the polyaspartic acid ester in the composition was greater than 0.060 and the antioxidant content of the composition was 1.67 % by weight and 0 % by weight.
Table 6 polyaspartic acid ester-containing compositions of Examples 14 and 16 and
Comparative Examples 1 and 10 and color values thereof
It can be seen from Comparative Examples 1 and 10 that the color value of the composition after being stored at 50°C for 15 weeks was much higher than 150, that is, the composition had poor color stability and was prone to yellowing, when the composition comprised no thiol. The 5% by weight of antioxidant in the composition of Comparative Example 10 could not improve the color stability of the composition.
It can be seen from Examples 14 and 16 that the color value of the transparent composition containing polyaspartic acid ester after being stored at 50°C for 15 weeks was much less than 150, that is, the composition was color stable and not prone to yellowing, when the molar ratio of mercapto groups of DMDS to amino groups of the polyaspartic acid ester in the composition was greater than 0.060 and the antioxidant content of the composition was 1.67 % by weight and 0 % by weight.
Those skilled in the art will readily understand that the present invention is not limited to the foregoing details, and can be implemented in other specific forms without departing from the spirit or main characteristics of the present invention. Therefore, the examples should be regarded as illustrative rather than restrictive from any point of view, so that the scope of the present invention is illustrated by the claims rather than the foregoing description. Therefore, any change shall be regarded as belonging to the present invention, as long as it falls into the meaning and scope of equivalents of the claims.
Claims
1. A polyaspartic acid ester-containing composition, comprising: a. a polyaspartic acid ester; b. a thiol with an active hydrogen group; and c. optionally an antioxidant in an amount of not more than 3% by weight, relative to the total weight of the composition; wherein the molar ratio of mercapto groups of the thiol of component b) to amino groups of the polyaspartic acid ester of component a) is of 0.060-0.720.
2. Composition according to claim 1, wherein the molar ratio of mercapto groups of the thiol of component b) to amino groups of the polyaspartic acid ester of component a) is of 0.070- 0.72, more preferably of 0.070-0.240, and most preferably of 0.070-0.200.
3. Composition according to claim 1 or 2, wherein the amount of the antioxidant is not more than 2% by weight, relative to the total weight of the composition; most preferably, the composition does not comprise an antioxidant.
4. Composition according to any one of claims 1-3, wherein the polyaspartic acid ester of component a) has the structure of formula I:
wherein X is an aliphatic residue,
R1 and R2 are each independently an organic group, which is non-reactive toward isocyanate groups under normal pressure and at a temperature of less than or equal to 100°C, n is an integer of not less than 2.
5. Composition according to any one of claims 1-4, wherein the thiol of component b) is one or more of tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate, pentaerythritol tetra(3- mercaptopropionate), bi s(2 -mercaptoethyl) sulfide, 2,3-bis[(2-mercaptoethyl)thio]-l- propanethiol, trimethylolpropane tri(2-mercaptoacetate), and pentaerythritol tetra(mercaptoacetate) .
6. Composition according to any one of claims 1-5, wherein the antioxidant is one or more of sterically hindered phenolic antioxidants and organic phosphite antioxidants; and most preferably one or more of triphenyl phosphite, trinonylphenyl phosphite, 3, 5 -di -tert-butyl -4- hydroxytoluene and isooctyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate.
7. A two-component coating composition comprising component A and component B, wherein said component A is the polyaspartic acid ester-containing composition according to any one of claims 1-6, and said component B is a crosslinking agent.
8. The two-component coating composition according to claim 7, wherein the crosslinking agent is one or more of isocyanate group-containing compounds and carbodiimides.
9. Use of the two-component coating composition according to claim 7 or 8 for protecting a surface of a substrate or a coating on the surface of a substrate.
10. A coating method comprising applying the two-component coating composition according to claim 7 or 8 to a surface of a substrate, and then curing and drying.
11. A product comprising a substrate and a coating formed by applying the two-component coating composition according to claim 7 or 8 to the substrate and then curing and drying.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011541617.6A CN114656866A (en) | 2020-12-23 | 2020-12-23 | Composition containing polyaspartic acid ester |
EP21161312.0A EP4056617A1 (en) | 2021-03-08 | 2021-03-08 | Polyaspartic acid ester-containing composition |
PCT/EP2021/086427 WO2022136155A1 (en) | 2020-12-23 | 2021-12-17 | Polyaspartic acid ester-containing composition |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4267641A1 true EP4267641A1 (en) | 2023-11-01 |
Family
ID=79283262
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP21839529.1A Pending EP4267641A1 (en) | 2020-12-23 | 2021-12-17 | Polyaspartic acid ester-containing composition |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP4267641A1 (en) |
WO (1) | WO2022136155A1 (en) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10050137A1 (en) | 2000-10-11 | 2002-04-18 | Bayer Ag | Stabilized mono- and polyaspartic acid esters |
US20100311890A1 (en) | 2009-06-05 | 2010-12-09 | Ppg Industries Ohio, Inc. | Curable compositions that form a low modulus polyurea |
US9790399B2 (en) | 2013-07-23 | 2017-10-17 | Axalta Coatings Systems Ip Co. Llc | Clear coat component |
EP3029129A1 (en) * | 2014-12-04 | 2016-06-08 | HILTI Aktiengesellschaft | Composition for the formation of an insulating layer and use of the same |
EP3677609A1 (en) * | 2019-01-03 | 2020-07-08 | Sika Technology Ag | Sprayable polyurea composition for corrosion protection |
-
2021
- 2021-12-17 EP EP21839529.1A patent/EP4267641A1/en active Pending
- 2021-12-17 WO PCT/EP2021/086427 patent/WO2022136155A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
WO2022136155A1 (en) | 2022-06-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10125290B2 (en) | Coating compositions comprising diisocyanate chain extended bisaspartates | |
US5866651A (en) | Hydroxycarbamoylalkoxysilane-based poly(ether-urethane) sealants having improved paint adhesion and laminates prepared therefrom | |
EP3824011B1 (en) | A coating composition | |
US6545117B1 (en) | Sprayable coating compositions comprising an oxazolidine functional compound, an isocyanate functional compound, and a compound selected from a mercapto and a sulfonic acid functional compound | |
US5283311A (en) | Fatty prepolymers and fatty-modified polyisocyanates as internal mold release agents | |
US11230522B2 (en) | Polyaspartic acid ester compositions which contain polyaspartic acid esters with primary amino groups and small amounts of fumaric acid dialkyl esters | |
US11572431B2 (en) | Non-aqueous crosslinkable composition | |
EP3877437B1 (en) | A coating composition | |
EP3666811A1 (en) | A coating composition | |
WO2020065456A1 (en) | One-part thermally curable composition | |
CA2047064C (en) | Binder compositions for stoving lacquers and a process for the production of coatings therefrom | |
US20210024793A1 (en) | Compositions, method of bonding, and assembly | |
US20100256286A1 (en) | Novel hydrophilic polyisocyanate compositions based on phosphate esters | |
CN110734693A (en) | coating compositions | |
WO2019175709A1 (en) | Compositions, method of bonding, and bonded assembly | |
WO2022136155A1 (en) | Polyaspartic acid ester-containing composition | |
EP4056617A1 (en) | Polyaspartic acid ester-containing composition | |
EP3626755A1 (en) | A coating composition | |
CN111154057A (en) | Coating composition | |
CN113412295B (en) | Novel two-component varnish system comprising polyaspartic esters | |
CN114656866A (en) | Composition containing polyaspartic acid ester | |
US6127514A (en) | One-component thermoset coating compositions | |
RU2787104C2 (en) | Non-aqueous crosslinked composition | |
EP3694900B1 (en) | Non-aqueous crosslinkable composition | |
EP1004645A1 (en) | One-component thermoset coating compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20230724 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) |