CA2111927A1 - Amino-functional polyester resins - Google Patents
Amino-functional polyester resinsInfo
- Publication number
- CA2111927A1 CA2111927A1 CA002111927A CA2111927A CA2111927A1 CA 2111927 A1 CA2111927 A1 CA 2111927A1 CA 002111927 A CA002111927 A CA 002111927A CA 2111927 A CA2111927 A CA 2111927A CA 2111927 A1 CA2111927 A1 CA 2111927A1
- Authority
- CA
- Canada
- Prior art keywords
- formula
- polyester resin
- molecular weight
- groups
- component
- 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.)
- Abandoned
Links
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 28
- 239000004645 polyester resin Substances 0.000 title claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 10
- 239000011527 polyurethane coating Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 9
- 238000007259 addition reaction Methods 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 26
- 229920001228 polyisocyanate Polymers 0.000 claims description 16
- 239000005056 polyisocyanate Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000007513 acids Chemical class 0.000 claims description 12
- 150000008064 anhydrides Chemical class 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 11
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 26
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000010137 moulding (plastic) Methods 0.000 abstract description 2
- 239000004922 lacquer Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 239000008199 coating composition Substances 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 12
- 239000000654 additive Substances 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- -1 aliphatic amines Chemical class 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 229920006305 unsaturated polyester Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 239000013638 trimer Substances 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Natural products CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 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
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- 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 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- FVCWZBVQRLEGDH-UHFFFAOYSA-N 1,2,2-trimethylcyclohexan-1-amine Chemical compound CC1(C)CCCCC1(C)N FVCWZBVQRLEGDH-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QTCNKIZNNWURDV-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol Chemical compound OCC(C)(C)CO.OCC(C)(C)CO QTCNKIZNNWURDV-UHFFFAOYSA-N 0.000 description 1
- XJEVHMGJSYVQBQ-UHFFFAOYSA-N 2,3-dihydro-1h-inden-1-amine Chemical compound C1=CC=C2C(N)CCC2=C1 XJEVHMGJSYVQBQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 1
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 description 1
- GELMWIVBBPAMIO-UHFFFAOYSA-N 2-methylbutan-2-amine Chemical compound CCC(C)(C)N GELMWIVBBPAMIO-UHFFFAOYSA-N 0.000 description 1
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 1
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 1
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 1
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 1
- MGYGFNQQGAQEON-UHFFFAOYSA-N 4-tolyl isocyanate Chemical compound CC1=CC=C(N=C=O)C=C1 MGYGFNQQGAQEON-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241001561902 Chaetodon citrinellus Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-O Htris Chemical compound OCC([NH3+])(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-O 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical class CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- CGGMCNLKDXNMLH-UHFFFAOYSA-N ctk4f7189 Chemical compound C1C2CCC1C1C2CC(CO)C1CO CGGMCNLKDXNMLH-UHFFFAOYSA-N 0.000 description 1
- KZZKOVLJUKWSKX-UHFFFAOYSA-N cyclobutanamine Chemical compound NC1CCC1 KZZKOVLJUKWSKX-UHFFFAOYSA-N 0.000 description 1
- HBGGBCVEFUPUNY-UHFFFAOYSA-N cyclododecanamine Chemical compound NC1CCCCCCCCCCC1 HBGGBCVEFUPUNY-UHFFFAOYSA-N 0.000 description 1
- VXVVUHQULXCUPF-UHFFFAOYSA-N cycloheptanamine Chemical compound NC1CCCCCC1 VXVVUHQULXCUPF-UHFFFAOYSA-N 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 1
- HSOHBWMXECKEKV-UHFFFAOYSA-N cyclooctanamine Chemical compound NC1CCCCCCC1 HSOHBWMXECKEKV-UHFFFAOYSA-N 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical class CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
- C08G18/4669—Addition products of unsaturated polyesters with amino 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
AMINO-FUNCTIONAL POLYESTER RESINS
ABSTRACT OF THE DISCLOSURE
The present invention relates to a process for the production of polyester resins containing 0 to 10% by weight of hydroxyl groups and 0.01 to 9%, preferably 0.05 to 2%, by weight of nitrogen (expressed as N = 14) in the form of primary and/or secondary amino groups, by reacting in an addition reaction at 0 to 120°C
i) polyester resins having a molecular weight (Mn) of 286 to 10,000 and containing an average per molecule of at least 2 structural units corresponding to the formula:
and optionally alcoholic hydroxyl groups with ii) ammonia or primary monoamines corresponding to the formula:
wherein R represents an aliphatic, cycloaliphatic or araliphatic radical optionally containing ether oxygen atoms and/or hydroxyl groups.
The present invention also relates to the amino-functional and optionally hydroxy-functional polyester resins obtained by this process and to their use as a binder component in two-component polyurethane coating compositions, particularly for coating plastic moldings.
ABSTRACT OF THE DISCLOSURE
The present invention relates to a process for the production of polyester resins containing 0 to 10% by weight of hydroxyl groups and 0.01 to 9%, preferably 0.05 to 2%, by weight of nitrogen (expressed as N = 14) in the form of primary and/or secondary amino groups, by reacting in an addition reaction at 0 to 120°C
i) polyester resins having a molecular weight (Mn) of 286 to 10,000 and containing an average per molecule of at least 2 structural units corresponding to the formula:
and optionally alcoholic hydroxyl groups with ii) ammonia or primary monoamines corresponding to the formula:
wherein R represents an aliphatic, cycloaliphatic or araliphatic radical optionally containing ether oxygen atoms and/or hydroxyl groups.
The present invention also relates to the amino-functional and optionally hydroxy-functional polyester resins obtained by this process and to their use as a binder component in two-component polyurethane coating compositions, particularly for coating plastic moldings.
Description
2 7 ~o3981 LeA 29,436 -us AMINO-FUNCTIONAL POLYESTER RESINS
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to a new process for the production of amino-functional and optionally hydroxy-functional polyester resins, to the resins obtained by this process and to their use as a binder component in two-component polyurethane coating compositions.
Descriotion of the Prior Art Two-component polyurethane coating compositions are known and are suitable for the production of high-quality coatings which can be made hard, elastic, abrasion resistant, solvent resistant and, above all, weather resistant. The basic chemistry of these lacquers and coatings is described inter alia in "Lackkunstharze", Hans-Wagner/Hans Friedrich Sarx, Carl Hanser Verlag, Munchen, pages 153 to 173 (1971). The polyesters described as resin component almost exclusively contain hydroxyl groups which react with the polyisocyanates used as curing -~
agents to form polyurethanes.
The reaction between the OH and NCO groups proceeds so slowly at room temperature that economical, i.e., rapid, drying is only possible at elevated temperatures. Although the relatively slow reaction at room --temperature can be accelerated by catalysts, the resulting coatings are adversely affected, for example, in their hardness, by the catalysts used -(S. Gunther, Ind. Lackierbetr. 57 (1989), No. 5, page 167).
The possibility of using the very much faster reaction between aliphatic amines and isocyanates has not satisfactorily been used in practice due to the extremely high reaction rate which prevents a controlled reaction. The fairly sluggishly reacting aromatic amines cannot be used for top coats due to their pronounced tendency towards -30 yellowing.
'' ~',:
.
EP-A-0,403,921 describes a simple process for reducing the excessive reactivity of aliphatic amines. This process is based on the addition of primary amines onto maleic acid esters which gives secondary amino groups that react with isocyanate groups in the coating 5 system. The main concern of this process was the presence of low molecular weight, low-viscosity aminic chain-extending agents for two-component polyurethane coating compositions.
It has now been found that relatively high molecular weight polyester resins, which, in addition to the optional presence of alcoholic 10 hydroxyl groups, are distinguished by a readily adjustable and controllable content of primary or secondary amino groups incorporated in the a-position to the ester groups, are particularly valuable binder components for two-component polyurethane coating compositions.
These amino-functional polyester resins are produced by addition of 15 ammonia or primary monoamines onto polyester resins containing olefinically unsaturated structural units of the type described in more detail hereinafter to form primary or secondary amino groups.
Although the production of amino-functional polyester resins by addition of amine onto unsaturated polyester polyols is already known 20 from EP-A-0,273,243, the amines mentioned there as starting material are diamines containing two primary amino groups. The products of this reference are distinguishable from the products of the present invention, which are described in detail hereinafter, in particular by the presence of primary amino groups which are not arranged in the a-position to the 25 ester groups (referred to in the Examples as "basic nitrogen") and which therefore show a reactivity to isocyanate groups which is much higher than that of the amino groups present in the end products according to the invention. In addition, the end products of the reference are not Mo3981 ~3~ 2,111927 recommended as a binder component for two-component polyurethane coating compositions, but instead for the production of adhesives and foams.
SUMMARY OF THE INVENTION
The present invention relates to a process for the production of polyester resins containing 0 to 10% by weight of hydroxyl groups and 0.01 to 9%, preferably 0.05 to 2%, by weight of nitrogen (expressed as ~ -N = 14) in the form of primary and/or secondary amino groups, -characterized by reacting in an addition reaction at 0 to 120C
i) polyester resins having a molecular weight (Mn of 286 to 10,û00 and containing an average per molecule of at least 2 structural units corresponding to the formula: -~, O O -:
--O C CH=CH C O-- -: ~ ................................................... ................................. :,:
and optionally alcoholic hydroxyl groups with ii) ammonia or primary monoamines corresponding to the formula~
. ~
wherein R represents an aliphatic, cycloaliphaticoraraliphaticradical ;~
optionally contalning ether oxygen atoms andlor hydroxyl groups.
The present invention also relates to the amino-functional and 25 optionally hydroxy-functional polyester resins obtained by this process and to their use as a binder component in two-component polyurethane coating compositions, particularly for coating plastic moldings.
"~', :
Mo3981 - ~ :
2 ~
DETAILED DESCRIPTION OF THE INVENTION
The olefinically unsaturated polyester resins used in the process according to the invention generally have an acid value below 10, preferably below 3 mg KOH/g; a hydroxyl value of 0 to 325, preferably 0 to 250 mg KOH/g, which corresponds to a hydroxyl group content of 0 to 10%, preferably 0 to 7% by weight; a molecular weight (Mn~ which may be calculated from the stoichiometry of the starting materials) of 286 to 10,000, preferably 488 to 8,000; and an average of at least 2, preferably at least 3, structural units corresponding to the formula:
1 1l --O--C--CH=CH C O--.
In a preferred embodiment, the unsaturated polyester resins are produced by esterifying ~ .
a) a polycarboxylic acid component containing maleic acid, maleic anhydride and/or fumaric acid, and optionally up to 95 carboxyl :
equivalent-%, based on the total equivalents of component (a), of other polycarboxylic acids having a molecular weight of 118 to 1,000, preferably of 118 to 400 and/or anhydrides of such acids with b) a polyol component having an maximum average hydroxyl functionality of 3 and containing at least one polyhydric alcohol having a molecular weight of 62 to 400 and - .
c) optionally a monocarboxylic acid component in a quantity of up to ~ .
50 carboxyl equivalent-%, based on the total equivalents of :
components a) and c), and containing at least one monocarboxylic -~
acid having a molecular weight of 60 to 400 and/or at least one Mo3981 5 ~ 7 anhydride of such monocarboxylic acids and d) optionally a monohydric alcohol component in a quantity of up to 50 hydroxyl equivalent-%, based on the total equivalents of components b) and d), and containing at least one monohydric alcohol having a molecular weight of 32 to 400, while maintaining an equivalent ratio of carboxyl groups to hydroxyl groups of 1:1.5 to 1:1 and terminating the reaction when the acid value is below 10 mg KOH/g.
Suitable polycarboxylic acids or polycarboxylic anhydrides a) other than those mentioned include succinic acid, glutaric acid, adipic acid, isophthalic acid, phthalic acid, terephthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, trimesic acid, trimellitic acid, commercial dimer or trimer fatty acids and trimellitic anhydride. Adipic acid is particularly preferred as the other acid a).
Suitable polyhydric alcohols b) include ethylene glycol, 1,2- and 1,3-propanediol, 1,2- and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,4-bis-(hydroxymethyl)-cyclo- hexane, cyclohexane-1,2- and -1,4-diol, 2,2-bis-(4-hydroxy-cyclohexyl)-propane, octahydro-4,7-methano-1 H-indene dimethanol, trimethylol propane, glycerol and/or pentaerythritol.
Optional monocarboxylic acids or monocarboxylic anhydrides c) inciude acetic acid, propionic acid, n-octane carboxylic acid, 2-ethyl hexanoic acid, stearic acid, benzoic acid, anhydrides of these acids and mixtures of monocarboxylic acids and/or monocarboxylic anhydrides.
Olefinically ùnsaturated monocarboxylic acids (such as acrylic acid or methacrylic acid) and unsaturated faUy acids or mixtures thereof (such as soybean fatty acid or dehydrated castor oil fatty acid) may also be used Mo3981 . ~ . . -. ~
L 9 2 rj1 as, or as part of, component c) in the process according to the invention.
Hydroxy-functional carboxylic acids (such as hydrogenated castor oll fatty acid, hydroxybenzoic acid and/or lactones, in particular e-caprolactone) may also be used.
Optional alcohol component c) is selected from monohydric alcohols such as methanol, ethanol, the isomeric propanols, butanols and hexanols, cyclohexanol, benzyl alcohol, fatty alcohols and mixtures of these alcohols.
The unsaturated polyesters are produced from the starting materials mentioned by way of example by known methods as described, for example, in "Ullmanns Encyclopadie der technischen Chemie", Verlag Chemie, Weinheim, 4th Edition (1980), Vol. 19, pages 61 et seq.; by H. Wagner and H.F. Sarx in "Lackkunstharze", Carl Hanser Verlag, Munchen (1971), pages 85 et seq.; by G. Gerber and H. Gruber in "Houben-Weyl", Methoden der organischen Chemie, Vol. E 20, Part 2, pages 1405 et seq.; or by R. Dhein, D. Reuter and G. Ruf, ditto, pages 1429 et seq. The esterification is optionally carried out in the presence of a catalytic quantity of a typical transesterification catalyst, e.g., acids, bases or transition metal compounds, such as titanium tetrabutylate, at -20 approx. 80 to 260C, preferably 100 to 230C. The esterification reaction is continued until the required hydroxyl and acid values are reached.
The type and quantities of components a) to d) used are selected so that the polyesters have the characteristics described above.
The equivalent ratio of carboxyl groups to hydroxyl groups is generally 1:1.5 to 1:1, preferably 1:1.3 to 1:1. Anhydride groups correspond to 2 carboxyl groups and are included as such in the calculation.
The production of the unsaturated polyester resins may also be Mo3981 carried out by transesterifying esters based on polycarboxylic acids and monohydric, readily volatile alcohols in combination with polyhydroxyl compounds example or by using esters based on monohydric, readily volatile carboxylic acids and polyhydroxyl compounds in combination with 5 polycarboxylic acids with elimination of the readily volatile alcohol or the readily volatile acid. However, this method of producing the polyester resins is less preferred.
In the process according to the invention, the olefinically unsaturated polyester resins are reacted with ammonia or primary 10 amines corresponding to the formula:
wherein R represents an aliphatic, cycloaliphatic or araliphatic radical which may contain ether groups andlor hydroxyl groups, preferably an aliphatic or cycloaliphatic hydrocarbon radical having up to 15 carbon atoms and optionally at least one alcoholic hydroxyl group.
Primary monoamines corresponding to the above formula wherein -the primary amino group is attached to a secondary or tertiary carbon atom, are particularly preferred reactants for the unsaturated polyester 20 resins.
Suitable amines corresponding to the above formula include methyl amine, ethyl amine, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-amino-2-methyl propane, 2-amino-2-methyl propane, 2-amino-2-methyl butane, 1-aminohexane, 1-amino-2-25 ethyl hexane, 1-aminodecane, 1-aminododecane, 1-aminotetradecane, 1-aminohexadecane, 1-aminooctadecane, allyl amine, cyclohexyl amine, 2-, 3- or 4-methyt cyclohexyl amine, aminomethyl cyclohexane, 3,3,5- .
trimethyl cyclohexyl amine, 1-aminomethyl-3- or 4-methyl-3-cyclohexene, Mo3981 -- , 9 ~ 7 benzyl amine, cyclopentyl amine, cyclooctyl amine, cyclopropyl amine, cycloheptyl amine, cyclobutyl amine, cyclododecyl amine, 1-aminoindane, 2-aminoethanol, 2-methoxyethyl amine, 3-amino-1-propanol, 3-methoxy-1-propyl amine, 3-ethoxy-1-propyl amine, 3-((2-ethylhexyl)oxy)-1-propyl 5 amine, 1-amino-2-propanol, 2-amino-1-butanol, 2-amino-2-methyl propanol, 2-amino-2-methyl-propane-1,3-diol and 2-amino-2-hydroxy-methyl propane-1,3-diol.
The addition of ammonia or primary amines to the unsaturated polyester resins results in the formation of structural units corresponding 10 to the formula . .: .
O O
R' 15 wherein R' represents -NH2 or -NHR.
The type and quantities of the reactants reacted with one another are selected so that amino-functional and optionally hydroxy-functional polyester resins have the characteristics mentioned above. When ammonia or amines which are gaseous at room temperature are used, -20 excess quantities of the base are often added followed by the subsequent removal of the unreacted excess under vacuum and/or by the introduction of inert gas. When amines which are liquid at room temperature are used, the equivalent ratio of primary amino groups to structural units corresponding to the formula O O '~
Il .
--0--C CH=CH C 0--~.
Mo3981 can vary within wide limits, for example, from 0.05:1 to 1:1, preferably 0.1:1 to 1:1 and more preferably 0.1:1 to 0.6:1.
The reactlon generally takes place at temperatures of 0 to 120C, preferably 20 to 100C. The reaction may be carried out in the presence 5 or absence of suitable solvents depending upon the viscosity of the unsaturated polyester. Suitable solvents include toluene; xylene; higher alkylbenzenes; esters such as ethyl acetate, n-butyl acetate, methyl glycol acetate, ethyl glycol acetate and methoxybutyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and mixtures of 10 these solvents.
As already mentioned, structural units corresponding to the formula:
il R ~:
R' wherein R' is defined as above, are formed in the reaction according to the invention. The reactivity of 20 the amino group R' is greatly reduced by the electron-attracting effect when compared with corresponding, electron-unhindered amino groups.
One possibility of variation regarding the reactivity of the products according to the invention is to vary the ratio of incorporated hydroxyl groups to incorporated amino groups by suitable choice of the starting 25 materials used in the process according to the invention and the quantities in which they are used.
Depending upon their molecular weight, the products obtained by the process according to the invention are generally low-viscosity to high-Mo3981 ~ ~ ~ 1927 viscosity, substantially colorless, clear resins which form clear solutions in the previously mentioned lacquer solvents.
The products obtained in accordance with the invention may be used in admixture with various quantities of other isocyanate-reactive compounds, preferably known polyester or polyacrylate polyols containina 0,5 to 10, preferably 1 to 5 % by weight of hydroxyl groups. This provides another possibility for controlling the reactivity of the component containing isocyanate-reactive groups. In general, the isocyanate-reactive component used in the application according to the invention contains up to 20 hydroxyl groups for every primary or secondary amino group. The ratio of (i) primary and/or secondary amino groups to (ii) hydroxyl groups in the binder component containing isocyanate-reactive groups is preferably 10:1 to 1:10. The percentage of products according to the invention in these mixtures is preferably 10 to 100% by weight. In a particularly preferred embodiment, the products according to the invention are used as sole isocyanate-reactive lacquer component. -Reactants for the "polyol component" in accordance with the invention are the known "lacquer polyisocyanates," i.e., the known ~ -~
urethane-modified, uretdione-modified or, in particular, biuret-modified or isocyanurate-modified diisocyanates. Examples of these diisocyanates include 1,6-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-iso-cyanatomethyl cyclohexane (isophorone diisocyanate~, 4,4-diiso-cyanatodicyclohexyl methane, 2,4- and 2,6-diisocyanatotoluene.
"Lacquerpolyisocyanates" containing aliphatically and/orcyclo-aliphatically bound isocyanate groups are particularly preferred. -. . .
Urethane-modified lacquer polyisocyanates are preferably reaction products of 2,4- and optionally 2,6-diisocyanatotoluene with less than equivalent quantities of trimethylol propane or mixtures thereof with Mo3981 ~''''" ~
--` 211~'~27 simple diols such as the isomeric propane or butane diols The production of these urethane-modified lacquer polyisocyanates in substantially monomer-free form is described, for example, in DE-PS
1,090, 1 96.
Uretdione-modified lacquer polyisocyanates are preferably prepared from 1,6-diisocyanatohexane as described, for example, in EP-A-0,377, 1 77.
Biuret-modified lacquer polyisocyanates, which are preferred for the use according to the invention, are preferably those prepared from 1,6-diisocyanatohexane as described, for example, in EP-B1 0,003,505, DE-PS 1,101,394, US-PS 3,358,010 and US-PS 3,903,127.
Isocyanurate-modified polyisocyanates, which are also preferred according to the invention, include in particular the isocyanate-functional trimers or mixed trimers of the previously disclosed diisocyanates.
Examples include the isocyanate group-containing polyisocyanates prepared from diisocyanatotoluene according to GB-PS 1,060,430, GB-PS 1,506,373 or GB-PS 1,485,564; the mixed trimers prepared from the diisocyanatotoluenes and 1,6-diisocyanatohexane in accordance with, for example, DE-PS 1,644,809 or DE-OS 3,144,672; and, in particular, the aliphatic or aliphatic-cycloaliphatic trimers or mixed trimers prepared from 1,6-diisocyanatohexane andlor isophorone diisocyanate in accordance with, for example, US-PS 4,324,879, US-PS 4,288,586, DE-OS 3,100,262, DE-OS 3,100,263, DE-OS 3,033,860 or DE-OS
3, 1 44,672.
The lacquer polyisocyanates employed in the use according to the invention preferably have an isocyanate content of 5 to 25% by weight and preferably have a residual content of the monomeric diisocyanates used for their production of less than 2% by weight. Mixtures of the Mo3981 . 1 .. . ~ ~ .. . . . -. ~ . . . - . ~ .
' ~ ` '' ' , ;, 1 ., ~ ` _ , , . ,, . ~ . . . .
~ ............... . . .
21~ ~927 previously mentioned lacquer polyisocyanates may also be used.
The two-component polyurethane coating compositions according to the invention are formulated to have an equivalent ratio of isocyanate groups to isocyanate-reactive groups of 5:1 to 1:2, preferably 1.5:1 to 1:1.2.
The two-component binders obtained by mixing the binder components have only a limited pot life of about 0.5 to 8 hours. They may be used for the production of clear or pigmented coating compositions which may contain known auxiliaries and additives. The auxiliaries and additives may be added either to the mixture or to the individual components before they are mixed.
Suitable auxiliaries and additives include the previously mentioned solvents; plasticizers such as tricresyl phosphate, phthalic acid diesters -and chloroparaffins; pigments and fillers such as titanium dioxide, barium sulfate, chalk and carbon black; catalysts such as N,N-dimethyl ~ --benzylamine, N-methyl morpholine, zinc octoate, tin octoate and dibutyl tin dilaurate; flow control agents; thickeners; stabilizers such as substituted phenols; organofunctional silanes as coupling agents; and light stabilizers. ;-~ -The light stabilizers include the sterically hindered amines described, for example, in DE-OS 2,417,353 (= US-PS 4,123,418 and US-PS 4,110,304) and DE-OS 2,456,864 (= US-PS 3,993,655 and US-PS 4,221,701). Partlcularly preferred compounds include bis- -(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate, bis-(2,2,6,6-tetramethyl-4- . -piperidyl)-sebacate, n-butyl-(3,5-ditert.butyl-4-hydroxybenzyl)-malonic acid and bis-(1,2,2,6,6-pentamethyl-4-piperidyl)-ester.
The moisture adhering to the fillers and pigments may be removed by preliminary drying or by the use of water-absorbing materials such as : ,.
Mo3981 ~ ~
.. .... . . . ,, . -- , -- --~;t ~ 2 7 -~3-molecular sieve zeolite.
The resulting coatings may be dried at room temperature. Drying does not require any increase in temperature to achieve optimum properties. However, elevated temperatures may be applied to 5 accelerate the drying reaction. Drying temperatures used for typical stoving conditions are possible, but less preferred. This is of consider-able practical significance because, even at the relatively high temperatures which may occur, for example, in the event of malfunctions of lacquering plants, the coatings do not undergo thermal degradation.
Two-component polyurethane coating compositions containing the products according to the invention as their principal binder component are suitable for the production of coating compositions for any substrates such as metals, plastics, wood or glass.
Because they are equally suitable for plastics and metals, the 15 coating compositions according to the invention are also particularly suitable for coating substrates such as the exterior parts of automobiles produced from modern plasticlmetal composites. The coating compositions according to the invention are particulariy suitable for "on-line" coating of exterior auto parts because the coatings cure at low 20 temperatures so that the plastics are not exposed to high temperatures.
Further, the resulting coatings show excellent weather resistance and elasticity so that decorative lacquer finishes remain unchanged for long periods and safely withstand impact stresses. The excellent chip resistance of automotive coatings produced in accordance with the 25 invention is also particularly emphasized in this regard. The coatings obtained with the two-component coating compositions according to the invention optimally satisfy basically conflicting requirements, i.e. excellent elasticity at low temperatures coupled with high resistance to solvents Mo3981 2 ~
and tar stains, high gloss retention and resistance to yellowing on exposure to light of short wave length, for example, short-wave UV light.
The coating compositions according to the invention may be applied to the substrates to be coated by any known methods, for example, by spread coating, spray coating, roll coating or dip coating.
The lacquers according to the invention are suitable for the production of base coats, intermediate coats and top coats.
In the following examples, all parts and percentages are by weight, unless otherwise indicated.
EXAMPLES .
1. General procedure for the production of the unsaturated polyester precursors:
The monohydric and polyhydric alcohols and the unsaturated dicarboxylic acid(s)/anhydride(s) were weighed into a reactor equipped with a stirrer, heating system, automatic temperature control, column and : .
receiver. The mixture was heated to 100-150C while a stream of nitrogen was passed through the inhomogeneous mixture of starting materials. After the remaining dicarboxylic acids had been added, the ~ :
mixture of starting materials was heated with stirring to 200C over a period of 4 to 8 hours while nitrogen was passed through the mixture.
The temperature measured at the head of the column was kept at a ..
maximum of 105C. The melt became homogeneous and clear. When the head temperature fell below 90C, the column was removed and the mixture was condensed with an increased throughput of nitrogen to an acid value of ~ 3 mg KOH/g. - .
Colorless resins were obtained and were dissolved in methoxy- ~
propyl acetate, butyl acetate or mixtures thereof. ;.
The composition and properties of the individual polyesters are ; ~ .
Mo3981 -15~
given in Examples 1 and 2. The abbreviation "mol" applies to the molar ratio and not to the actual number of "moles," as can be seen from the quantities by weight in "g."
Exam~le 1 PolyesterA Quantity weighed in 1.0 Mol hexane-1,6-diol 526 9 1.0 Mol trimethylol propane 596 g 1.5 Mol cyclohexane dimethanol 962 g 1.5 Mol neopentyl glycol 696 g 2.2 Mol adipic acid 1431 g 1.8 Mol maleic anhydride 786 g Hydroxyl value: 145 mg KOHtg Acid value: 0.7 mg KOH/g Molecular weight: 1700 Example 2 Polyester B Quantity weighed in 4.00 Mol hexane-1,6-diol 1949 g 1.00 Mol trimethylol propane 553 g 0.52 Mol adipic acid 314 g 0.52 Mol maleic anhydride 211 g 2.48 Mol Isophthalic acid 1701 g 0.48 Mol phthalic anhydride 293 9 Hydroxyl value: 140 mg KOH/g Acid value: 1.2 rng KOH/g Molecular weight: 1800 Mo3981 ~ (3 2 7 2. General procedure for the reaction of unsaturated polyesters with primary amines Polyester precursors A and B from Examples 1 and 2 were optionally dissolved in a suitable solvent and introduced into a 2-liter four-5 necked flask equipped with a stirrer, thermometer, reflux condenser anddropping funnel and heated to 60C. The corresponding primary amine was then added in one portion. The mixture was then stirred for 2 hours at 60C, heated to 80C and stirred until no more primary amino groups could be detected by titrimetry or until the solids content corresponded to 10 the theoretical value of the amine addition. The product was then cooled and packed in containers.
3. General procedure for the reaction of unsaturated polyesters with ammonia -Polyester precursors A and B from Examples 1 and 2 were 15 optionally dissolved in a suitable solvent and introduced into a 2 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and inlet pipe. Ammonia from a steel boffle was then passed through the -flask for about 4 hours at room temperature. The reaction mixture heated up to about 30C. The reaction mixture was then stirred for about 20 4 hours at room temperature, after which unreacted ammonia was driven out with nitrogen at 50C. The product was then cooled and packed in containers.
~, ,.
' ~, Mo3981 ,::
: ~ ~; '' .' :, ~
~ 192 7 Y o a, O Oo O ~ O
N 't U'~
o ~ O U'~ .
U~ C~l CO
o) oU~ O
c~ o ~ O O 0 0 ~o a~ ~ ,~
~D ~ O ~ O
.c o ~ a~ O ~ O
._ CO U~ ~
~r o ~ ~ o 8 O o ~ C5~ o E W i~ 8 Mo3981 - ~111927 ExamPle 12 (Use) This example describes the production of ready-to-use coating compositions prepared from the aminopolyesters of Examples 3 to 10 as well as from the polyesters of examples 1 and 2 ~comparison)~ their application to substrates and the testing of the resulting coatings.
To evaluate the properties of the coating compositions, white 10 compositions were produced by blending the polyesters of Examples 1 to 10 with various additives and white pigments and grinding on a Red Devil shaker. ~ - -A lacquer polyisocyanate was then added to provide an NCO/NH+OH
equivalent ratio of about 1.3:1. -The "lacquer polyisocyanate" used was an isocyanurate group-containing polyisocyanate prepared from 1,6-diisocyanatohexane (Desmodur N 3390, a product of Bayer AG) which is present at 90% solids in a 1:1 ratio by volume of butyl acetate and Solvent Naphtha 100 solvent (NCO content of the solution: 19.4% by weight).
The following percentages of additives were used, based on solids - -(sum of the solid components of polyester and polyisocyanate):
, "~
Mo3981 Table 2 o/o Additives Solid on solid Zinc octoate t10% in 1-methoxypropyl-2-acetate) 0.2 Silicone oil as flow control agent (Baysilon lacquer additive OL 17, a product of Bayer AG; 10% in 1-methoxy-propyl-2-acetate) 0.1 Tinuvin 292 (a light stabilizer pro-duced by Ciba-Geigy, Basel; 10% in xylene) 1.0 Tinuvin 900 (a light stabilizer pro-duced by Ciba-Geigy, Basel; 10% in xylene) 1.0 Titanium dioxide (rutile type; Kronos 2160, a product of Kronos-Titan, Leverkusen) 60.0 Antisedimenting agent (Bentone 38, a product of Kronos-Titan, Leverkusen;
10% suspension in a 17:1 blend of Solvesso 100 solvent and Antiterra U 17:1 additive) 1.0 The solvent used was a mixture of ethyl acetate, 1-methoxypropyl-2-acetate and methyl ethyl ketone (1:1:1). The coating composition was diluted to a content of:
33% binder 20% pigment approx. 1% additive approx. 46% solvent The flow time (DIN 53211; 4 mm orifice) was approx. 18 seconds. The coating compositions were ready for spraying.
Mo3981 The lacquers were applied to glass plates (wet film thickness approx, 100 ,um), dried for 45 minutes at 80C and stored for 14 days at room temperature. The dry film thickness was approx. 50 ,um.
Konig hardness (DIN 53157), Gardner gloss at 60 (DIN 67530), 5 dissolvability by various solvents and resistance to tar were then determined.The resistance of the coatings to tar stains was a critical aspect of the invention.
To test their flexibility at low temperatures, the coating compositions were sprayed onto primed 3 mm thick plastic plates of 10 Bayflex 91 (a product of Bayer AG, Leverkusen), dried for 45 minutes at 80C and stored for 14 days at room temperature. The dry film thickness was approximately 35 ,um. 2 cm wide and 15 cm long strips prepared therefrom were stored for approx. 30 minutes at various temperatures (room temperature: 5C, 0C, -5C, ..., -40C) in a low-temperature chamber and then bent around a 1 inch mandrel at the particular temperature prevailing in the chamber. The temperature at which the coating broke was the criterion for low-temperature flexibility. The lacquers produced from the polyesters polyols of Examples 1 to 10 satisfied stringent elasticity requirements, even at low temperatures.
The test results of the coatings based on the aminopolyesters ~ -according to the invention of Examples 3 to 10 and Comparison Examples 1 and 2 are set out in Table 3.
Mo3981 :~' : .
0 ~ `- o o ~ ~y E ' 0 a~ ---- --o ~ a~ ~ O o _ O O
CL
E r` U~ 0o o o _ o o o o o ~, w a~ 0 0 0 _ O O O O O
_ u) a~ ~o --C _ g .C~ U~ ~ _ o ~ o o o o o U,~ o ~~ ~ _ _ _ o o o o o ~
o o ~ u~ _ _ _ o o -- 91 ~ ~ 2 ~ :
E _o co _ _ _ o O -- ~ ~ c~
o e O ~
E o o ~ O
S ~ E el N 2 ~ e E ~ E ¦ Q E ~ 8 E E O ' J ~ ~ ~ ~ o Mo3981 -9 ~ 7 5 Discussion of the results:
Highly flexible coatings were obtained with coatings based on the polyesters of Examples 1 to 10, the coatings of Examples 1, 3 and 4 providing the best results in regard to elasticity. The results of the tar resistance tests reflect in particular the excellent resistance to tar of the 10 coatings of Examples 3 to 10 according to the invention in contrast to comparison coatings 1 and 2.
ExamPle 13 (Use) The aminopolyester (K) of Example 11 was used to formulate clear coatings with the lacquer polyisocyanate of Example 12 and applied 15 to glass plates (dry film thickness approx. 60 ,um). The crosslinking ratio and the solids content are set out in Table 4. Solvent resistance was tested by the cotton wool pad method under the drying conditions shown in Table 4. Hardness was determined by the pencil method. -~
Mo3981 -23- i~J11~927 Table 4:
Clear coating compositions based on the aminopolyester of Example 11 according to the invention Results of the solvent resistance and pencil hardness tests Example 13 .. . .
Aminopolyester of Ex. 11 NCO/NH+OH ratio 1.2 Solvent BuAc Solids content (%) 70 Drying 40'/80C
+ 1d RT :
Dissolvability" by xylene o Exposure time: MPA 0 1 minute acetone EtOH/H2O 1:1 0 Pencil hardness 3H
" 0 best value, 5 poorest value Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of ~ -~
25 the invention except as it may be limited by the claims.
Mo3981 :~
:: :
~'''.,.' ,
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to a new process for the production of amino-functional and optionally hydroxy-functional polyester resins, to the resins obtained by this process and to their use as a binder component in two-component polyurethane coating compositions.
Descriotion of the Prior Art Two-component polyurethane coating compositions are known and are suitable for the production of high-quality coatings which can be made hard, elastic, abrasion resistant, solvent resistant and, above all, weather resistant. The basic chemistry of these lacquers and coatings is described inter alia in "Lackkunstharze", Hans-Wagner/Hans Friedrich Sarx, Carl Hanser Verlag, Munchen, pages 153 to 173 (1971). The polyesters described as resin component almost exclusively contain hydroxyl groups which react with the polyisocyanates used as curing -~
agents to form polyurethanes.
The reaction between the OH and NCO groups proceeds so slowly at room temperature that economical, i.e., rapid, drying is only possible at elevated temperatures. Although the relatively slow reaction at room --temperature can be accelerated by catalysts, the resulting coatings are adversely affected, for example, in their hardness, by the catalysts used -(S. Gunther, Ind. Lackierbetr. 57 (1989), No. 5, page 167).
The possibility of using the very much faster reaction between aliphatic amines and isocyanates has not satisfactorily been used in practice due to the extremely high reaction rate which prevents a controlled reaction. The fairly sluggishly reacting aromatic amines cannot be used for top coats due to their pronounced tendency towards -30 yellowing.
'' ~',:
.
EP-A-0,403,921 describes a simple process for reducing the excessive reactivity of aliphatic amines. This process is based on the addition of primary amines onto maleic acid esters which gives secondary amino groups that react with isocyanate groups in the coating 5 system. The main concern of this process was the presence of low molecular weight, low-viscosity aminic chain-extending agents for two-component polyurethane coating compositions.
It has now been found that relatively high molecular weight polyester resins, which, in addition to the optional presence of alcoholic 10 hydroxyl groups, are distinguished by a readily adjustable and controllable content of primary or secondary amino groups incorporated in the a-position to the ester groups, are particularly valuable binder components for two-component polyurethane coating compositions.
These amino-functional polyester resins are produced by addition of 15 ammonia or primary monoamines onto polyester resins containing olefinically unsaturated structural units of the type described in more detail hereinafter to form primary or secondary amino groups.
Although the production of amino-functional polyester resins by addition of amine onto unsaturated polyester polyols is already known 20 from EP-A-0,273,243, the amines mentioned there as starting material are diamines containing two primary amino groups. The products of this reference are distinguishable from the products of the present invention, which are described in detail hereinafter, in particular by the presence of primary amino groups which are not arranged in the a-position to the 25 ester groups (referred to in the Examples as "basic nitrogen") and which therefore show a reactivity to isocyanate groups which is much higher than that of the amino groups present in the end products according to the invention. In addition, the end products of the reference are not Mo3981 ~3~ 2,111927 recommended as a binder component for two-component polyurethane coating compositions, but instead for the production of adhesives and foams.
SUMMARY OF THE INVENTION
The present invention relates to a process for the production of polyester resins containing 0 to 10% by weight of hydroxyl groups and 0.01 to 9%, preferably 0.05 to 2%, by weight of nitrogen (expressed as ~ -N = 14) in the form of primary and/or secondary amino groups, -characterized by reacting in an addition reaction at 0 to 120C
i) polyester resins having a molecular weight (Mn of 286 to 10,û00 and containing an average per molecule of at least 2 structural units corresponding to the formula: -~, O O -:
--O C CH=CH C O-- -: ~ ................................................... ................................. :,:
and optionally alcoholic hydroxyl groups with ii) ammonia or primary monoamines corresponding to the formula~
. ~
wherein R represents an aliphatic, cycloaliphaticoraraliphaticradical ;~
optionally contalning ether oxygen atoms andlor hydroxyl groups.
The present invention also relates to the amino-functional and 25 optionally hydroxy-functional polyester resins obtained by this process and to their use as a binder component in two-component polyurethane coating compositions, particularly for coating plastic moldings.
"~', :
Mo3981 - ~ :
2 ~
DETAILED DESCRIPTION OF THE INVENTION
The olefinically unsaturated polyester resins used in the process according to the invention generally have an acid value below 10, preferably below 3 mg KOH/g; a hydroxyl value of 0 to 325, preferably 0 to 250 mg KOH/g, which corresponds to a hydroxyl group content of 0 to 10%, preferably 0 to 7% by weight; a molecular weight (Mn~ which may be calculated from the stoichiometry of the starting materials) of 286 to 10,000, preferably 488 to 8,000; and an average of at least 2, preferably at least 3, structural units corresponding to the formula:
1 1l --O--C--CH=CH C O--.
In a preferred embodiment, the unsaturated polyester resins are produced by esterifying ~ .
a) a polycarboxylic acid component containing maleic acid, maleic anhydride and/or fumaric acid, and optionally up to 95 carboxyl :
equivalent-%, based on the total equivalents of component (a), of other polycarboxylic acids having a molecular weight of 118 to 1,000, preferably of 118 to 400 and/or anhydrides of such acids with b) a polyol component having an maximum average hydroxyl functionality of 3 and containing at least one polyhydric alcohol having a molecular weight of 62 to 400 and - .
c) optionally a monocarboxylic acid component in a quantity of up to ~ .
50 carboxyl equivalent-%, based on the total equivalents of :
components a) and c), and containing at least one monocarboxylic -~
acid having a molecular weight of 60 to 400 and/or at least one Mo3981 5 ~ 7 anhydride of such monocarboxylic acids and d) optionally a monohydric alcohol component in a quantity of up to 50 hydroxyl equivalent-%, based on the total equivalents of components b) and d), and containing at least one monohydric alcohol having a molecular weight of 32 to 400, while maintaining an equivalent ratio of carboxyl groups to hydroxyl groups of 1:1.5 to 1:1 and terminating the reaction when the acid value is below 10 mg KOH/g.
Suitable polycarboxylic acids or polycarboxylic anhydrides a) other than those mentioned include succinic acid, glutaric acid, adipic acid, isophthalic acid, phthalic acid, terephthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, trimesic acid, trimellitic acid, commercial dimer or trimer fatty acids and trimellitic anhydride. Adipic acid is particularly preferred as the other acid a).
Suitable polyhydric alcohols b) include ethylene glycol, 1,2- and 1,3-propanediol, 1,2- and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,4-bis-(hydroxymethyl)-cyclo- hexane, cyclohexane-1,2- and -1,4-diol, 2,2-bis-(4-hydroxy-cyclohexyl)-propane, octahydro-4,7-methano-1 H-indene dimethanol, trimethylol propane, glycerol and/or pentaerythritol.
Optional monocarboxylic acids or monocarboxylic anhydrides c) inciude acetic acid, propionic acid, n-octane carboxylic acid, 2-ethyl hexanoic acid, stearic acid, benzoic acid, anhydrides of these acids and mixtures of monocarboxylic acids and/or monocarboxylic anhydrides.
Olefinically ùnsaturated monocarboxylic acids (such as acrylic acid or methacrylic acid) and unsaturated faUy acids or mixtures thereof (such as soybean fatty acid or dehydrated castor oil fatty acid) may also be used Mo3981 . ~ . . -. ~
L 9 2 rj1 as, or as part of, component c) in the process according to the invention.
Hydroxy-functional carboxylic acids (such as hydrogenated castor oll fatty acid, hydroxybenzoic acid and/or lactones, in particular e-caprolactone) may also be used.
Optional alcohol component c) is selected from monohydric alcohols such as methanol, ethanol, the isomeric propanols, butanols and hexanols, cyclohexanol, benzyl alcohol, fatty alcohols and mixtures of these alcohols.
The unsaturated polyesters are produced from the starting materials mentioned by way of example by known methods as described, for example, in "Ullmanns Encyclopadie der technischen Chemie", Verlag Chemie, Weinheim, 4th Edition (1980), Vol. 19, pages 61 et seq.; by H. Wagner and H.F. Sarx in "Lackkunstharze", Carl Hanser Verlag, Munchen (1971), pages 85 et seq.; by G. Gerber and H. Gruber in "Houben-Weyl", Methoden der organischen Chemie, Vol. E 20, Part 2, pages 1405 et seq.; or by R. Dhein, D. Reuter and G. Ruf, ditto, pages 1429 et seq. The esterification is optionally carried out in the presence of a catalytic quantity of a typical transesterification catalyst, e.g., acids, bases or transition metal compounds, such as titanium tetrabutylate, at -20 approx. 80 to 260C, preferably 100 to 230C. The esterification reaction is continued until the required hydroxyl and acid values are reached.
The type and quantities of components a) to d) used are selected so that the polyesters have the characteristics described above.
The equivalent ratio of carboxyl groups to hydroxyl groups is generally 1:1.5 to 1:1, preferably 1:1.3 to 1:1. Anhydride groups correspond to 2 carboxyl groups and are included as such in the calculation.
The production of the unsaturated polyester resins may also be Mo3981 carried out by transesterifying esters based on polycarboxylic acids and monohydric, readily volatile alcohols in combination with polyhydroxyl compounds example or by using esters based on monohydric, readily volatile carboxylic acids and polyhydroxyl compounds in combination with 5 polycarboxylic acids with elimination of the readily volatile alcohol or the readily volatile acid. However, this method of producing the polyester resins is less preferred.
In the process according to the invention, the olefinically unsaturated polyester resins are reacted with ammonia or primary 10 amines corresponding to the formula:
wherein R represents an aliphatic, cycloaliphatic or araliphatic radical which may contain ether groups andlor hydroxyl groups, preferably an aliphatic or cycloaliphatic hydrocarbon radical having up to 15 carbon atoms and optionally at least one alcoholic hydroxyl group.
Primary monoamines corresponding to the above formula wherein -the primary amino group is attached to a secondary or tertiary carbon atom, are particularly preferred reactants for the unsaturated polyester 20 resins.
Suitable amines corresponding to the above formula include methyl amine, ethyl amine, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-amino-2-methyl propane, 2-amino-2-methyl propane, 2-amino-2-methyl butane, 1-aminohexane, 1-amino-2-25 ethyl hexane, 1-aminodecane, 1-aminododecane, 1-aminotetradecane, 1-aminohexadecane, 1-aminooctadecane, allyl amine, cyclohexyl amine, 2-, 3- or 4-methyt cyclohexyl amine, aminomethyl cyclohexane, 3,3,5- .
trimethyl cyclohexyl amine, 1-aminomethyl-3- or 4-methyl-3-cyclohexene, Mo3981 -- , 9 ~ 7 benzyl amine, cyclopentyl amine, cyclooctyl amine, cyclopropyl amine, cycloheptyl amine, cyclobutyl amine, cyclododecyl amine, 1-aminoindane, 2-aminoethanol, 2-methoxyethyl amine, 3-amino-1-propanol, 3-methoxy-1-propyl amine, 3-ethoxy-1-propyl amine, 3-((2-ethylhexyl)oxy)-1-propyl 5 amine, 1-amino-2-propanol, 2-amino-1-butanol, 2-amino-2-methyl propanol, 2-amino-2-methyl-propane-1,3-diol and 2-amino-2-hydroxy-methyl propane-1,3-diol.
The addition of ammonia or primary amines to the unsaturated polyester resins results in the formation of structural units corresponding 10 to the formula . .: .
O O
R' 15 wherein R' represents -NH2 or -NHR.
The type and quantities of the reactants reacted with one another are selected so that amino-functional and optionally hydroxy-functional polyester resins have the characteristics mentioned above. When ammonia or amines which are gaseous at room temperature are used, -20 excess quantities of the base are often added followed by the subsequent removal of the unreacted excess under vacuum and/or by the introduction of inert gas. When amines which are liquid at room temperature are used, the equivalent ratio of primary amino groups to structural units corresponding to the formula O O '~
Il .
--0--C CH=CH C 0--~.
Mo3981 can vary within wide limits, for example, from 0.05:1 to 1:1, preferably 0.1:1 to 1:1 and more preferably 0.1:1 to 0.6:1.
The reactlon generally takes place at temperatures of 0 to 120C, preferably 20 to 100C. The reaction may be carried out in the presence 5 or absence of suitable solvents depending upon the viscosity of the unsaturated polyester. Suitable solvents include toluene; xylene; higher alkylbenzenes; esters such as ethyl acetate, n-butyl acetate, methyl glycol acetate, ethyl glycol acetate and methoxybutyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and mixtures of 10 these solvents.
As already mentioned, structural units corresponding to the formula:
il R ~:
R' wherein R' is defined as above, are formed in the reaction according to the invention. The reactivity of 20 the amino group R' is greatly reduced by the electron-attracting effect when compared with corresponding, electron-unhindered amino groups.
One possibility of variation regarding the reactivity of the products according to the invention is to vary the ratio of incorporated hydroxyl groups to incorporated amino groups by suitable choice of the starting 25 materials used in the process according to the invention and the quantities in which they are used.
Depending upon their molecular weight, the products obtained by the process according to the invention are generally low-viscosity to high-Mo3981 ~ ~ ~ 1927 viscosity, substantially colorless, clear resins which form clear solutions in the previously mentioned lacquer solvents.
The products obtained in accordance with the invention may be used in admixture with various quantities of other isocyanate-reactive compounds, preferably known polyester or polyacrylate polyols containina 0,5 to 10, preferably 1 to 5 % by weight of hydroxyl groups. This provides another possibility for controlling the reactivity of the component containing isocyanate-reactive groups. In general, the isocyanate-reactive component used in the application according to the invention contains up to 20 hydroxyl groups for every primary or secondary amino group. The ratio of (i) primary and/or secondary amino groups to (ii) hydroxyl groups in the binder component containing isocyanate-reactive groups is preferably 10:1 to 1:10. The percentage of products according to the invention in these mixtures is preferably 10 to 100% by weight. In a particularly preferred embodiment, the products according to the invention are used as sole isocyanate-reactive lacquer component. -Reactants for the "polyol component" in accordance with the invention are the known "lacquer polyisocyanates," i.e., the known ~ -~
urethane-modified, uretdione-modified or, in particular, biuret-modified or isocyanurate-modified diisocyanates. Examples of these diisocyanates include 1,6-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-iso-cyanatomethyl cyclohexane (isophorone diisocyanate~, 4,4-diiso-cyanatodicyclohexyl methane, 2,4- and 2,6-diisocyanatotoluene.
"Lacquerpolyisocyanates" containing aliphatically and/orcyclo-aliphatically bound isocyanate groups are particularly preferred. -. . .
Urethane-modified lacquer polyisocyanates are preferably reaction products of 2,4- and optionally 2,6-diisocyanatotoluene with less than equivalent quantities of trimethylol propane or mixtures thereof with Mo3981 ~''''" ~
--` 211~'~27 simple diols such as the isomeric propane or butane diols The production of these urethane-modified lacquer polyisocyanates in substantially monomer-free form is described, for example, in DE-PS
1,090, 1 96.
Uretdione-modified lacquer polyisocyanates are preferably prepared from 1,6-diisocyanatohexane as described, for example, in EP-A-0,377, 1 77.
Biuret-modified lacquer polyisocyanates, which are preferred for the use according to the invention, are preferably those prepared from 1,6-diisocyanatohexane as described, for example, in EP-B1 0,003,505, DE-PS 1,101,394, US-PS 3,358,010 and US-PS 3,903,127.
Isocyanurate-modified polyisocyanates, which are also preferred according to the invention, include in particular the isocyanate-functional trimers or mixed trimers of the previously disclosed diisocyanates.
Examples include the isocyanate group-containing polyisocyanates prepared from diisocyanatotoluene according to GB-PS 1,060,430, GB-PS 1,506,373 or GB-PS 1,485,564; the mixed trimers prepared from the diisocyanatotoluenes and 1,6-diisocyanatohexane in accordance with, for example, DE-PS 1,644,809 or DE-OS 3,144,672; and, in particular, the aliphatic or aliphatic-cycloaliphatic trimers or mixed trimers prepared from 1,6-diisocyanatohexane andlor isophorone diisocyanate in accordance with, for example, US-PS 4,324,879, US-PS 4,288,586, DE-OS 3,100,262, DE-OS 3,100,263, DE-OS 3,033,860 or DE-OS
3, 1 44,672.
The lacquer polyisocyanates employed in the use according to the invention preferably have an isocyanate content of 5 to 25% by weight and preferably have a residual content of the monomeric diisocyanates used for their production of less than 2% by weight. Mixtures of the Mo3981 . 1 .. . ~ ~ .. . . . -. ~ . . . - . ~ .
' ~ ` '' ' , ;, 1 ., ~ ` _ , , . ,, . ~ . . . .
~ ............... . . .
21~ ~927 previously mentioned lacquer polyisocyanates may also be used.
The two-component polyurethane coating compositions according to the invention are formulated to have an equivalent ratio of isocyanate groups to isocyanate-reactive groups of 5:1 to 1:2, preferably 1.5:1 to 1:1.2.
The two-component binders obtained by mixing the binder components have only a limited pot life of about 0.5 to 8 hours. They may be used for the production of clear or pigmented coating compositions which may contain known auxiliaries and additives. The auxiliaries and additives may be added either to the mixture or to the individual components before they are mixed.
Suitable auxiliaries and additives include the previously mentioned solvents; plasticizers such as tricresyl phosphate, phthalic acid diesters -and chloroparaffins; pigments and fillers such as titanium dioxide, barium sulfate, chalk and carbon black; catalysts such as N,N-dimethyl ~ --benzylamine, N-methyl morpholine, zinc octoate, tin octoate and dibutyl tin dilaurate; flow control agents; thickeners; stabilizers such as substituted phenols; organofunctional silanes as coupling agents; and light stabilizers. ;-~ -The light stabilizers include the sterically hindered amines described, for example, in DE-OS 2,417,353 (= US-PS 4,123,418 and US-PS 4,110,304) and DE-OS 2,456,864 (= US-PS 3,993,655 and US-PS 4,221,701). Partlcularly preferred compounds include bis- -(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate, bis-(2,2,6,6-tetramethyl-4- . -piperidyl)-sebacate, n-butyl-(3,5-ditert.butyl-4-hydroxybenzyl)-malonic acid and bis-(1,2,2,6,6-pentamethyl-4-piperidyl)-ester.
The moisture adhering to the fillers and pigments may be removed by preliminary drying or by the use of water-absorbing materials such as : ,.
Mo3981 ~ ~
.. .... . . . ,, . -- , -- --~;t ~ 2 7 -~3-molecular sieve zeolite.
The resulting coatings may be dried at room temperature. Drying does not require any increase in temperature to achieve optimum properties. However, elevated temperatures may be applied to 5 accelerate the drying reaction. Drying temperatures used for typical stoving conditions are possible, but less preferred. This is of consider-able practical significance because, even at the relatively high temperatures which may occur, for example, in the event of malfunctions of lacquering plants, the coatings do not undergo thermal degradation.
Two-component polyurethane coating compositions containing the products according to the invention as their principal binder component are suitable for the production of coating compositions for any substrates such as metals, plastics, wood or glass.
Because they are equally suitable for plastics and metals, the 15 coating compositions according to the invention are also particularly suitable for coating substrates such as the exterior parts of automobiles produced from modern plasticlmetal composites. The coating compositions according to the invention are particulariy suitable for "on-line" coating of exterior auto parts because the coatings cure at low 20 temperatures so that the plastics are not exposed to high temperatures.
Further, the resulting coatings show excellent weather resistance and elasticity so that decorative lacquer finishes remain unchanged for long periods and safely withstand impact stresses. The excellent chip resistance of automotive coatings produced in accordance with the 25 invention is also particularly emphasized in this regard. The coatings obtained with the two-component coating compositions according to the invention optimally satisfy basically conflicting requirements, i.e. excellent elasticity at low temperatures coupled with high resistance to solvents Mo3981 2 ~
and tar stains, high gloss retention and resistance to yellowing on exposure to light of short wave length, for example, short-wave UV light.
The coating compositions according to the invention may be applied to the substrates to be coated by any known methods, for example, by spread coating, spray coating, roll coating or dip coating.
The lacquers according to the invention are suitable for the production of base coats, intermediate coats and top coats.
In the following examples, all parts and percentages are by weight, unless otherwise indicated.
EXAMPLES .
1. General procedure for the production of the unsaturated polyester precursors:
The monohydric and polyhydric alcohols and the unsaturated dicarboxylic acid(s)/anhydride(s) were weighed into a reactor equipped with a stirrer, heating system, automatic temperature control, column and : .
receiver. The mixture was heated to 100-150C while a stream of nitrogen was passed through the inhomogeneous mixture of starting materials. After the remaining dicarboxylic acids had been added, the ~ :
mixture of starting materials was heated with stirring to 200C over a period of 4 to 8 hours while nitrogen was passed through the mixture.
The temperature measured at the head of the column was kept at a ..
maximum of 105C. The melt became homogeneous and clear. When the head temperature fell below 90C, the column was removed and the mixture was condensed with an increased throughput of nitrogen to an acid value of ~ 3 mg KOH/g. - .
Colorless resins were obtained and were dissolved in methoxy- ~
propyl acetate, butyl acetate or mixtures thereof. ;.
The composition and properties of the individual polyesters are ; ~ .
Mo3981 -15~
given in Examples 1 and 2. The abbreviation "mol" applies to the molar ratio and not to the actual number of "moles," as can be seen from the quantities by weight in "g."
Exam~le 1 PolyesterA Quantity weighed in 1.0 Mol hexane-1,6-diol 526 9 1.0 Mol trimethylol propane 596 g 1.5 Mol cyclohexane dimethanol 962 g 1.5 Mol neopentyl glycol 696 g 2.2 Mol adipic acid 1431 g 1.8 Mol maleic anhydride 786 g Hydroxyl value: 145 mg KOHtg Acid value: 0.7 mg KOH/g Molecular weight: 1700 Example 2 Polyester B Quantity weighed in 4.00 Mol hexane-1,6-diol 1949 g 1.00 Mol trimethylol propane 553 g 0.52 Mol adipic acid 314 g 0.52 Mol maleic anhydride 211 g 2.48 Mol Isophthalic acid 1701 g 0.48 Mol phthalic anhydride 293 9 Hydroxyl value: 140 mg KOH/g Acid value: 1.2 rng KOH/g Molecular weight: 1800 Mo3981 ~ (3 2 7 2. General procedure for the reaction of unsaturated polyesters with primary amines Polyester precursors A and B from Examples 1 and 2 were optionally dissolved in a suitable solvent and introduced into a 2-liter four-5 necked flask equipped with a stirrer, thermometer, reflux condenser anddropping funnel and heated to 60C. The corresponding primary amine was then added in one portion. The mixture was then stirred for 2 hours at 60C, heated to 80C and stirred until no more primary amino groups could be detected by titrimetry or until the solids content corresponded to 10 the theoretical value of the amine addition. The product was then cooled and packed in containers.
3. General procedure for the reaction of unsaturated polyesters with ammonia -Polyester precursors A and B from Examples 1 and 2 were 15 optionally dissolved in a suitable solvent and introduced into a 2 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and inlet pipe. Ammonia from a steel boffle was then passed through the -flask for about 4 hours at room temperature. The reaction mixture heated up to about 30C. The reaction mixture was then stirred for about 20 4 hours at room temperature, after which unreacted ammonia was driven out with nitrogen at 50C. The product was then cooled and packed in containers.
~, ,.
' ~, Mo3981 ,::
: ~ ~; '' .' :, ~
~ 192 7 Y o a, O Oo O ~ O
N 't U'~
o ~ O U'~ .
U~ C~l CO
o) oU~ O
c~ o ~ O O 0 0 ~o a~ ~ ,~
~D ~ O ~ O
.c o ~ a~ O ~ O
._ CO U~ ~
~r o ~ ~ o 8 O o ~ C5~ o E W i~ 8 Mo3981 - ~111927 ExamPle 12 (Use) This example describes the production of ready-to-use coating compositions prepared from the aminopolyesters of Examples 3 to 10 as well as from the polyesters of examples 1 and 2 ~comparison)~ their application to substrates and the testing of the resulting coatings.
To evaluate the properties of the coating compositions, white 10 compositions were produced by blending the polyesters of Examples 1 to 10 with various additives and white pigments and grinding on a Red Devil shaker. ~ - -A lacquer polyisocyanate was then added to provide an NCO/NH+OH
equivalent ratio of about 1.3:1. -The "lacquer polyisocyanate" used was an isocyanurate group-containing polyisocyanate prepared from 1,6-diisocyanatohexane (Desmodur N 3390, a product of Bayer AG) which is present at 90% solids in a 1:1 ratio by volume of butyl acetate and Solvent Naphtha 100 solvent (NCO content of the solution: 19.4% by weight).
The following percentages of additives were used, based on solids - -(sum of the solid components of polyester and polyisocyanate):
, "~
Mo3981 Table 2 o/o Additives Solid on solid Zinc octoate t10% in 1-methoxypropyl-2-acetate) 0.2 Silicone oil as flow control agent (Baysilon lacquer additive OL 17, a product of Bayer AG; 10% in 1-methoxy-propyl-2-acetate) 0.1 Tinuvin 292 (a light stabilizer pro-duced by Ciba-Geigy, Basel; 10% in xylene) 1.0 Tinuvin 900 (a light stabilizer pro-duced by Ciba-Geigy, Basel; 10% in xylene) 1.0 Titanium dioxide (rutile type; Kronos 2160, a product of Kronos-Titan, Leverkusen) 60.0 Antisedimenting agent (Bentone 38, a product of Kronos-Titan, Leverkusen;
10% suspension in a 17:1 blend of Solvesso 100 solvent and Antiterra U 17:1 additive) 1.0 The solvent used was a mixture of ethyl acetate, 1-methoxypropyl-2-acetate and methyl ethyl ketone (1:1:1). The coating composition was diluted to a content of:
33% binder 20% pigment approx. 1% additive approx. 46% solvent The flow time (DIN 53211; 4 mm orifice) was approx. 18 seconds. The coating compositions were ready for spraying.
Mo3981 The lacquers were applied to glass plates (wet film thickness approx, 100 ,um), dried for 45 minutes at 80C and stored for 14 days at room temperature. The dry film thickness was approx. 50 ,um.
Konig hardness (DIN 53157), Gardner gloss at 60 (DIN 67530), 5 dissolvability by various solvents and resistance to tar were then determined.The resistance of the coatings to tar stains was a critical aspect of the invention.
To test their flexibility at low temperatures, the coating compositions were sprayed onto primed 3 mm thick plastic plates of 10 Bayflex 91 (a product of Bayer AG, Leverkusen), dried for 45 minutes at 80C and stored for 14 days at room temperature. The dry film thickness was approximately 35 ,um. 2 cm wide and 15 cm long strips prepared therefrom were stored for approx. 30 minutes at various temperatures (room temperature: 5C, 0C, -5C, ..., -40C) in a low-temperature chamber and then bent around a 1 inch mandrel at the particular temperature prevailing in the chamber. The temperature at which the coating broke was the criterion for low-temperature flexibility. The lacquers produced from the polyesters polyols of Examples 1 to 10 satisfied stringent elasticity requirements, even at low temperatures.
The test results of the coatings based on the aminopolyesters ~ -according to the invention of Examples 3 to 10 and Comparison Examples 1 and 2 are set out in Table 3.
Mo3981 :~' : .
0 ~ `- o o ~ ~y E ' 0 a~ ---- --o ~ a~ ~ O o _ O O
CL
E r` U~ 0o o o _ o o o o o ~, w a~ 0 0 0 _ O O O O O
_ u) a~ ~o --C _ g .C~ U~ ~ _ o ~ o o o o o U,~ o ~~ ~ _ _ _ o o o o o ~
o o ~ u~ _ _ _ o o -- 91 ~ ~ 2 ~ :
E _o co _ _ _ o O -- ~ ~ c~
o e O ~
E o o ~ O
S ~ E el N 2 ~ e E ~ E ¦ Q E ~ 8 E E O ' J ~ ~ ~ ~ o Mo3981 -9 ~ 7 5 Discussion of the results:
Highly flexible coatings were obtained with coatings based on the polyesters of Examples 1 to 10, the coatings of Examples 1, 3 and 4 providing the best results in regard to elasticity. The results of the tar resistance tests reflect in particular the excellent resistance to tar of the 10 coatings of Examples 3 to 10 according to the invention in contrast to comparison coatings 1 and 2.
ExamPle 13 (Use) The aminopolyester (K) of Example 11 was used to formulate clear coatings with the lacquer polyisocyanate of Example 12 and applied 15 to glass plates (dry film thickness approx. 60 ,um). The crosslinking ratio and the solids content are set out in Table 4. Solvent resistance was tested by the cotton wool pad method under the drying conditions shown in Table 4. Hardness was determined by the pencil method. -~
Mo3981 -23- i~J11~927 Table 4:
Clear coating compositions based on the aminopolyester of Example 11 according to the invention Results of the solvent resistance and pencil hardness tests Example 13 .. . .
Aminopolyester of Ex. 11 NCO/NH+OH ratio 1.2 Solvent BuAc Solids content (%) 70 Drying 40'/80C
+ 1d RT :
Dissolvability" by xylene o Exposure time: MPA 0 1 minute acetone EtOH/H2O 1:1 0 Pencil hardness 3H
" 0 best value, 5 poorest value Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of ~ -~
25 the invention except as it may be limited by the claims.
Mo3981 :~
:: :
~'''.,.' ,
Claims (17)
1. process for the production of a polyester resin containing 0 to 10% by weight of hydroxyl groups and 0.01 to 9% by weight of nitrogen (expressed as N = 14) in the form of primary and/or secondary amino groups which comprises reacting in an addition reaction at 0 to 120°C
i) a polyester resin having a molecular weight (Mn) of 286 to 10,000 and containing an average per molecule of at least 2 structural units corresponding to the formula:
and optionally alcoholic hydroxyl groups with ii) ammonia or a primary monoamine corresponding to the formula:
wherein R represents an aliphatic, cycloaliphatic or araliphatic radical optionally containing ether oxygen atoms and/or hydroxyl groups.
i) a polyester resin having a molecular weight (Mn) of 286 to 10,000 and containing an average per molecule of at least 2 structural units corresponding to the formula:
and optionally alcoholic hydroxyl groups with ii) ammonia or a primary monoamine corresponding to the formula:
wherein R represents an aliphatic, cycloaliphatic or araliphatic radical optionally containing ether oxygen atoms and/or hydroxyl groups.
2. The process of Claim 1 wherein component i) comprises an unsaturated polyester resin having a molecular weight of 488 to 8,000, a hydroxyl group content of 0 to 7% an average content of in all at least 3 structural units corresponding to the formula:
and is the reaction product of a) a polycarboxylic acid component consisting essentially of maleic acid, maleic anhydride and/or fumaric acid and up to 95 carboxyl equivalent-%, based on the total equivalents of component (a), of one or more polycarboxylic acids having a molecular weight of 118 to 1,000 and anhydrides of such acids with b) a polyol component having an average maximum hydroxyl functionality of 3 and consisting essentially of at least one polyhydric alcohol having a molecular weight of 62 to 400 and c) optionally a monocarboxylic acid component in a quantity of up to 50 carboxyl equivalent-%, based on the total equivalents of components a) and c), and consisting essentially of least one monocarboxylic acid having a molecular weight of 60 to 400 and/or at least one anhydride of said monocarboxylic acid and/or d) optionally a monohydric alcohol component in a quantity of up to 50 hydroxyl equivalent-%, based on the total equivalents of components b) and d), and consisting essentially of at least one monohydric alcohol having a molecular weight of 32 to 400, while maintaining an equivalent ratio of carboxyl groups to hydroxyl groups of 1:1.5 to 1:1 and terminating the reaction when the acid value is below 10 mg KOH/g.
and is the reaction product of a) a polycarboxylic acid component consisting essentially of maleic acid, maleic anhydride and/or fumaric acid and up to 95 carboxyl equivalent-%, based on the total equivalents of component (a), of one or more polycarboxylic acids having a molecular weight of 118 to 1,000 and anhydrides of such acids with b) a polyol component having an average maximum hydroxyl functionality of 3 and consisting essentially of at least one polyhydric alcohol having a molecular weight of 62 to 400 and c) optionally a monocarboxylic acid component in a quantity of up to 50 carboxyl equivalent-%, based on the total equivalents of components a) and c), and consisting essentially of least one monocarboxylic acid having a molecular weight of 60 to 400 and/or at least one anhydride of said monocarboxylic acid and/or d) optionally a monohydric alcohol component in a quantity of up to 50 hydroxyl equivalent-%, based on the total equivalents of components b) and d), and consisting essentially of at least one monohydric alcohol having a molecular weight of 32 to 400, while maintaining an equivalent ratio of carboxyl groups to hydroxyl groups of 1:1.5 to 1:1 and terminating the reaction when the acid value is below 10 mg KOH/g.
3. The process of Claim 1 wherein R represents an aliphatic or cycloaliphatic hydrocarbon radical having up to 15 carbon atoms optionally containing at least one alcoholic hydroxyl group.
4. The process of Claim 2 wherein R represents an aliphatic or cycloaliphatic hydrocarbon radical having up to 15 carbon atoms optionally containing at least one alcoholic hydroxyl group.
5. The process of Claim 1 characterized in that the reactants are present in amounts sufficient to provide 0.1 to 10 primary amino groups for each structural unit corresponding to the formula:
6. The process of Claim 2 characterized in that the reactants are present in amounts sufficient to provide 0.1 to 10 primary amino groups for each structural unit corresponding to the formula:
7. The process of Claim 3 characterized in that the reactants are present in amounts sufficient to provide 0.1 to 10 primary amino groups for each structural unit corresponding to the formula:
8. The process of Claim 4 characterized in that the reactants are present in amounts sufficient to provide 0.1 to 10 primary amino groups for each structural unit corresponding to the formula:
9. A polyester resin containing 0 to 10% by weight of hydroxyl groups and 0.01 to 9% by weight of nitrogen (expressed as N = 14) in the form of primary and/or secondary amino groups which is prepared by a process which comprises reacting in an addition reaction at 0 to 120°C
i) a polyester resin having a molecular weight (Mn) of 286 to 10,000 and containing an average per molecule of at least 2 structural units corresponding to the formula:
and optionally alcoholic hydroxyl groups with ii) ammonia or a primary monoamine corresponding to the formula:
wherein R represents an aliphatic, cycloaliphatic or araliphatic radical optionally containing ether oxygen atoms and/or hydroxyl groups.
i) a polyester resin having a molecular weight (Mn) of 286 to 10,000 and containing an average per molecule of at least 2 structural units corresponding to the formula:
and optionally alcoholic hydroxyl groups with ii) ammonia or a primary monoamine corresponding to the formula:
wherein R represents an aliphatic, cycloaliphatic or araliphatic radical optionally containing ether oxygen atoms and/or hydroxyl groups.
10. The polyester resin of Claim 9 wherein component i) comprises an unsaturated polyester resin having a molecular weight of 488 to 8,000, a hydroxyl group content of 0 to 7% an average content of in all at least 3 structural units corresponding to the formula:
and is the reaction product of a) a polycarboxylic acid component consisting essentially of maleic acid, maleic anhydride and/or fumaric acid and up to 95 carboxyl equivalent-%, based on the total equivalents of component (a), of one or more polycarboxylic acids having a molecular weight of 118 to 1,000 and anhydrides of such acids with b) a polyol component having an average maximum hydroxyl functionality of 3 and consisting essentially of at least one polyhydric alcohol having a molecular weight of 62 to 400 and c) optionally a monocarboxylic acid component in a quantity of up to 50 carboxyl equivalent-%, based on the total equivalents of components a) and c), and consisting essentially of least one monocarboxylic acid having a molecular weight of 60 to 400 and/or at least one anhydride of said monocarboxylic acid and/or d) optionally a monohydric alcohol component in a quantity of up to 50 hydroxyl equivalent-%, based on the total equivalents of components b) and d), and consisting essentially of at least one monohydric alcohol having a molecular weight of 32 to 400, while maintaining an equivalent ratio of carboxyl groups to hydroxyl groups of 1:1.5 to 1:1 and terminating the reaction when the acid value is below 10 mg KOH/g.
and is the reaction product of a) a polycarboxylic acid component consisting essentially of maleic acid, maleic anhydride and/or fumaric acid and up to 95 carboxyl equivalent-%, based on the total equivalents of component (a), of one or more polycarboxylic acids having a molecular weight of 118 to 1,000 and anhydrides of such acids with b) a polyol component having an average maximum hydroxyl functionality of 3 and consisting essentially of at least one polyhydric alcohol having a molecular weight of 62 to 400 and c) optionally a monocarboxylic acid component in a quantity of up to 50 carboxyl equivalent-%, based on the total equivalents of components a) and c), and consisting essentially of least one monocarboxylic acid having a molecular weight of 60 to 400 and/or at least one anhydride of said monocarboxylic acid and/or d) optionally a monohydric alcohol component in a quantity of up to 50 hydroxyl equivalent-%, based on the total equivalents of components b) and d), and consisting essentially of at least one monohydric alcohol having a molecular weight of 32 to 400, while maintaining an equivalent ratio of carboxyl groups to hydroxyl groups of 1:1.5 to 1:1 and terminating the reaction when the acid value is below 10 mg KOH/g.
11. The polyester resin of Claim 9 wherein R represents an aliphatic or cycloaliphatic hydrocarbon radical having up to 15 carbon atoms optionally containing at least one alcoholic hydroxyl group.
12. The polyester resin of Claim 10 wherein R represents an aliphatic or cycloaliphatic hydrocarbon radical having up to 15 carbon atoms optionally containing at least one alcoholic hydroxyl group.
13. The polyester resin of Claim 9 characterized in that the reactants are present in amounts sufficient to provide 0.1 to 10 primary amino groups for each structural unit corresponding to the formula:
14. The polyester resin of Claim 10 characterized in that the reactants are present in amounts sufficient to provide 01 to 10 primary amino groups for each structural unit corresponding to the formula:
15. The polyester resin of Claim 11 characterized in that the reactants are present in amounts sufficient to provide 0.1 to 10 primary amino groups for each structural unit corresponding to the formula:
16. The polyester resin of Claim 12 characterized in that the reactants are present in amounts sufficient to provide 0.1 to 10 primary amino groups for each structural unit corresponding to the formula:
17. A two-component polyurethane coating composition wherein the binder comprises a polyisocyanate, the polyester resin of Claim 9 and optionally other one or more other compounds containing isocyanate-reactive groups.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4244030A DE4244030A1 (en) | 1992-12-24 | 1992-12-24 | Amine-containing polyester resins |
DEP4244030.0 | 1992-12-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2111927A1 true CA2111927A1 (en) | 1994-06-25 |
Family
ID=6476508
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002111927A Abandoned CA2111927A1 (en) | 1992-12-24 | 1993-12-20 | Amino-functional polyester resins |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0604814A1 (en) |
JP (1) | JPH06228295A (en) |
KR (1) | KR940014506A (en) |
CA (1) | CA2111927A1 (en) |
DE (1) | DE4244030A1 (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5925711A (en) * | 1996-07-10 | 1999-07-20 | Bayer Aktiengesellschaft | Polyamines and their use in aqueous coating compositions |
US20120225991A1 (en) * | 2009-11-17 | 2012-09-06 | Nuplex Resins B.V. | Amino and hydroxyl functional polyesters |
WO2016069572A1 (en) | 2014-10-27 | 2016-05-06 | Eastman Chemical Company | Resole phenolic resins curable with functional polyesters |
WO2016164196A1 (en) | 2015-04-10 | 2016-10-13 | Eastman Chemical Company | Curable benzoxazine-based phenolic resins and coating compositions thereof |
US9469779B2 (en) | 2010-09-30 | 2016-10-18 | Valspar Sourcing, Inc. | Coating compositions incorporating ingredients having secondary amine, hydroxyl and isocyanate functionality |
US9487619B2 (en) | 2014-10-27 | 2016-11-08 | Eastman Chemical Company | Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol |
US9598602B2 (en) | 2014-11-13 | 2017-03-21 | Eastman Chemical Company | Thermosetting compositions based on phenolic resins and curable poleyester resins made with diketene or beta-ketoacetate containing compounds |
US9650539B2 (en) | 2014-10-27 | 2017-05-16 | Eastman Chemical Company | Thermosetting compositions based on unsaturated polyesters and phenolic resins |
US9988553B2 (en) | 2016-02-22 | 2018-06-05 | Eastman Chemical Company | Thermosetting coating compositions |
US10011737B2 (en) | 2016-03-23 | 2018-07-03 | Eastman Chemical Company | Curable polyester polyols and their use in thermosetting soft feel coating formulations |
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US10526444B2 (en) | 2015-09-25 | 2020-01-07 | Eastman Chemical Company | Polymers containing cyclobutanediol and 2,2-bis(hydroxymethyl)alkylcarboxylic acid |
US10676565B2 (en) | 2015-05-19 | 2020-06-09 | Eastman Chemical Company | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0731121A3 (en) * | 1995-03-09 | 1997-06-11 | Basf Ag | Aminomodified urethane-acrylates |
US20050059791A1 (en) * | 2003-09-17 | 2005-03-17 | Roesler Richard R. | Flexibilized polyaspartic esters |
DE102007030669A1 (en) | 2007-07-02 | 2009-01-08 | Evonik Degussa Gmbh | Amino-containing polyesters |
CN111393626B (en) * | 2020-03-06 | 2022-09-16 | 嘉宝莉化工集团股份有限公司 | Secondary amino modified alkyd resin and preparation method and application thereof |
US20230303772A1 (en) | 2020-08-04 | 2023-09-28 | Basf Se | Branched Polyaspartic Acid Esters and Their Preparation |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2969335A (en) * | 1957-06-25 | 1961-01-24 | Quaker Chemical Products Corp | Reaction products of polyesters and primary amines |
DE1157773B (en) * | 1962-08-11 | 1963-11-21 | Bayer Ag | Process for the production of plastics, including foams, using the isocyanate polyaddition process |
FR2607139B1 (en) * | 1986-11-21 | 1989-08-18 | Inst Francais Du Petrole | POLYMERS WITH NITROGEN FUNCTIONS DERIVED FROM UNSATURATED POLYESTERS AND THEIR USE AS ADDITIVES FOR LOWERING THE FLOW POINT OF MEDIUM HYDROCARBON DISTILLATES |
US4874837A (en) * | 1988-01-11 | 1989-10-17 | Owens-Corning Fiberglas Corporation | Aminated hydroxylated polyester polyol resin and molding compositions comprised thereof |
-
1992
- 1992-12-24 DE DE4244030A patent/DE4244030A1/en not_active Withdrawn
-
1993
- 1993-12-13 EP EP93120058A patent/EP0604814A1/en not_active Withdrawn
- 1993-12-20 CA CA002111927A patent/CA2111927A1/en not_active Abandoned
- 1993-12-22 JP JP5345476A patent/JPH06228295A/en active Pending
- 1993-12-23 KR KR1019930029222A patent/KR940014506A/en not_active Application Discontinuation
Cited By (14)
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US5925711A (en) * | 1996-07-10 | 1999-07-20 | Bayer Aktiengesellschaft | Polyamines and their use in aqueous coating compositions |
US20120225991A1 (en) * | 2009-11-17 | 2012-09-06 | Nuplex Resins B.V. | Amino and hydroxyl functional polyesters |
US9469779B2 (en) | 2010-09-30 | 2016-10-18 | Valspar Sourcing, Inc. | Coating compositions incorporating ingredients having secondary amine, hydroxyl and isocyanate functionality |
US9650539B2 (en) | 2014-10-27 | 2017-05-16 | Eastman Chemical Company | Thermosetting compositions based on unsaturated polyesters and phenolic resins |
WO2016069572A1 (en) | 2014-10-27 | 2016-05-06 | Eastman Chemical Company | Resole phenolic resins curable with functional polyesters |
US9487619B2 (en) | 2014-10-27 | 2016-11-08 | Eastman Chemical Company | Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol |
US9598602B2 (en) | 2014-11-13 | 2017-03-21 | Eastman Chemical Company | Thermosetting compositions based on phenolic resins and curable poleyester resins made with diketene or beta-ketoacetate containing compounds |
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US10676565B2 (en) | 2015-05-19 | 2020-06-09 | Eastman Chemical Company | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol |
US10526444B2 (en) | 2015-09-25 | 2020-01-07 | Eastman Chemical Company | Polymers containing cyclobutanediol and 2,2-bis(hydroxymethyl)alkylcarboxylic acid |
US9988553B2 (en) | 2016-02-22 | 2018-06-05 | Eastman Chemical Company | Thermosetting coating compositions |
US10011737B2 (en) | 2016-03-23 | 2018-07-03 | Eastman Chemical Company | Curable polyester polyols and their use in thermosetting soft feel coating formulations |
EP3409707A1 (en) | 2017-05-30 | 2018-12-05 | Henkel AG & Co. KGaA | Method for producing functionalized polyesters |
WO2018219574A1 (en) | 2017-05-30 | 2018-12-06 | Henkel Ag & Co. Kgaa | Method for producing functionalized polyesters |
Also Published As
Publication number | Publication date |
---|---|
JPH06228295A (en) | 1994-08-16 |
EP0604814A1 (en) | 1994-07-06 |
KR940014506A (en) | 1994-07-18 |
DE4244030A1 (en) | 1994-06-30 |
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