US20010018516A1 - Oxazoline or oxazine acetoacetate aqueous coating compositions - Google Patents
Oxazoline or oxazine acetoacetate aqueous coating compositions Download PDFInfo
- Publication number
- US20010018516A1 US20010018516A1 US09/819,242 US81924201A US2001018516A1 US 20010018516 A1 US20010018516 A1 US 20010018516A1 US 81924201 A US81924201 A US 81924201A US 2001018516 A1 US2001018516 A1 US 2001018516A1
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- US
- United States
- Prior art keywords
- alkyl
- aryl
- hydrogen
- compound
- polymer
- 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.)
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- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 title claims description 17
- 239000008199 coating composition Substances 0.000 title description 3
- HKMCZKUUCRJTEH-UHFFFAOYSA-N 2h-oxazine;3-oxobutanoic acid Chemical compound N1OC=CC=C1.CC(=O)CC(O)=O HKMCZKUUCRJTEH-UHFFFAOYSA-N 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 39
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 125000003118 aryl group Chemical group 0.000 claims abstract description 35
- 229920001577 copolymer Polymers 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 29
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 5
- 239000013011 aqueous formulation Substances 0.000 claims description 19
- -1 O-ethyl-O Chemical group 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 19
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 239000000976 ink Substances 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 239000002966 varnish Substances 0.000 abstract description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 12
- 239000008096 xylene Substances 0.000 description 12
- 0 CC(=O)CC(=O)**C1=NC(C)(C)CCO1 Chemical compound CC(=O)CC(=O)**C1=NC(C)(C)CCO1 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical compound CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical class O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- NYEZZYQZRQDLEH-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1=NCCO1 NYEZZYQZRQDLEH-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical group CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 4
- JUTGVXOSFVZIQA-UHFFFAOYSA-N 4-(4,5-dihydro-1,3-oxazol-2-yl)aniline Chemical compound C1=CC(N)=CC=C1C1=NCCO1 JUTGVXOSFVZIQA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XFRBXZCBOYNMJP-UHFFFAOYSA-N 2,2,6-trimethyl-1,3-dioxin-4-one Chemical compound CC1=CC(=O)OC(C)(C)O1 XFRBXZCBOYNMJP-UHFFFAOYSA-N 0.000 description 3
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 description 3
- FUHDTKZENWNCEC-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazol-4-amine Chemical compound NC1COC(C=2C=CC=CC=2)=N1 FUHDTKZENWNCEC-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N C=O Chemical compound C=O WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- AEWOYSOMXYFKAQ-UHFFFAOYSA-N NC(=O)OCO Chemical compound NC(=O)OCO AEWOYSOMXYFKAQ-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 150000004893 oxazines Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- ZMPALKWGZDRORH-UHFFFAOYSA-N 3-(4,5-dihydro-1,3-oxazol-2-yl)aniline Chemical compound NC1=CC=CC(C=2OCCN=2)=C1 ZMPALKWGZDRORH-UHFFFAOYSA-N 0.000 description 2
- VEERNCWDIVHRAJ-UHFFFAOYSA-N 3-(4,5-dihydro-1,3-oxazol-2-yl)propan-1-ol Chemical compound OCCCC1=NCCO1 VEERNCWDIVHRAJ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FAHGFEDQAASJPB-UHFFFAOYSA-N CC(=O)CC(=O)NC1=CC=C(C2=NCCO2)C=C1 Chemical compound CC(=O)CC(=O)NC1=CC=C(C2=NCCO2)C=C1 FAHGFEDQAASJPB-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N O=CCO Chemical compound O=CCO WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- BLFLLBZGZJTVJG-UHFFFAOYSA-N benzocaine Chemical compound CCOC(=O)C1=CC=C(N)C=C1 BLFLLBZGZJTVJG-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- WSRZFRZYFAEPRQ-UHFFFAOYSA-N n-[2-(4,5-dihydro-1,3-oxazol-2-yl)ethyl]-n-methyl-3-oxobutanamide Chemical compound CC(=O)CC(=O)N(C)CCC1=NCCO1 WSRZFRZYFAEPRQ-UHFFFAOYSA-N 0.000 description 2
- BDLJSQSHTWFMJJ-UHFFFAOYSA-N n-[4-(4,4-dimethyl-5h-1,3-oxazol-2-yl)phenyl]-3-oxobutanamide Chemical compound C1=CC(NC(=O)CC(=O)C)=CC=C1C1=NC(C)(C)CO1 BDLJSQSHTWFMJJ-UHFFFAOYSA-N 0.000 description 2
- KRXOLXJZFXKJPQ-UHFFFAOYSA-N n-[4-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-n-methyl-3-oxobutanamide Chemical compound C1=CC(N(C(=O)CC(C)=O)C)=CC=C1C1=NCCO1 KRXOLXJZFXKJPQ-UHFFFAOYSA-N 0.000 description 2
- 150000002918 oxazolines Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JKUYRAMKJLMYLO-UHFFFAOYSA-N tert-butyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC(C)(C)C JKUYRAMKJLMYLO-UHFFFAOYSA-N 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PCXJASANFWPUMO-UHFFFAOYSA-N 1-(methylamino)propan-1-ol Chemical compound CCC(O)NC PCXJASANFWPUMO-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 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
- NACDQEGSPSVRIA-UHFFFAOYSA-N 2-(4,5-dihydro-1,3-oxazol-2-yl)-n-methylethanamine Chemical compound CNCCC1=NCCO1 NACDQEGSPSVRIA-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
- NQDAXIZYJRXVHV-UHFFFAOYSA-N 2-[4-(4,5-dihydro-1,3-oxazol-2-yl)phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1=NCCO1 NQDAXIZYJRXVHV-UHFFFAOYSA-N 0.000 description 1
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 description 1
- BTDQXGUEVVTAMD-UHFFFAOYSA-N 2-hydroxyethyl carbamate Chemical compound NC(=O)OCCO BTDQXGUEVVTAMD-UHFFFAOYSA-N 0.000 description 1
- FNWUQNABSKTOCF-UHFFFAOYSA-N 2-methylprop-2-enoic acid;2h-oxazine Chemical compound CC(=C)C(O)=O.N1OC=CC=C1 FNWUQNABSKTOCF-UHFFFAOYSA-N 0.000 description 1
- UNIJBMUBHBAUET-UHFFFAOYSA-N 3-(methylamino)propanenitrile Chemical compound CNCCC#N UNIJBMUBHBAUET-UHFFFAOYSA-N 0.000 description 1
- NJXPYZHXZZCTNI-UHFFFAOYSA-N 3-aminobenzonitrile Chemical compound NC1=CC=CC(C#N)=C1 NJXPYZHXZZCTNI-UHFFFAOYSA-N 0.000 description 1
- DPTAAAWYRZKBJK-UHFFFAOYSA-N 4,5-dihydro-1,3-oxazole;3-oxobutanoic acid Chemical class C1CN=CO1.CC(=O)CC(O)=O DPTAAAWYRZKBJK-UHFFFAOYSA-N 0.000 description 1
- JQUIMYYTLMGJGA-UHFFFAOYSA-N 4-(4,5-dihydro-1,3-oxazol-2-yl)-n-methylaniline Chemical compound C1=CC(NC)=CC=C1C1=NCCO1 JQUIMYYTLMGJGA-UHFFFAOYSA-N 0.000 description 1
- JEDXDYXIRZOEKG-UHFFFAOYSA-N 4-(methylamino)benzonitrile Chemical compound CNC1=CC=C(C#N)C=C1 JEDXDYXIRZOEKG-UHFFFAOYSA-N 0.000 description 1
- XFKYYYBLPPBMFP-UHFFFAOYSA-N 4-(oxazin-2-yl)aniline Chemical compound C1=CC(N)=CC=C1N1C=CC=CO1 XFKYYYBLPPBMFP-UHFFFAOYSA-N 0.000 description 1
- HSROVARPCNJMKS-UHFFFAOYSA-N 5-(4,5-dihydro-1,3-oxazol-2-yl)pentan-1-ol Chemical compound OCCCCCC1=NCCO1 HSROVARPCNJMKS-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LPZIJXAMOZMEPU-UHFFFAOYSA-N C1=CC=CC=C1.CC1=NCCO1.COCCOCCO Chemical compound C1=CC=CC=C1.CC1=NCCO1.COCCOCCO LPZIJXAMOZMEPU-UHFFFAOYSA-N 0.000 description 1
- NXXHWSKTYHMUBE-UHFFFAOYSA-N C=O.CC(N)=O Chemical compound C=O.CC(N)=O NXXHWSKTYHMUBE-UHFFFAOYSA-N 0.000 description 1
- UXTFKIJKRJJXNV-UHFFFAOYSA-N CC(=O)=O Chemical compound CC(=O)=O UXTFKIJKRJJXNV-UHFFFAOYSA-N 0.000 description 1
- NIVUXMVQJBFTQN-UHFFFAOYSA-N CC(=O)CC(=O)NC1=CC=C(C2=NCCCO2)C=C1 Chemical compound CC(=O)CC(=O)NC1=CC=C(C2=NCCCO2)C=C1 NIVUXMVQJBFTQN-UHFFFAOYSA-N 0.000 description 1
- PGZKOLAGOGPAIM-UHFFFAOYSA-N CC(=O)CC(=O)OCCCC1=NCCO1 Chemical compound CC(=O)CC(=O)OCCCC1=NCCO1 PGZKOLAGOGPAIM-UHFFFAOYSA-N 0.000 description 1
- VCNORBUSWCKSHL-UHFFFAOYSA-N CC(=O)CC(=O)OCCCCC(=O)NC1=CC=C(C2=NCCO2)C=C1 Chemical compound CC(=O)CC(=O)OCCCCC(=O)NC1=CC=C(C2=NCCO2)C=C1 VCNORBUSWCKSHL-UHFFFAOYSA-N 0.000 description 1
- MNTXFLPNUYOGNA-UHFFFAOYSA-N CC(=O)CC(=O)OCCCCCC1=NCCO1 Chemical compound CC(=O)CC(=O)OCCCCCC1=NCCO1 MNTXFLPNUYOGNA-UHFFFAOYSA-N 0.000 description 1
- JWFMVVPPJYVUNC-UHFFFAOYSA-N CC(=O)CC(=O)OCCOC(=O)NC1=CC=C(C2=NCCO2)C=C1 Chemical compound CC(=O)CC(=O)OCCOC(=O)NC1=CC=C(C2=NCCO2)C=C1 JWFMVVPPJYVUNC-UHFFFAOYSA-N 0.000 description 1
- HMYWIYPSQDSWCA-UHFFFAOYSA-N CC(=O)CC(=O)OCCOC1=CC=C(C2=NCCO2)C=C1 Chemical compound CC(=O)CC(=O)OCCOC1=CC=C(C2=NCCO2)C=C1 HMYWIYPSQDSWCA-UHFFFAOYSA-N 0.000 description 1
- JYVNDCLJHKQUHE-UHFFFAOYSA-N CC(=O)OCO Chemical compound CC(=O)OCO JYVNDCLJHKQUHE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- LBNWQMYFARJHDM-UHFFFAOYSA-N NC(=O)OCO.O=CCO Chemical compound NC(=O)OCO.O=CCO LBNWQMYFARJHDM-UHFFFAOYSA-N 0.000 description 1
- GCAAQXMOAWBLPW-UHFFFAOYSA-N NC1=CC=C(C2=NCCCO2)C=C1 Chemical compound NC1=CC=C(C2=NCCCO2)C=C1 GCAAQXMOAWBLPW-UHFFFAOYSA-N 0.000 description 1
- RQGNEYFWHWFECS-UHFFFAOYSA-N NOC=O Chemical compound NOC=O RQGNEYFWHWFECS-UHFFFAOYSA-N 0.000 description 1
- RGCVEPTUNMSMHB-UHFFFAOYSA-N O=C(NC1=CC=C(C2=NCCO2)C=C1)OCCO Chemical compound O=C(NC1=CC=C(C2=NCCO2)C=C1)OCCO RGCVEPTUNMSMHB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- RNIPBGMVTAUWNH-UHFFFAOYSA-N [F].[I] Chemical compound [F].[I] RNIPBGMVTAUWNH-UHFFFAOYSA-N 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004075 acetic anhydrides Chemical class 0.000 description 1
- 150000004729 acetoacetic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229960005274 benzocaine Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000007156 chain growth polymerization reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000007155 step growth polymerization reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
Definitions
- This invention relates to an aqueous coating composition such as coatings, inks, coverprint varnish and surface treatment applications containing an oxazoline or oxazine acetoacetate polymer.
- Organic compounds or polymers with the acetoacetamide, acetoacetanilide, or acetoacetate type functionality are known to react with a variety of other functional chemicals (1-5), including such things as amines, aldehydes, and isocyanates, giving various adducts in excellent yields at low reaction temperatures (2).
- the acetoacetamide, acetoacetanilide, or acetoacetate group, with amine catalysts will combine readily with the acrylate functionality, via what is commonly called the Michael addition reaction (2,5,6).
- acetoacetanilide, acetoacetamide, or acetoacetate groups are known to readily react with various metal compounds, such as CaO, Ca(OH) 2 , BaO, CoCl 2 , NiCI 2 , etc. to form metal complexes (1,3), where the chemistry has been used to prepare polymeric catalysts (2,7,8) and crosslinked coatings (6,9-1 1).
- metal compounds such as CaO, Ca(OH) 2 , BaO, CoCl 2 , NiCI 2 , etc.
- cyclic imino ethers such as oxazolines and oxazines will undergo cationic, ring-opening polymerizations (12) and zwitterionic copolymerization with such things as acrylic acid, maleimides, anhydrides, lactones, etc. (13-17).
- molecules with the oxazoline or oxazine residues will undergo ring-opening reactions with compounds such as carboxylic acids, thiols (HS-groups), phenols, alkyl halides, etc., giving 1-to-1 adducts (18-24), allowing for step-growth copolymerizations to be readily achieved with difunctional monomers.
- oxazolines and oxazines are excellent intermediates for synthesis of variety of polymeric materials, both thermoplastics and thermosets, by chain-growth and step-growth polymerization mechanisms or combinations thereof.
- synthesis and polymerization of oxazoline and oxazine methacrylate aqueous coating compositions are also known (27).
- novel compound of this invention has the following formula:
- R is an alkyl group containing 1-5 carbon atoms or an aryl, substituted aryl, substituted or unsubstituted heteroaryl, alkyl-aryl, alkylether-aryl or O;
- R. and R 2 are hydrogen or a methyl group;
- X is O, NH, NR′ wherein R′ is an alkyl group containing 1-5 carbon atoms, or O—R′′ or NR′′ wherein O—R′′ is O-alkyl-O or O-alkyl, NR′′ is O-alkyl-ONH, or
- alkyl contains 1-5 carbon atoms and n is 0 or 1.
- the compounds of this invention are monomers which may be polymerized or copolymerized, via cationic, ring-opening polymerization of the cyclic imino ether residues, producing polymers with pendant acetoacetamide, acetoacetanilide and/or acetoacetate groups.
- Polymers of the aforesaid type may be readily crosslinked, via a variety of reactions as explained in the background art, to produce crosslinked materials useful in coatings, adhesives, and other applications. Further, these monomers and polymers are shown to readily form metal complexes with a variety of metal salts, giving in many cases, highly colored monomer-metal or macromolecular-metal complexes.
- the compound where R is aryl, X is NH, R, R 1 and R 2 are CH 3 and n is 0 is prepared by reacting ethylaminobenzoate with methylaminopropanol to yield a dimethyl derivative of aminophenyl oxazoline with the resulting oxazaline treated with TDO.
- the compound where R is alkyl, X is alkyl, R 1 and R 2 are hydrogen and n is 0 is prepared by reacting an alkylamino alkylnitrile with ethanolamine to obtain alkylamino alkyloxazoline which is subsequently treated with TDO.
- R, R 1 , R 2 and n are as immediately and previously described but X is O-alkyl, it is obtained by reacting hydroxyalkyl oxazoline and TDO.
- R 1 and R 2 are hydrogen, n is 0 and X is O-alkyl-O, O-alkyl-CNH or
- aminophenyl oxazoline was treated with an alkylene carbonate to obtain an intermediate carbamate deriviative which is subsequently treated with diketene.
- a substituted aminobenzonitrile such as methyl substituted aminobenzonitrile is reacted with 2-aminoethanol in the presence of a zinc acetate catalyst as set forth in Example 1 to provide an amino and methyl substituted phenyloxazoline.
- the resulting substituted phenylaxazoline is reacted with diketene in the manner of Example 4 to produce the desired substituted aryl oxazoline.
- the substituents on the phenyl group can be alkyl and other functionalties can include nitro and hydroxyl.
- alkyl as used herein means an alkyl group having 1-5 carbon atoms.
- Example 1 procedure was followed starting with 3-aminobenzonitrile in place of the 4-amino compound, providing white, crystalline APOXO isomer in a 75% yield, with mp 126-128° C.
- FT-IR and 1 H NMR confirmed the structure shown below:
- Example 1 was followed, with replacement of the 2-aminoethanol by 3-aminopropanol (3-hydroxypropyl amine) for the oxazine synthesis procedure.
- This Example illustrates an alternative synthesis of the above compound.
- 4-APOXO was reacted with t-butyl acetoacetate to yield 4-AAOXO in excess of 85% accordinging to the following reaction conditions: 30 g of 4-APOXO were charged to a 500 ml round bottom flask equipped with a mechanical stirrer, thermometer, Dean-Stark trap and reflux condenser. 200 ml of xylene was added followed by 29.3 g of t-butyl acetoacetate. The reaction mixture was heated with stirring to 105° C. The rapid evolution of t-butanol began at this point and continued for 15-20 minutes. The solvent was removed under reduced pressure and the solid residue of the desired product was recrystallized twice from acetonitrile and had a m.p. 170-171° C.
- Example 4 This is a duplication of Example 4, except using different starting material.
- a 250 ml three-neck, round bottom flask was fitted with a nitrogen gas inlet tube, magnetic stirrer, thermometer, and condenser.
- 4-APOXO, 8.0 g (54 mmol) was mixed with 2,2,6-trimethyl-1,3-dioxin-4-one (TDO), 8.0 ml (61 mmol), and 120 ml of xylene.
- TDO 2,2,6-trimethyl-1,3-dioxin-4-one
- TDO 2,2,6-trimethyl-1,3-dioxin-4-one
- xylene 120 ml
- Example 4 Using Example 4 procedure, 4-APOXI was treated with a slight excess of diketene to produce crude 4-AAOXI in essentially quantitative yield. Recrystallization from acetonitrile gave the new monomer in 88% yield, having mp 133-134° C. The structure, shown below, was confirmed by elemental analysis, FT-IR and 1 H NMR spectroscopy.
- This compound was prepared by treating 4-aminobenzonitrile with a slight excess, on a molar equivalents basis, of methyl iodide in tetrahydrofuran solvent for 4 hrs at room temperature. Removal of the THF and other volatiles, followed by recrystallization, gave a 76% yield of 4-(N-methyl)aminobenzonitrile, mp 85-87° C. Using Example 1 procedure, the aforesaid substituted nitrile was treated with ethanolamine to obtain a 70% yield of 2-[4-(N-methyl) aminophenyl]oxazoline, mp 145-147° C.
- Example 6 Following the Example 6 procedure, the aforesaid compound was treated with TDO to form the oxazoline shown below, having a methyl group attached to the nitrogen in the acetoacetanilide segment.
- the product was recrystallized from ethyl acetate, mp 102-105° C. Elemental analysis, FT-IR, exhibiting 1726 (C—O) and 1635 (—C ⁇ N—) cm ⁇ 1 absorptions, and with 1 H NMR confirmed the below drawn structure.
- This compound has the following structure:
- Example 6 Using the Example 6 procedure, the aforesaid intermediate was treated with a slight molar excess of TDO in xylene solvent, obtaining the desired N-methyl-N-[2-(2-oxazolin-2-yl)ethyl] acetoacetamide as a yellow colored liquid.
- the FT-IR, with peaks centered at 3304, 2941, 1718, and 1649 cm ⁇ 1 , and 1 H NMR spectra supported the following structure.
- Example 18 Using Example 18 procedure, the copolymer of 3-AAOXO and 2-phenyloxazoline was obtained in high yield. FT-IR confirmed that the copolymer contained both monomer residues.
- the desired molecular weights for the copolymers of Examples 19 and 20 are in the range of 6,000-25,000.
- Example 18 Using Example 18 procedure, the copolymer of 4-AAOXI and 2-phenyloxazoline was obtained in high yield. FT-IR and 1 H NMR confirmed that the copolymer contained both monomer residues.
- Example 19 illustrates the copolymerization of 4-AAOXO with ethyl oxazoline, it is obvious that the corresponding oxazine compounds could be employed.
- Aqueous formulations of the compounds of this invention can be produced by copolymerizing the compounds with ethyl oxazoline. Specifically the ethyl oxazoline should be present in an amount of 90 mole percent. When 4-AAOXO was employed, these solutions can be mixed with a crosslinker and drawn down over any substrate.
- the monomers of this invention when further crosslinked at room temperature result in polymers useful in coatings, inks, overprint varnishes, and surface treatment applications.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Description
- NONE
- NONE
- 1. Technical Field
- This invention relates to an aqueous coating composition such as coatings, inks, coverprint varnish and surface treatment applications containing an oxazoline or oxazine acetoacetate polymer.
- 2. Background Art
- In the following description of the prior art and in the Examples, the parenthetical numbers are described in the following Reference section. Acetoacetamide, acetoacetanilide, and acetoacetate functionalized chemicals are readily available, via reaction of amines or hydroxyl substituted molecules with diketene (1-3), alkyl acetoacetates, or the readily used acetoacetalation compound 2,2,6-trimethyl-1,3-dioxin-4-one, which is prepared from reaction of diketene with acetone (2,4). Organic compounds or polymers with the acetoacetamide, acetoacetanilide, or acetoacetate type functionality are known to react with a variety of other functional chemicals (1-5), including such things as amines, aldehydes, and isocyanates, giving various adducts in excellent yields at low reaction temperatures (2). Also, the acetoacetamide, acetoacetanilide, or acetoacetate group, with amine catalysts, will combine readily with the acrylate functionality, via what is commonly called the Michael addition reaction (2,5,6). Further, these acetoacetanilide, acetoacetamide, or acetoacetate groups are known to readily react with various metal compounds, such as CaO, Ca(OH)2, BaO, CoCl2, NiCI2, etc. to form metal complexes (1,3), where the chemistry has been used to prepare polymeric catalysts (2,7,8) and crosslinked coatings (6,9-1 1). These chemicals with the acetoacetamide, acetoacetanilide, and/or acetoacetate functionality, which have three active centers, have found extensive utility in the formation of metal-complexes, manufacture of dyes and synthesis of heterocycles (1-3).
- It is well known that cyclic imino ethers, such as oxazolines and oxazines will undergo cationic, ring-opening polymerizations (12) and zwitterionic copolymerization with such things as acrylic acid, maleimides, anhydrides, lactones, etc. (13-17). It is also well known that molecules with the oxazoline or oxazine residues will undergo ring-opening reactions with compounds such as carboxylic acids, thiols (HS-groups), phenols, alkyl halides, etc., giving 1-to-1 adducts (18-24), allowing for step-growth copolymerizations to be readily achieved with difunctional monomers. Further, it has been shown that alkyl halides will initiate ring-opening polymerization of cyclic imino ethers, as well as give 1:1 adducts (18, 25). Thus oxazolines and oxazines are excellent intermediates for synthesis of variety of polymeric materials, both thermoplastics and thermosets, by chain-growth and step-growth polymerization mechanisms or combinations thereof. In addition, the synthesis and polymerization of oxazoline and oxazine methacrylate aqueous coating compositions are also known (27).
- 1. U.S. Pat. No. 3,304,328 (Feb. 14, 1967) to FMC Corporation.
- 2. N. Moszner, U. Salz, V. Rheinberger, MACROAKRON '94, 35th IUPAC Int. Symp. on Macromolecules, Jul. 11-15, 1994 paper.
- 3. S. M. Hussain, A. M. El-Reedy, S. A. El-Sherabasy, J. Heterocyclic Chem., 25, 9-22 (1988).
- 4. Wacker Chemicals (USA), Inc. literature, p. 16.
- 5. R. J. Clemens, J. S. Witzman, F. Del Rector, Communications of Eastman Chemical Products, Inc.
- 6. K. J. Edgar, K. M. Arnold, W. W. Blount, J. E. Lawniczak, and D. W. Lowman, Macromolecules 1995, 28, 4122-4128.
- 7. T. Sato, A. Morita, I. Kamiya, T. Ota, Makromol. Chem., Rapid Comm. 11 (1990) 553.
- 8. R. Ran, D. Fu, J. Macromol. Sci.-Chem. A27 (1990) 625.
- 9. D. L. Trumbo, Polymer Bull. 26 (1991) 265,481.
- 10. J. R. Grawe, B. G. Bufkin, J. Coatings Technol. 52 (1980) 73.
- 11. U.S. Pat. No. 4,247,671 (Jan. 27, 1981) to Rohm and Haas Co.
- 12. S. Kobayashi and T. Saegusa, Encyclopedia of Polymer Science and Engineering, Wiley & Sons, New York, Vol. 4, pp. 525-537, 1986.
- 13. G. Odian, M. P. O'Callaghan, C. K. Chien, P. Gunatillake, M. Periyasay and D. L. Schmidt, Macromolecules, 23(4), 918-927 (1990).
- 14. C. I. Simionescu, et.al., Polymer. Bull. (Berlin), 14(1), 79-83 (1985).
- 15. T. Saegusa, Makromol. Chem., Suppl., 4, 73-84 (1981).
- 16. B. L. Rivas and G. D. Pizarro, Eur. Polym. J., 25(10), 1001-1005 (1989).
- 17. G. S. Canessa, A. S. Pooley, M. Parra and B. L. Rivas, Polym. Bull. (Berlin),
- 11(5), 465-70 (1984).
- 18. J. A. Frump, Chem. Rev., 71(5), 483-505 (1971).
- 19. U.S. Pat. No. 3,758,62, (Sep. 11, 1973), to Dow Chemical.
- 20. U.S. Pat. No. 4,600,766 (Jul. 15, 1986) to Takeda Chemical Co.
- 21. T. Nishikubo, T. Iizawa and A. Tokairin, Mackromol. Chem., 185, 1307-1316 (1984).
- 22. T. Kagiya, S. Narisawa, T. Maeda and K. Fukui, Polymer Letters, 4, 257-260 (1966).
- 23. U.S. Pat. No. 4,430,491 (Feb. 7, 1984) to Ashland Chemical Co.
- 24. B. M. Culbertson, M. L. Deviney, O. Tiba and D. D. Carlos, 33rd SAMPE Symp., Mar. 7-10, pp. 1530-1545 (1988), Ibid.34th SAMPE Symp. May 8-11, 1989. PP.2483-2497.
- 25. S. Kobayashi, H. Uyama, Y. Narita and J. Ishiyama, Macromolecules, 25(12), 3232-3236 (1992).
- 26.H. Witte and W. Seelinger, Liebigs Arn. Chem., 996-1009 (1974).
- 27.H. A. A. Rasoul, D. B. Obuchowski, D. L. Trumbo, B. M. Culbertson, and Y. Xue, Oxazoline Hydrolysis, Synthesis and Polymerization of a New Oxazoline Methacrylate, PP. 871-872 (1997).
- The prior art fails to disclose chemical compositions, monomeric or polymeric having both the cyclic imino ether and the acetoacetamide, acetoacetenilide or acetoacetate residues on the same molecule.
-
-
- wherein each instance alkyl contains 1-5 carbon atoms and n is 0 or 1.
- The compounds of this invention are monomers which may be polymerized or copolymerized, via cationic, ring-opening polymerization of the cyclic imino ether residues, producing polymers with pendant acetoacetamide, acetoacetanilide and/or acetoacetate groups. Polymers of the aforesaid type may be readily crosslinked, via a variety of reactions as explained in the background art, to produce crosslinked materials useful in coatings, adhesives, and other applications. Further, these monomers and polymers are shown to readily form metal complexes with a variety of metal salts, giving in many cases, highly colored monomer-metal or macromolecular-metal complexes.
-
- the following procedures were employed. Where X is O-alkyl-O, hydroxy-alkylphenyl oxazoline was reacted with TDO; where X is O-alkyl-CONH aminophenyl oxazoline was reacted with an alkyllactone resulting in a hydroxyalkyl substituted amide of the oxazoline compound which is subsequently treated with TDO; where X is
- aminophenyl oxazoline was treated with an alkylene carbonate to obtain an intermediate carbamate deriviative which is subsequently treated with diketene.
- To synthesize substituted aryl oxazolines, a substituted aminobenzonitrile such as methyl substituted aminobenzonitrile is reacted with 2-aminoethanol in the presence of a zinc acetate catalyst as set forth in Example 1 to provide an amino and methyl substituted phenyloxazoline. The resulting substituted phenylaxazoline is reacted with diketene in the manner of Example 4 to produce the desired substituted aryl oxazoline. As indicated, the substituents on the phenyl group can be alkyl and other functionalties can include nitro and hydroxyl.
-
-
- which is subsequently reacted with diketene. In the foregoing formula X=sulfur, oxygen, or NH or NR where R is alkyl and Y=hydrogen, bromine, chlorine, iodine fluorine, amino or hydroxyl.
-
-
- which is subsequently heated with diketene to produce the desired alky-aryl substituted or unsubstituted acetoacetoxazoaline. In this instance X=hydrogen, carboxyl, halogen, alkyl or aryl.
- To synthesize compounds of the general formula where R is alkylether-aryl, a hydroxybenzonitrile is reacted with 2-aminoethanol as previously described to result in a hydroxy substituted phenyloxazoline. This intermediate oxazoline is reacted with, for example ethylene oxide, to produce a compound of the formula:
- which is further reacted with diketene to produce the desired alkylether-aryl substituted acetoacetate oxazoline.
- The term “alkyl” as used herein means an alkyl group having 1-5 carbon atoms.
- The Examples which follow are intended as an illustration of certain preferred embodiments of the invention, and no limitation of the invention is implied.
- Using known procedures for the synthesis of cyclic imino ethers from nitriles (18,26), 4-aminobenzonitrile was treated with an excess of 2-aminoethanol (1 part nitrile/2 parts aminoalcohol) in refluxing xylene, with 3.5 wt. % zinc acetate catalyst, with all under a slow nitrogen stream. The solution was heated until no NH3 was detected in the off gas. After removal of the xylene, the crude solid product was obtained in high yield. The crude product was recrystallized from acetonitrile to obtain an 82% yield of white, crystalline 4-APOXO having mp 163-165° C., reported 158-160° C. The structure of the monomer was confirmed by FT-IR and 1H NMR. Structure of 4-APOXO is as follows:
-
- While this monomer is new to the literature, it is obvious the monomer may be made by published techniques used for Example 1 and 2 compositions. Example 1 procedure was followed, with replacement of the 2-aminoethanol by 3-aminopropanol (3-hydroxypropyl amine) for the oxazine synthesis procedure. The heretofore unreported crystalline 4-APOXI, with mp 177-178° C., was obtained in 92% yield. The structure, shown below, was confirmed by elemental analysis, FT-IR and1H NMR.
-
- This Example illustrates an alternative synthesis of the above compound. 4-APOXO was reacted with t-butyl acetoacetate to yield 4-AAOXO in excess of 85% acording to the following reaction conditions: 30 g of 4-APOXO were charged to a 500 ml round bottom flask equipped with a mechanical stirrer, thermometer, Dean-Stark trap and reflux condenser. 200 ml of xylene was added followed by 29.3 g of t-butyl acetoacetate. The reaction mixture was heated with stirring to 105° C. The rapid evolution of t-butanol began at this point and continued for 15-20 minutes. The solvent was removed under reduced pressure and the solid residue of the desired product was recrystallized twice from acetonitrile and had a m.p. 170-171° C.
- This is a duplication of Example 4, except using different starting material. A 250 ml three-neck, round bottom flask was fitted with a nitrogen gas inlet tube, magnetic stirrer, thermometer, and condenser. 4-APOXO, 8.0 g (54 mmol), was mixed with 2,2,6-trimethyl-1,3-dioxin-4-one (TDO), 8.0 ml (61 mmol), and 120 ml of xylene. The solution was heated at reflux, under a slow nitrogen stream, for 4 hrs. On cooling, the crude 4-AAOXO precipated from solution. The 4-AAOXO was collected, washed with diethyl ether, and dried in a vacuum to obtain the slightly yellow, crystalline monomer in 83% yield, having mp 169-171° C. FT-IR and1H NMR confirmed the product to be the same as that prepared in Example 4.
-
- Using Example 4 procedure, 4-APOXI was treated with a slight excess of diketene to produce crude 4-AAOXI in essentially quantitative yield. Recrystallization from acetonitrile gave the new monomer in 88% yield, having mp 133-134° C. The structure, shown below, was confirmed by elemental analysis, FT-IR and1H NMR spectroscopy.
- This compound was prepared by treating 4-aminobenzonitrile with a slight excess, on a molar equivalents basis, of methyl iodide in tetrahydrofuran solvent for 4 hrs at room temperature. Removal of the THF and other volatiles, followed by recrystallization, gave a 76% yield of 4-(N-methyl)aminobenzonitrile, mp 85-87° C. Using Example 1 procedure, the aforesaid substituted nitrile was treated with ethanolamine to obtain a 70% yield of 2-[4-(N-methyl) aminophenyl]oxazoline, mp 145-147° C. Following the Example 6 procedure, the aforesaid compound was treated with TDO to form the oxazoline shown below, having a methyl group attached to the nitrogen in the acetoacetanilide segment. The product was recrystallized from ethyl acetate, mp 102-105° C. Elemental analysis, FT-IR, exhibiting 1726 (C—O) and 1635 (—C═N—) cm−1 absorptions, and with 1H NMR confirmed the below drawn structure.
-
- Ethyl p-aminobenzoate, 20.65 g (0.125 mol), 2-methyl-2-aminopropanol, 22.3 g (0.25 mol) 150 ml of xylene, and 0.25 g of lithium amide were combined and heated at the reflux temperature for 50 hr. The alcohol and water liberated was collected in a Dean-Stark trap, providing indication when the reaction was complete. The xylene solvent was removed and the viscous liquid was added to water to precipitate the product. After drying, a 15.5 g (65%) yield of the 4,4-dimethyl derivative of 4-aminophenyl oxazoline was obtained. The product was recrystallized from ethyl acetate, giving white, crystalline material with mp 172° C. FT-IR, with peaks centered at 3445 (NH), 1635 (—C═N—), and 1602 (phenyl) cm−1 confirmed the desired amino functionalized oxazoline. Following the Example 6 procedure, TDO was used to covert the aforesaid compound to the desired acetoacetamide. The structure of this new composition is as follows:
-
- The compound 3-hydroxypropyl-2-oxazoline was prepared by techniques known in the patent (1 1) literature. A reaction flask was charged with 10.6 g (0.5mol) of 3-hydroxypropyl-2-oxazoline, 11.4 g (0.08 mol) of TDO, and 100 ml of xylene. Heating with stirring under nitrogen at the reflux temperature of xylene for 6 hr. followed by removal of volatiles, gave a viscous oil. The FT-IR and1H NMR spectra were supportive of the following structure.
-
- A 250 ml. round bottom, three-neck flask was charged with 2-(p-hydroxyethoxyphenyl) oxazoline, 8.28 g (0.04 mol TDO, 11.36 g (0.08 mol) and 120 ml of xylene. The solution was stirred and heated at reflux, under nitrogen, for 5 hr. Evaporation of the solvent gave a high yield of the crude, solid product. After washing with ethyl acetate, the product was recrystalized from petroleum ether to give a good yield of the desired compound, mp 72-75° C. Elemental analysis, FT-IR and1H NMR spectra supported the structure shown below.
- The monomer 2-(4-aminophenyl)oxazoline was combined and heated under nitrogen with a slight excess of butyrolactone, giving an excellent yield of the desired hydroxyalkyl substituted amide of the starting aminophenyl oxazoline compound. The latter composition was treated with an excess of TDO to obtain the compound with the following structure in excellent yield, with structure confirmed by FT-IR and1H NMR spectroscopy.
-
-
- The monomer 4-AAOXO, 4.0g, and anisole (50 ml) solvent, along with a catalytic amount (0.15 g.) of the cationic polymerization initiator, methyl tosylate (TsOCH3), were combined under nitrogen and sealed in a small reaction flask containing a magnetic stir bar. With stirring, the polymerization was run for 10 hr at 135° C. After cooling, the anisole solution was combined with hexane to precipitate the polymer. After collection and drying under vacuum at 45° C., the poly (4-AAOXO), soluble with difficulty in N, N-dimethylformamide (DMF), was obtained in essentially quantitative yield. The polymer structure was confirmed by FT-IR and 1H NMR analysis. Polymerization under the same procedure with acetonitrile solvent and SnCl4 initiator produced poly (4-AAOXO) which was readily soluble in DMF.
- The monomer 2-(4-acetoacetanilide) oxazoline [4-AAOXO], 2.5 g. and 2-phenyloxazoline (2.5g.), with 0.15 g of TsOCH3 were mixed in a small glass vial containing 45 ml of anisole. The vial was flushed with nitrogen, sealed, and placed in a thermostatted bath at 120° C. for 13 hr. The polymer solution, after cooling, was combined with vigorously stirred petroleum ether to precipitate the copolymer. The copolymer was collected, washed with petroleum ether, and dried under vacuum at 45° C. FT-IR and 1H NMR spectra confirmed the copolymer contained both monomer residues.
- Using the procedure described in Example 18, a copolymer of 4-AAOXO and 2-ethyloxazoline was produced and isolated in high yield. FT-IR and1H NMR confirmed that the copolymer contained both monomer residues.
- Using Example 18 procedure, the copolymer of 3-AAOXO and 2-phenyloxazoline was obtained in high yield. FT-IR confirmed that the copolymer contained both monomer residues.
- The desired molecular weights for the copolymers of Examples 19 and 20 are in the range of 6,000-25,000.
- Using Example 18 procedure, the copolymer of 4-AAOXI and 2-phenyloxazoline was obtained in high yield. FT-IR and1H NMR confirmed that the copolymer contained both monomer residues.
- While Example 19 illustrates the copolymerization of 4-AAOXO with ethyl oxazoline, it is obvious that the corresponding oxazine compounds could be employed.
- Aqueous formulations of the compounds of this invention can be produced by copolymerizing the compounds with ethyl oxazoline. Specifically the ethyl oxazoline should be present in an amount of 90 mole percent. When 4-AAOXO was employed, these solutions can be mixed with a crosslinker and drawn down over any substrate.
- The monomers of this invention when further crosslinked at room temperature result in polymers useful in coatings, inks, overprint varnishes, and surface treatment applications.
Claims (60)
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US09/819,242 US6433116B2 (en) | 1999-05-06 | 2001-03-28 | Oxazoline or oxazine acetoacetate aqueous coating compositions |
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US09/306,302 US6235901B1 (en) | 1999-05-06 | 1999-05-06 | Oxazoline or oxazine acetoacetate aqueous coating compositions |
US09/819,242 US6433116B2 (en) | 1999-05-06 | 2001-03-28 | Oxazoline or oxazine acetoacetate aqueous coating compositions |
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US09/306,302 Division US6235901B1 (en) | 1999-05-06 | 1999-05-06 | Oxazoline or oxazine acetoacetate aqueous coating compositions |
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US20010018516A1 true US20010018516A1 (en) | 2001-08-30 |
US6433116B2 US6433116B2 (en) | 2002-08-13 |
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US09/819,242 Expired - Lifetime US6433116B2 (en) | 1999-05-06 | 2001-03-28 | Oxazoline or oxazine acetoacetate aqueous coating compositions |
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AU (1) | AU4821800A (en) |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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KR101799618B1 (en) | 2010-12-14 | 2017-11-20 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Oxazolinyl-containing polymers and grafted compounds prepared from the oxazolinyl-containing polymers |
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US6235901B1 (en) * | 1999-05-06 | 2001-05-22 | S. C. Johnson Commercial Markets, Inc. | Oxazoline or oxazine acetoacetate aqueous coating compositions |
EP4081603A4 (en) * | 2019-12-26 | 2023-08-23 | Dow Global Technologies LLC | Aqueous coating composition and process for preparing the same |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3304328A (en) | 1963-10-25 | 1967-02-14 | Fmc Corp | Preparation of acetoacetarylamides |
US3563920A (en) * | 1969-06-16 | 1971-02-16 | Dow Chemical Co | Bi-2-oxazoline and oxazine ethers and thioethers |
US3758629A (en) | 1971-05-07 | 1973-09-11 | Dow Chemical Co | By reaction with a di-2-oxazoline cross linking of addition polymers containing combined free carboxyl |
US4016192A (en) * | 1974-12-30 | 1977-04-05 | The Dow Chemical Company | Unsaturated acrylic acid-oxazoline reaction products |
US4247671A (en) | 1979-04-11 | 1981-01-27 | Rohm And Haas Company | Hydrocurable compositions containing oxazoline groups |
US4430491A (en) | 1982-09-30 | 1984-02-07 | Ashland Oil, Inc. | Poly(ether-amide) polymeric compositions |
JPS6090219A (en) | 1983-10-21 | 1985-05-21 | Takeda Chem Ind Ltd | Production of thermosetting resin |
US4889765A (en) * | 1987-12-22 | 1989-12-26 | W. R. Grace & Co. | Ink-receptive, water-based, coatings |
NL9000762A (en) * | 1990-03-31 | 1991-10-16 | Stamicarbon | BLOCK COPOLYMERS OF TETRAHYDROFURAN AND OXAZOLINE, HYDROLYSIS PRODUCTS THEREOF AND A PROCESS FOR MANUFACTURING THESE BLOCK COPOLYMERS. |
US5418277A (en) * | 1994-04-26 | 1995-05-23 | E. I. Du Pont De Nemours And Company | Aqueous ink jet inks containing fluorinated polymers |
US6060554A (en) * | 1997-01-24 | 2000-05-09 | Kansai Paint Co., Ltd. | Aqueous coating and method for film formation using the same |
US6063885A (en) * | 1998-03-10 | 2000-05-16 | S. C. Johnson Commercial Markets, Inc. | Oxazoline or oxazine methacrylate aqueous coating compositions |
US6235901B1 (en) * | 1999-05-06 | 2001-05-22 | S. C. Johnson Commercial Markets, Inc. | Oxazoline or oxazine acetoacetate aqueous coating compositions |
-
1999
- 1999-05-06 US US09/306,302 patent/US6235901B1/en not_active Expired - Lifetime
-
2000
- 2000-05-05 AU AU48218/00A patent/AU4821800A/en not_active Abandoned
- 2000-05-05 WO PCT/US2000/012280 patent/WO2000068212A1/en active Application Filing
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2001
- 2001-03-28 US US09/819,242 patent/US6433116B2/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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KR101799618B1 (en) | 2010-12-14 | 2017-11-20 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Oxazolinyl-containing polymers and grafted compounds prepared from the oxazolinyl-containing polymers |
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US6235901B1 (en) | 2001-05-22 |
US6433116B2 (en) | 2002-08-13 |
WO2000068212A1 (en) | 2000-11-16 |
AU4821800A (en) | 2000-11-21 |
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