US20020055609A1 - Condensation polymer containing hydroxyalkylamide groups - Google Patents
Condensation polymer containing hydroxyalkylamide groups Download PDFInfo
- Publication number
- US20020055609A1 US20020055609A1 US09/941,793 US94179301A US2002055609A1 US 20020055609 A1 US20020055609 A1 US 20020055609A1 US 94179301 A US94179301 A US 94179301A US 2002055609 A1 US2002055609 A1 US 2002055609A1
- Authority
- US
- United States
- Prior art keywords
- polymer
- aryl
- cyclo
- alkyl
- groups
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 128
- 238000009833 condensation Methods 0.000 title claims description 6
- 230000005494 condensation Effects 0.000 title claims description 6
- -1 cyclic anhydride Chemical class 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000003973 paint Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 10
- 125000004185 ester group Chemical group 0.000 claims abstract description 7
- 125000003368 amide group Chemical group 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 39
- 238000000576 coating method Methods 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 29
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 25
- 239000004971 Cross linker Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 10
- 229920006149 polyester-amide block copolymer Polymers 0.000 abstract description 7
- 229920000728 polyester Polymers 0.000 description 28
- 150000007513 acids Chemical class 0.000 description 14
- 238000004821 distillation Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- 235000019198 oils Nutrition 0.000 description 14
- 0 *C(=O)BC(=O)N([Y])C(C)(C)C([H])(C)OC Chemical compound *C(=O)BC(=O)N([Y])C(C)(C)C([H])(C)OC 0.000 description 13
- 150000008064 anhydrides Chemical class 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 10
- 229940043276 diisopropanolamine Drugs 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 150000001735 carboxylic acids Chemical class 0.000 description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 8
- 229920000058 polyacrylate Polymers 0.000 description 8
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 229940102253 isopropanolamine Drugs 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 6
- GLSPZOVVXNTNTN-UHFFFAOYSA-N [H]C(C)(OC)C(C)(C)C Chemical compound [H]C(C)(OC)C(C)(C)C GLSPZOVVXNTNTN-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000005907 alkyl ester group Chemical group 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 4
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- NJQACFVMBSAECJ-UHFFFAOYSA-N COC(C)CNCC(C)OC Chemical compound COC(C)CNCC(C)OC NJQACFVMBSAECJ-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MNGKKDLHXAQION-UHFFFAOYSA-M II.[H]OC([H])(C)C(C)(C)N([Y])C(=O)BC(C)=O Chemical compound II.[H]OC([H])(C)C(C)(C)N([Y])C(=O)BC(C)=O MNGKKDLHXAQION-UHFFFAOYSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- VHQGWFIYSLJYJC-UHFFFAOYSA-N [H]C(C)(OC)C(C)(C)N(C)[Y] Chemical compound [H]C(C)(OC)C(C)(C)N(C)[Y] VHQGWFIYSLJYJC-UHFFFAOYSA-N 0.000 description 2
- FTMVECQKADVZKQ-UHFFFAOYSA-N [H]C(C)(OC)C([H])([H])N(C)[Y] Chemical compound [H]C(C)(OC)C([H])([H])N(C)[Y] FTMVECQKADVZKQ-UHFFFAOYSA-N 0.000 description 2
- UVKJPNFJFSKFKR-UHFFFAOYSA-M [H]OC([H])(C)C(C)(C)N([Y])C(=O)BC(C)=O Chemical compound [H]OC([H])(C)C(C)(C)N([Y])C(=O)BC(C)=O UVKJPNFJFSKFKR-UHFFFAOYSA-M 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
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- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 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
- 150000002596 lactones Chemical class 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
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- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
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- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- RDMHXWZYVFGYSF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RDMHXWZYVFGYSF-LNTINUHCSA-N 0.000 description 1
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- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- PFJZOBRGDTYDQC-UHFFFAOYSA-N 1,4-diisocyanato-4-methylpentane Chemical compound O=C=NC(C)(C)CCCN=C=O PFJZOBRGDTYDQC-UHFFFAOYSA-N 0.000 description 1
- XXPLPVREXQZANT-UHFFFAOYSA-N 1,5-diisocyanato-2,2,5-trimethylhexane Chemical compound O=C=NCC(C)(C)CCC(C)(C)N=C=O XXPLPVREXQZANT-UHFFFAOYSA-N 0.000 description 1
- QBIMMUGHCHUVDL-UHFFFAOYSA-N 1,5-diisocyanato-5-methylhexane Chemical compound O=C=NC(C)(C)CCCCN=C=O QBIMMUGHCHUVDL-UHFFFAOYSA-N 0.000 description 1
- AQXHKHLEOAFNAT-UHFFFAOYSA-N 1,6-diisocyanato-6-methylheptane Chemical compound O=C=NC(C)(C)CCCCCN=C=O AQXHKHLEOAFNAT-UHFFFAOYSA-N 0.000 description 1
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
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- 239000000312 peanut oil Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003568 thioethers 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
- 239000004408 titanium dioxide Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24058—Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in respective layers or components in angular relation
- Y10T428/24074—Strand or strand-portions
- Y10T428/24091—Strand or strand-portions with additional layer[s]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the invention relates to a linear or branched condensation polymer containing ester groups and at least one amide group in the backbone, having at least one hydroxyalkylamide endgroup and having a weight average molecular mass of ⁇ 800 g/mol.
- the polymer contains at-least two groups according to formula (I)
- B (C 2 -C 24 ), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical,
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may, independently of one another, be the same or different, H, (C 6 -C 10 ) aryl or (C 1 -C 8 )(cyclo)alkyl radical and
- n 1-4.
- the polymer contains at least two groups according to formula (II):
- B (C 2 -C 24 ), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical, and
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may, independently of one another, be the same or different, H, (C 6 -C 10 ) aryl or (C 1 -C 8 )(cyclo)alkyl radical.
- the polymer containing hydroxyalkylamide groups is a polymer according to formula (III):
- B (C 2 -C 24 ), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical,
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may, independently of one another, be the same or different, H, (C 6 -C 10 ) aryl or (C 1 -C 8 )(cyclo)alkyl radical or CH 2 -OX 2 .
- R groups may together or with neighbouring carbon atoms form part of a cycloalkyl group.
- the polymer containing ⁇ -hydroxyalkylamide groups is a polymer according to formula (IV):
- B (C 2 -C 20 ), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical,
- R 3 H or (C 6 -C 10 ) aryl or (C 1 -C 8 )alkyl radical and
- R 6 H or (C 6 -C 10 ) aryl or (C 1 -C 8 )alkyl radical.
- the weight average molecular mass of the polymer according to the invention is generally between 800 and 50,000, and preferably between 1000 g/mol and 25,000 g/mol.
- the number average molecular mass is generally between 600 and 10,000 and preferably between 700 and 4000.
- the hydroxyalkylamide functionality is generally between 2 and 250 and preferably between 5 and 50.
- Functionality is the average number of reactive groups of the specific type per molecule in the polymer composition.
- the polymer's hydroxyalkylamide functionality of the polymer is ⁇ 5 and the polymer containing ⁇ -hydroxyalkylamide groups is a polymer represented by formula (V):
- B (C 2 C 12 ), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical,
- R 3 H or (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo)alkyl radical and
- R 6 H or (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo)alkyl radical
- R 3 and R 6 are (C 1 -C 4 ) alkyl.
- R 3 and R 6 are methyl or ethyl.
- B may be saturated or unsaturated.
- B may be substituted with for example a (C 1 -C 26 ) alkyl group, which may be saturated or unsaturated; preferably C 1 is used.
- B may be for example a (methyl-)1,2-ethylene, (methyl-)1,2-ethylidene, 1,3-propylene, (methyl-)1,2-cyclohexyl, (methyl-)1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,3-norbornyl, 2,3-norbornen-5-yl and/or (methyl-)1,2 cyclohex-4-enyl radical.
- variables B, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 in the molecule or mixture of molecules can be selected to be the same or different per variable.
- the polymer composition according to the invention is generally a composition comprising higher and lower oligomers, which usually contains less than 50 wt. %, preferably less than 30 wt. %, of oligomers having a molecular weight smaller than 600.
- the polyesteramide according to the invention can for example be obtained through polycondensation of mono- and/or bis-hydroxyalkylamides of bivalent carboxylic acids.
- the monohydroxyalkylamide of a bivalent carboxylic acid generally has the formula (VI):
- R 1 , R R 3 and R 4 may, independently of one another, be the same or different, H, (C 6 -C 10 ) aryl or (C 1 -C 8 )(cyclo)alkyl radical.
- a lineair polymer according to the invention generally comprises the amide and the ester groups alternating along the chain as follows:
- a branched polymer according to the invention generally comprises the amide and the ester groups alternating along the main and side chains as follows:
- the molar amount of amide bounds in the chain is higher than the amount of ester bounds.
- the polymer according to the invention comprises at least 60% by weight of the products represented by the formulas (III)-(V).
- composition according to the invention comprises also for example depoty amine groups having the formula (VIII):
- R 1 , R 2 , R 3 and R 4 may, independently of one another, be the same or different, H, (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo)alkyl radical.
- the polymer according to the invention can, also be obtained in a one-step procedure by reacting a cyclic anhydride and an alkanolamine, at a temperature between for example about 20° C. and about 100° C., to form a hydroxyalkylamide, after which, at a temperature between, for example, 120° C. and 250° C., a polyesteramide is obtained through polycondensation with water being removed through distillation.
- reaction can take place without a solvent, but also in water or in an organic solvent.
- the removal of water through distillation can take place at a pressure higher than 1 bar, in a vacuum or azeotropically.
- the cyclic anhydride is an anhydride according to formula (IX):
- Suitable cyclic anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, naphtalenic dicarboxylic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornene-2,3-dicarboxylic anhydride, naphtalenic dicarboxylic anhydride, 2-dodecene-1-yl-succinic anhydride, maleic anhydride, (methyl)succinic anhydride, glutaric anhydride, 4-methylphthalic anhydride, 4-methylhexahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride and the maleinised alkylester of an unsaturated fatty acid.
- alkanol is an alkanolamine according to formula (X):
- the alkanolamine may be a monoalkanolamine, a dialkanolamine, a trialkanolamine or a mixture hereof.
- linear polymers with a functionality of 2 can be obtained.
- a linear or an entirely or partly branched polymer can be chosen, in which case the degree of branching can be set via the alkanolamines chosen.
- Examples of suitable mono- ⁇ -alkanolamines include ethanolamine, 1-(m)ethyl ethanolamine, n-butyl ethanolamine, 1-(m)ethyl isopropanolamine, isobutanolamine, ⁇ -cyclohexanolamine, n-butyl isopropanolamine and n-propanolamine.
- Examples of suitable di- ⁇ -alkanolamines are 3-amino-1,2-propanediol, 2-amino-1,3-propanediol diisobutanolamine (bis-2-hydroxy-1-butyl)amine), di- ⁇ -cyclohexanolamine and diisopropanolamine (bis-2-hydroxy-1-propyl)amine).
- a suitable trialkanolamine is, for example, tris(hydroxymethyl)aminomethane.
- a ⁇ -alkyl-substituted ⁇ -hydroxyalkylamide is used.
- examples are (di) isopropanolamine, cyclohexyl isopropanolamine, 1-(m)ethyl isopropanolamine, (di)isobutanolamine, di- ⁇ -cyclohexanolamine and/or n-butyl isopropanolamine.
- the anhydride: alkanolamine equivalent ratio is generally between 1.0:1.0 and 1.0:1.8. Preferably, this ratio is between 1:1.05 and 1:1.5.
- the compound according to the invention can also be obtained via a reaction between an alkanolamine, as for example described above, and a compound containing one acid group and one activated acid group, after which a polyesteramide is obtained through polycondensation.
- the compound containing an acid group and an activated acid group is preferably a compound according to formula (XI):
- R 7 is a (C 1 -C 12 ) branched or linear alkyl group.
- alkyl esters such as, for example, mono(m)ethyl adipate and mono(m)ethyl sebacate, anhydrides and thioesters.
- the compound according to the invention can also be obtained via a reaction between a cyclic anhydride, as for example described above, and an alcohol, after which the reaction product obtained reacts in situ with an alkanolamine and a polyesteramide is subsequently obtained through polycondensation.
- Suitable alcohols are (C 1 -C 10 ) alcohols.
- methanol or ethanol is used.
- the polymer may also contain carboxyl groups, in amounts of between 0.01 and 2.0 mg equivalent/gram of polymer.
- the number of carboxylic acids present in the polymer can be controlled via the anhydride/alkanolamine ratio and via the degree of conversion. If an alkanolamine excess is used and the polycondensationreaction is (almost) complete, less than 0.2 mg equivalent acid/gram of polymer is usually present.
- carboxyl groups may in a subsequent step react with compounds containing one or more groups that can react with carboxylic acid, such as for example epoxy groups or ⁇ -hydroxyalkylamide groups.
- the amount of carboxylic acid is preferably as low as possible, for example between 0.01 and 0.2 mg equivalent/gram of polymer.
- the degree of branching and the functionality of the polymer are dependent on the starting materials and the molecular weight of the polymer.
- a molecular weight higher than 2000 and the use of di- and/or trialkanolamines generally lead to highly branched structures with a functionality of ⁇ 10.
- the invention also relates to entirely or partly modified polymers.
- the modification can for example take place via a reaction between the polymer according to any one of formulas (III), (IV) or (V) with a monomer, oligomer or polymer containing reactive groups that can react with the hydroxyalkylamide.
- Suitable reactive groups include carboxyl groups, carboxylic esters, carboxylic anhydrides, epoxy groups, alkoxysilane groups, isocyanate groups, acid chloride groups, epoxychlorohydrine groups, amine groups, phenolic groups, methylolated amidegroups and combinations hereof.
- the monomer, oligomer or polymer contains only one group that can react with hydroxylalkylamide, as a result of which no crosslinking takes place during the modification.
- the polymer according to formula (III), (IV) or (V) has preferably been modified with a compound containing a carboxylic acid group.
- a modified polymer can for example be represented by one of the formulas (III), (IV) or (V) in which
- [0099] is derived from a monomeric, oligomeric or polymeric monofunctional carboxylic acid.
- Suitable carboxylic acids are, for example, saturated aliphatic (C 1 -C 26 ) acids, unsaturated (C 1 -C 20 ) fatty acids, aromatic acids and ⁇ , ⁇ -unsaturated acids.
- Suitable ⁇ , ⁇ -unsaturated acids are (meth)acrylic acid, crotonic acid and monoesters or monoamides of itaconic acid, maleic acid, 12-hydroxystearic acid, polyether carboxylic acid, and fumaric acid.
- Suitable saturated aliphatic acids are for example acetic acid, propionic acid, butyric acid, 2-ethyl hexanoic acid, laurylic acid and stearic acid.
- Suitable aromatic acid are for example benzoic acid and tertiairy butyl benzoic acid.
- Z can be chosen from, for example, a saturated or unsaturated (C 1 -C 40 ) alkyl or aromatic group, a polymer or an oligomer.
- suitable polymers are polyesters, polyethers and poly(capro)lactones.
- Z can be substituted with for example ester groups, ether groups, amide groups and alcohol groups.
- the modified polymer may consist of the same or different Z groups.
- the branched polymer according to the invention can also react with a diisocyanate, after which the isocyanate-functional polymer obtained reacts with a compound capable of reacting with isocyanates.
- a diisocyanate use is preferably made of a compound containing two or more isocyanate groups with different reactivities. This is preferably an aliphatic diisocyanate with one sterically more accessible isocyanate group bound to a primary carbon atom and one sterically less accessible isocyanate group bound to a tertiary carbon atom.
- Examples of suitable diisocyanates are 1,4-diisocyanato-4-methyl-pentane, 1,5-diisocyanato-5-methylhexane, 3(4)-isocyanatomethyl-1-methylcyclohexylisocyanate, 1,6-diisocyanato-6-methyl-heptane, 1,5-diisocyanato-2,2,5-trimethylhexane and 1,7-diisocyanato-3,7-dimethyloctane, and 1-isocyanato-1-methyl-4-(4-isocyanatobut-2-yl)-cyclohexane, 1-isocyanato-1,2,2-trimethyl-3-(2-isocyanato-ethyl)-cyclopentane, 1-isocyanato-1,4-dimethyl-4-isocyanatomethyl-cyclohexane, 1-isocyanato-1,3-dimethyl-3-isocyanatomethyl-cyclopentan
- the preferred isocyanates are 3(4)-isocyanato-methyl-1-methylcyclohexylisocyanate (IMCI) and isophorone diisocyanate.
- Monomers, oligomers and polymers can all be used as the compounds that can react with isocyanate groups. Such compounds contain reactive groups that can form a chemical bond with isocyanate groups.
- Examples of suitable reactive groups are alcohols and amine groups.
- Suitable compounds are hydroxyethyl(meth)acrylate, hydroxy(C 2 -C 12 )alkyl vinyl ether, 4-hydroxybutyl(meth)acrylate, aminopropyl vinyl ethers, aminoalkyl vinyl ether, aminopropyl-tri(m)ethoxysilane and aminoalkyltrialkoxysilane.
- the diisocyanate for example IMCI
- a selective catalyst as a result of which no chain lengthening or crosslinking will take place.
- catalyst use can be made of an ionogenic metal complex based on a metallic element from any one of groups III, IV or VII of the Periodic System with exchangeable counterions.
- suitable catalysts are titanium (IV) butoxide, zirconium (IV) acetylacetonate, zirconium (IV) butoxide, tin (IV) acetate, manganese (III) acetylacetonate, titanium (IV) isopropoxide, zirconium (IV) 2-ethylhexanoate and tin (IV) chloride.
- the modified and the unmodified polymers can be very widely used in technically different fields, both in thermosetting and in thermoplastic applications.
- Examples are powder-paint compositions, coating systems based on water or solvent, can- or coil-coating systems, radiation-curable coating compositions, alkyd resins for coatings, unsaturated resins for construction purposes (for example putties, sealants, castings, compounds and molding compounds), inks, toner, film rormers for glass fibre sizings, adhesives, hot melts and in rubber compositions.
- Unmodified or partly modified polymers according to the invention will generally be used in powder-paint systems, in can- or coil-coating systems or in solvent-based coating systems.
- the polymers according to the invention can be used as airdrying systems.
- a modification with radically curable compounds offers possibilities in the technical fields of radiation-curable coatings and construction resins.
- modification can be directed at any of a wide range of technical applications.
- the polymers according to the invention can be used in thermosetting powder-paint compositions. Preferably use is made of the polymers containing ⁇ -hydroxyalkylamide groups.
- thermosetting powder paints have a better resistance to chemicals than thermoplastic powder paints.
- intensive efforts have for a long time been made to develop crosslinkers and polymers for thermosetting powder coatings.
- a thermosetting powder-paint binder composition generally contains more than 50 wt. % polymer and less than 50 wt. % crosslinker.
- the polymer according to the invention can be used in a powder-paint composition as a polymer and as a crosslinker.
- the glass transition temperature (Tg) of the polymer according to the invention lies between 0° C. and 150° C., preferably between 50° C. and 110° C., depending on the selected starting materials and the molecular weight.
- a compound according to any one of formulas (I), (II), (III), (IV) or (V) is used in powder-paint compositions. It is also possible to use a polymer in which up to for example 50 wt. %, preferably less than 30 wt. %, of the hydroxyalkylamide groups are modified.
- a coating that ultimately obtained with a powder paint must meet many varying requirements.
- Various systems are known. Some systems release volatile components during the curing. These systems present the drawback that they form coatings with bubbles and/or that undesirable emissions are released. As far as the latter is concerned, the volatile component, if organic in origin, may cause undesirable environmental or health problems. It has moreover been found that all the desired properties of the powder paint or powder coating are not always realized.
- Systems comprising hydroxyalkylamide crosslinkers such as for example according to EP-A-322834, contain bubbles above a layer thickness limit of about 100 ⁇ m as a result of the reaction water released.
- the crosslinker according to the invention described above can also be used in combination with another crosslinker, such as for example triglycidyl isocyanurate (TGIC), polybisphenol-A-epoxides such as, for instance, the various EpikoteTM grades, compounds containing (blocked) isocyanate groups, such as for example the caprolactam-blocked isophorone diisocyanate trimer, crosslinkers containing ⁇ -hydroxyalkylamide groups such as for example Primid XL 522TM (Rohm and Haas) and/or polyfunctional oxazolines.
- TGIC triglycidyl isocyanurate
- polybisphenol-A-epoxides such as, for instance, the various EpikoteTM grades
- compounds containing (blocked) isocyanate groups such as for example the caprolactam-blocked isophorone diisocyanate trimer
- crosslinkers containing ⁇ -hydroxyalkylamide groups such as for example Primi
- the crosslinker according to the invention is preferably combined with a crosslinker comprising at least one linear or branched aliphatic chain with 5-26 carbon atoms and having an epoxy functionality of more than 1, with the proviso that the epoxy groups are carried on the at least one aliphatic chain.
- crosslinkers include, for example, epoxidized oils in which the oil is linseed oil, soybean oil, safflower oil, oiticica oil, carraway seed oil, rapeseed oil, castor oil, dehydrated castor oil, cottonseed oil, wood oil, vernonia oil (a natural oil), sunflower oil, peanut oil, olive oil, soyleaf oil, maize oil, fish oil such as, for instance, herring or sardine oil, and non-cyclic terpene oils.
- epoxidized oils in which the oil is linseed oil, soybean oil, safflower oil, oiticica oil, carraway seed oil, rapeseed oil, castor oil, dehydrated castor oil, cottonseed oil, wood oil, vernonia oil (a natural oil), sunflower oil, peanut oil, olive oil, soyleaf oil, maize oil, fish oil such as, for instance, herring or sardine oil, and non-cyclic terpene
- the epoxidized oil is preferably epoxidized soybean oil and/or epoxidized linseed oil.
- a powder-paint-binder composition may contain the polymer according to the invention and as the polymer a polymer containing carboxyl groups or containing anhydride groups.
- a polyether such for example a polyether based on bisphenol or a phenol-aldehyde novolak
- a polyurethane such for example a polyether based on bisphenol or a phenol-aldehyde novolak
- a polyurethane such for example a polyether based on bisphenol or a phenol-aldehyde novolak
- a polyurethane such for example a polyether based on bisphenol or a phenol-aldeh
- polymers having an acid value higher than 40 mg KOH/gram resins are applied because a relatively high acid value results in better reactivity with the polymer according to the invention.
- the molecular weight (Mn) of this polymer is usually higher than 800, but preferably higher than 1500.
- the polymer must flow well at temperatures between 100° C. and 200° C. and therefore has a molecular weight (Mn) that is lower than approximately 10,000, preferably lower than approximately 7000.
- This polymer generally has a viscosity at 158° C. that is lower than 8000 dpas.
- the viscosity will usually be higher than 100 dpas.
- the viscosity can advantageously vary from approximately 300 to approximately 5000 dpas.
- the viscosity used here was measured according to the Emila method described by Misev in Powder Coatings; Chemistry and Technology, pages 287-288 (1991).
- the Tg of this polymer is generally higher than approximately 20° C., preferably higher than 30° C., and may be higher than 40° C.
- the polymer's Tg is usually lower than 120° C. because otherwise the binder composition may become somewhat difficult to prepare.
- the choice of the polymer's Tg can be based on the Tg recommended for the binder composition.
- the polymer has an average functionality (capable of reacting with the hydroxyalkylamide groups) of more than 1.6, preferably more than 2.
- the polymer generally has an average functionality of less than 10, preferably less than approximately 6. If use is made of polymers—such as polyacrylates—with appended functional groups, the average functionality will be higher than approximately 1.6, and preferably higher than 2.
- Such a polymer generally has an average functionality of less than 8, preferably less than 4.
- polyesters and polyacrylates are polyesters and polyacrylates.
- polyacrylates are highly resistant to yellowing and to weather influences.
- the polyacrylates that can be used as the polymer may be based on (meth)acrylic acid, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, propyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, cyclohexyl(meth)acrylate, decyl(meth)acrylate, isodecyl(meth)acrylate, benzyl(meth)acrylate and hydroxyalkyl(meth)acrylates such as hydroxyethyl and hydroxypropyl(meth)acrylate and/or glycidyl esters or glycidyl ethers of alkyl(meth)acrylates.
- the polyacrylates can be obtained via known processes. In these processes use can be made of comonomers such as for instance styrene, maleic acid or maleic anhydride and of small amounts of ethylene, propylene and acrylonitrile. Other vinyl or alkyl monomers, such as octene, triallyl isocyanurate and diallyl phthalate, can be added in small amounts.
- a polyacrylate containing acid groups is generally obtained through copolymerization of the desired amount of acid, such as for example (meth)acrylic acid, maleic acid or fumaric acid.
- the polyacrylate's viscosity usually lies between 100 and 8000 dPas (measured at 158° C.; Emila).
- polyurethanes that can be used as the polymer that can react with ⁇ -hydroxyalkylamide groups include for example also the polyurethanes terminated with an acid group and a (blocked) isocyanate group.
- Polyesters are usually based on the residues of aliphatic polyalcohols and polycarboxylic acids.
- the polycarboxylic acids are generally chosen from the group consisting of aromatic and cycloaliphatic polycarboxylic acids because these acids usually have a Tg-raising effect on the polyester. In particular, use is made of dibasic acids. Examples of polycarboxylic acids are isophthalic acid, terephthalic acid, hexahydroterepthalic acid, 2,6-naphthalene dicarboxylic acid and 4,4-oxybisbenzoic acid and, subject to availability, their anhydrides, acid chlorides or lower alkyl esters, such as for example the dimethyl ester of naphthalene dicarboxylic acid. Although not required, the carboxylic acid component generally contains at least approximately 50 mol. %, preferably at least approximately 70 mol. %, isophthalic acid and/or terephthalic acid.
- aromatic cycloaliphatic and/or acyclic polycarboxylic acids are for example 3,6-dichlorophthalic acid, tetrachlorophthalic acid, tetrahydrophthalic acid, hexahydroterephthalic acid, hexachloroendomethylene tetrahydrophthalic acid, phthalic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, adipic acid, succinic acid, trimellitic acid and maleic acid.
- These different carboxylic acids can be used in amounts of at most 50 mol. % of the total amount of carboxylic acids. These acids can be used as such or, subject to availability, in the form of their anhydrides, acid chlorides or lower alkyl esters.
- Hydroxycarboxylic acids and/or optionally lactones can also be used, for example 12-hydroxystearic acid, hydroxypivalic acid and ⁇ -caprolactone. If so desired, monocarboxylic acids, such as benzoic acid, tert.-butylbenzoic acid, hexahydrobenzoic acid and saturated aliphatic monocarboxylic acids can be used in smaller amounts.
- Small amounts such as less than approximately 4 wt. %, but preferably less than 2 wt. %, of trifunctional alcohols or acids can be used to obtain branched polyesters.
- suitable polyols and polyacids are glycerol, hexanetriol, trimethylolethane, trimethylolpropane, tris-(2-hydroxyethyl)-isocyanurate and trimellitic acid.
- Tetrafunctional monomers are usually not preferred, because they can cause excessive branching or gelling, although it is possible to use them in very small amounts.
- suitable polyfunctional alcohols and acids are sorbitol, pentaerythritol and pyromellitic acid. Trifunctional monomers are however preferred for synthesizing branched polyesters.
- the coating properties can be influenced via for example the choice of diol. If for example good weather resistance is required, the alcohol component preferably contains at least 70 mol. % neopentyl glycol, 1,4-dimethylolhexane and/or hydrogenated bisphenol-A. Caprolactone and hydropivalic acid can also be used if good weather resistance is required.
- the polyesters are prepared via the usual processes, through esterification or trans-esterification, optionally in the presence of the usual esterification catalysts such as for example dibutyl tin oxide or tetrabutyl titanate.
- esterification catalysts such as for example dibutyl tin oxide or tetrabutyl titanate.
- the preparation conditions and the COOH/OH ratio can be chosen so that end products having an acid number or hydroxyl value that lies within the desired range of values are obtained.
- a carboxylic-acid-functional polyester is preferably prepared in a series of steps. In the last step thereof an aromatic or, preferably, aliphatic acid is esterified so that an acid-functional polyester is obtained.
- terephthalic acid is in a first step caused to react in the presence of excess diol. Such reactions result in a substantially hydroxyl-functional polyester.
- an acid-functional polyester is obtained by causing further acid to react with the product of the first step.
- Further acids are for example isophthalic acid, adipic acid, succinic anhydride, 1,4-cyclohexanedicarboxylic acid and trimellitic anhydride.
- trimellitic anhydride is used at a temperature of 170-200° C., because then a polyester with a relatively large number of trimellitic acid terminal groups is obtained, as a result of which the reactivity of the binder system is increased and better coating properties are obtained.
- the polyester may be a crystalline polyester, but amorphous polyesters are preferred. Mixtures of crystalline and amorphous polyesters can also be used. Amorphous polyesters have a viscosity that generally lies within a range from 100 to 8000 dPas (measured at 158° C., Emila). Crystalline polyesters usually have a lower viscosity in the range from approximately 2 to approximately 200 dPas.
- the polyester's acid number is chosen so that the desired amount of crosslinker can be used.
- the acid number is preferably higher than 10 and more preferably higher than 40.
- the polyester's Tg is chosen so that the Tg of the polyester-crosslinker mixture lies between for example 30° C. and 80° C., as a result of which powder paints or binders prepared from them are physically stable at room temperature.
- Combinations of polyester and crosslinker having a lower Tg can optionally be used in the preparation of a powder coating composition. To retain the powder stability, such powders are however stored in cooled condition.
- the selection of the polymer: crosslinker weight ratio depends on the desired final application and this ratio will generally be between 60:40 and 90:10, preferably between 75:25 and 85:15.
- the polymer according to the invention is used as a resin in powder-paint compositions
- compounds containing two or more functional groups that can react with ⁇ -hydroxyamide groups can be used as the crosslinker.
- groups are anhydrides, carboxylic acids, carboxylic esters, epoxides, isocyanates and alkoxysilanes.
- anhydride groups, carboxylic acids and blocked isocyanates are used.
- Examples are adipic acid, decanedicarboxylic acid, trimellitic anhydride, phthalic acid or phthalic anhydride, tetrahydrophthalic acid or tetrahydrophthalic anhydride, hexahydrophthalic acid or hexahydrophthalic anhydride and IPDI-trimer or HDI-trimer, optionally blocked with caprolactam or triazole.
- thermosetting powder coatings in general and the chemical reactions for curing powder paints to form cured coatings are described by Misev in Powder Coatings, Chemistry and Technology (1991, John Wiley) on pp. 42-54, pp. 148 and 224-226.
- a thermosetting binder composition is generally defined as the resinous part of the powder paint consisting of polymer and crosslinker.
- the usual additives can be used in the binder composition and in the powder-paint system according to the invention, such as for example pigments, fillers, degassing agents, flow agents and stabilizers.
- Suitable pigments are for example inorganic pigments, such as for example titanium dioxide, zinc sulphide, iron oxide and chromium oxide, and also organic pigments such as for example azo compounds.
- Suitable fillers are for example metal oxides, silicates, carbonates and sulphates.
- UV stabilizers such as quinones, (sterically hindered) phenolic compounds, phosphonites, phosphites, thioethers and HALS compounds (hindered amine light stabilizers) can for example be used as stabilizers.
- degassing agents are benzoin and cyclohexane dimethanol bisbenzoate.
- the flow agents include for example polyalkylacrylates, fluorohydrocarbons and silicone fluids.
- Other suitable additives are for example additives for improving tribocharging, such as sterically hindered tertiary amines that are described in EP-B-371528.
- Powder paints according to the invention can be applied in the usual manner, for example by electrostatically spraying the powder onto an earthed substrate and curing the coating by exposing it to heat at a suitable temperature for a sufficient length of time.
- the applied powder can for example be heated in a gas oven, an electric oven or with the aid of infrared radiation.
- compositions according to the present invention can be used in powder paints for use on, for example, metal, wooden and plastic substrates.
- Examples are industrial coatings, coatings for machines and tools, household applications and parts of buildings.
- the coatings are also suitable for use in the automotive industry for coating parts and accessories.
- DE-A-19703952 discloses a copolyester containing ⁇ -hydroxyalkylamide groups as endgroups.
- the polyester polymer backbone does not comprise amide groups.
- the copolyester is prepared in a three step process by mixing a hydroxy polyester with a polycarboxylic acid dialkyl ester to form an alkylester group containing copolyester followed by reaction with an aminoalcohol.
- the polymer according to the invention is a polyesteramide having amide and ester groups along the backbone in addition to the ⁇ -hydroxyalkylamide endgroups. This polyesteramide results in improved mechanical coating properties by more extensive hydrogen bridge formation, improved crosslinkdensity and improved hydrolysis resistance.
- the concentration of hydroxyl groups was titrimetrically found to be 5.4 meq/g.
- the number average molecular mass was determined with the aid of GPC (universal calibration) and was 1500 g/mol; the weight average molecular mass was 7700 g/mol.
- the concentration of hydroxyl groups was titrimetrically found to be 5.8 meq/g.
- the number average molecular mass was determined with the aid of GPC (universal calibration) and was 1100 g/mol; the weight average molecular mass 4900 g/mol.
- the concentration of hydroxyl groups was titrimetrically found to be 5.2 meq/g.
- the number average molecular mass was determined with the aid of GPC (universal calibration) and was 1550 g/mol; the weight average molecular was mass 7000 g/mol.
- the concentration of hydroxyl groups was titrimetrically found to be 6.1 meq/g.
- the number average molecular mass was determined with the aid of GPC (universal calibration) and was 1010 g/mol; the weight average molecular mass 4600 g/mol.
- Powder-paint Compositions Comprising a Polymer According to any One of Examples I-IV
- Powder-paint compositions according to Table 1 were prepared by mixing and extrusion (PRISM extruder, 120° C.).
- the polyesters (Uralac 5040TM and Uralac 5261TM from DSM Resins) comprise units of terephthalic acid, adipic acid, neopentyl glycol and trimellitic anhydride.
- compositions were in the usual manner ground, sieved and electrostatically sprayed (Corona) onto aluminium and steel test panels. After a cure cycle of 10 minutes at 200° C. or 15 minutes at 180° C. in a circulation oven, the panels were tested to determine their appearance (visually), flexibility (penetration in mm according to Erichsen ISO 1520/DIN 53156), reverse impact resistance (ASTM-2794/69 in inch-pound), acetone resistance (acetone double rubs), adhesion (cross hatch adhesion test) and hardness (König, seconds). The test results are shown in Table 1.
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Abstract
Description
- The invention relates to a linear or branched condensation polymer containing ester groups and at least one amide group in the backbone, having at least one hydroxyalkylamide endgroup and having a weight average molecular mass of ≧800 g/mol.
-
-
- (C1-C20)(cyclo)alkyl, or (C6-C10) aryl,
- B=(C2-C24), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical,
- R1, R2, R3, R4, R5 and R6 may, independently of one another, be the same or different, H, (C6-C10) aryl or (C1-C8)(cyclo)alkyl radical and
- n=1-4.
-
-
- (C1-C20)(cyclo)alkyl, or (C6-C10) aryl,
- B=(C2-C24), optionally substituted, aryl or (cyclo)alkyl aliphatic diradical, and
- R1, R2, R3, R4, R5 and R6 may, independently of one another, be the same or different, H, (C6-C10) aryl or (C1-C8)(cyclo)alkyl radical.
-
-
-
- or OH,
-
- X2=H or X1 and
- R1, R2, R3, R4, R5 and R6 may, independently of one another, be the same or different, H, (C6-C10) aryl or (C1-C8)(cyclo)alkyl radical or CH2-OX2.
- In formulas (I), (II) and (III) R groups may together or with neighbouring carbon atoms form part of a cycloalkyl group.
-
-
-
- or OH,
-
- X2=H or X1,
- R3=H or (C6-C10) aryl or (C1-C8)alkyl radical and
- R6=H or (C6-C10) aryl or (C1-C8)alkyl radical.
- The weight average molecular mass of the polymer according to the invention is generally between 800 and 50,000, and preferably between 1000 g/mol and 25,000 g/mol.
- The number average molecular mass is generally between 600 and 10,000 and preferably between 700 and 4000.
- The hydroxyalkylamide functionality is generally between 2 and 250 and preferably between 5 and 50.
- Functionality is the average number of reactive groups of the specific type per molecule in the polymer composition.
-
-
-
- X2=H or X1,
- R3=H or (C6-C10) aryl or (C1-C8) (cyclo)alkyl radical and
- R6=H or (C6-C10) aryl or (C1-C8) (cyclo)alkyl radical Preferably R3 and R6 are (C1-C4) alkyl.
- According to another preferred embodiment of the invention R3 and R6 are methyl or ethyl.
- B may be saturated or unsaturated.
- B may be substituted with for example a (C1-C26) alkyl group, which may be saturated or unsaturated; preferably C1 is used.
- B may be for example a (methyl-)1,2-ethylene, (methyl-)1,2-ethylidene, 1,3-propylene, (methyl-)1,2-cyclohexyl, (methyl-)1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,3-norbornyl, 2,3-norbornen-5-yl and/or (methyl-)1,2 cyclohex-4-enyl radical.
- Depending on the starting monomers chosen, the variables B, R1, R2, R3, R4, R5 and R6 in the molecule or mixture of molecules can be selected to be the same or different per variable.
- The polymer composition according to the invention is generally a composition comprising higher and lower oligomers, which usually contains less than 50 wt. %, preferably less than 30 wt. %, of oligomers having a molecular weight smaller than 600.
- The polyesteramide according to the invention can for example be obtained through polycondensation of mono- and/or bis-hydroxyalkylamides of bivalent carboxylic acids.
-
-
- wherein
- R1, R R3 and R4 may, independently of one another, be the same or different, H, (C6-C10) aryl or (C1-C8)(cyclo)alkyl radical.
- Consequently a lineair polymer according to the invention generally comprises the amide and the ester groups alternating along the chain as follows:
- E-A-E-A-A-E-A-E-A-E
- wherein a diamide is coupled with alternating ester (E)—amide (A) groups.
-
- wherein a diamide is coupled with alternating ester (E)—amide (A) groups.
-
-
- Generally, the molar amount of amide bounds in the chain is higher than the amount of ester bounds.
- The polymer according to the invention comprises at least 60% by weight of the products represented by the formulas (III)-(V).
-
- wherein:
- R1, R2, R3 and R4 may, independently of one another, be the same or different, H, (C6-C10) aryl or (C1-C8) (cyclo)alkyl radical.
- The polymer according to the invention can, also be obtained in a one-step procedure by reacting a cyclic anhydride and an alkanolamine, at a temperature between for example about 20° C. and about 100° C., to form a hydroxyalkylamide, after which, at a temperature between, for example, 120° C. and 250° C., a polyesteramide is obtained through polycondensation with water being removed through distillation.
- The reaction can take place without a solvent, but also in water or in an organic solvent.
- The removal of water through distillation can take place at a pressure higher than 1 bar, in a vacuum or azeotropically.
-
- in which B has the meaning specified above.
- Examples of suitable cyclic anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, naphtalenic dicarboxylic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornene-2,3-dicarboxylic anhydride, naphtalenic dicarboxylic anhydride, 2-dodecene-1-yl-succinic anhydride, maleic anhydride, (methyl)succinic anhydride, glutaric anhydride, 4-methylphthalic anhydride, 4-methylhexahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride and the maleinised alkylester of an unsaturated fatty acid.
-
-
- (C1-C20)(cyclo)alkyl, R1, R2, R3, R4, R5 and R6 may, independently of one another, be the same or different, H, (C6-C10) aryl or (C1-C8)(cyclo)alkyl radical or CH2OH and n=1-4.
- More preferably n=1. The alkanolamine may be a monoalkanolamine, a dialkanolamine, a trialkanolamine or a mixture hereof.
- If monoalkanolamines are used in one of the possible polymer syntheses, linear polymers with a functionality of 2 can be obtained. Depending on the application desired, a linear or an entirely or partly branched polymer can be chosen, in which case the degree of branching can be set via the alkanolamines chosen.
- If a highly branched structure with a high functionality is desired, di- or trialkanolamines are used as the starting compound.
- Examples of suitable mono-β-alkanolamines include ethanolamine, 1-(m)ethyl ethanolamine, n-butyl ethanolamine, 1-(m)ethyl isopropanolamine, isobutanolamine, β-cyclohexanolamine, n-butyl isopropanolamine and n-propanolamine.
- Examples of suitable di-β-alkanolamines are 3-amino-1,2-propanediol, 2-amino-1,3-propanediol diisobutanolamine (bis-2-hydroxy-1-butyl)amine), di-β-cyclohexanolamine and diisopropanolamine (bis-2-hydroxy-1-propyl)amine).
- A suitable trialkanolamine is, for example, tris(hydroxymethyl)aminomethane.
- Preferably a β-alkyl-substituted β-hydroxyalkylamide is used. Examples are (di) isopropanolamine, cyclohexyl isopropanolamine, 1-(m)ethyl isopropanolamine, (di)isobutanolamine, di-β-cyclohexanolamine and/or n-butyl isopropanolamine.
- This results in polymer compositions with improved resistance to hydrolysis.
- Most preferable are diisopropanolamine and diisobutanolamine.
- The anhydride: alkanolamine equivalent ratio is generally between 1.0:1.0 and 1.0:1.8. Preferably, this ratio is between 1:1.05 and 1:1.5.
- The compound according to the invention can also be obtained via a reaction between an alkanolamine, as for example described above, and a compound containing one acid group and one activated acid group, after which a polyesteramide is obtained through polycondensation.
-
- in which
-
- in which R7 is a (C1-C12) branched or linear alkyl group.
- Examples of suitable compounds containing one acid group and one activated acid group are alkyl esters, such as, for example, mono(m)ethyl adipate and mono(m)ethyl sebacate, anhydrides and thioesters.
- The compound according to the invention can also be obtained via a reaction between a cyclic anhydride, as for example described above, and an alcohol, after which the reaction product obtained reacts in situ with an alkanolamine and a polyesteramide is subsequently obtained through polycondensation.
- Examples of suitable alcohols are (C1-C10) alcohols.
- Preferably, methanol or ethanol is used.
- In addition to hydroxyalkylamide groups, the polymer may also contain carboxyl groups, in amounts of between 0.01 and 2.0 mg equivalent/gram of polymer. The number of carboxylic acids present in the polymer can be controlled via the anhydride/alkanolamine ratio and via the degree of conversion. If an alkanolamine excess is used and the polycondensationreaction is (almost) complete, less than 0.2 mg equivalent acid/gram of polymer is usually present. If carboxyl groups are present, they may in a subsequent step react with compounds containing one or more groups that can react with carboxylic acid, such as for example epoxy groups or β-hydroxyalkylamide groups. The amount of carboxylic acid is preferably as low as possible, for example between 0.01 and 0.2 mg equivalent/gram of polymer.
- The degree of branching and the functionality of the polymer are dependent on the starting materials and the molecular weight of the polymer. A molecular weight higher than 2000 and the use of di- and/or trialkanolamines generally lead to highly branched structures with a functionality of ≧10.
- Due to the presence in amounts of less than 10% by weight (of the total amount of anhydrides) of bis- and dianhydrides instead of the anhydrides according to formula (IX) it is possible that the polymer does not comprise only products according to formulas (III)-(V)
- The invention also relates to entirely or partly modified polymers.
- The modification can for example take place via a reaction between the polymer according to any one of formulas (III), (IV) or (V) with a monomer, oligomer or polymer containing reactive groups that can react with the hydroxyalkylamide.
- Examples of suitable reactive groups include carboxyl groups, carboxylic esters, carboxylic anhydrides, epoxy groups, alkoxysilane groups, isocyanate groups, acid chloride groups, epoxychlorohydrine groups, amine groups, phenolic groups, methylolated amidegroups and combinations hereof.
- Preferably the monomer, oligomer or polymer contains only one group that can react with hydroxylalkylamide, as a result of which no crosslinking takes place during the modification.
- The polymer according to formula (III), (IV) or (V) has preferably been modified with a compound containing a carboxylic acid group.
-
-
- is derived from a monomeric, oligomeric or polymeric monofunctional carboxylic acid.
- Suitable carboxylic acids are, for example, saturated aliphatic (C1-C26) acids, unsaturated (C1-C20) fatty acids, aromatic acids and α,β-unsaturated acids.
- Examples of suitable α, β-unsaturated acids are (meth)acrylic acid, crotonic acid and monoesters or monoamides of itaconic acid, maleic acid, 12-hydroxystearic acid, polyether carboxylic acid, and fumaric acid.
- Suitable saturated aliphatic acids are for example acetic acid, propionic acid, butyric acid, 2-ethyl hexanoic acid, laurylic acid and stearic acid.
- Suitable aromatic acid are for example benzoic acid and tertiairy butyl benzoic acid.
- Z can be chosen from, for example, a saturated or unsaturated (C1-C40) alkyl or aromatic group, a polymer or an oligomer. Examples of suitable polymers are polyesters, polyethers and poly(capro)lactones.
- Z can be substituted with for example ester groups, ether groups, amide groups and alcohol groups.
- The modified polymer may consist of the same or different Z groups.
- The branched polymer according to the invention can also react with a diisocyanate, after which the isocyanate-functional polymer obtained reacts with a compound capable of reacting with isocyanates. As the diisocyanate use is preferably made of a compound containing two or more isocyanate groups with different reactivities. This is preferably an aliphatic diisocyanate with one sterically more accessible isocyanate group bound to a primary carbon atom and one sterically less accessible isocyanate group bound to a tertiary carbon atom.
- Examples of suitable diisocyanates are 1,4-diisocyanato-4-methyl-pentane, 1,5-diisocyanato-5-methylhexane, 3(4)-isocyanatomethyl-1-methylcyclohexylisocyanate, 1,6-diisocyanato-6-methyl-heptane, 1,5-diisocyanato-2,2,5-trimethylhexane and 1,7-diisocyanato-3,7-dimethyloctane, and 1-isocyanato-1-methyl-4-(4-isocyanatobut-2-yl)-cyclohexane, 1-isocyanato-1,2,2-trimethyl-3-(2-isocyanato-ethyl)-cyclopentane, 1-isocyanato-1,4-dimethyl-4-isocyanatomethyl-cyclohexane, 1-isocyanato-1,3-dimethyl-3-isocyanatomethyl-cyclohexane, 1-isocyanatol-n-butyl-3-(4-isocyanatobut-1-yl)-cyclopentane and 1-isocyanato-1,2-dimethyl-3-ethyl-3-isocyanatomethyl-cyclopentane, respectively.
- The preferred isocyanates are 3(4)-isocyanato-methyl-1-methylcyclohexylisocyanate (IMCI) and isophorone diisocyanate.
- Monomers, oligomers and polymers can all be used as the compounds that can react with isocyanate groups. Such compounds contain reactive groups that can form a chemical bond with isocyanate groups.
- Examples of suitable reactive groups are alcohols and amine groups.
- Examples of suitable compounds are hydroxyethyl(meth)acrylate, hydroxy(C2-C12)alkyl vinyl ether, 4-hydroxybutyl(meth)acrylate, aminopropyl vinyl ethers, aminoalkyl vinyl ether, aminopropyl-tri(m)ethoxysilane and aminoalkyltrialkoxysilane.
- Preferably the diisocyanate, for example IMCI, is combined with a selective catalyst, as a result of which no chain lengthening or crosslinking will take place.
- As the catalyst use can be made of an ionogenic metal complex based on a metallic element from any one of groups III, IV or VII of the Periodic System with exchangeable counterions. Examples of suitable catalysts are titanium (IV) butoxide, zirconium (IV) acetylacetonate, zirconium (IV) butoxide, tin (IV) acetate, manganese (III) acetylacetonate, titanium (IV) isopropoxide, zirconium (IV) 2-ethylhexanoate and tin (IV) chloride.
- The modified and the unmodified polymers can be very widely used in technically different fields, both in thermosetting and in thermoplastic applications. Examples are powder-paint compositions, coating systems based on water or solvent, can- or coil-coating systems, radiation-curable coating compositions, alkyd resins for coatings, unsaturated resins for construction purposes (for example putties, sealants, castings, compounds and molding compounds), inks, toner, film rormers for glass fibre sizings, adhesives, hot melts and in rubber compositions.
- Unmodified or partly modified polymers according to the invention will generally be used in powder-paint systems, in can- or coil-coating systems or in solvent-based coating systems.
- If the modification has been realized with the aid of for example fatty acids, the polymers according to the invention can be used as airdrying systems.
- A modification with radically curable compounds offers possibilities in the technical fields of radiation-curable coatings and construction resins.
- Considering the many possibilities of modification of the polymer according to the invention, modification can be directed at any of a wide range of technical applications.
- The polymers according to the invention can be used in thermosetting powder-paint compositions. Preferably use is made of the polymers containing β-hydroxyalkylamide groups.
- Thermosetting powder paints have a better resistance to chemicals than thermoplastic powder paints. As a result of this, intensive efforts have for a long time been made to develop crosslinkers and polymers for thermosetting powder coatings. Attempts are still being made to find binder compositions for thermosetting powder paints with a good flow behaviour, good storage stability and a good reactivity. A thermosetting powder-paint binder composition generally contains more than 50 wt. % polymer and less than 50 wt. % crosslinker.
- The polymer according to the invention can be used in a powder-paint composition as a polymer and as a crosslinker.
- The glass transition temperature (Tg) of the polymer according to the invention lies between 0° C. and 150° C., preferably between 50° C. and 110° C., depending on the selected starting materials and the molecular weight.
- Preferably a compound according to any one of formulas (I), (II), (III), (IV) or (V) is used in powder-paint compositions. It is also possible to use a polymer in which up to for example 50 wt. %, preferably less than 30 wt. %, of the hydroxyalkylamide groups are modified.
- A coating that ultimately obtained with a powder paint must meet many varying requirements. Various systems are known. Some systems release volatile components during the curing. These systems present the drawback that they form coatings with bubbles and/or that undesirable emissions are released. As far as the latter is concerned, the volatile component, if organic in origin, may cause undesirable environmental or health problems. It has moreover been found that all the desired properties of the powder paint or powder coating are not always realized.
- Systems comprising hydroxyalkylamide crosslinkers, such as for example according to EP-A-322834, contain bubbles above a layer thickness limit of about 100 μm as a result of the reaction water released.
- In other systems use is made of polyesters and the usual crosslinkers containing an epoxy group. No volatile components are generally released from these systems. However, the use of bisphenol-A-epoxy resins in the so-called hybrid systems results in coatings that exhibit a relatively great extent of yellowing and powdering when exposed to UV light, while the frequently used triglycidylisocyanurate (TGIC) crosslinker is toxicologically suspect.
- It has been found that use of the polymer according to the invention as the crosslinker in binder compositions for powder paints results in a combination of highly desirable properties such as for instance good flow behaviour and good resistance to chemicals, desired gloss without bubble formation at the surface up to and including layer thicknesses of at least 120 μm, a high resistance to scratching, good mechanical properties, good powder stability, good weather resistance and good colour stability of the powder coating.
- It is surprising that use of the highly functional crosslinkers according to the invention leads to good flow behaviour, because generally a crosslinker having a functionality higher than, for example, 6 results in reduced flow behaviour.
- Depending on the final application desired, the crosslinker according to the invention described above can also be used in combination with another crosslinker, such as for example triglycidyl isocyanurate (TGIC), polybisphenol-A-epoxides such as, for instance, the various Epikote™ grades, compounds containing (blocked) isocyanate groups, such as for example the caprolactam-blocked isophorone diisocyanate trimer, crosslinkers containing β-hydroxyalkylamide groups such as for example Primid XL 522™ (Rohm and Haas) and/or polyfunctional oxazolines. The weight ratio between the crosslinkers can be selected depending on the final application.
- The crosslinker according to the invention is preferably combined with a crosslinker comprising at least one linear or branched aliphatic chain with 5-26 carbon atoms and having an epoxy functionality of more than 1, with the proviso that the epoxy groups are carried on the at least one aliphatic chain. These crosslinkers are described in EP-A-600546 and include, for example, epoxidized oils in which the oil is linseed oil, soybean oil, safflower oil, oiticica oil, carraway seed oil, rapeseed oil, castor oil, dehydrated castor oil, cottonseed oil, wood oil, vernonia oil (a natural oil), sunflower oil, peanut oil, olive oil, soyleaf oil, maize oil, fish oil such as, for instance, herring or sardine oil, and non-cyclic terpene oils.
- The epoxidized oil is preferably epoxidized soybean oil and/or epoxidized linseed oil.
- As the crosslinker, a powder-paint-binder composition may contain the polymer according to the invention and as the polymer a polymer containing carboxyl groups or containing anhydride groups.
- A polyester, a polyacrylate, a polyether (such for example a polyether based on bisphenol or a phenol-aldehyde novolak), a polyurethane, a polycarbonate, a trifluoroethylene copolymer or a pentafluoropropylene copolymer, a polybutadiene, a polystyrene or a styrene maleic anhydride copolymer can for example be chosen as the polymer.
- Generally, polymers having an acid value higher than 40 mg KOH/gram resins are applied because a relatively high acid value results in better reactivity with the polymer according to the invention.
- The molecular weight (Mn) of this polymer is usually higher than 800, but preferably higher than 1500. The polymer must flow well at temperatures between 100° C. and 200° C. and therefore has a molecular weight (Mn) that is lower than approximately 10,000, preferably lower than approximately 7000.
- This polymer generally has a viscosity at 158° C. that is lower than 8000 dpas. The viscosity will usually be higher than 100 dpas. The viscosity can advantageously vary from approximately 300 to approximately 5000 dpas. The viscosity used here was measured according to the Emila method described by Misev in Powder Coatings; Chemistry and Technology, pages 287-288 (1991).
- The Tg of this polymer is generally higher than approximately 20° C., preferably higher than 30° C., and may be higher than 40° C. The polymer's Tg is usually lower than 120° C. because otherwise the binder composition may become somewhat difficult to prepare. As already indicated above, the choice of the polymer's Tg can be based on the Tg recommended for the binder composition.
- If use is made of polymers having only terminal groups that can react with a hydroxyalkylamide functionality, the polymer has an average functionality (capable of reacting with the hydroxyalkylamide groups) of more than 1.6, preferably more than 2. The polymer generally has an average functionality of less than 10, preferably less than approximately 6. If use is made of polymers—such as polyacrylates—with appended functional groups, the average functionality will be higher than approximately 1.6, and preferably higher than 2. Such a polymer generally has an average functionality of less than 8, preferably less than 4.
- Most preferable of the suitable polymers are polyesters and polyacrylates.
- With the polymers described various properties can be obtained in the binder and in the powder coating itself. Polyacrylates are highly resistant to yellowing and to weather influences. The polyacrylates that can be used as the polymer may be based on (meth)acrylic acid, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, propyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, cyclohexyl(meth)acrylate, decyl(meth)acrylate, isodecyl(meth)acrylate, benzyl(meth)acrylate and hydroxyalkyl(meth)acrylates such as hydroxyethyl and hydroxypropyl(meth)acrylate and/or glycidyl esters or glycidyl ethers of alkyl(meth)acrylates.
- The polyacrylates can be obtained via known processes. In these processes use can be made of comonomers such as for instance styrene, maleic acid or maleic anhydride and of small amounts of ethylene, propylene and acrylonitrile. Other vinyl or alkyl monomers, such as octene, triallyl isocyanurate and diallyl phthalate, can be added in small amounts.
- A polyacrylate containing acid groups is generally obtained through copolymerization of the desired amount of acid, such as for example (meth)acrylic acid, maleic acid or fumaric acid.
- The polyacrylate's viscosity usually lies between 100 and 8000 dPas (measured at 158° C.; Emila).
- Polyacrylates are described in the patents U.S. Pat. No. 3,752,870, U.S. Pat. No. 3,787,340 and U.S. Pat. No. 3,758,334 and in the British patent 1,333,361, and what is disclosed in said patents is included herein by means of this reference.
- The polyurethanes that can be used as the polymer that can react with β-hydroxyalkylamide groups include for example also the polyurethanes terminated with an acid group and a (blocked) isocyanate group.
- Polyesters are usually based on the residues of aliphatic polyalcohols and polycarboxylic acids.
- The polycarboxylic acids are generally chosen from the group consisting of aromatic and cycloaliphatic polycarboxylic acids because these acids usually have a Tg-raising effect on the polyester. In particular, use is made of dibasic acids. Examples of polycarboxylic acids are isophthalic acid, terephthalic acid, hexahydroterepthalic acid, 2,6-naphthalene dicarboxylic acid and 4,4-oxybisbenzoic acid and, subject to availability, their anhydrides, acid chlorides or lower alkyl esters, such as for example the dimethyl ester of naphthalene dicarboxylic acid. Although not required, the carboxylic acid component generally contains at least approximately 50 mol. %, preferably at least approximately 70 mol. %, isophthalic acid and/or terephthalic acid.
- Other suitable aromatic cycloaliphatic and/or acyclic polycarboxylic acids are for example 3,6-dichlorophthalic acid, tetrachlorophthalic acid, tetrahydrophthalic acid, hexahydroterephthalic acid, hexachloroendomethylene tetrahydrophthalic acid, phthalic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, adipic acid, succinic acid, trimellitic acid and maleic acid. These different carboxylic acids can be used in amounts of at most 50 mol. % of the total amount of carboxylic acids. These acids can be used as such or, subject to availability, in the form of their anhydrides, acid chlorides or lower alkyl esters.
- Hydroxycarboxylic acids and/or optionally lactones can also be used, for example 12-hydroxystearic acid, hydroxypivalic acid and ε-caprolactone. If so desired, monocarboxylic acids, such as benzoic acid, tert.-butylbenzoic acid, hexahydrobenzoic acid and saturated aliphatic monocarboxylic acids can be used in smaller amounts.
- The polyalcohols, in particular diols, that can be caused to react with the carboxylic acids to obtain the polyester include aliphatic diols such as for example ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,4-diol, butane-1,3-diol, 2,2-dimethylpropanediol-1,3 (=neopentyl glycol), hexane-2,5-diol, hexane-1,6-diol, 2,2-bis-(4-hydroxy-cyclohexyl)-propane (hydrogenated bisphenol-A), 1,4-dimethylolcyclohexane, diethylene glycol, dipropylene glycol and 2,2-bis[4-2-hydroxylethoxy)-phenyl]propane and the hydroxypivalic ester of neopentyl glycol.
- Small amounts, such as less than approximately 4 wt. %, but preferably less than 2 wt. %, of trifunctional alcohols or acids can be used to obtain branched polyesters. Examples of suitable polyols and polyacids are glycerol, hexanetriol, trimethylolethane, trimethylolpropane, tris-(2-hydroxyethyl)-isocyanurate and trimellitic acid.
- Tetrafunctional monomers are usually not preferred, because they can cause excessive branching or gelling, although it is possible to use them in very small amounts. Examples of suitable polyfunctional alcohols and acids are sorbitol, pentaerythritol and pyromellitic acid. Trifunctional monomers are however preferred for synthesizing branched polyesters.
- The coating properties can be influenced via for example the choice of diol. If for example good weather resistance is required, the alcohol component preferably contains at least 70 mol. % neopentyl glycol, 1,4-dimethylolhexane and/or hydrogenated bisphenol-A. Caprolactone and hydropivalic acid can also be used if good weather resistance is required.
- The polyesters are prepared via the usual processes, through esterification or trans-esterification, optionally in the presence of the usual esterification catalysts such as for example dibutyl tin oxide or tetrabutyl titanate. The preparation conditions and the COOH/OH ratio can be chosen so that end products having an acid number or hydroxyl value that lies within the desired range of values are obtained.
- A carboxylic-acid-functional polyester is preferably prepared in a series of steps. In the last step thereof an aromatic or, preferably, aliphatic acid is esterified so that an acid-functional polyester is obtained. As known to a person skilled in the art, terephthalic acid is in a first step caused to react in the presence of excess diol. Such reactions result in a substantially hydroxyl-functional polyester. In a second or subsequent step an acid-functional polyester is obtained by causing further acid to react with the product of the first step. Further acids are for example isophthalic acid, adipic acid, succinic anhydride, 1,4-cyclohexanedicarboxylic acid and trimellitic anhydride.
- Preferably trimellitic anhydride is used at a temperature of 170-200° C., because then a polyester with a relatively large number of trimellitic acid terminal groups is obtained, as a result of which the reactivity of the binder system is increased and better coating properties are obtained.
- The polyester may be a crystalline polyester, but amorphous polyesters are preferred. Mixtures of crystalline and amorphous polyesters can also be used. Amorphous polyesters have a viscosity that generally lies within a range from 100 to 8000 dPas (measured at 158° C., Emila). Crystalline polyesters usually have a lower viscosity in the range from approximately 2 to approximately 200 dPas.
- If the polyester contains groups that can react with carboxylic acid, the polyester's acid number is chosen so that the desired amount of crosslinker can be used. The acid number is preferably higher than 10 and more preferably higher than 40.
- The polyester's Tg is chosen so that the Tg of the polyester-crosslinker mixture lies between for example 30° C. and 80° C., as a result of which powder paints or binders prepared from them are physically stable at room temperature. Combinations of polyester and crosslinker having a lower Tg can optionally be used in the preparation of a powder coating composition. To retain the powder stability, such powders are however stored in cooled condition.
- The selection of the polymer: crosslinker weight ratio depends on the desired final application and this ratio will generally be between 60:40 and 90:10, preferably between 75:25 and 85:15.
- If the polymer according to the invention is used as a resin in powder-paint compositions, compounds containing two or more functional groups that can react with β-hydroxyamide groups can be used as the crosslinker. Examples of such groups are anhydrides, carboxylic acids, carboxylic esters, epoxides, isocyanates and alkoxysilanes. Preferably anhydride groups, carboxylic acids and blocked isocyanates are used. Examples are adipic acid, decanedicarboxylic acid, trimellitic anhydride, phthalic acid or phthalic anhydride, tetrahydrophthalic acid or tetrahydrophthalic anhydride, hexahydrophthalic acid or hexahydrophthalic anhydride and IPDI-trimer or HDI-trimer, optionally blocked with caprolactam or triazole.
- The preparation of thermosetting powder coatings in general and the chemical reactions for curing powder paints to form cured coatings are described by Misev in Powder Coatings, Chemistry and Technology (1991, John Wiley) on pp. 42-54, pp. 148 and 224-226. A thermosetting binder composition is generally defined as the resinous part of the powder paint consisting of polymer and crosslinker.
- If so desired, the usual additives can be used in the binder composition and in the powder-paint system according to the invention, such as for example pigments, fillers, degassing agents, flow agents and stabilizers. Suitable pigments are for example inorganic pigments, such as for example titanium dioxide, zinc sulphide, iron oxide and chromium oxide, and also organic pigments such as for example azo compounds. Suitable fillers are for example metal oxides, silicates, carbonates and sulphates.
- Primary and/or secondary antioxidants, UV stabilizers such as quinones, (sterically hindered) phenolic compounds, phosphonites, phosphites, thioethers and HALS compounds (hindered amine light stabilizers) can for example be used as stabilizers.
- Examples of degassing agents are benzoin and cyclohexane dimethanol bisbenzoate. The flow agents include for example polyalkylacrylates, fluorohydrocarbons and silicone fluids. Other suitable additives are for example additives for improving tribocharging, such as sterically hindered tertiary amines that are described in EP-B-371528.
- Powder paints according to the invention can be applied in the usual manner, for example by electrostatically spraying the powder onto an earthed substrate and curing the coating by exposing it to heat at a suitable temperature for a sufficient length of time. The applied powder can for example be heated in a gas oven, an electric oven or with the aid of infrared radiation.
- Thermosetting coatings of powder-paint (coating) compositions intended for industrial applications are described further in a general sense in Powder Coatings, Chemistry and Technology, Misev, pages 141-173 (1991).
- Compositions according to the present invention can be used in powder paints for use on, for example, metal, wooden and plastic substrates. Examples are industrial coatings, coatings for machines and tools, household applications and parts of buildings. The coatings are also suitable for use in the automotive industry for coating parts and accessories.
- DE-A-19703952 discloses a copolyester containing β-hydroxyalkylamide groups as endgroups. The polyester polymer backbone does not comprise amide groups. The copolyester is prepared in a three step process by mixing a hydroxy polyester with a polycarboxylic acid dialkyl ester to form an alkylester group containing copolyester followed by reaction with an aminoalcohol. In contrast, the polymer according to the invention is a polyesteramide having amide and ester groups along the backbone in addition to the β-hydroxyalkylamide endgroups. This polyesteramide results in improved mechanical coating properties by more extensive hydrogen bridge formation, improved crosslinkdensity and improved hydrolysis resistance.
- The invention will be elucidated with reference to the following, non-limiting examples.
- Preparation of a Highly Branched Polymer Comprising Units of Phthalic Anhydride and Diisopropanolamine
- 384 g of phthalic anhydride and 415 g of diisopropanolamine were introduced into a double-walled glass reactor, which could be heated by means of thermal oil, fitted with a mechanical stirrer, a distillation head and nitrogen and vacuum connections. The reaction mixture was gradually heated, with stirring, to approx. 70° C. and then more slowly to 170° C. A vacuum was created during the heating. The pressure in the reactor was adjusted to the release of reaction water, so that this could be removed from the reactor through distillation. After a total reaction time of 6 hours the viscous polymer contained less than 0.1 meq/g carboxylic acid (titrimetrically determined) and no more water could be removed through distillation. After cooling the polymer was obtained as a very pale yellow glassy mass. The concentration of hydroxyl groups was titrimetrically found to be 5.4 meq/g. The number average molecular mass was determined with the aid of GPC (universal calibration) and was 1500 g/mol; the weight average molecular mass was 7700 g/mol.
- Preparation of a Highly Branched Polymer Comprising Units of Phthalic Anhydride and Diisopropanolamine
- 232 g of phthalic anhydride and 270 g of diisopropanolamine were introduced into a double-walled glass reactor, which could be heated by means of thermal oil, fitted with a mechanical stirrer, a distillation head and nitrogen and vacuum connections. The reaction mixture was gradually heated, with stirring, to approx. 70° C. and then more slowly to 170° C. A vacuum was created during the heating. The pressure in the reactor was adjusted to the release of reaction water, so that this could be removed from the reactor through distillation. After a total reaction time of 5 hours the viscous polymer contained less than 0.2 meq/g of carboxylic acid (titrimetrically determined) and no more water could be removed through distillation. After cooling the polymer was obtained as a pale yellow glassy mass. The concentration of hydroxyl groups was titrimetrically found to be 5.8 meq/g. The number average molecular mass was determined with the aid of GPC (universal calibration) and was 1100 g/mol; the weight average molecular mass 4900 g/mol.
- Preparation of a Highly Branched Polymer Comprising Units of Hexahydrophthalic Anhydride and Diisopropanolamine
- 398 g of hexahydrophthalic anhydride and 408 g of diisopropanolamine were introduced into a double-walled glass reactor, which could be heated by means of thermal oil, fitted with a mechanical stirrer, a distillation head and nitrogen and vacuum connections. The reaction mixture was gradually heated, with stirring, to approx. 70° C. and then more slowly to 160° C. A vacuum was created during the heating. The pressure in the reactor was adjusted to the release of reaction water, so that this could be removed from the reactor by means of distillation. After a total reaction time of 3.5 hours the viscous polymer contained less than 0.2 meq/g of carboxylic acid (titrimetrically determined) and no more water could be removed through distillation. After cooling the polymer was obtained as an almost colourless glassy mass. The concentration of hydroxyl groups was titrimetrically found to be 5.2 meq/g. The number average molecular mass was determined with the aid of GPC (universal calibration) and was 1550 g/mol; the weight average molecular was mass 7000 g/mol.
- Preparation of a Highly Branched Polymer Comprising Units of Hexahydrophthalic Anhydride and Diisopropanolamine
- 378 g of hexahydrophthalic anhydride and 436 g of diisopropanolamine were introduced into a double-walled glass reactor, which could be heated by means of thermal oil, fitted with a mechanical stirrer, a distillation head and nitrogen and vacuum connections. The reaction mixture was gradually heated, with stirring, to approx. 70° C. and then more slowly to 160° C. A vacuum was created during the heating. The pressure in the reactor was adjusted to the release of reaction water, so that this could be removed from the reactor through distillation. After a total reaction time of 5 hours the viscous polymer contained less than 0.1 meq/g carboxylic acid (titrimetrically determined) and no more water could be removed through distillation. After cooling the polymer was obtained as an almost colourless glassy mass. The concentration of hydroxyl groups was titrimetrically found to be 6.1 meq/g. The number average molecular mass was determined with the aid of GPC (universal calibration) and was 1010 g/mol; the weight average molecular mass 4600 g/mol.
- Powder-paint Compositions Comprising a Polymer According to any One of Examples I-IV
- Powder-paint compositions according to Table 1 were prepared by mixing and extrusion (PRISM extruder, 120° C.). The polyesters (Uralac 5040™ and Uralac 5261™ from DSM Resins) comprise units of terephthalic acid, adipic acid, neopentyl glycol and trimellitic anhydride.
- The compositions were in the usual manner ground, sieved and electrostatically sprayed (Corona) onto aluminium and steel test panels. After a cure cycle of 10 minutes at 200° C. or 15 minutes at 180° C. in a circulation oven, the panels were tested to determine their appearance (visually), flexibility (penetration in mm according to Erichsen ISO 1520/DIN 53156), reverse impact resistance (ASTM-2794/69 in inch-pound), acetone resistance (acetone double rubs), adhesion (cross hatch adhesion test) and hardness (König, seconds). The test results are shown in Table 1.
- These examples show that the polymers according to the invention result in coatings having good to very good chemical, mechanical and optical properties and a high blister limit (visually).
TABLE 1 Compositions and coating properties Composition A B C D E F Polyester resin: Uralac p5261 ™ 155 g 159 g 164 g Uralac p5040 ™ 156 g 162 g 160 g Crosslinker according to: Example I 45 g 44 g Example II 38 g Example III 43 g 42 g Example IV 36 g Additives: TiO2 2160 100 g 100 g 100 g 100 g 100 g 100 g Benzoin 3.0 g 3.0 g 3.0 g 3.0 g 3.0 g 3.0 g BYK 361 1.5 g 1.5 g 1.5 g 1.5 g 1.5 g 1.5 g cure cycle 10′ 200° C. 10′ 200° C. 10′ 200° C. 15′ 180° C. 15′ 180° C. 15′ 180° C. Hardness 235 s 225 s 215 s 215 s 210 s 195 s Impact resistance1) >160 ip 160 ip >160 ip >160 ip >160 ip >160 ip ESP2) >8 mm >8 mm >8 mm >8 mm >8 mm >8 mm Adhesion3) Gt0 Gt0 Gt0 Gt0 Gt0 Gt0 Gel time4) n.d.5) 151 80 116 85 100 Flow behaviour OK OK OK OK OK OK Blister limit 120 μ 120 μ 130 μ 140 μ 140 μ 140 μ - 1) reverse impact test; on steel ASTM-2794/69. The impact resistance is usually given as inch x pound. If no cracks are visible in the coating at 160 i.p., 160 i.p. is quoted as the result. An impact resistance of 160 i.p. stands for 1.84 m.kg.
- 2) Erichsen Slow Penetration; ISO 1520/DIN 53156
- 3) Cross-hatch adhesion; ISO 2409/DIN 5315
- 4) DIN 55990; part B.
- 5) not determined.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100152376A1 (en) * | 2006-12-12 | 2010-06-17 | Ciba Corporation | Flame retardant composition comprising dendritic polymers |
US20140296185A1 (en) * | 2011-11-03 | 2014-10-02 | Rhodia Operations | Solid formulations suitable for oilfield applications |
WO2021144061A1 (en) | 2020-01-13 | 2021-07-22 | Dsm Ip Assets B.V. | Non-porous microparticles |
Families Citing this family (96)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL1008041C2 (en) * | 1998-01-16 | 1999-07-19 | Tidis B V I O | Application of a water-soluble binder system for the production of glass or rock wool. |
WO2000034354A1 (en) * | 1998-12-07 | 2000-06-15 | Dsm N.V. | Two-component coating system |
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EP1086932A1 (en) * | 1999-07-16 | 2001-03-28 | Rockwool International A/S | Resin for a mineral wool binder comprising the reaction product of an amine with a first and second anhydride |
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DE102004039102A1 (en) * | 2004-08-11 | 2006-02-23 | Basf Ag | Process for the preparation of highly branched polyesteramides |
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DE102005045228A1 (en) | 2005-09-22 | 2007-04-05 | Basf Coatings Ag | Use of phosphonic diesters and diphosphonic diesters, and silane-containing, curable mixtures containing phosphonic and Diphosphonsäurediester |
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DE102006024823A1 (en) | 2006-05-29 | 2007-12-06 | Basf Coatings Ag | Use of curable mixtures containing silane-containing compounds and phosphonic or Diphosphonsäurediester as adhesion promoters |
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Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3652501A (en) | 1970-05-28 | 1972-03-28 | Eastman Kodak Co | Water soluble alkyd resins |
US3709858A (en) * | 1971-06-10 | 1973-01-09 | Eastman Kodak Co | Polyesteramide coating compositions |
BE1006097A3 (en) * | 1992-07-29 | 1994-05-10 | Dsm Nv | POWDER PAINT BASED ON WITH POLYMER free carboxylic acid groups AS A BINDER AND A BETA-hydroxyalkylamide containing compound as CROSSLINKER. |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100152376A1 (en) * | 2006-12-12 | 2010-06-17 | Ciba Corporation | Flame retardant composition comprising dendritic polymers |
US20140296185A1 (en) * | 2011-11-03 | 2014-10-02 | Rhodia Operations | Solid formulations suitable for oilfield applications |
WO2021144061A1 (en) | 2020-01-13 | 2021-07-22 | Dsm Ip Assets B.V. | Non-porous microparticles |
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JP2001518539A (en) | 2001-10-16 |
AU746623B2 (en) | 2002-05-02 |
KR20010030837A (en) | 2001-04-16 |
EP1036106B1 (en) | 2003-08-13 |
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US6387496B1 (en) | 2002-05-14 |
IL135396A0 (en) | 2001-05-20 |
MY125719A (en) | 2006-08-30 |
DE69817216T2 (en) | 2004-06-09 |
CN1281478A (en) | 2001-01-24 |
KR100524455B1 (en) | 2005-10-26 |
ATE247143T1 (en) | 2003-08-15 |
JP3643032B2 (en) | 2005-04-27 |
NL1007186C2 (en) | 1999-04-07 |
TW588069B (en) | 2004-05-21 |
US6392006B1 (en) | 2002-05-21 |
CN1158334C (en) | 2004-07-21 |
EP1036106A1 (en) | 2000-09-20 |
CA2305364A1 (en) | 1999-04-08 |
IL135396A (en) | 2005-07-25 |
WO1999016810A1 (en) | 1999-04-08 |
AU9190298A (en) | 1999-04-23 |
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