MXPA06008121A - An acrylic composition and a curable coating composition including the same - Google Patents
An acrylic composition and a curable coating composition including the sameInfo
- Publication number
- MXPA06008121A MXPA06008121A MXPA/A/2006/008121A MXPA06008121A MXPA06008121A MX PA06008121 A MXPA06008121 A MX PA06008121A MX PA06008121 A MXPA06008121 A MX PA06008121A MX PA06008121 A MXPA06008121 A MX PA06008121A
- Authority
- MX
- Mexico
- Prior art keywords
- set forth
- acrylic
- functionality
- reactive
- compound
- Prior art date
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 239000000203 mixture Substances 0.000 title claims abstract description 143
- 239000008199 coating composition Substances 0.000 title claims abstract description 41
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 111
- -1 carboxylic acid compound Chemical class 0.000 claims abstract description 110
- 239000000178 monomer Substances 0.000 claims abstract description 93
- 150000001875 compounds Chemical class 0.000 claims abstract description 73
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 28
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 25
- 239000004593 Epoxy Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 34
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 claims description 32
- 239000012948 isocyanate Substances 0.000 claims description 21
- 229920002554 vinyl polymer Polymers 0.000 claims description 21
- 229920000877 Melamine resin Polymers 0.000 claims description 19
- 150000002513 isocyanates Chemical class 0.000 claims description 19
- 229920001228 polyisocyanate Polymers 0.000 claims description 15
- 239000005056 polyisocyanate Substances 0.000 claims description 15
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 14
- 229920003180 amino resin Polymers 0.000 claims description 14
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 13
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 12
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 9
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- 125000002524 organometallic group Chemical group 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- ZPOUDMYDJJMHOO-UHFFFAOYSA-N 1-(1-hydroxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(O)CCCCC1 ZPOUDMYDJJMHOO-UHFFFAOYSA-N 0.000 claims description 6
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 6
- 125000004849 alkoxymethyl group Chemical group 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 6
- 150000007974 melamines Chemical class 0.000 claims description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 4
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- GRDAOWHTCXWIGG-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] carbamate Chemical compound NC(=O)OCC(CO)(CO)CO GRDAOWHTCXWIGG-UHFFFAOYSA-N 0.000 claims description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 3
- UNXHWFMMPAWVPI-QWWZWVQMSA-N D-threitol Chemical compound OC[C@@H](O)[C@H](O)CO UNXHWFMMPAWVPI-QWWZWVQMSA-N 0.000 claims description 3
- 239000004386 Erythritol Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- SKKTUOZKZKCGTB-UHFFFAOYSA-N butyl carbamate Chemical compound CCCCOC(N)=O SKKTUOZKZKCGTB-UHFFFAOYSA-N 0.000 claims description 3
- VYFFHOFPEGQURX-UHFFFAOYSA-N carbamic acid;propane-1,2-diol Chemical compound NC(O)=O.CC(O)CO VYFFHOFPEGQURX-UHFFFAOYSA-N 0.000 claims description 3
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 3
- 229940009714 erythritol Drugs 0.000 claims description 3
- 235000019414 erythritol Nutrition 0.000 claims description 3
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 150000002432 hydroperoxides Chemical class 0.000 claims description 3
- YNTOKMNHRPSGFU-UHFFFAOYSA-N n-Propyl carbamate Chemical compound CCCOC(N)=O YNTOKMNHRPSGFU-UHFFFAOYSA-N 0.000 claims description 3
- 238000000518 rheometry Methods 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims description 2
- DBXBTMSZEOQQDU-UHFFFAOYSA-N 3-hydroxyisobutyric acid Chemical compound OCC(C)C(O)=O DBXBTMSZEOQQDU-UHFFFAOYSA-N 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 150000008360 acrylonitriles Chemical class 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- AYWRZPKVTAIGRX-UHFFFAOYSA-N carbamic acid;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound NC(O)=O.CCC(CO)(CO)CO AYWRZPKVTAIGRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910001869 inorganic persulfate Inorganic materials 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 150000002976 peresters Chemical class 0.000 claims description 2
- 229920000582 polyisocyanurate Polymers 0.000 claims description 2
- 150000003440 styrenes Chemical class 0.000 claims description 2
- 238000004383 yellowing Methods 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000002843 carboxylic acid group Chemical group 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 37
- 150000003254 radicals Chemical class 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 235000013877 carbamide Nutrition 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 210000003041 ligament Anatomy 0.000 description 4
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- KCZQSKKNAGZQSZ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazin-2,4,6-trione Chemical compound O=C=NCCCCCCN1C(=O)N(CCCCCCN=C=O)C(=O)N(CCCCCCN=C=O)C1=O KCZQSKKNAGZQSZ-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- ZVEMLYIXBCTVOF-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-3-prop-1-en-2-ylbenzene Chemical group CC(=C)C1=CC=CC(C(C)(C)N=C=O)=C1 ZVEMLYIXBCTVOF-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- LHOKCCUPZYSAJG-UHFFFAOYSA-N 6-oxohexyl acetate Chemical compound CC(=O)OCCCCCC=O LHOKCCUPZYSAJG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 229920003265 Resimene® Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JEAVSZCYOGCXEB-UHFFFAOYSA-N carbamic acid;1,3,5-triazine-2,4,6-triamine Chemical compound NC(O)=O.NC1=NC(N)=NC(N)=N1 JEAVSZCYOGCXEB-UHFFFAOYSA-N 0.000 description 1
- 238000012711 chain transfer polymerization Methods 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
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- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
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Abstract
An acrylic composition includes the reaction product of an acrylic polymer, a carboxylic acid compound, and an alkyl carbamate. The acrylic polymer includes the reaction product of a functionalized monomer, a first compound reactive with the functionalized monomer to form a functionalized intermediate, and a highly branched, polyfunctional core molecule reactive with the functionalized intermediate. The first compound includes vinyl functionality reactive with the functionalized monomer and epoxy functionality. The carboxylic acid compound has carboxylic acid functionality that is reactive with the acrylic polymer. The alkyl carbamate is reactive with the hydroxyl-functional acrylic polymer to form the acrylic composition. The acrylic composition is highly-branched and, when used in coating compositions in combination with a suitable cross-linking agent, enhances recoat adhesion and produces cured films that have optimum scratch, mar, and chip performance, and acid etch resistance.
Description
A COMPOSITION OF ACRYLIC AND TINA COMPOSITION OF CURABLE COATING THAT INCLUDES THE SAME
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates generally to an acrylic composition. More particularly, the present invention relates to an acrylic composition that can be incorporated into a curable coating composition and then used in coating applications, such as an automotive coating application, that produce films that have adequate performance to tear, wear usual and peeling paint.
2. Description of the Related Art Acrylic compositions and their use in a wide variety of coating applications are known in the art. In a curable coating composition, the acrylic compositions, together with a suitable crosslinking agent, generally produce a film having good film properties, such as tear resistance, usual wear and peeling paint. Curable coating compositions using acrylic compositions usually require solvents that dissolve or otherwise reduce the acrylic composition for processing and application purposes. Solvents are required due mainly to a high molecular weight and a correspondingly high viscosity for the acrylic composition. Although conventional acrylic compositions are generally inexpensive to prepare, these particular compositions with large proportions of non-functional alkyl acrylic monomers provide poor new coating adhesion due to the formation of pendant and non-functional acrylic chains during curing. These acrylic chains migrate to an upper surface of a cured film of a coating composition having the conventional acrylic composition and inhibit the adhesion of the coating compositions that are substantially applied to the cured film. It is also known in the art that other properties of the cured film, including the tear resistance and the usual wear, can be compromised when the coating composition includes the conventional acrylic composition due to the formation of the acrylic chains described above. In addition, conventional acrylic compositions that do not include carbamate functionality for subsequent crosslinking with aminoplasts exhibit poor etch resistance. As a result, the cured film formed from conventional acrylic compositions is susceptible to damage due to acid rain. It is known that there is a move towards using acrylic compositions having lower molecular weights so that the total amount of the solvents, ie the volatile organic compounds (VOCs), required in the coating composition is reduced. However, it is also known that coating compositions using conventional acrylic compositions with lower molecular weights produce films having poorer film properties as evidenced by reduced performance to tearing, usual wear and peeling of the paint. Highly branched compositions, eg, star, are more frequently used because they offer higher molecular weights although they exhibit low viscosity, when compared to the viscosity of conventional acrylic compositions, ie, acrylic compositions which are not highly branched. These highly branched compositions have been based to date, mainly on polyester. However, some highly branched acrylic compositions have been developed by complex methods such as Attribute Radical Transfer Polymerization (ATRP) and Reversible Fragmentation Chain Transfer Polymerization (RAFT). These methods are complex, and therefore are generally undesirable for a variety of reasons including, but not limited to slow reaction times, poor manufacturing process, use of metal or sulfur containing compounds, and a requirement for the subsequent purification of the acrylic composition . Due to the inadequacy associated with the acrylic polymers of the prior art, especially the highly branched acrylic compositions developed by ATRP and RAFT, it is desirable to provide a novel acrylic composition that is economical and highly branched. It is also advantageous to provide an acrylic composition, and a curable coating composition comprising the acrylic composition, which promotes acid attack resistance, improves the new coating adhesion, and is optimized for crosslinking when used in coating compositions.
SUMMARY OF THE INVENTION AND ADVANTAGES The subject of the invention provides an acrylic composition and a curable coating composition that includes the acrylic composition. The acrylic composition includes an acrylic polymer. The acrylic polymer includes the reaction product of a functionalized monomer, a first compound reactive with the functionalized monomer that forms a functionalized intermediate, and a highly branched polyfunctional core molecule, with the intermediate functionalized to form the acrylic polymer. The first compound includes a functionality of the reactive vinyl with the functionalized monomer and an epoxy functionality. The acrylic polymer is highly branched and cost effective, when compared to conventional acrylic polymers that are highly branched. The acrylic composition further includes a carboxylic acid compound that includes a carboxylic acid functionality and an alkyl carbamate. The carboxylic acid compound is reactive with the functionality of the epoxy of the acrylic polymer to form an acrylic polymer functional with hydroxyl. The alkyl carbamate is reactive with the hydroxyl-functional acrylic polymer. Thus, the final acrylic composition includes a carbamate functionality. The curable coating composition includes the acrylic composition and a crosslinking agent that is reactive with the carbamate functionality of the acrylic composition. When used in the curable coating composition, in combination with the crosslinking agent, the acrylic composition produces films, especially clearcoated films, which have optimum performance to tearing, usual wear and tear of the paint, and resistance to attack. acid. In addition, the acrylic compositions improves the new coating adhesion.
DETAILED DESCRIPTION OF THE PREFERRED MODALITY The acrylic composition of the present invention is preferably used in curable coating compositions and cured films to improve certain properties of the cured film including, but not limited to, the acid etch resistance and the adhesion of new coating. More specifically, the acrylic composition has carbamate functionality, and optionally, the functionality of the hydroxyl that can be crosslinked with a crosslinking agent in the curable coating compositions. As referred to herein, the acrylic composition can include the reaction product of the acrylic polymer, a carboxylic acid compound and an alkyl carbamate, after the reaction of those components. The final acrylic composition formed after the reaction of the aforementioned components includes a carbamate functionality. Alternatively, the acrylic composition may include the acrylic polymer, the carboxylic acid compound and / or an unreactive alkyl carbamate.
That is, the acrylic composition can include the acrylic polymer and the carboxylic acid compound, the acrylic polymer and the alkyl carbamate, or the acrylic polymer, the carboxylic acid compound and the alkyl carbamate before the reaction between those components . The acrylic polymer is also referred to in the art as a star acrylic polymer or a star polymer having a core and a plurality of functionalized acrylate branches (also referred to as chains, arms, appendages and the like). Preferably, the acrylic polymer is formed through a free radical acrylic polymerization method which is further described below. More specifically, the acrylic polymer is the reaction product of a functionalized monomer, a first compound that is reactive with the functionalized monomer that forms a functionalized intermediate, and a highly branched polyfunctional core molecule, reactive with the functionalized intermediate that forms the polymer acrylic. The first compound includes a functionality of the vinyl that is reactive with the monomer. The first compound also includes an epoxy functionality that remains non-reactive in the acrylic polymer. The highly branched polyfunctional nucleus molecule, is referred to below simply as the core molecule, which functions as the core of the acrylic polymer. The first compound and the core molecule are further described below. In one embodiment, the functionalized monomer, hereinafter referred to simply as the monomer, includes a functionality reactive to the hydroxyl and a functionality of the vinyl. The functionalized descriptive terminology 'preceding the monomers refers to any functionality that can react with the functionality from the core molecule. The vinyl functionality of the monomer is suitable for stopping chain growth during the free radical acrylic polymerization of the monomer and the first compound. Preferably, the hydroxyl-reactive functionality remains non-reactive in the functionalized intermediate, after polymerization between the monomer and the first compound, and is reactive with the functionality of the hydroxyl present in the core molecule. For example, the monomer may include an aliphatic isocyanate functionality, which is reactive with the functionality of the hydroxyl and may also be referred to as isocyanate functionality, if the core molecule includes a polyol, which has hydroxyl functionality. A more preferred monomer is α, α-dimethyl isopropenylbenzyl isocyanate, which has both the functionality of the vinyl and the aliphatic isocyanate functionality as well as the hydroxyl-reactive functionality. The α-dimethyl isopropenylbenzyl isocyanate is also known in the art as TMI® Unsaturated Aliphatic Isocyanate (Meta) and is commercially available from Cytec Industries. The a, a-dimethyl isopropenylbenzyl isocyanate is also referred to in the art as isocyanate of 3-isopropenyl-α, α-dimethylbenzyl and isocyanate of α, α-dimethyl meta-isopropenylbenzyl. In addition, although less preferred, the ortho and para forms of the isocyanate of α, ocdimethyl isopropenylbenzyl are also feasible. The a, -dimethyl isopropenylbenzyl isocyanate has the effect of chain stop by limiting the number of -NCO functionality under normal acrylic polymerization conditions. For descriptive purposes, a chemical representation of an isocyanate of a, -dimethyl isopropenylbenzyl is described below.
Other suitable examples of hydroxyl-reactive functionality of the monomer may include cyano functionality, carboxylic acid halide functionality, melamine functionality and combinations thereof. In other embodiments, the functionality reactive to the hydroxyl can be replaced with a hydroxyl functionality. It will be appreciated that when the functionality of the hydroxyl replaces the reactive functionality to the hydroxyl, the core molecule has a reactive hydroxyl functionality, which will be reacted with the functionality of the monomer hydroxyl. A preferred monomer TMI which has had the functionality of the isocyanate replaced by the functionality of methylol is modified. Other monomers are suitable for the acrylic composition as long as the monomers are functionalized for subsequent reaction with the core molecule and have either the ability to stop chain growth during free radical acrylic polymerization, or have the ability to disintegrate upon initiation of free radical acrylic polymerization with the first compound. Examples of other suitable monomers that have the ability to stop chain growth include, but are not limited to, functionalized styrene (preferably with substituents at positions 2 and 6), functionalized vinyltoluene, functionalized α-methylstyrene, functionalized diphenylethylene, dinaphthaleethylene functionalized and combinations thereof. In any case, the monomer is preferably present in the acrylic polymer in an amount from 1 to 20, more preferably from 3 to 10 parts by weight based on the total weight of the acrylic polymer. When the monomer including the functionality of the vinyl is used, an initiator is used to initiate free radical acrylic polymerization between the monomer and the first compound. As understood by those skilled in the art, a wide variety of primers can be used. However, it is preferred that the initiator be selected from the group of inorganic persulfates such as ammonium persulfate, (NH) 2S208, potassium persulfate, K2S208 and sodium persulfate, Na2S208, dialkyl peroxides such as di-terbonate peroxide. butyl and dicumyl peroxide, hydroperoxides such as eumeno hydroperoxides and tert-butyl hydroperoxide, peresters such as tert-butyl peroctoate (TBPO), which is also known as tert-butyl peroxy-2-ethylhexanoate, tert-butyl perbenzoate , tert-butyl perpivalate, tert-butyl per-3, 4, 5-tritylhexanoate and tert-butyl per-2-ethylhexanoate, azo compounds and combinations thereof. Suitable azo compounds include, but are not limited to Vazo® 52, 64, 67 and the like. Vazo® 52, 64 and 67 are respectively 2, 2'-azobis (2,4-dimethylpentan-nitrile), 2,2'-azobis (2-methylpropan-nitrile), and 2, 2'-azobis (2-methylbutan -nitrile). Inorganic peroxodisulfates and ammonium or alkali metal peroxydiphosphates can also be used to initiate the free-radical acrylic polymerization method. More preferably, the initiator is tert-butyl peroctoate. In another embodiment, the monomer includes a radical-forming portion instead of the functionality of the vinyl. The term "radical-forming portion" is defined as any portion of the monomer that disassociates in the presence of a catalyst, up to the application of heat or through any other known method for disassociating the monomer. In addition, the monomer includes a functionality that may be functional with hydroxyl or a hydroxyl-reactive functionality, depending on the functionality of the core molecule that is used. After the dissociation of the monomer, the radical-forming portion of the monomer has a free radical. Preferably, the monomer includes the radical-forming portion, which preferably includes a peroxide and a hydroxyl functionality. The functionality of the hydroxyl can be reacted with the core molecule which includes a functionality reactive to the hydroxyl. A preferred monomer is Cyclonox®E, which is commercially available from A zo-Nobel. Cyclonox® E is di- (1-hydroxycyclohexyl) peroxide, which is of the formula: The di- (1-hydroxycyclohexyl) d soc ac ndix results in oxygen-oxygen bond division, leaving two compounds radicalized that each has the free radical in the oxygen atom that was part of the oxygen-oxygen bond before dissociation, as shown by the following formula:
where "*" indicates the free radical. Other monomers that include the radical-forming portion and the functionality of the hydroxy are also suitable. Examples of such other monomers include, but are not limited to, VA-085 and VA-086, which may be characterized by azo compounds having hydroxyl functionality. VA-085 is of the formula:
and VA-086 is of the formula:
In other embodiments, instead of the functionality of the hydroxyl, the monomer may include a hydroxyl-reactive functionality and a radical-forming portion. The hydroxyl-reactive functionality can react with the core molecule which includes a hydroxyl functionality. A suitable monomer can be formed from Vazo 67 by converting the cyano functionality to an amino or amido functionality. The amino or amido functionality can then be reacted with isocyanate or aminoplast, respectively. As stated previously, the first compound is reactive with the monomer that forms the functionalized intermediate. When the monomer which includes the functionality of the vinyl is used, the first compound is reactive with the functionality of the vinyl after the initiator initiates free radical acrylic polymerization. When the monomer including the radical-forming portion is used, the first compound is reactive with the radical-forming portion of the monomer. More specifically, it is the functionality of the vinyl of the first compound that is reactive with either the functionality of the vinyl monomer after initiation or the free radical portion of the monomer after dissociation, depending on the monomer used. The first compound having the functionality of the vinyl and the functionality of the epoxy can be an acrylate or methacrylate of epoxy functionality. Preferably, the first compound is selected from the group consisting of glycidyl acrylate, glycidyl acrylates and combinations thereof. For descriptive purposes, a chemical representation of glycidyl methacrylate is described below.
As stated above, the functionality of the vinyl is reactive with the monomer. The functionality of the epoxy is non-reactive with the hydroxyl or the reactive functionality of the hydroxyl either of the monomer or of the core molecule under conditions of objective reaction. In other words, the functionality of the epoxy remains non-reactive in the acrylic polymer and is presented to participate in the additional reactions, which will be described in further detail below.
The acrylic polymer may further include the reaction product of a second compound that is reactive with the monomer and the first compound to form the functionalized intermediate. The second compound can be included to modify a glass transition temperature Tg of the cured film formed from the curable coating composition, which curable coating composition will be described in further detail below. In addition, the second compound can also function to modify the equivalent weight and, therefore, the crosslink density in the cured film. Preferably, the second compound is selected from the group of, but is not limited to, acrylates, methacrylates, acrylonitriles, styrenes, alkenes, alkene anhydrides (cyclic or acyclic), and combinations thereof, each of which It has vinyl functionality. The second compound can be functionalized or non-functionalized with an additional functionality different from the functionality of the vinyl. More specifically, the second compound may include additional functionality as long as the additional functionality of the second compound is non-reactive with the functionalities of the monomer, the first compound or the core molecule. Preferably, the second compound is free of functionality different from the functionality of the vinyl.
In the preferred embodiment, the first compound, and optionally the second compound, is presented in a total amount from 10 to 99, more preferably from 15 to
90 parts by weight based on the total weight of the acrylic polymer. Preferably, the acrylic polymer has a molecular weight, Mw of 700 to 48,000. For the acrylic polymer having the molecular weight, Mw, within the above range, the functionalized intermediate described below preferably has a molecular weight Mw of about 300 to 12,000, more preferably from 1,000 to 4,000. Of course, higher molecular weights, Mw for the functionalized intermediate, are possible, but such functionalized intermediates are not ideal for curable coating compositions due to excessive resultant viscosity in the acrylic composition. As stated above, the first compound and the monomer react to form the functionalized intermediate. Assuming that the monomer is an isocyanate of a, a-dimethyl isopropenylbenzyl, that is, the monomer has the functionality reactive with hydroxyl and the functionality of the vinyl, with the first compound being glycidyl methacrylate, the functionalized intermediate described below is formed, in where INIT. represents the initiator and m varies from 1 to 80, most preferably from 15 to 30
The functionalized intermediate described above is equivalent to the functionalized acrylate ramifications of the acrylic polymer. That is, this functionalized intermediary functions as the branches for subsequent connection, through condensation, to the core of the acrylic polymer. The functionalized acrylate branches are formed first and the core, i.e., the core molecule, is then condensed with the functionalized acrylate branches. It will be understood that the intermediary functionalized above is simply an example of many different functionalized intermediates that can be formed during the reaction to form the acrylic composition and the subject invention is not necessarily limited to this particular functionalized intermediate and subsequent derivatives thereof. For example, when the monomer is di (1-hydroxycyclohexyl) peroxide, that is, the monomer having the radical forming portion and the functionality of the hydroxyl, and the first compound is glycidyl methacrylate, the functionalized intermediate is formed, where m varies preferably from 1 to 80, more preferably from 15 to 30. The functionalized intermediate is described below.
where "*" indicates the free radical. The functionalized intermediate can be terminated, in the free radical, through a number of termination reactions such as through a proton extraction from a solvent reaction with another radicalized compound, the decomposition that forms a double bond at the site of free radical or any combination of those reactions. Once the functionalized intermediate is formed, the core molecule is introduced to react with the functionalized intermediate that forms the acrylic polymer. The core molecule is selected to provide a functionality that is reactive with the functionality of the monomer that remains non-reactive after polymerization with the first compound. As described above, the core molecule is highly branched and is polyfunctional, that is, it has a functionality greater than or equal to 2. For the purposes of this invention, the term "highly branched" indicates core molecules that initiate with a core and branches into at least two, preferably at least three or more directions. Although excessive branching is not required, it is more preferred that the core molecule, preferably an isocyanate or a polyol, be highly branched to achieve the desired viscosity benefits. The core molecules can also be described as branched compounds having a plurality of functionalities. The functionalities can be primary functionalities, secondary and tertiary. The core molecule is selected from the group of isocyanates, isocyanurates, melamines, polyols, polycarboxylic acid halides and combinations thereof, with the core molecule reactive with the intermediate functionalized to form the acrylic polymer. However, other potential core molecules could be different than those mentioned above and could provide functionality different from those described above. For example, the core molecule can also be a melamine-formaldehyde resin. Preferred core molecules when the functionalized intermediate has the functionality reactive with hydroxyl, ie, wherein the monomer is a, a-dimethyl isopropenylbenzyl isocyanate having the functionality of the aliphatic isocyanate, including polyols that are reactive with the functionalized intermediate for form the acrylic polymer. Preferably, the polyols are selected from the group of glycerol, propylene glycol, erythritol, pentaerythritol, dipentaerythritol, trimethylolethane, trimethylolpropane, dulcitol, threitol and combinations thereof. For descriptive purposes, a chemical representation of pentaerythritol is described below.
The preferred core molecules for reacting with the functionalized intermediate having the functionality of the hydroxyl, ie, wherein the monomer is the peroxide having the functionality of the hydroxyl, which includes isocyanates, isocyanurates, melamines, carboxylic acid halides and combinations of the same ones that are reactive with the functionalized intermediate to form the acrylic polymer. More preferred core molecules for reacting with the functionalized intermediate having hydroxyl functionality include isocyanates. Preferably, isocyanates are selected from the group of trimethylolpropane carbamate with toluene diisocyanate, pentaerythritol carbamate with toluene diisocyanate, and combinations thereof. Other preferred isocyanates include polyisocyanate Desmodur® or Mondur® commercially available from Mobay Corporation of Pittsburgh, PA. For descriptive purposes, a chemical representation of the pentaerythritol carbamate with toluene diisocyanate is described below.
The core molecule is condensed with the functionalized intermediate, that is, with the functionalized acrylate branches. More specifically, the core molecule and the functionalized intermediate are reacted to form the acrylic polymer. The success of the condensation of the core molecule and the functionalized intermediate depends on the observation that when the monomer is used to polymerize the first compound, each of the polymer strands formed will have one and only one functionality that originates from the monomer in the greater one of the cases. The amount of the core molecule present in the reaction must be balanced with the amount of the functionalized intermediate, i.e., the branching of functionalized acrylate, which is formed through the reaction of the monomer, the first compound, and, optionally, the second compound. For this purpose, it is preferred that the molar ratio of the core molecule to the functionalized intermediate is from 1:20 to 1: 1, more preferably from 1:10 to 1: 3. The core molecule establishes a foundation for the acrylic polymer. Preferably, the core molecule is present in an amount from 0.1 to 20, more preferably from 0.5 to 10, and more preferably from 0.5 to 1.5 parts by weight based on the total weight of the acrylic polymer. When the monomer is a, a-dimethyl isopropenylbenzyl isocyanate, the first compound is glycidyl methacrylate, the second compound is not present, and the core molecule is pentaerythritol, the acrylic polymer is described below, wherein INIT. represents the initiator and m varies from 1 to 80, most preferably from 15 to 30.
When the monomer is di- (1-hydroxy cyclohexyl) peroxide, the first compound is glycidyl methacrylate, and the core molecule is pentaerythritol carbamate with toluene diisocyanate, the acrylic polymer is described below, wherein m varies from 1 to 80, more preferably from 15 to 30, and the "*" indicates the free radical, which can be terminated as described above.
Preferably, the acrylic polymer is present in the acrylic composition in an amount of from 10 to 80 parts by weight based on the total weight of the acrylic composition, more preferably from 30 to 60 parts by weight based on the weight total of the acrylic composition. As suggested above, the acrylic composition also includes, in addition to the acrylic polymer, the carboxylic acid compound and / or the alkyl carbamate.
In one embodiment, the acrylic polymer, the carboxylic acid compound and the alkyl carbamate are reacted as soon as those components are combined. Alternatively, the acrylic polymer, the carboxylic acid compound and the alkyl carbamate are combined together and remain unreactive until such time as the reaction between the acrylic polymer is desired., the carboxylic acid compound and the alkyl carbamate. During the reaction, the acrylic polymer and the carboxylic acid compound react to form an acrylic polymer functional with hydroxyl. The reaction between the acrylic polymer and the carboxylic acid compound can be achieved by heating the acrylic composition including those components at a temperature of about 130 ° C. A trans-esterification process is used to react the hydroxyl-functional acrylic polymer with the alkyl carbamate. More specifically, the functionality of the hydroxyl functional hydroxyl acrylic polymer and the alkyl carbamate reacts to form the acrylic composition that includes the functionality of the primary carbamate. This reaction is carried out at elevated temperatures, preferably in the presence of an organometallic catalyst, and may occur at the same time with the reaction between the acrylic polymer and the carboxylic acid compound, when the acrylic polymer, the carboxylic acid compound and the alkyl carbamate are presented together. In another embodiment, the acrylic polymer and the carboxylic acid compound are reacted to form the hydroxyl-functional acrylic polymer. The alkyl carbamate is subsequently added to, and reacted with the hydroxyl-functional acrylic polymer to form the acrylic composition. The organometallic catalyst can also be added before or during the addition of the alkyl carbamate to the hydroxyl functional acrylic polymer. The acrylic composition can be combined with the crosslinking agent which is reactive with the acrylic composition to form the curable coating composition. As suggested above, the carboxylic acid compound has a carboxylic acid functionality and preferably a hydroxyl functionality. The carboxylic acid functionality is reactive with the functionality of the epoxy of the acrylic polymer to form the hydroxyl-functional acrylic polymer. Preferably, when the hydroxyl functionality is presented, the carboxylic acid compound is selected from the group of hydroxy acid compounds, dihydroxy acid compounds, trihydroxy acid compounds and combinations thereof. The amount of hydroxyl functionalities in the carboxylic acid compound contribute to the crosslink density in the cured film, with more hydroxyl functionalities corresponding to a higher crosslink density. The carboxylic acid compound includes at least one carboxylic acid functionality. The carboxylic acid compound can be further defined as an alkanoic acid having from 1 to 30 carbon atoms, such as acetic acid, nanoic acid, etc. Suitable alkanoic acids can be selected from the group of, but not limited to glycolic acid, 3-hydroxypropionic acid and isomers thereof, 3-hydroxypropionic acid and isomers thereof, 3-hydroxybutyric acid, 3-hydroxyisobutyric acid, dimethylolpropionic acid , lactic acid, 12-hydroxystearic acid and combinations thereof. For descriptive purposes, a chemical representation of dimethylolpropionic acid, which has a carboxylic acid functionality and two hydroxyl functionalities, is described below.
Preferably, the carboxylic acid compound is present in the acrylic composition in an amount from 1 to 30, more preferably from 5 to 20, parts by weight based on the total weight of the acrylic composition. For descriptive purposes, a chemical representation of a portion of the hydroxyl-functional acrylic polymer formed by the reaction of one mole of dimethylpropionic acid and one mole of the acrylic polymer is described below.
Acrylic
where the label of "Acrylic Polymer" corresponds to the structure of any of the acrylic polymers represented graphically above, R corresponds to either the initiator or the free radical, depending on the monomer used, and m is from 1 to 80, greater Preferably from 15 to 30. As illustrated, the functionality of the carboxylic acid of the carboxylic acid compound and the functionality of the epoxy of the acrylic polymer have reacted through a ring opening reaction, which results in the formation of the functionality of the hydroxyl and the binding of the carboxylic acid compound to the acrylic polymer. The above chemical representation is not limited to any of the two specific embodiments of the acrylic polymer as described above. The alkyl carbamate is reactive with the hydroxyl functional acrylic polymer, more specifically the functionality of the hydroxyl functional hydroxyl acrylic polymer, to form the acrylic composition, which has carbamate functionality. Preferably, the alkyl carbamate has from 1 to 20 carbon atoms in the alkyl chain, and is generally defined as
wherein R is the alkyl chain having from 1 to 20 carbon atoms. Preferably, the alkyl carbamate is selected from the group of, but not limited to, methyl carbamate, ethyl carbamate, propyl carbamate, butyl carbamate, propylene glycol monocarbamate and combinations thereof. The most preferred alkyl carbamate compound comprises methyl carbamate. Preferably, the alkyl carbamate is present in the acrylic composition in an amount of from 5 to 30, preferably from 15 to 25 parts by weight based on 100 parts by weight of the acrylic composition. Also, the preferred ratio of effective equivalents of the carboxylic acid compound to the alkyl carbamate compound is from 1: 1 to 1:10. The amount of the alkyl carbamate used in the acrylic composition is dependent on the number of hydroxyl functionalities in the hydroxyl-functional acrylic polymer. The total number of moles of the carbamate compound is generally equal to the number of hydroxyl functionalities in the hydroxyl-functional acrylic polymer, which results preferably in the consumption of all hydroxyl functionality in the hydroxyl-functional acrylic polymer. Therefore, in the preferred embodiment, the molar ratio of the carbamate compound, for example, methyl carbamate to the carboxylic acid compound, for example, dimethylolpropionic acid, is 3: 1 because, after the reaction of one mol of dimethylolpropionic acid with the functionality of the epoxy of the acrylic polymer, three moles of hydroxyl functionality are presented in the acrylic composition. If the carboxylic acid compound is lactic acid, which has a hydroxyl functionality and a carboxylic acid functionality, then two moles of the carbamate compound are preferably used for each mole of the lactic acid to prepare the acrylic composition, since two moles of functionality of the hydroxyl are presented in the acrylic composition after the lactic acid and the acrylic polymer react. Of course, acrylic compositions formed from lower equivalents of the alkyl carbamate were not excluded. For example, as a non-limiting example, if there are three moles of hydroxyl functionality, and only two moles of the carbamate compound are used, then the acrylic composition will have both the carbamate and the hydroxyl functionality. When the functionality of the carbamate and hydroxyl are presented, the amount of the crosslinking agent can be limited, as described in further detail below, to avoid crosslinking with the functionality of the hydroxyl. For descriptive purposes, a chemical representation of the acrylic composition formed by the reaction of the methyl carbamate and the acrylic polymer, with a 3: 1 ratio of the alkyl carbamate to the dimethylolpropionic acid, is described below.
Acrylic Polymer
The above chemical representation is valid for any of the two preferred embodiments of the acrylic polymer as described above, wherein the label "Acrylic Polymer" corresponds to the structure of the respective embodiment of the acrylic polymer, R corresponds to either the initiator or the radical free, depending on the monomer used, and m is from 1 to 80, more preferably from 15 to 30. The chemical representation of the acrylic composition described above is merely illustrative of the subject invention. The acrylic composition described above has three carbamate functionalities which are derived from the structures of the carboxylic acid compound and the alkyl carbamate, in the dimethylolpropionic acid and the methyl carbamate of the preferred embodiment, respectively. It will be understood that if the alternative compounds are selected for the carboxylic acid compound and the alkyl carbamate, then the acrylic compositions may be different than those described above, and may have more or less carbamate functionalities. As suggested above, the curable coating composition including the acrylic composition also includes the crosslinking agent which is reactive with the carbamate functionality and, optionally, the hydroxyl functionality of the acrylic composition. Suitable cross-linking agents are selected from the group of, but are not limited to, polyisocyanates, polyisocyanurates, melamine-formaldehyde resins, polycarboxylic acid halides and combinations thereof. Also suitable for the crosslinking agent are aminoplast resins which are reactive with the functionality of the carbamate. As understood by those skilled in the art, an aminoplast resin is formed by the reaction product of a formaldehyde and an amine wherein the preferred amine is a urea or a melamine. In other words, the aminoplast resin may include urea resins and melamine-formaldehyde resins. The melamine-formaldehyde resins of the preferred embodiment include either a methylol functionality, an alkoxymethyl functionality or both. The functionality of the alkoxymethyl is of the general formula -CH20R, wherein Ri is an alkyl chain having from 1 to 20 carbon atoms. As understood by those skilled in the art, the functionality of the methylol and the functionality of the alkoxymethyl are reactive with the carbamate functionality of the acrylic composition. The functionalities of methylol and alkoxymethyl are preferably reactive with the functionality of the carbamate, when they are opposed to any functionality of the hydroxyl, for? "crosslinking" the curable coating composition to cure. Examples of suitable aminoplast resins include, but are not limited to, monomeric or polymeric melamine-formaldehyde resins, including melamine resins that are partially or fully alkylated using alcohols preferably having one to six, more preferably one to four, carbon atoms. , such as melamine methylated with hexametoxy; urea formaldehyde resins including methylol ureas and siloxy ureas such as a butylated urea formaldehyde resin, alkylated benzoguanimines, guanyl ureas, guanidines, biguanidines, polyiguanidines and the like. Although urea and melamine are the preferred amines, other amines such as triazines, triazoles, diazines, guanidines or guanamines can also be used to prepare the aminoplast resins. In addition, although formaldehyde is preferred to form the aminoplast resin, other aldehydes, such as acetaldehyde, crotonaldehyde and benzaldehyde may also be used. The monomeric melamine-formaldehyde resins are particularly preferred. The melamine-formaldehyde resin includes hexametoxymethylmelamine (HMMM). The HMMM is commercially available from Solutia under its Amino Resimene Retinulant Resins. HMMM is shown in the following chemical presentation.
Until the addition of the crosslinking agent to the acrylic composition, the functionality of the alkoxymethyl of the HJYMM, specifically the group CH2OCH3 and the functionality of the carbamate of the acrylic polymer reacts to establish urethane ligaments (-NH-C0-0-). The urethane ligament between the acrylic composition and the crosslinking agent is from the carbamate-melamine reaction and is ideal for resistance to environmental acid attack. Because the acrylic composition of the present invention has functionality of the terminal carbamate and because the aminoplast is reactive with the functionality of the carbamate, the ether ligaments resulting from a hydroxyl-aminoplast cure functionality, and the which are particularly susceptible to acid attack, can be avoided as the primary crosslinking mechanism. To achieve this, the amount of the crosslinking agent, for example, the aminoplast resin, can be limited so that the crosslinking agent reacts only with the functionality of the available carbamate in the acrylic composition. That is, in the preferred embodiment, the aminoplast crosslinking agent preferably reacts with a carbamate functionality available before any substantial reaction with the hydroxyl functionality that occurs in the acrylic composition. It is therefore possible to control the amount of ether ligaments that are formed when the acrylic composition and the crosslinking agent are crosslinked. The amount of the crosslinking agent can be increased if crosslinking with hydroxyl functionality is desired. Although not necessarily preferred, an alternative crosslinking agent for use in the subject invention is the polyisocyanate crosslinking agent. The most preferred polyisocyanate crosslinking agent is a triisocyanurate. The polyisocyanate crosslinking agent can be an aliphatic polyisocyanate including a cycloaliphatic polyisocyanate or an aromatic polyisocyanate. The term "polyisocyanate" as used herein refers to any compound having a plurality of isocyanate functionalities on average per molecule. The polyisocyanates include, for example, monomeric polyisocyanates including monomeric diisocyanates, biurets and isocyanurates of monomeric polyisocyanates, extended polyfunctional isocyanates formed by reacting one mole of a diol with two moles of a diisocyanate or one mole of a triol with three moles of a diisocyanate and the like . Useful examples of suitable polyisocyanate crosslinking agents include, without limitation, ethylene diisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, 1,4-butylene diisocyanate, lysine diisocyanate, 1,4-methylene bis (isocyanate of cyclohexyl), isophorone diisocyanate, toluene diisocyanate, toluene diisocyanate isocyanurate, 4,4'-diphenylmethane diisocyanate, 4,4'-isocyanurate diphenylmethane diisocyanate, methylenebis-4,4'-isocyanatocyclohexane, diisocyanate of isophorone, isocyanurate of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate isocyanurate, 1,4-cyclohexane diisocyanate, p-phenylene diisocyanate, 4,4'4" Triphenylmethane triisocyanate, tetramethylxylene diisocyanate, metaxylene diisocyanate and combinations thereof Aliphatic polyisocyanates are preferred when the curable coating composition is used as a finishing composition or automotive end. Generally, the acrylic composition is presented in an amount from 65 to 90, preferably from 75 to 90 parts by weight based on the total weight of the curable coating composition and the crosslinking agent is presented in an amount from 1 to 35, preferably from 5 to 25, and more preferably from 7 to 15 parts by weight based on 100 parts by weight of the curable coating composition. The ratio of the effective equivalents of the acrylic composition to the crosslinking agent is from 3: 1 to 1: 3. The curable coating composition may also include an additive or a combination of additives. Such additives include, but are not limited to solvents, catalysts, hindered amine light stabilizers (HALs), ultraviolet absorbers (UVAs), rheology control agents, anti-yellowing agents, adhesion promoting agents and the like. Specific examples of some of the above additives include n-methyl pyrrolidone and oxo-hexyl acetate as solvents for affecting such characteristics as launch and release resistance, and polybutyl acrylate, fumed silica and silicone as rheology control agents. The following examples illustrating the formation and use of the acrylic composition of the present invention, as presented therein, are intended to illustrate and not limit the invention.
EXAMPLES In the Examples, Polymer A Acrylic was prepared by adding and reacting the following components, in parts by weight based on the total weight of the acrylic composition, unless otherwise indicated.
Table 1
To form Acrylic Polymer A, 75.0 grams of Solvesso® 100 (also referred to as Aromatic 100) were added into a reactor, and the reactor was heated through a conventional heat supply at a temperature of 150 ° C. Once the reactor reached 150 ° C, a mixture of the Functionalized Monomer, the First Compound, the Second Compound A, the Second Compound B, and the Initiator were added to the reactor for about 3 hours to form the functionalized intermediate. Once the functionalized intermediate was formed, the temperature was decreased until the temperature of the functionalized intermediate reached approximately 100-110 ° C. Then, Nucleus A Molecule was added to the reactor along with an additional 11 grams of Solvesso® 100. One drop of DBTDL was added. The reaction was maintained up to 100 ° C until the% measured of? CO was less than 0.1 meq in solids. Polymer B Acrylic was prepared by adding and reacting the following components, in parts by weight based on the total weight of the acrylic composition, unless otherwise indicated.
Table 2
To form the acrylic polymer, 75.0 grams of Solvesso® 100 (also referred to as Aromatic 100) would be added into a reactor, and the reactor would be heated through a conventional heat supply at a temperature of 121 ° C. Once the reactor reached 121 ° C, a mixture of the Functionalized Monomer, the First Compound, the Second Compound A and the Second Compound B according to Table 2 would be added to the reactor for about 3 hours to form the functionalized intermediate. Once the functionalized intermediate is formed, the temperature will be lowered until the temperature of the functionalized intermediate reaches approximately 100-110 ° C. Then, the core molecule will be added to the reactor along with an additional 11 grams of Solvesso® 100. A drop of DBTDL will also be added and the reaction will be maintained at 100 ° C until the% of NCO measurements is less than 0.02 meq. solid Acrylic Composition A is prepared and the
Composition B of Acrylic would be prepared by adding and reacting the following components, in parts by weight based on the total weight of the acrylic composition, unless otherwise indicated.
Table 1
For Table 3 above, 40 grams of DMPA and 220 grams of Acrylic Polymer A were reacted at 110 ° C in a reaction flask until more than 90% of the epoxide of Polymer A Acrylic had reacted. Alternatively, 272 grams of Acrylic Polymer B for Acrylic Polymer A can be substituted and reacted in the same manner as above. After verification of IR spectroscopy to confirm that the majority (> 90%) of DMPA had reacted, 30 grams of toluene, 75 grams of methyl carbamate and 0.1 grams of dibutyltin oxide were charged into the reaction flask. The reaction flask, including the reaction product of DMPA and Polymer A Acrylic, together with the methyl carbamate, dibutyltin oxide and toluene is heated with a conventional heat supply at a temperature of 120 to 135 ° C for Form Acrylic Composition A that has carbamate functionality. The secondary product of methanol, which results from the production of Acrylic Composition A, is removed during the reaction. The extension of the reaction was monitored by titrating the presence of the hydroxyl functionality. When more than 90% of the hydroxyl functionalities were converted into carbamate functionalities, vacuum was applied to the reaction flask to remove any methyl carbamate that remained unreactive until less than 0.2 parts by weight of the methyl carbamate were present., based on the total solids in the reaction flask. The reaction mixture was cooled to about 60 to 70 ° C and 100 grams of amyl acetate was added to completely disperse Acrylic Composition A. The total reaction time for the Acrylic Polymer A to react with the DMPA, and then the subsequent reaction with the methyl carbamate is about 30 hours. Acrylic Composition A has a non-volatile% of about 70 parts by weight based on the total weight of Acrylic Composition A. The invention has been described in an illustrative manner, and it will be understood that the terminology which has been used is intended to be in the nature of the words of the description rather than limitation. Obviously, many modifications and variations of the present invention are possible in light of the above teachings, and the invention may be practiced otherwise than as specifically described.
Claims (53)
- CLAIMS 1. An acrylic composition, comprising the reaction product of: A) an acrylic polymer comprising the reaction product of; i) a functionalized monomer; ii) a first compound reactive with such functionalized monomer to form a functionalized intermediate, the first compound comprises a functionality of the vinyl reactive with the functionalized monomer and an epoxy functionality; and iii) a highly branched polyfunctional core molecule reactive with the functionalized intermediate to form the acrylic polymer; B) a carboxylic acid compound comprising a carboxylic acid functionality that is reactive with such functionality of the epoxy of the acrylic polymer to form an acrylic polymer functional with hydroxyl; and C) an alkyl carbamate that is reactive with an acrylic polymer functional with hydroxyl to form the acrylic composition.
- 2. An acrylic composition as set forth in claim 1, wherein the carboxylic acid compound further comprises a hydroxyl functionality.
- 3. An acrylic composition as set forth in claim 1, wherein the carboxylic acid compound has at least one carboxylic acid functionality.
- 4. An acrylic composition as set forth in claim 3, wherein the carboxylic acid compound is further defined as an alkanoic acid having from 1 to 30 carbon atoms.
- An acrylic composition as set forth in claim 4, wherein the alkanoic acid is selected from the group of glycolic acid, 3-hydroxypropionic acid and isomers thereof, 3-hydroxypropionic acid and isomers thereof, 3-hydroxybutyric acid , 3-hydroxyisobutyric acid, dimethylolpropionic acid, lactic acid, 12-hydroxystearic acid and combinations thereof.
- 6. An acrylic composition as set forth in claim 1, wherein the alkyl carbamate has from 1 to 20 carbon atoms in the alkyl chain.
- 7. An acrylic composition as set forth in claim 6, wherein the alkyl carbamate is selected from the group of methyl carbamate, ethyl carbamate, propyl carbamate, butyl carbamate, propylene glycol monocarbamate and combinations thereof.
- 8. An acrylic composition as set forth in claim 1, wherein the ratio of the effective equivalents of the carboxylic acid compound to the alkyl carbamate is from 1: 1 to 1:10.
- 9. An acrylic composition as set forth in claim 1, further comprising an organometallic catalyst for catalyzing the reaction between the alkyl carbamate and the hydroxyl functional acrylic polymer.
- 10. An acrylic composition as set forth in claim 9, wherein the organometallic catalyst comprises dibutyltin oxide.
- 11. An acrylic composition as set forth in claim 1, wherein the functionalized monomer comprises the hydroxyl reactive functionality and the functionality of the vinyl.
- 12. An acrylic composition as set forth in claim 11, wherein the hydroxyl-reactive functionality comprises an aliphatic isocyanate functionality.
- 13. An acrylic composition as set forth in claim 12, wherein the functionalized monomer comprises a, a-dimethyl isopropenylbenzyl isocyanate.
- 14. An acrylic composition as set forth in claim 11, wherein the first compound is selected from the group of glycidyl acrylate, glycidyl acrylates and combinations thereof.
- 15. An acrylic composition as set forth in claim 11, wherein the core molecule comprises a polyol reactive with the intermediate functionalized to form the acrylic polymer.
- 16. An acrylic composition as set forth in claim 15, wherein the polyol is selected from the glycerol group, propylene glycol, erythritol, pentaerythritol, dipentaerythritol, trimethylolethane, trimethylolpropane, dulcitol, threitol and combinations thereof.
- 17. An acrylic composition as set forth in claim 11, wherein the acrylic polymer further comprises the reaction product of an initiator selected from the group of inorganic persulfates, dialkyl peroxides, hydroperoxides, peresters, azo compounds and combinations of the same .
- 18. An acrylic composition as set forth in claim 1, wherein the functionalized monomer comprises a hydroxyl functionality and a vinyl functionality.
- 19. An acrylic composition as set forth in claim 18, wherein the core molecule is selected from the group of isocyanates, isocyanurates, melamines, carboxylic acid halides, and combinations thereof with the core molecule reactive with the functionalized intermediate. to form the acrylic polymer.
- 20. An acrylic composition as set forth in claim 1, wherein the functionalized monomer comprises a radical-forming portion and a hydroxyl functionality.
- 21. An acrylic composition as set forth in claim 20, wherein the functionalized monomer comprises di- (1-hydroxycyclohexyl) peroxide.
- 22. An acrylic composition as set forth in claim 20, wherein the first compound is selected from the group of glycidyl acrylate, glycidyl acrylates and combinations thereof.
- 23. An acrylic composition as set forth in claim 20, wherein the core molecule is selected from the group of isocyanates, isocyanurates, melamines, carboxylic acid halides, and combinations thereof with the core molecule reactive with the intermediate. functionalized to form the acrylic polymer.
- 24. An acrylic composition as set forth in claim 1, wherein the functionalized monomer comprises a radical-forming portion and a hydroxyl-reactive functionality.
- 25. An acrylic composition as set forth in claim 24, wherein the functionalized monomer is selected from the group of isocyanates, isocyanurates, melamines, carboxylic acid halides and combinations thereof.
- 26. An acrylic composition as set forth in claim 24, wherein the first compound is selected from the group of glycidyl acrylate, glycidyl acrylates and combinations thereof.
- 27. An acrylic composition as set forth in claim 24, wherein the core molecule comprises a polyol reactive with the intermediate functionalized to form the acrylic polymer.
- 28. An acrylic composition as set forth in claim 1, wherein the acrylic polymer further comprises the reaction product of a second compound that comprises a functionality of the vinyl and is reactive with the functionalized monomer and the first compound to form the intermediate functionalized
- 29. An acrylic composition as set forth in claim 28, wherein the second compound is selected from the group of acrylates, methacrylates, acrylonitriles, styrenes and combinations thereof.
- 30. An acrylic composition as set forth in claim 1, wherein the functionalized monomer comprises a, a-dimethyl isopropenylbenzyl isocyanate, the first compound comprises glycidyl acrylate or glycidyl methacrylate, the core molecule comprises pentaerythritol, the compound of carboxylic acid comprises dimethylolpropionic acid, and the alkyl carbamate comprises methyl carbamate.
- 31. An acrylic composition as set forth in claim 1, wherein the functionalized monomer comprises di- (1-hydroxycyclohexyl) peroxide, the first compound comprises glycidyl acrylate or glycidyl methacrylate, the core molecule comprises trimethylolpropane carbamate. with toluene diisocyanate or pentaerythritol carbamate with toluene diisocyanate, the carboxylic acid compound comprises dimethylolpropionic acid, and the alkyl carbamate comprises methyl carbamate.
- 32. A curable coating composition, comprising: (A) an acrylic composition comprising the reaction product of; i) an acrylic polymer comprising the reaction product of; a) a functionalized monomer; b) a first compound reactive with the functionalized monomer to form a functionalized intermediate, the first compound comprises a functionality of the vinyl reactive with the monomer and the functionality of the epoxy; and c) a highly branched polyfunctional core molecule reactive with the functionalized intermediate to form the acrylic polymer; ii) a carboxylic acid compound comprising a carboxylic acid functionality that is reactive with the functionality of the epoxy of the acrylic polymer to form an acrylic polymer functional with hydroxyl; and iii) an alkyl carbamate which is reactive with a hydroxyl-functional acrylic polymer to form the acrylic composition; and (B) a crosslinking agent reactive with the acrylic composition.
- 33. A curable coating composition as set forth in claim 32, wherein the carboxylic acid compound comprises dimethylolpropionic acid.
- 34. A curable coating composition as set forth in claim 33, wherein the alkyl carbamate comprises methyl carbamate.
- 35. A curable coating composition as set forth in claim 34, wherein the first compound is selected from the group of glycidyl acrylate, glycidyl acrylates and combinations thereof.
- 36. A curable coating composition as set forth in claim 35, wherein the functionalized monomer comprises a, a-dimethyl isopropenylbenzyl isocyanate.
- 37. A curable coating composition as set forth in claim 36, wherein the core molecule is selected from the group of glycerol, propylene glycol, erythritol, pentaerythritol, dipentaerythritol, trimethylolethane, trimethylolpropane, dulcitol, threitol and combinations thereof with the reactive nucleus with the functionalized intermediate to form the acrylic polymer.
- 38. A curable coating composition as set forth in claim 35, wherein the functionalized monomer comprises di- (1-hydroxy cyclohexyl) peroxide.
- 39. A curable coating composition as set forth in claim 38, wherein the core molecule is selected from the group of isocyanates, isocyanurates, melamines, carboxylic acid halides and combinations thereof with the core molecule reactive with the intermediate functionalized to form the acrylic polymer.
- 40. A curable coating composition as set forth in claim 32, wherein the acrylic composition further comprises dibutyltin oxide to catalyze the reaction between the alkyl carbamate and the hydroxyl functional acrylic polymer.
- 41. A curable coating composition as set forth in claim 32, wherein the crosslinking agent is selected from the group of polyisocyanates, polyisocyanurates, melamine-formaldehyde resins, polycarboxylic acid halides and combinations thereof.
- 42. A curable coating composition as set forth in claim 32, wherein the crosslinking agent comprises an aminoplast resin reactive with the functionality of the carbamate.
- 43. A curable coating composition as set forth in claim 42, wherein the aminoplast resin is selected from the group of melamine-formaldehyde resins having methylol functionality, alkoxymethyl functionality and combinations thereof, which are reactive with the carbamate functionality.
- 44. A curable coating composition as set forth in claim 32, wherein the ratio of the effective equivalents of the acrylic composition to the crosslinking agent is from 3: 1 to 1: 3.
- 45. A curable coating composition as set forth in claim 32, further comprising at least one additive selected from the group of solvents, catalysts, hindered amine light stabilizers, ultraviolet absorbers, rheology control agents, anti-yellowing agents , adhesion promotion agents and combinations thereof.
- 46. An acrylic composition, comprising: A) an acrylic polymer comprising the reaction product of; i) a functionalized monomer; ii) a first compound reactive with the functionalized monomer to form a functionalized intermediate, the first compound comprises a functionality of the vinyl reactive with the functionalized monomer and an epoxy functionality; and iii) a highly branched polyfunctional core molecule reactive with the functionalized intermediate to form the acrylic polymer; and B) a carboxylic acid compound comprising a carboxylic acid functionality that is reactive with such an epoxy functionality of the acrylic polymer.
- 47. An acrylic composition as set forth in claim 46, further comprising an alkyl carbamate.
- 48. An acrylic composition as set forth in claim 47, further comprising an organometallic catalyst.
- 49. An acrylic composition as set forth in claim 48, wherein the functionalized monomer comprises a, a-dimethyl isopropenylbenzyl isocyanate, the first compound comprises glycidyl acrylate or glycidyl methacrylate, the core molecule comprises pentaerythritol, the compound of The carboxylic acid comprises dimethylolpropionic acid, the alkyl carbamate comprises methyl carbamate, and the organometallic catalyst comprises dibutyltin oxide.
- 50. An acrylic composition as set forth in claim 48, wherein the functionalized monomer comprises a, a-dimethyl isopropenylbenzyl isocyanate, the first compound comprises glycidyl acrylate or glycidyl methacrylate, the core molecule comprises pentaerythritol, the carboxylic acid compound comprises dimethylolpropionic acid, the alkyl carbamate comprises carbamate, methyl and the organometallic catalyst comprises dibutyltin oxide.
- 51. An acrylic composition, comprising: A) an acrylic polymer comprising the reaction product of; i) a functionalized monomer; ii) a first compound reactive with the functionalized monomer to form a functionalized intermediate, the first compound comprises a functionality of the vinyl reactive with the functionalized monomer and an epoxy functionality; and iii) a highly branched polyfunctional core molecule reactive with the functionalized intermediate to form the acrylic polymer; and B) an alkyl carbamate.
- 52. An acrylic composition as set forth in claim 51, wherein the alkyl carbamate has from 1 to 20 carbon atoms in the alkyl chain.
- 53. An acrylic composition as set forth in claim 52, wherein the alkyl carbamate is selected from the group of methyl carbamate, ethyl carbamate, propyl carbamate, butyl carbamate, propylene glycol monocarbamate and combinations thereof.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11088217 | 2005-03-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA06008121A true MXPA06008121A (en) | 2007-04-20 |
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