EP2820064A1 - Alkyd resin in aqueous emulsion, in particular of vegetable origin - Google Patents
Alkyd resin in aqueous emulsion, in particular of vegetable originInfo
- Publication number
- EP2820064A1 EP2820064A1 EP13711078.9A EP13711078A EP2820064A1 EP 2820064 A1 EP2820064 A1 EP 2820064A1 EP 13711078 A EP13711078 A EP 13711078A EP 2820064 A1 EP2820064 A1 EP 2820064A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- carbon
- alkyd resin
- resin according
- fatty acid
- 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.)
- Withdrawn
Links
- 229920000180 alkyd Polymers 0.000 title claims abstract description 50
- 239000000839 emulsion Substances 0.000 title claims abstract description 28
- 235000013311 vegetables Nutrition 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 40
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 29
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 claims abstract description 25
- -1 unsaturated fatty acid ester Chemical class 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 239000003973 paint Substances 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 6
- 239000000976 ink Substances 0.000 claims abstract description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 58
- 239000000194 fatty acid Substances 0.000 claims description 58
- 229930195729 fatty acid Natural products 0.000 claims description 58
- 150000004665 fatty acids Chemical class 0.000 claims description 51
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002736 nonionic surfactant Substances 0.000 claims description 13
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 11
- 239000002563 ionic surfactant Substances 0.000 claims description 10
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 8
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000000600 sorbitol Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000013638 trimer Substances 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002966 varnish Substances 0.000 claims description 4
- 229920000223 polyglycerol Polymers 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 2
- 239000004386 Erythritol Substances 0.000 claims description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 2
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 2
- 235000019414 erythritol Nutrition 0.000 claims description 2
- 229940009714 erythritol Drugs 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 229960002479 isosorbide Drugs 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 238000009472 formulation Methods 0.000 abstract description 8
- 235000021122 unsaturated fatty acids Nutrition 0.000 abstract description 7
- 150000004670 unsaturated fatty acids Chemical class 0.000 abstract description 4
- 125000003158 alcohol group Chemical group 0.000 abstract description 3
- 239000002253 acid Substances 0.000 description 32
- 235000019198 oils Nutrition 0.000 description 21
- 239000003921 oil Substances 0.000 description 18
- 239000000539 dimer Substances 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 150000007513 acids Chemical class 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- WQZGKKKJIJFFOK-UHFFFAOYSA-N alpha-D-glucopyranose Natural products OCC1OC(O)C(O)C(O)C1O WQZGKKKJIJFFOK-UHFFFAOYSA-N 0.000 description 4
- 230000002421 anti-septic effect Effects 0.000 description 4
- 229930182470 glycoside Natural products 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- PYIDGJJWBIBVIA-IHAUNJBESA-N (3r,4s,5s,6r)-2-dodecoxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound CCCCCCCCCCCCOC1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O PYIDGJJWBIBVIA-IHAUNJBESA-N 0.000 description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical group OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- 244000020551 Helianthus annuus Species 0.000 description 3
- 235000003222 Helianthus annuus Nutrition 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000010685 fatty oil Chemical group 0.000 description 3
- 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 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
- 241001133760 Acoelorraphe Species 0.000 description 2
- 101100247531 Arabidopsis thaliana RBOHC gene Proteins 0.000 description 2
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- 244000020518 Carthamus tinctorius Species 0.000 description 2
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- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
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- 238000013019 agitation Methods 0.000 description 2
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- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
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- AJBZENLMTKDAEK-UHFFFAOYSA-N 3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-1,2,3,4,5,6,7,7a,9,10,11,11b,12,13,13a,13b-hexadecahydrocyclopenta[a]chrysene-4,9-diol Chemical compound CC12CCC(O)C(C)(C)C1CCC(C1(C)CC3O)(C)C2CCC1C1C3(C)CCC1C(=C)C AJBZENLMTKDAEK-UHFFFAOYSA-N 0.000 description 1
- UXHQLGLGLZKHTC-CUNXSJBXSA-N 4-[(3s,3ar)-3-cyclopentyl-7-(4-hydroxypiperidine-1-carbonyl)-3,3a,4,5-tetrahydropyrazolo[3,4-f]quinolin-2-yl]-2-chlorobenzonitrile Chemical compound C1CC(O)CCN1C(=O)C1=CC=C(C=2[C@@H]([C@H](C3CCCC3)N(N=2)C=2C=C(Cl)C(C#N)=CC=2)CC2)C2=N1 UXHQLGLGLZKHTC-CUNXSJBXSA-N 0.000 description 1
- MLBYBBUZURKHAW-UHFFFAOYSA-N 4-epi-Palustrinsaeure Natural products CC12CCCC(C)(C(O)=O)C1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- JBYXPOFIGCOSSB-GOJKSUSPSA-N 9-cis,11-trans-octadecadienoic acid Chemical compound CCCCCC\C=C\C=C/CCCCCCCC(O)=O JBYXPOFIGCOSSB-GOJKSUSPSA-N 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 235000003880 Calendula Nutrition 0.000 description 1
- 240000001432 Calendula officinalis Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UDHXJZHVNHGCEC-UHFFFAOYSA-N Chlorophacinone Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)C(=O)C1C(=O)C2=CC=CC=C2C1=O UDHXJZHVNHGCEC-UHFFFAOYSA-N 0.000 description 1
- 240000009226 Corylus americana Species 0.000 description 1
- 235000001543 Corylus americana Nutrition 0.000 description 1
- 235000007466 Corylus avellana Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- RWWVEQKPFPXLGL-ONCXSQPRSA-N L-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC=C(C(C)C)C=C2CC1 RWWVEQKPFPXLGL-ONCXSQPRSA-N 0.000 description 1
- RWWVEQKPFPXLGL-UHFFFAOYSA-N Levopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CC=C(C(C)C)C=C1CC2 RWWVEQKPFPXLGL-UHFFFAOYSA-N 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 1
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- MLBYBBUZURKHAW-MISYRCLQSA-N Palustric acid Chemical compound C([C@@]12C)CC[C@@](C)(C(O)=O)[C@@H]1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-MISYRCLQSA-N 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229940108924 conjugated linoleic acid Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Chemical group 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001982 diacylglycerols Chemical class 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002759 monoacylglycerols Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical class CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000001959 sucrose esters of fatty acids Substances 0.000 description 1
- 235000010965 sucrose esters of fatty acids Nutrition 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/104—Polyesters
- C09D11/105—Alkyd resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/022—Emulsions, e.g. oil in water
Definitions
- Alkyd resin in aqueous emulsion in particular of plant origin.
- the present invention relates to an alkyd resin and its method of production. It also relates to its formulation in the form of an aqueous emulsion and its use in the field of inks, coatings and particularly relates to paint binders.
- alkyd resins were synthesized from petrochemical products and dissolved in organic solvents.
- aqueous emulsion alkyd resins prepared from products mainly of natural origin and renewable.
- the application WO2011 / 051612 also describes an alkyd resin prepared from plant products of natural origin, obtained by polycondensation of at least one polyol, at least one polyacid and at least one fatty acid and / or oil.
- binders prepared from alkyd resins from renewable materials have poor performance compared to binders synthesized from alkyd resins from petrochemicals.
- these binders prepared from alkyd resins derived from renewable materials have limited properties in terms of quality of application of the product on a carrier, drying, hardness, gloss and resistance to launderability.
- the present invention thus relates to an alkyd resin having improved properties, in particular:
- the alkyd resin according to the invention is capable of being obtained by polycondensation from a mixture comprising: at least one fatty acid comprising a carbon-carbon double bond and / or a fatty acid ester comprising at least one double carbon-carbon bond and hydroxyl group (OH);
- polymerized abietic acid also referred to as “polyabetic acid” is meant a mixture of abietic and di-abietic acids (abietic acid dimer) and, optionally, triabetic acid (trimer of abietic acid). ).
- Polymerized rosin and polymerized resin acids include such "polymerized abietic acid”.
- the polymerized rosin and the polymerized resin acids are obtained for example by treatment with sulfuric acid. The polymerization is carried out partially and generally results in a mixture of dimers (di-abietic acid), trimers (tri-abietic acid) and unpolymerized abietic acids.
- Abietic acid is a carboxylic acid of the formula C1 9 H2 9 COOH.
- isomers use will advantageously those of the pimaric and abietic type.
- Preferred isomers are those comprising conjugated double bonds and in particular palustric acid, levopimaric acid, neoabietic acid and dehydroabietic acid and mixtures thereof.
- polyabetic acid is however preferred.
- the polymerized abietic acid comprises triabetic acid.
- the polymerized abietic acid comprises diabetic acid, preferably more than 40% by weight of said polymerized abietic acid.
- the polymerized abietic acid (and / or one of its isomers) used for carrying out the invention will be a mixture of mono-, di- and tri-mers having the following proportions:
- trimers from 4 to 10%, preferably from 4 to 9% by weight of trimers
- the fatty acids are preferably natural fatty acids comprising from 4 to 36 carbon atoms, more particularly from 8 to 24 carbon atoms.
- the resin comprises more than one unsaturated fatty acid and / or an unsaturated fatty acid ester comprising at least one alcohol function.
- the fatty acids having at least one unsaturation are selected from the group consisting of sunflower fatty acids, soybean fatty acids, safflower fatty acids, palm fatty acids, coconut fatty acids, olive oil fat, rapeseed fatty acids and their mixture.
- the fatty acid is linoleic acid.
- the fatty acid and / or the fatty acid ester may be introduced into the pure reaction mixture or as a mixture, such as in an oil.
- the oil used is an oil of vegetable origin.
- the fatty acid or fatty acid ester used is chosen from fatty acids, or esters of fatty acids, polyunsaturated and / or conjugated, that is to say having more than one carbon-carbon double bond. Preferably at least two of these carbon-carbon double bonds are conjugated.
- the conjugated fatty acid is selected from the group consisting of the fatty acids of dehydrated castor oil, the conjugated soybean fatty acids, the conjugated sunflower fatty acids (predominantly C18: 2 fatty acids such as conjugated linoleic acid) and mixtures thereof.
- the fatty acid ester is a monoglyceride (monoacylglycerol) or an unsaturated diglyceride (diacylglycerol).
- monoglyceride monoacylglycerol
- diacylglycerol unsaturated diglyceride
- Such compounds are advantageously obtained by alcoholysis of triglycerides present in vegetable oils. This alcoholysis reaction is known and is carried out by placing in the presence of triglycerides and an alcohol.
- This alcohol may be a polyol as described below, for example glycerol or sorbitol.
- the alcoholysis can advantageously be a preliminary step to the synthesis of the alkyd resin according to the invention.
- the vegetable oil is treated so as to have a concentration of unsaturated monoglyceride (s) greater than 30%, preferably 40 to 45% by weight.
- the oil is chosen from drying oils. More particularly the oil is selected from semi-drying oils.
- drying oil is selected from the group consisting of tung (Chinese wood oil), oiticica, linseed, dehydrated castor oil, tall oil, calendula oils and mixtures thereof.
- the semi-drying oils are selected from the group consisting of sunflower, soybean, olive, nut, hazelnut, corn, safflower, palm, coconut, peanut and rapeseed and their mixtures.
- the polyol is selected from the group consisting of xylose, sucrose, lactose, sorbose, sorbitol, glycerol, polyglycerols, saccharic acid, erythritol, glucose, xylitol, maltose, mannitol, pentaerythritol, di-pentaerythritol, mannose, 1,2-propanediol, 1,3-propanediol, isosorbide and mixtures thereof. More particularly, the polyol is sorbitol.
- the polyacid is a fatty acid oligomer, in particular a dimer or trimer acid, a diacid, a triacid or mixtures thereof.
- a dimer acid is generally obtained from an oil comprising unsaturated fatty acids, for example, rapeseed oil, soybean oil, tung oil or tall oil fatty acid. This oil is hydrolyzed and then a dimerization operation is carried out. A mixture of monomers, dimers and trimers is obtained, the fractions of which are separated. It is possible to use only the dimer or trimeric fraction or a mixture of these two fractions.
- the diacid is chosen from the group consisting of adipic acid, azelaic acid, fumaric acid, maleic acid, glutaric acid, succinic acid, sebacic acid, and acid. tartaric acid, di-abetic acid and mixtures thereof.
- the triacid is citric acid.
- cyclic anhydride is meant an anhydride of formula R1 -CO-O-CO-R2, in which the groups R1 and R2 together form a ring including the anhydride function -CO-O-CO-.
- the cyclic anhydride is selected from the group consisting of adipic anhydride, fumaric anhydride, maleic anhydride, glutaric anhydride, succinic anhydride, tartaric anhydride and mixtures thereof.
- the alkyd resin according to the invention is synthesized exclusively from vegetable raw materials and / or renewable.
- the alkyd resin according to the invention is capable of being obtained by polycondensation from a mixture comprising:
- the alkyd resin according to the invention has a weight average molecular weight Mw measured by steric exclusion chromatography (liquid chromatography method, the resin being diluted in 0.2 g / mol of chloroform before being analyzed. ) of between 15,000 and 100,000 g / mol, preferably between 16,000 and 60,000 g / mol, more preferably between 18,000 and 60,000 g / mol, more preferably between 40,000 and 60,000 g / mol. It is also advantageous that the alkyd resin has a dynamic viscosity at 80 ° C. of from 200 to 4500dPa.s, preferably from 350 to 3200 dPa.s, more preferably from 700 to 2700dPa.s.
- the alkyd resin may have one or more of the following characteristics:
- a final acid number in mg KOH / g of resin of between 5 and 24, preferably between 12 and 20, and more particularly between 14 and 20 (measured according to the AFNOR Standard: NFT 60 204 NF EN ISO 660), an index iodine in gl 2 / 100g produced between 40 and 120, preferably 60 and 100,
- the term "theoretical oil length" means the fatty acid content, that is to say the weight of fatty acids relative to the weight of the resin (usually called resin mass).
- the theoretical mean functionality is defined as the ratio of the total number of reactive groups to the total number of molecules in attendance. It is important to pay attention to the fact that, as in general acid groups are in default, the number of hydroxyl functions that can react is equal to the number of acid groups. The result is the expression:
- n a and f a are respectively the number of acid moles and the number of functions of the reactive starting acid and n is the total number of moles in the medium.
- the alkyd resins according to the invention advantageously have a thermal profile as shown in FIG. 1 and in Table A. This profile is obtained by Differential Scanning Calorimetry (DSC) and shows the evolution of the physical properties of resins subjected to a ramp. programmed temperature.
- DSC Differential Scanning Calorimetry
- the thermal analysis of two alkyd resins analyzed shows the presence of two thermal phenomena: the glass transition and crystallization.
- the glass transition characterized by a temperature close to -10 ° C (for example -12 to -8 ° C) may correspond to the passage of the polymer from a hard and brittle state to a soft and flexible state.
- thermogram characterizing a melting phenomenon of the crystalline lattices formed during the crystallization step.
- the absence of a melting peak makes it possible to assume the degradation of the polymer when the temperature is above 200 ° C.
- the resin does not contain solvents organic.
- the invention also discloses a process for preparing an alkyd resin according to the invention, comprising a step of mixing the following products:
- the mixture will be prepared according to the proportions described above.
- the process can be carried out using only the ingredients described above.
- the alkyd resin can be obtained by any conventional method of manufacturing alkyd resins known to those skilled in the art.
- the alkyd resin according to the invention is particularly suitable for the manufacture of binders, in particular binders for coatings such as paint, varnish, stain, etc.
- the synthesized resins have a high viscosity, it is advantageous to prepare these resins in the form of an emulsion, in particular when these will be used in the formulation of coating binder.
- the present application therefore also discloses an emulsion, in particular an aqueous emulsion comprising an alkyd resin according to the invention.
- the aqueous emulsion according to the invention can thus comprise, in addition to the alkyd resin according to the invention and water:
- an ionic surfactant or an ionic and nonionic surfactant is used.
- the emulsion comprises from 30 to 60% by weight of alkyd resin according to the invention, from 1 to 7% by weight of nonionic surfactant, from 1 to 7% by weight of the ionic surfactant and from 1 to 6% by weight. neutralizer weight, the percentages by weight being given on the total weight of the emulsion.
- the nonionic surfactant is a polymeric nonionic surfactant having an HLB (Hydrophilic-Lipophilic Balance, hydrophilic / hydrophobic balance) greater than or equal to 12 on the Davies scale.
- HLB Hydrophilic-Lipophilic Balance, hydrophilic / hydrophobic balance
- the nonionic surfactant is chosen from the group consisting of alkylpolyglycosides (APG), alkylpolyglucoside polypentoside (APP-APG), sucrose esters of fatty acids, esters of glycerol and polyglycerol and mixtures thereof.
- APG alkylpolyglycosides
- APP-APG alkylpolyglucoside polypentoside
- sucrose esters of fatty acids esters of glycerol and polyglycerol and mixtures thereof.
- the nonionic surfactant is oligomeric D-glucopyranose, C10-16 alkyl glycosides, CAS No. 110615-47-9 where D-glucopyranose, oligomeric, C10-16 alkyl glycosides).
- Sucroesters of fatty acids are nonionic surfactants consisting of a hydrophilic group (sucrose) and a lipophilic group (fatty acid). Knowing that sucrose has 8 hydroxyl functions, it is possible to produce a range of esters from sucrose monoesters to sucrose octaester.
- the glycerol and (poly) glycerol esters are derived from the reaction between a glycerol or (poly) glycerol molecule and a fatty acid molecule.
- (Poly) glycerol comes from the condensation of glycerol on itself in acidic or basic medium.
- the ionic surfactant is of the alkylarylsulphonate type and / or of disproportionated rosin potash soap.
- the ionic surfactant dodecylbenzenesulphonic acid and isopropylamine (1: 1), no. CAS: 26264-05-1.
- Simulsol SL26C (SEPPIC SA, France) is a polyglucoside alkyd.
- This nonionic surfactant has an HLB of 15 and is in 50% solution in water (CAS No. 110615-47-9: D-glucopyranose, oligomeric, C10-16 alkyl glycosides).
- the neutralizer is a base in aqueous solution and preferably a 10% aqueous solution of lithium hydroxide (LiOH).
- an antiseptic may be added thereto, although the emulsion itself has good resistance to contamination.
- the present application also discloses a process for preparing an emulsion according to the invention, comprising mixing, with stirring, the following products:
- the mixing is carried out at a temperature between 60 and 80 ° C, preferably 70 ° C.
- a premix is performed with the resin, the surfactant (s) and the neutralizer and the water is introduced so as to perform a phase inversion.
- This premix can be done at temperatures above.
- Emulsions are systems formed by the dispersion of fine droplets from one liquid to another, thus containing a dispersed phase and a continuous phase. They are generally formed of three components: an aqueous phase, an oily phase and a surfactant. When the continuous phase of an emulsion becomes the dispersed phase, it is called phase inversion.
- Phase inversion therefore takes place when the continuous phase of an emulsion becomes the dispersed phase, and vice versa.
- the alkyd resin is preheated, preferably at one of the abovementioned temperatures.
- the neutralizer and / or the surfactant (s) is / are then added (s) so as to achieve a premix.
- the stirring is then advantageously increased so as to reach at least 200 rpm.
- the stirring speed can reach up to 1000 rpm. Once this speed is reached, water can then be introduced at a low rate into the premix with vigorous stirring until an oil-in-water (w / o) emulsion is obtained.
- the emulsions according to the invention are particularly suitable for the preparation of coatings.
- varnishes for example, varnishes, stains and paints, especially satin, glossy or matte paints.
- FIG 1 shows the thermal profile of alkyd resins according to the invention obtained by Differential Scanning Calorimetry (DSC).
- Iodine value 85gl 2 / 100g
- the fatty acids exhibiting at least one unsaturation are fatty acids originating from sunflower oil, that is to say from a mixture of linoleic and oleic acid. Traces of C18: 3 may also be present.
- the conjugated fatty acids used in formulations 1 to 5 are C 18 fatty acids derived from the dehydration of castor oil. Most of these are dehydrated ricinoleic acid.
- the abietic acid polymerized in formulas 1 to 5 has the following composition: 49.7% of monoabetic acid, 45.7% of acid diabetic and 4.6% triabetic acid.
- the resins of formulas 1 to 5 are prepared according to the following preparation method:
- fatty acids having at least one unsaturation the conjugated fatty acids and sorbitol, optionally diluted to 70% in water, in a reactor.
- the dynamic viscosity at 80 ° C measured by the test of the fall of a steel ball is between 350 and 3200 dPa.s.
- emulsion formulations were prepared for each of the above-mentioned resole formulas 1-5.
- the emulsion formulations are as follows:
- Potassium soap Gresinox 578M 80% (Granel SA, France, CAS No. 61790-50-9): Soap of disproportioned rosin (mainly composed of dehydroabietic acid) to 56%. This ionic surfactant is in 80% solution in water.
- Simulsol SL26C (SEPPIC SA, France) is a polyglucoside alkyd.
- This nonionic surfactant has a H LB of 15 and is in 50% solution in water (CAS No. 110615-47-9: D-glucopyranose, oligomeric, C10-16 alkyl glycosides).
- the emulsion is prepared according to the method of preparation described below:
- the dry extract advantageously constitutes approximately 50%
- Paints were prepared using each of the alkyd resins of formula 1 to 5. These paints have the following formulas:
- Disperbyk 0.79 Dispersant BYK-Chemie GmbH 190 (Germany)
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Abstract
The present invention relates to an alkyd resin and to the process for obtaining same. The alkyd resin according to the invention is obtained by polycondensation of a mixture comprising at least one unsaturated fatty acid and/or one unsaturated fatty acid ester comprising at least one alcohol function, a polyol, a polyacid, and polymerized abietic acid. It also relates to the formulation thereof in the form of an aqueous emulsion and to the use thereof in the field of inks, coatings and, in particular, binders for paint.
Description
Résine alkyde en émulsion aqueuse, en particulier d'origine végétale. Alkyd resin in aqueous emulsion, in particular of plant origin.
La présente invention concerne une résine alkyde et son procédé d'obtention. Elle concerne également sa formulation sous la forme d'une émulsion aqueuse et son utilisation dans le domaine des encres, revêtements et concerne en particulier les liants pour peinture. The present invention relates to an alkyd resin and its method of production. It also relates to its formulation in the form of an aqueous emulsion and its use in the field of inks, coatings and particularly relates to paint binders.
Les résines alkydes sont des polymères issus de polycondensations aléatoires entre des polyols et des polyacides modifiés par des acides gras ou des huiles. Il s'agit de macromolécules tridimensionnelles appartenant à la grande classe des polyesters. Ces résines dites modifiées ont la propriété lorsqu'elles sont étalées en couche mince de sécher par réaction d'auto-oxydation (siccativation) avec l'oxygène de l'air pour donner un film dur et insoluble. Ce phénomène est rendu possible par la présence des doubles liaisons C=C qui peuvent être présentes sur des acides gras ou des huiles. Cette propriété a favorisé l'utilisation de ces résines alkydes modifiées comme liant dans divers revêtements, en particulier les peintures, lasures, vernis, etc. Alkyd resins are polymers derived from random polycondensations between polyols and polyacids modified with fatty acids or oils. These are three-dimensional macromolecules belonging to the high class of polyesters. These so-called modified resins have the property when they are spread in thin layer to dry by auto-oxidation reaction (siccativation) with the oxygen of the air to give a hard and insoluble film. This phenomenon is made possible by the presence of C = C double bonds which may be present on fatty acids or oils. This property has favored the use of these modified alkyd resins as binder in various coatings, in particular paints, stains, varnishes, etc.
A l'origine, ces résines alkydes étaient synthétisées à partir de produits issus de la pétrochimie et mis en solution dans des solvants organiques. Toutefois, pour faire face à la demande croissante de matériaux plus écologiques et aux réglementations, il a été proposé des résines alkydes en émulsion en phase aqueuse, préparées à partir de produits majoritairement d'origine naturelle et renouvelables. Originally, these alkyd resins were synthesized from petrochemical products and dissolved in organic solvents. However, to cope with the increasing demand for greener materials and regulations, it has been proposed aqueous emulsion alkyd resins, prepared from products mainly of natural origin and renewable.
La demande WO2011/051612 décrit d'ailleurs une résine alkyde préparée à partir de produits végétaux d'origine naturelle, obtenue par polycondensation d'au moins un polyol, au moins un polyacide et au moins un acide gras et/ou huile. The application WO2011 / 051612 also describes an alkyd resin prepared from plant products of natural origin, obtained by polycondensation of at least one polyol, at least one polyacid and at least one fatty acid and / or oil.
Toutefois, les liants préparés à partir de résines alkydes issues de matières renouvelables, actuellement disponibles, présentent de faibles performances en comparaison des liants synthétisées à partir de résines alkydes issues de la pétrochimie. En particulier, ces liants préparés à partir de résines alkydes issues de matières renouvelables ont des propriétés limitées en termes de qualité d'application du produit sur un support, de séchage, de dureté, de brillant et de résistance à la lessivabilité. However, binders prepared from alkyd resins from renewable materials, currently available, have poor performance compared to binders synthesized from alkyd resins from petrochemicals. In particular, these binders prepared from alkyd resins derived from renewable materials have limited properties in terms of quality of application of the product on a carrier, drying, hardness, gloss and resistance to launderability.
La présente invention concerne donc une résine alkyde présentant des propriétés améliorées, en particulier : The present invention thus relates to an alkyd resin having improved properties, in particular:
- une plus grande facilité d'application du produit formulé à partir de la résine, une réduction du temps de séchage du film formé par le liant lors de l'application,
une augmentation de la dureté pendulaire, - greater ease of application of the product formulated from the resin, a reduction in the drying time of the film formed by the binder during application, an increase in pendulum hardness,
une augmentation de la résistance à l'abrasion, et/ou an increase in resistance to abrasion, and / or
une réduction du jaunissement du film. La résine alkyde selon l'invention est susceptible d'être obtenue par polycondensation à partir d'un mélange comportant : - au moins un acide gras comprenant une double liaison carbone-carbone et/ou un ester d'acide gras comprenant au moins une double liaison carbone-carbone et groupe hydroxyle (OH) ; a reduction of yellowing of the film. The alkyd resin according to the invention is capable of being obtained by polycondensation from a mixture comprising: at least one fatty acid comprising a carbon-carbon double bond and / or a fatty acid ester comprising at least one double carbon-carbon bond and hydroxyl group (OH);
un polyol ; a polyol;
un polyacide et/ou un anhydride cyclique ; et a polyacid and / or a cyclic anhydride; and
- de l'acide abiétique, et/ou un de ses isomères, polymérisé(s). - Abietic acid, and / or one of its isomers, polymerized (s).
Par « acide abiétique polymérisé », également désigné sous l'appellation « acide polyabiétique », on désigne un mélange d'acides abiétique et di-abiétique (dimère de l'acide abiétique) et, éventuellement, triabiétique (trimère de l'acide abiétique). La colophane polymérisée et les acides résiniques polymérisés comportent un tel «acide abiétique polymérisé ». La colophane polymérisée et les acides résiniques polymérisés sont obtenus par exemple par traitement à l'acide sulfurique. La polymérisation s'effectue de manière partielle et résulte généralement en un mélange de dimères (acide di-abiétique), de trimères (acide tri-abiétique) et d'acides abiétiques non polymérisés. By "polymerized abietic acid", also referred to as "polyabetic acid", is meant a mixture of abietic and di-abietic acids (abietic acid dimer) and, optionally, triabetic acid (trimer of abietic acid). ). Polymerized rosin and polymerized resin acids include such "polymerized abietic acid". The polymerized rosin and the polymerized resin acids are obtained for example by treatment with sulfuric acid. The polymerization is carried out partially and generally results in a mixture of dimers (di-abietic acid), trimers (tri-abietic acid) and unpolymerized abietic acids.
L'acide abiétique est un acide carboxylique de formule brute C19H29COOH. Parmi ses isomères, on utilisera avantageusement ceux de type pimarique et abiétique. Des isomères préférés sont ceux comprenant des doubles liaisons conjuguées et notamment l'acide palustrique, l'acide levopimarique, l'acide néoabiétique et l'acide déhydroabiétique et leurs mélanges. Abietic acid is a carboxylic acid of the formula C1 9 H2 9 COOH. Among its isomers, use will advantageously those of the pimaric and abietic type. Preferred isomers are those comprising conjugated double bonds and in particular palustric acid, levopimaric acid, neoabietic acid and dehydroabietic acid and mixtures thereof.
L'utilisation d"acide polyabiétique est cependant préférée. The use of polyabetic acid is however preferred.
De préférence l'acide abiétique polymérisé comprend de l'acide triabiétique. De préférence l'acide abiétique polymérisé comprend de l'acide diabiétique, de préférence à plus de 40% en poids dudit acide abiétique polymérisé. Preferably, the polymerized abietic acid comprises triabetic acid. Preferably, the polymerized abietic acid comprises diabetic acid, preferably more than 40% by weight of said polymerized abietic acid.
De préférence, l'acide abiétique (et/ou un de ses isomères) polymérisé utilisé pour la réalisation de l'invention sera un mélange de mono-, di- et tri-mères ayant les proportions suivantes : Preferably, the polymerized abietic acid (and / or one of its isomers) used for carrying out the invention will be a mixture of mono-, di- and tri-mers having the following proportions:
de 27 à 50%, préférablement de 30 à 50% et plus préférablement de 30 à 45%, en poids de monomères, from 27 to 50%, preferably from 30 to 50% and more preferably from 30 to 45%, by weight of monomers,
- de 34 à 70%, préférablement de 36 à 55%, ou de 34 à 48%, en poids de dimères, et from 34 to 70%, preferably from 36 to 55%, or from 34 to 48%, by weight of dimers, and
de 4 à 10%, préférablement de 4 à 9% en poids de trimères, from 4 to 10%, preferably from 4 to 9% by weight of trimers,
Les pourcentages en poids étant donnés sur le poids total du mélange.
Il est précisé que dans toute la présente demande, les gammes de valeurs s'entendent bornes incluses. The percentages by weight being given on the total weight of the mixture. It is specified that throughout the present application, the ranges of values are included limits.
Les acides gras sont de préférence des acides gras naturels comprenant de 4 à 36 atomes de carbones, plus particulièrement de 8 à 24 atomes de carbones. De préférence, la résine comporte plus d'un acide gras insaturé et/ou d'un ester d'acide gras insaturé comprenant au moins une fonction alcool. The fatty acids are preferably natural fatty acids comprising from 4 to 36 carbon atoms, more particularly from 8 to 24 carbon atoms. Preferably, the resin comprises more than one unsaturated fatty acid and / or an unsaturated fatty acid ester comprising at least one alcohol function.
De préférence, les acides gras présentant au moins une insaturation sont choisis parmi le groupe constitué par les acides gras de tournesol, les acides gras de soja, les acides gras de carthame, les acides gras de palme, les acides gras de coprah, les acides gras d'huile d'olive, les acides gras de colza et leur mélange. De préférence l'acide gras est l'acide linoléique. Preferably, the fatty acids having at least one unsaturation are selected from the group consisting of sunflower fatty acids, soybean fatty acids, safflower fatty acids, palm fatty acids, coconut fatty acids, olive oil fat, rapeseed fatty acids and their mixture. Preferably the fatty acid is linoleic acid.
L'acide gras, et/ou l'ester d'acide gras, peut être introduit dans le mélange de réaction pur ou sous forme de mélange, tel que dans une huile. The fatty acid and / or the fatty acid ester may be introduced into the pure reaction mixture or as a mixture, such as in an oil.
Dans le contexte de la présente invention une huile est un composé contenant plus d'un acide gras comprenant au moins une double liaison C=C (insaturé) et/ou plus d'un ester d'acide gras comprenant au moins une double liaison C=C (insaturé) et au moins un groupe hydroxyle (OH) . De préférence l'huile utilisée est une huile d'origine végétale. In the context of the present invention an oil is a compound containing more than one fatty acid comprising at least one C = C double bond (unsaturated) and / or more than one fatty acid ester comprising at least one C double bond = C (unsaturated) and at least one hydroxyl group (OH). Preferably the oil used is an oil of vegetable origin.
Avantageusement, l'acide gras, ou l'ester d'acide gras, utilisé est choisi parmi les acides gras, ou les esters d'acides gras, polyinsaturés et/ou conjugués, c'est-à- dire ayant plus d'une double liaison carbone-carbone. De préférence au moins deux de ces doubles liaisons carbone-carbone sont conjuguées. Advantageously, the fatty acid or fatty acid ester used is chosen from fatty acids, or esters of fatty acids, polyunsaturated and / or conjugated, that is to say having more than one carbon-carbon double bond. Preferably at least two of these carbon-carbon double bonds are conjugated.
De préférence, l'acide gras conjugué est choisi parmi le groupe constitué par les acides gras de l'huile de ricin déshydraté, les acides gras de soja conjugués, les acides gras de tournesol conjugués (majoritairement des acides gras en C18:2 tel que l'acide linoléique conjugué) et leurs mélanges. Preferably, the conjugated fatty acid is selected from the group consisting of the fatty acids of dehydrated castor oil, the conjugated soybean fatty acids, the conjugated sunflower fatty acids (predominantly C18: 2 fatty acids such as conjugated linoleic acid) and mixtures thereof.
De préférence l'ester d'acide gras est un monoglycéride (monoacylglycérol) ou un diglycéride (diacylglycérol) insaturé. De tels composés sont avantageusement obtenus par alcoolyse des triglycérides présents dans des huiles végétales. Cette réaction d'alcoolyse, est connue et s'effectue par mise en présence de triglycérides et d'un alcool. Cet alcool peut être un polyol tel que décrit ci-dessous, par exemple le glycérol ou le sorbitol. Ainsi, l'alcoolyse peut avantageusement être une étape préliminaire à la synthèse de la résine alkyde selon l'invention. Preferably, the fatty acid ester is a monoglyceride (monoacylglycerol) or an unsaturated diglyceride (diacylglycerol). Such compounds are advantageously obtained by alcoholysis of triglycerides present in vegetable oils. This alcoholysis reaction is known and is carried out by placing in the presence of triglycerides and an alcohol. This alcohol may be a polyol as described below, for example glycerol or sorbitol. Thus, the alcoholysis can advantageously be a preliminary step to the synthesis of the alkyd resin according to the invention.
Selon un mode de réalisation préféré de l'invention, l'huile végétale est traitée de manière à présenter une concentration de monoglycéride(s) insaturé(s) supérieure à 30%, préférentiellement de 40 à 45% en poids. According to a preferred embodiment of the invention, the vegetable oil is treated so as to have a concentration of unsaturated monoglyceride (s) greater than 30%, preferably 40 to 45% by weight.
Avantageusement l'huile est choisie parmi les huiles siccatives. Plus
particulièrement l'huile est choisie parmi les huiles semi-siccatives. Advantageously, the oil is chosen from drying oils. More particularly the oil is selected from semi-drying oils.
De préférence l'huile siccative est choisie parmi le groupe constitué par les huiles de tung (huile de bois de chine), d'oiticica, de lin, de ricin déshydratée, de tall, de calendula et leurs mélanges. Preferably the drying oil is selected from the group consisting of tung (Chinese wood oil), oiticica, linseed, dehydrated castor oil, tall oil, calendula oils and mixtures thereof.
De préférence, les huiles semi-siccatives sont choisies parmi le groupe constitué par les huiles de tournesol, de soja, d'olive, de noix, de noisette, de maïs, de carthame, de palme, de coprah, d'arachide et de colza et leurs mélanges. Preferably, the semi-drying oils are selected from the group consisting of sunflower, soybean, olive, nut, hazelnut, corn, safflower, palm, coconut, peanut and rapeseed and their mixtures.
De préférence, le polyol est choisi parmi le groupe constitué par le xylose, le sucrose, le lactose, le sorbose, le sorbitol, le glycérol, les polyglycérols, l'acide saccharique, l'éryth ritol, le glucose, le xylitol, le maltose, le mannitol, le pentaérythritol, le di-pentaéryth ritol, le mannose, le 1 ,2-propanediol, le 1 ,3- propanediol, l'isosorbide et leurs mélanges. Plus particulièrement, le polyol est du sorbitol. Preferably, the polyol is selected from the group consisting of xylose, sucrose, lactose, sorbose, sorbitol, glycerol, polyglycerols, saccharic acid, erythritol, glucose, xylitol, maltose, mannitol, pentaerythritol, di-pentaerythritol, mannose, 1,2-propanediol, 1,3-propanediol, isosorbide and mixtures thereof. More particularly, the polyol is sorbitol.
De préférence, le polyacide est un oligomère d'acide gras, en particulier un acide dimère ou trimère, un diacide, un triacide ou leurs mélanges. Preferably, the polyacid is a fatty acid oligomer, in particular a dimer or trimer acid, a diacid, a triacid or mixtures thereof.
Un acide dimère est généralement obtenu à partir d'une huile comprenant des acides gras insaturés, par exemple, de l'huile de colza, de soja, de tung ou d'acide gras de tall. Cette huile est hydrolysée puis une opération de dimérisation est effectuée. Un mélange de monomères, dimères et trimères est obtenu, dont les fractions sont séparées. Il est possible d'utiliser seulement la fraction dimères ou trimères ou un mélange de ces deux fractions. A dimer acid is generally obtained from an oil comprising unsaturated fatty acids, for example, rapeseed oil, soybean oil, tung oil or tall oil fatty acid. This oil is hydrolyzed and then a dimerization operation is carried out. A mixture of monomers, dimers and trimers is obtained, the fractions of which are separated. It is possible to use only the dimer or trimeric fraction or a mixture of these two fractions.
Plus préférentiellement, le diacide est choisi parmi le groupe constitué par l'acide adipique, l'acide azélaïque, l'acide fumarique, l'acide maléique, l'acide glutarique, l'acide succinique, l'acide sébacique, l'acide tartrique, l'acide di- abiétique et leurs mélanges. More preferentially, the diacid is chosen from the group consisting of adipic acid, azelaic acid, fumaric acid, maleic acid, glutaric acid, succinic acid, sebacic acid, and acid. tartaric acid, di-abetic acid and mixtures thereof.
De préférence, le triacide est l'acide citrique. Preferably, the triacid is citric acid.
Par « anhydride cyclique », on entend un anhydride de formule R1 -CO-0-CO- R2, dans laquelle les groupements R1 et R2 forment ensemble un cycle incluant la fonction anhydride -CO-0-CO-. By "cyclic anhydride" is meant an anhydride of formula R1 -CO-O-CO-R2, in which the groups R1 and R2 together form a ring including the anhydride function -CO-O-CO-.
Plus préférentiellement, l'anhydride cyclique est choisi parmi le groupe constitué par l'anhydride adipique, l'anhydride fumarique, l'anhydride maléique, l'anhydride glutarique, l'anhydride succinique, l'anhydride tartrique et leurs mélanges. More preferably, the cyclic anhydride is selected from the group consisting of adipic anhydride, fumaric anhydride, maleic anhydride, glutaric anhydride, succinic anhydride, tartaric anhydride and mixtures thereof.
De préférence, la résine alkyde selon l'invention est synthétisée exclusivement à partir de matières premières végétales et/ou renouvelables. Preferably, the alkyd resin according to the invention is synthesized exclusively from vegetable raw materials and / or renewable.
Plus particulièrement, la résine alkyde selon l'invention est susceptible d'être obtenue par polycondensation à partir d'un mélange comportant : More particularly, the alkyd resin according to the invention is capable of being obtained by polycondensation from a mixture comprising:
de 10 à 66% en poids d'un acide gras et/ou d'une huile, préférentiellement
de 12 à 34%, from 10 to 66% by weight of a fatty acid and / or an oil, preferentially from 12 to 34%,
de 4 à 35% en poids de polyol, préférentiellement de 15 à 27%, from 4 to 35% by weight of polyol, preferably from 15 to 27%,
de 10 à 50% en poids de polyacide et/ou d'anhydride cyclique, préférentiellement de 15 à 37%, et from 10 to 50% by weight of polyacid and / or cyclic anhydride, preferably from 15 to 37%, and
- de 20 à 60% en poids d'acide abiétique (et/ou d'un isomère) polymérisé, préférentiellement de 22 à 53%, from 20 to 60% by weight of abietic acid (and / or a isomer) polymerized, preferably from 22 to 53%,
les pourcentages en poids étant donnés par rapport au poids total du mélange.the percentages by weight being given relative to the total weight of the mixture.
Avantageusement, la résine alkyde selon l'invention a une masse moléculaire moyenne en poids Mw mesurée par chromatographie d'exclusion stérique (méthode de chromatographie en phase liquide, la résine étant diluée dans 0,2 g/mol de chloroforme avant d'être analysée) comprise entre 15 000 et 100 000 g/mol, préférentiellement entre 16 000 et 60 000 g/mol, plus préférentiellement entre 18000 et 60 000 g/mol, encore plus préférentiellement entre 40 000 et 60 000 g/mol. Il est également avantageux que la résine alkyde présente une viscosité dynamique à 80°C de 200 à 4500dPa.s, préférentiellement de 350 à 3200 dPa.s, plus préférentiellement de 700 à 2700dPa.s. Advantageously, the alkyd resin according to the invention has a weight average molecular weight Mw measured by steric exclusion chromatography (liquid chromatography method, the resin being diluted in 0.2 g / mol of chloroform before being analyzed. ) of between 15,000 and 100,000 g / mol, preferably between 16,000 and 60,000 g / mol, more preferably between 18,000 and 60,000 g / mol, more preferably between 40,000 and 60,000 g / mol. It is also advantageous that the alkyd resin has a dynamic viscosity at 80 ° C. of from 200 to 4500dPa.s, preferably from 350 to 3200 dPa.s, more preferably from 700 to 2700dPa.s.
Plus particulièrement, la résine alkyde pourra présenter une ou plusieurs des caractéristiques suivantes : More particularly, the alkyd resin may have one or more of the following characteristics:
un indice de polydispersité Ip compris entre 1 et 20 (mesuré par chromatographie d'exclusion stérique) a polydispersity index Ip of between 1 and 20 (measured by steric exclusion chromatography)
un indice d'acide final en mg KOH/g de résine compris entre 5 et 24, préférentiellement entre 12 et 20, et plus particulièrement entre 14 et 20 (mesuré suivant la Norme AFNOR : NFT 60 204 NF EN ISO 660), un indice d'iode en gl2/100g produit entre 40 et 120, de préférence 60 et 100, a final acid number in mg KOH / g of resin of between 5 and 24, preferably between 12 and 20, and more particularly between 14 and 20 (measured according to the AFNOR Standard: NFT 60 204 NF EN ISO 660), an index iodine in gl 2 / 100g produced between 40 and 120, preferably 60 and 100,
une longueur moyenne théorique en huile en prenant compte des acides dimères comprise entre 29 et 50%, de préférence de 37 à 45%, a theoretical average length of oil, taking into account dimer acids of between 29 and 50%, preferably of 37 to 45%,
un pourcentage en acide gras compris entre 10 et 20%, de préférence entre 13 et 17%, a fatty acid percentage of between 10 and 20%, preferably between 13 and 17%,
- une fonctionnalité théorique moyenne comprise entre 1 ,5 et 2, 1 , de préférence entre 1 ,7 et 2 ; et a mean theoretical functionality of between 1, 5 and 2, 1, preferably between 1, 7 and 2; and
un indice d'hydroxyde théorique final compris entre 40 et 80 mg KOH/g de résine, de préférence entre 45 et 60 mg KOH/g. a final theoretical hydroxyl number of between 40 and 80 mg KOH / g of resin, preferably between 45 and 60 mg KOH / g.
Pour formuler une résine alkyde, il est avantageux de connaître la fonctionnalité moyenne théorique du mélange réactionnel, ce qui permet de déterminer le degré de gélification de la résine résultante. Ainsi une fonctionnalité moyenne théorique du mélange réactionnel supérieure à 2 est, en général, à éviter.
Par longueur théorique en huile, on entend, au sens de la présente invention la teneur en acides gras, c'est-à-dire le poids en acides gras par rapport au poids de la résine (usuellement appelée résine masse). In order to formulate an alkyd resin, it is advantageous to know the theoretical average functionality of the reaction mixture, which makes it possible to determine the degree of gelation of the resulting resin. Thus a theoretical average functionality of the reaction mixture greater than 2 is, in general, to be avoided. For the purposes of the present invention, the term "theoretical oil length" means the fatty acid content, that is to say the weight of fatty acids relative to the weight of the resin (usually called resin mass).
La fonctionnalité moyenne théorique est définie comme étant le rapport du nombre total de groupes réactifs sur le nombre totale de molécules en présences. Il est important de porter attention au fait que comme en générale les groupes acides sont en défaut, le nombre de fonctions hydroxyles pouvant réagir est égale au nombre de groupes acides. Il en résulte l'expression : The theoretical mean functionality is defined as the ratio of the total number of reactive groups to the total number of molecules in attendance. It is important to pay attention to the fact that, as in general acid groups are in default, the number of hydroxyl functions that can react is equal to the number of acid groups. The result is the expression:
f= 2 ∑i nafa / n, avec na et fa étant respectivement le nombre de mole acide et le nombre de fonction de l'acide de départ susceptible de réagir et n le nombre de moles total dans le milieu. f = 2 Σin a f a / n, where n a and f a are respectively the number of acid moles and the number of functions of the reactive starting acid and n is the total number of moles in the medium.
Les résines alkydes selon l'invention ont avantageusement un profil thermique tel que présenté en Figure 1 et dans le tableau A. Ce profil est obtenu par calorimétrie à balayage différentiel (DSC) et montre l'évolution des propriétés physiques de résines soumises à une rampe de température programmée. The alkyd resins according to the invention advantageously have a thermal profile as shown in FIG. 1 and in Table A. This profile is obtained by Differential Scanning Calorimetry (DSC) and shows the evolution of the physical properties of resins subjected to a ramp. programmed temperature.
L'analyse thermique de deux résines alkydes analysées met en évidence la présence de deux phénomènes thermiques : la transition vitreuse et la cristallisation. La transition vitreuse caractérisée par une température proche de - 10°C (par exemple de -12 à -8°C) peut correspondre au passage du polymère d'un état dur et cassant à un état mou et flexible. The thermal analysis of two alkyd resins analyzed shows the presence of two thermal phenomena: the glass transition and crystallization. The glass transition characterized by a temperature close to -10 ° C (for example -12 to -8 ° C) may correspond to the passage of the polymer from a hard and brittle state to a soft and flexible state.
Il est également observé un phénomène d'exothermie à une température proche de 145°C (par exemple de 144 à 146°C). Ce phénomène peut être provoqué par la formation de réseaux cristallins dans la structure du polymère entraînant une libération d'énergie observée par la présence d'un pic exothermique. La formation de réseaux cristallins permet de faire l'hypothèse de la mobilité des chaînes carbonées dans le polymère. It is also observed an exothermic phenomenon at a temperature close to 145 ° C (for example 144 to 146 ° C). This phenomenon can be caused by the formation of crystal lattices in the polymer structure resulting in energy release observed by the presence of an exothermic peak. The formation of crystal lattices makes it possible to assume the mobility of the carbon chains in the polymer.
Enfin, on constate l'absence d'un pic endothermique sur le thermogramme caractérisant un phénomène de fusion des réseaux cristallins formés lors de l'étape de cristallisation. L'absence de pic de fusion, permet de faire l'hypothèse de la dégradation du polymère lorsque la température est supérieure à 200°C. Finally, there is the absence of an endothermic peak on the thermogram characterizing a melting phenomenon of the crystalline lattices formed during the crystallization step. The absence of a melting peak makes it possible to assume the degradation of the polymer when the temperature is above 200 ° C.
Tableau A - Résultats des analyses DSC de résines alkydes Table A - DSC Results of Alkyd Resins
Selon un aspect préféré de l'invention, la résine ne contient pas de solvants
organiques. According to a preferred aspect of the invention, the resin does not contain solvents organic.
L'invention divulgue également un procédé de préparation d'une résine alkyde selon l'invention, comportant une étape de mélange des produits suivants : The invention also discloses a process for preparing an alkyd resin according to the invention, comprising a step of mixing the following products:
au moins un acide gras insaturé et/ou un ester d'acide gras insaturé présentant au moins une fonction alcool et/ou une huile, at least one unsaturated fatty acid and / or an unsaturated fatty acid ester having at least one alcohol function and / or an oil,
un polyol, a polyol,
un polyacide et/ou un anhydride cyclique, et a polyacid and / or a cyclic anhydride, and
de l'acide abiétique polymérisé. polymerized abietic acid.
Avantageusement, le mélange sera préparé selon les proportions décrites ci- avant. Advantageously, the mixture will be prepared according to the proportions described above.
Selon un aspect particulier de l'invention le procédé peut être mise en œuvre en n'utilisant que les ingrédients décrits ci-avant. According to a particular aspect of the invention, the process can be carried out using only the ingredients described above.
La résine alkyde peut être obtenue par tout procédé conventionnel de fabrication de résines alkydes connu par l'homme de l'art. The alkyd resin can be obtained by any conventional method of manufacturing alkyd resins known to those skilled in the art.
La résine alkyde selon l'invention est particulièrement adaptée pour la fabrication de liants, en particulier de liants pour revêtements type peinture, vernis, lasure, etc. The alkyd resin according to the invention is particularly suitable for the manufacture of binders, in particular binders for coatings such as paint, varnish, stain, etc.
Les résines synthétisées présentant une forte viscosité, il est avantageux de préparer ces résines sous forme d'une émulsion, en particulier lorsque celles-ci vont être utilisées dans la formulation de liant pour revêtement. Since the synthesized resins have a high viscosity, it is advantageous to prepare these resins in the form of an emulsion, in particular when these will be used in the formulation of coating binder.
La présente demande divulgue donc également une émulsion, en particulier une émulsion aqueuse comportant une résine alkyde selon l'invention. The present application therefore also discloses an emulsion, in particular an aqueous emulsion comprising an alkyd resin according to the invention.
L'émulsion aqueuse selon l'invention peut ainsi comprendre, outre la résine alkyde selon l'invention et de l'eau : The aqueous emulsion according to the invention can thus comprise, in addition to the alkyd resin according to the invention and water:
- un tensioactif ionique et/ou un tensioactif non-ionique, et an ionic surfactant and / or a nonionic surfactant, and
un neutralisant. a neutralizer.
Préférablement on utilise soit un tensioactif ionique, soit un tensioactif ionique et non-ionique. Preferably, either an ionic surfactant or an ionic and nonionic surfactant is used.
Avantageusement, l'émulsion comporte de 30 à 60% en poids de résine alkyde selon l'invention, de 1 à 7% en poids de tensioactif non ionique, de 1 à 7% en poids du tensioactif ionique et de 1 à 6% en poids de neutralisant, les pourcentages en poids étant donné sur le poids total de l'émulsion. Advantageously, the emulsion comprises from 30 to 60% by weight of alkyd resin according to the invention, from 1 to 7% by weight of nonionic surfactant, from 1 to 7% by weight of the ionic surfactant and from 1 to 6% by weight. neutralizer weight, the percentages by weight being given on the total weight of the emulsion.
Préférentiellement, le tensioactif non ionique est un tensioactif non ionique polymérique présentant une HLB (Hydrophilic-Lipophilic Balance, balance hydrophile/hydrophobe) supérieure ou égale à 12 sur l'échelle de Davies. Preferably, the nonionic surfactant is a polymeric nonionic surfactant having an HLB (Hydrophilic-Lipophilic Balance, hydrophilic / hydrophobic balance) greater than or equal to 12 on the Davies scale.
De préférence, le tensioactif non ionique est choisi parmi le groupe constitué par les alkylpolyglycosides (APG), l'alkylpolyglucoside polypentoside (APP-APG), les
sucroesters d'acides gras, les esters de glycérol et de polyglycérol et leurs mélanges. Par exemple le tensioactif non-ionique est le D-glucopyranose, oligomèrique, C10-16 glycosides alkyles, n° CAS : 110615-47-9 où D- glucopyranose, oligomèrique, C10-16 glycosides alkyles). Preferably, the nonionic surfactant is chosen from the group consisting of alkylpolyglycosides (APG), alkylpolyglucoside polypentoside (APP-APG), sucrose esters of fatty acids, esters of glycerol and polyglycerol and mixtures thereof. For example, the nonionic surfactant is oligomeric D-glucopyranose, C10-16 alkyl glycosides, CAS No. 110615-47-9 where D-glucopyranose, oligomeric, C10-16 alkyl glycosides).
Les sucroesters d'acides gras sont des tensioactifs non ioniques constitués d'un groupe hydrophile (saccharose) et d'un groupe lipophile (acide gras). Sachant que le saccharose comporte 8 fonctions hydroxyle, il est possible de produire une gamme d'esters depuis les monoesters de saccharose jusqu'à l'octaester de saccharose. Sucroesters of fatty acids are nonionic surfactants consisting of a hydrophilic group (sucrose) and a lipophilic group (fatty acid). Knowing that sucrose has 8 hydroxyl functions, it is possible to produce a range of esters from sucrose monoesters to sucrose octaester.
Les esters de glycérol et de (poly)glycérols sont issus de la réaction entre une molécule de glycérol ou (poly)glycérol et une molécule d'acide gras. Le (poly)glycérol provient de la condensation du glycérol sur lui-même en milieu acide ou basique. The glycerol and (poly) glycerol esters are derived from the reaction between a glycerol or (poly) glycerol molecule and a fatty acid molecule. (Poly) glycerol comes from the condensation of glycerol on itself in acidic or basic medium.
Préférentiellement, le tensioactif ionique est de type alkylarylsulfonate et/ou du savon de potasse de colophane dismutée. Par exemple le tensioactif ionique l'acide dodecylbenzènesulphonique et isopropylamine (1 :1 ), n°. CAS : 26264-05-1 . Preferably, the ionic surfactant is of the alkylarylsulphonate type and / or of disproportionated rosin potash soap. For example the ionic surfactant dodecylbenzenesulphonic acid and isopropylamine (1: 1), no. CAS: 26264-05-1.
Simulsol SL26C (SEPPIC SA, France) est un alkyde polyglucoside. Ce tensioactif non ionique présente une HLB de 15 et est en solution à 50% dans l'eau (n° CAS : 110615-47-9 : D-glucopyranose, oligomèrique, C10-16 glycosides alkyles). Simulsol SL26C (SEPPIC SA, France) is a polyglucoside alkyd. This nonionic surfactant has an HLB of 15 and is in 50% solution in water (CAS No. 110615-47-9: D-glucopyranose, oligomeric, C10-16 alkyl glycosides).
Avantageusement, le neutralisant est une base en solution aqueuse et préférentiellement une solution aqueuse de lithine (LiOH) à 10%. Advantageously, the neutralizer is a base in aqueous solution and preferably a 10% aqueous solution of lithium hydroxide (LiOH).
Selon les applications visées pour cette émulsion, un antiseptique peut être ajouté à celle-ci, bien que l'émulsion présente par elle-même une bonne résistance aux contaminations. Depending on the intended applications for this emulsion, an antiseptic may be added thereto, although the emulsion itself has good resistance to contamination.
La présente demande divulgue également un procédé de préparation d'une émulsion selon l'invention, comportant le mélange, sous agitation, des produits suivants : The present application also discloses a process for preparing an emulsion according to the invention, comprising mixing, with stirring, the following products:
une résine alkyde selon l'invention, an alkyd resin according to the invention,
- un tensioactif non ionique, et/ou un tensioactif ionique, a nonionic surfactant and / or an ionic surfactant,
de l'eau, et water, and
un neutralisant. a neutralizer.
Préférentiellement, le mélange est effectué à une température comprise entre 60 et 80°C, préférablement 70°C. Preferably, the mixing is carried out at a temperature between 60 and 80 ° C, preferably 70 ° C.
Avantageusement, un pré-mélange est effectué avec la résine, le ou les tensioactif(s) et le neutralisant puis l'eau est introduite de manière à effectuer une inversion de phase. Ce pré-mélange peut être effectué aux températures
susmentionnées. Advantageously, a premix is performed with the resin, the surfactant (s) and the neutralizer and the water is introduced so as to perform a phase inversion. This premix can be done at temperatures above.
Les émulsions sont des systèmes formés par la dispersion de fines gouttelettes d'un liquide dans un autre, elles contiennent ainsi une phase dispersée et une phase continue. Elles sont en général formées de trois composants : une phase aqueuse, une phase huileuse et un tensioactif. Lorsque la phase continue d'une émulsion devient la phase dispersée, on parle d'inversion de phase. Emulsions are systems formed by the dispersion of fine droplets from one liquid to another, thus containing a dispersed phase and a continuous phase. They are generally formed of three components: an aqueous phase, an oily phase and a surfactant. When the continuous phase of an emulsion becomes the dispersed phase, it is called phase inversion.
Une inversion de phase a donc lieu quand la phase continue d'une émulsion devient la phase dispersée, et inversement. Phase inversion therefore takes place when the continuous phase of an emulsion becomes the dispersed phase, and vice versa.
Avantageusement, la résine alkyde est préalablement chauffée, préférablement à une des températures susmentionnées. Le neutralisant et le, ou les, tensioactif(s) est/sont ensuite ajouté(s) de manière à réaliser un pré-mélange. Advantageously, the alkyd resin is preheated, preferably at one of the abovementioned temperatures. The neutralizer and / or the surfactant (s) is / are then added (s) so as to achieve a premix.
L'agitation est alors avantageusement augmentée de manière à atteindre au moins 200 rpm. Avantageusement la vitesse d'agitation peut atteindre jusqu'à 1000 rpm. Une fois cette vitesse atteinte, de l'eau peut être ensuite introduite à faible débit dans le pré-mélange sous forte agitation jusqu'à l'obtention d'une émulsion huile-dans-eau (w/o). The stirring is then advantageously increased so as to reach at least 200 rpm. Advantageously, the stirring speed can reach up to 1000 rpm. Once this speed is reached, water can then be introduced at a low rate into the premix with vigorous stirring until an oil-in-water (w / o) emulsion is obtained.
Les émulsions selon l'invention sont particulièrement adaptées pour la préparation de revêtements. The emulsions according to the invention are particularly suitable for the preparation of coatings.
A titre d'exemples de revêtement, on peut citer les vernis, les lasures et les peintures, en particulier les peintures satinées, brillantes ou mates. As examples of coating, there may be mentioned varnishes, stains and paints, especially satin, glossy or matte paints.
Description de la Figure Description of the Figure
Figure 1 représente le profil thermique de résines alkydes selon l'invention obtenu par calorimétrie à balayage différentiel (DSC). Figure 1 shows the thermal profile of alkyd resins according to the invention obtained by Differential Scanning Calorimetry (DSC).
L'invention sera mieux comprise à la lecture de la description qui va suivre de modes préférentiels de réalisations, donnés uniquement à titre d'exemple. Exemple 1 : Préparation de résines alkyde selon l'invention The invention will be better understood on reading the following description of preferred embodiments, given solely by way of example. Example 1 Preparation of Alkyd Resins According to the Invention
Différentes formulations de résines ont été préparées dont les proportions d'ingrédients sont indiqués dans les formules suivantes :
Formule 1 : Different resin formulations have been prepared whose proportions of ingredients are indicated in the following formulas: Formula 1 :
Indice d'hydroxyde final : 70 mgKOH/g Indice d'acide final : 18 mgKOH/g Final hydroxide number: 70 mgKOH / g Final acid number: 18 mgKOH / g
Formule 3 : Formula 3:
Indice d'hydroxyde final : 80mgKOH/g Indice d'acide final : 18mgKOH/g
Formule 4 : Final hydroxide number: 80mgKOH / g Final acid number: 18mgKOH / g Form 4:
Ingrédient Pourcentage en poids Ingredient Percentage by weight
Sorbitol à 70% dans eau 16,55 70% sorbitol in water 16.55
Acides gras présentant au moins une 4,60 Fatty acids having at least 4.60
insaturation unsaturated
Acide gras conjugués 10,86 Conjugated fatty acid 10,86
Acide abiétique polymérisé 34,50 Polymeric abietic acid 34,50
Acides dimères 33,80 Dimeric acids 33.80
Indice d'hydroxyde final : 49mgKOH/g Final hydroxide number: 49mgKOH / g
Indice d'acide final: 18mgKOH/g Final acid number: 18mgKOH / g
Indice d'iode : 76gl2/100g Iodine number: 76gl 2 / 100g
Formule 5 : Formula 5:
Ingrédient Pourcentage en poids Ingredient Percentage by weight
Sorbitol à 70% dans eau 16,53 70% sorbitol in water 16.53
Acides gras présentant au moins 6,45 Fatty acids with at least 6.45
une insaturation unsaturation
Acide gras conjugués 6,45 Conjugated fatty acid 6.45
Acide abiétique polymérisé 41 , 15 Polymeric abietic acid 41, 15
Acides dimères 29,42 Dimer acids 29,42
Indice d'hydroxyde final : 50.46mgKOH/g Final hydroxide number: 50.46mgKOH / g
Indice d'acide final : 18mgKOH/g Final acid number: 18mgKOH / g
Indice d'iode : 85gl2/100g Iodine value: 85gl 2 / 100g
Dans les formules 1 à 5 les acides dimères qui ont été utilisés sont les acides dimères obtenus à partir d'huile de colza (C18 :1 =65% ; C18 :2 =20% ; C18 :3 =7%). In the formulas 1 to 5, the dimer acids which have been used are the dimer acids obtained from rapeseed oil (C18: 1 = 65%, C18: 2 = 20%, C18: 3 = 7%).
Dans les formules 1 à 5 les acides gras présentant au moins une insaturation sont des acides gras provenant d'huile de tournesol, c'est-à-dire d'un mélange d'acide linoléique et oléique. Des traces de C18:3 peuvent également être présentes. In formulas 1 to 5, the fatty acids exhibiting at least one unsaturation are fatty acids originating from sunflower oil, that is to say from a mixture of linoleic and oleic acid. Traces of C18: 3 may also be present.
Les acides gras conjugués utilisés dans les formulations 1 à 5 sont des acides gras en C18 provenant de la déshydratation de l'huile de ricin.. Il s'agit en majorité d'acide ricinoléique déshydraté. L'acide abiétique polymérisé dans les formules 1 à 5 a la composition suivante : 49,7 % d'acide monoabiétique, 45,7 % d'acide
diabiétique et 4,6% d'acide triabiétique. The conjugated fatty acids used in formulations 1 to 5 are C 18 fatty acids derived from the dehydration of castor oil. Most of these are dehydrated ricinoleic acid. The abietic acid polymerized in formulas 1 to 5 has the following composition: 49.7% of monoabetic acid, 45.7% of acid diabetic and 4.6% triabetic acid.
Les résines des formules 1 à 5 sont préparées selon le procédé de préparation suivant : The resins of formulas 1 to 5 are prepared according to the following preparation method:
charger les acides gras présentant au moins une insaturation, les acides gras conjugués et le sorbitol, éventuellement dilué à 70% dans l'eau, dans un réacteur. charge the fatty acids having at least one unsaturation, the conjugated fatty acids and sorbitol, optionally diluted to 70% in water, in a reactor.
chauffer sous azote à 150°C. heat under nitrogen at 150 ° C.
après départ de l'eau du sorbitol, arrêter le chauffage et refroidir, after leaving the water of sorbitol, stop heating and cool,
après refroidissement charger les acides dimères et l'acide abiétique polymérisé et chauffer à 240°C sous azote. after cooling, charge the dimer acids and polymerized abietic acid and heat to 240 ° C under nitrogen.
contrôler l'avancement de la réaction en mesurant l'indice d'acide et la viscosité Noury, check the progress of the reaction by measuring the acid number and the Noury viscosity,
quand l'indice d'acide est proche de 45 mg de KOH par gramme de résine, mettre sous vide à 50 mBar. when the acid number is close to 45 mg KOH per gram of resin, evacuate to 50 mbar.
- lorsque la viscosité Noury à 110°C est comprise entre 80 et 90 Poises, refroidir. - When the Noury viscosity at 110 ° C is between 80 and 90 Poises, cool.
Pour toutes ces formules, la viscosité dynamique à 80°C mesurée par le test de la chute d'une bille en acier, est comprise entre 350 et 3200 dPa.s. Exemple 2 : Préparation d'une émulsion selon l'invention For all these formulas, the dynamic viscosity at 80 ° C measured by the test of the fall of a steel ball, is between 350 and 3200 dPa.s. Example 2 Preparation of an Emulsion According to the Invention
Trois formulations d'émulsion ont été préparées pour chacune des formules de résines 1 à 5 mentionnées ci-dessus. Les formulations d'émulsion sont les suivantes : Three emulsion formulations were prepared for each of the above-mentioned resole formulas 1-5. The emulsion formulations are as follows:
Formule 1 : Formula 1 :
Ingrédient Pourcentage en poids Ingredient Percentage by weight
Résine alkyde 45,77Alkyd resin 45,77
Simulsol SL26C 2,68Simulsol SL26C 2,68
Savon de potassium Gresinox 578M 80% 1 , 14Potassium soap Gresinox 578M 80% 1, 14
Solution de lithine à 10% 3,0810% Lithium Solution 3.08
Eau 47, 13Water 47, 13
Antiseptique 0,2
Formule 2 : Antiseptic 0.2 Formula 2:
Savon de potassium Gresinox 578M 80% (Granel SA, France, No. CAS 61790- 50-9): Savon de potasse de colophane dismutée (majoritairement composé d'acide déhydroabiétique) à 56%. Ce tensioactif ionique est en solution à 80% dans l'eau.Potassium soap Gresinox 578M 80% (Granel SA, France, CAS No. 61790-50-9): Soap of disproportioned rosin (mainly composed of dehydroabietic acid) to 56%. This ionic surfactant is in 80% solution in water.
Simulsol SL26C (SEPPIC SA, France) est un alkyde polyglucoside. Ce tensioactif non ionique présente une H LB de 15 et est en solution à 50% dans l'eau (n° CAS : 110615-47-9 : D-glucopyranose, oligomèrique, C10-16 glycosides alkyles). Simulsol SL26C (SEPPIC SA, France) is a polyglucoside alkyd. This nonionic surfactant has a H LB of 15 and is in 50% solution in water (CAS No. 110615-47-9: D-glucopyranose, oligomeric, C10-16 alkyl glycosides).
Bien que le produit présente une très bonne résistance aux contaminations sans agent biocide, un antiseptique, la benzisothiazolinone (No. CAS 2634-33-5) est toutefois ajoutée. Although the product has a very good resistance to contaminations without a biocidal agent, an antiseptic, benzisothiazolinone (CAS No. 2634-33-5) is however added.
L 'émulsion est préparée selon le procédé de préparation décrit ci-après : The emulsion is prepared according to the method of preparation described below:
charger de la résine dans le réacteur préalablement chauffé à 50-80°C, puis mettre sous légère agitation et laisser thermostater à 75° pendant 30min, introduire les deux tensioactifs et mélanger sous agitation, environ 200 à 1000 tpm, charge the resin in the reactor previously heated to 50-80 ° C, then stir gently and allow thermostating at 75 ° for 30min, introduce the two surfactants and mix with stirring, about 200 to 1000 rpm,
introduire la solution de lithine et mélanger sous agitation, environ 200 à 1000 tpm, introduce the lithium hydroxide solution and mix with stirring, about 200 to 1000 rpm,
introduire l'eau en continue à faible débit sous forte agitation (200 à 400 tpm)
pour effectuer une inversion de phase en continue et obtenir une émulsion de type huile dans eau, introduce water continuously at a low flow rate under heavy agitation (200 to 400 rpm) to perform a continuous phase inversion and obtain an oil-in-water emulsion,
à la fin de l'introduction d'eau, refroidir jusqu'à atteindre la température ambiante et diminuer l'agitation pour éviter la formation de mousse, ajouter l'antiseptique, at the end of the introduction of water, cool to room temperature and reduce agitation to prevent foaming, add antiseptic,
éventuellement contrôler la quantité d'eau à l'aide d'un dessiccateur possibly control the amount of water using a desiccator
(METTLER Toledo). L'extrait sec constitue avantageusement environ 50%(METTLER Toledo). The dry extract advantageously constitutes approximately 50%
±5 en poids de l'émulsion. La quantité d'eau peut alors être ajustée si nécessaire, ± 5 by weight of the emulsion. The amount of water can then be adjusted if necessary,
filtrer et conditionner. filter and condition.
Exemple 3 : Formulation d'une peinture Example 3: Painting Formulation
Des peintures ont préparées en utilisant chacune des résines alkydes de formule 1 à 5. Ces peintures ont les formules suivantes : Paints were prepared using each of the alkyd resins of formula 1 to 5. These paints have the following formulas:
Formule 1 Formula 1
Ingrédient % en poids Fonction Fournisseur Ingredient% by weight Function Supplier
Résine alkyde 52,67 Liant Alkyd Resin 52.67 Binder
Eau 12,27 Water 12.27
Disperbyk 190 0,78 Dispersant BYK-Chemie Disperbyk 190 0.78 Dispersant BYK-Chemie
GmbH (Allemagne) GmbH (Germany)
Byk 024 0,22 Antimousse BYK-Chemie Byk 024 0.22 Antifreeze BYK-Chemie
GmbH (Allemagne) GmbH (Germany)
Nuosept BMC422 0,20 Agent de ISP / Ashland Nuosept BMC422 0.20 ISP / Ashland Agent
protection Specialty Ingrédients Protection Ingredients
(Etats-Unis) (United States)
Tioxide RHD2 32, 16 Pigment HUNSTMA N Tioxide RHD2 32, 16 Pigment HUNSTMA N
ADVANCED MATERIAL ADVANCED MATERIAL
( Suisse) ( Swiss)
Borchi®OXY 0,55 Siccatif OMG BORCHERS Coat 1101 GmbH (Allemagne) Borchi®OXY 0.55 Drying Agent OMG BORCHERS Coat 1101 GmbH (Germany)
Coapur 2025 1 ,05 Epaississant COATEX SAS (France)Coapur 2025 1, 05 Thickener COATEX SAS (France)
Acrysol RM12W 0,08 Epaississant SAS ROHM & HAAS Acrysol RM12W 0.08 Thickener SAS ROHM & HAAS
France (France)
peinture obtenue présente les caractéristiques suivantes France France) obtained paint has the following characteristics
Formule 2 : Formula 2:
Ingrédient % en poids Fonction Fournisseur Ingredient% by weight Function Supplier
Résine 32,62 Liant Resin 32,62 Binder
alkyde alkyd
Eau 28,35 Water 28.35
Disperbyk 0,79 Dispersant BYK-Chemie GmbH 190 (Allemagne) Disperbyk 0.79 Dispersant BYK-Chemie GmbH 190 (Germany)
Byk 024 0,22 Antimousse BYK-Chemie GmbH Byk 024 0.22 Antifoam BYK-Chemie GmbH
(Allemagne) (Germany)
Nuosept 0,20 Agent de ISP / Ashland Specialty BMC422 protection Ingrédients (Etats-Unis)
ASPG90 2,89 Charge LAVOLLEE SA (France)Nuosept 0.20 ISP Agent / Ashland Specialty BMC422 Protection Ingredients (USA) ASPG90 2,89 Charge LAVOLLEE SA (France)
Stéopac 2,89 Charge TALC DE LUZENAC Stéopac 2,89 Charge TALC DE LUZENAC
RIO TINTO/EMERYS SA RIO TINTO / EMERYS SA
Tioxide 28,98 Pigment HUNSTMAN ADVANCED RHD2 MATERIAL ( Suisse)Tioxide 28.98 Pigment HUNSTMAN ADVANCED RHD2 MATERIAL (Switzerland)
Natrosol 0,06 Epaississant ASHLAND Specialty Ingrédients HE10K cellulosique (Etats-Unis) Natrosol 0.06 Thickener ASHLAND Specialty Ingredients HE10K Cellulose (United States)
Borchi®OXY 0,34 Siccatif OMG BORCHERS GmbH Coat 1101 (Allemagne) Borchi®OXY 0.34 Drying Agent OMG BORCHERS GmbH Coat 1101 (Germany)
Aquaflow 2,64 Epaississant ASHLAND Specialty Ingrédients NHS300 (Etats-Unis) Aquaflow 2,64 Thickener ASHLAND Specialty Ingredients NHS300 (USA)
Aquaflow 0,01 Epaississant ASHLAND Specialty Ingrédients XLS 525 (Etats-Unis) Aquaflow 0.01 Thickener ASHLAND Specialty Ingredients XLS 525 (USA)
La peinture obtenue présente les caractéristiques suivantes : The resulting paint has the following characteristics:
Viscosité ICI / 10000s-1 1 ,9 Poises Viscosity ICI / 10000s-1 1, 9 Poles
Viscosité Brookfield, M4 / 10rpm / 23°C 6000 Cps Brookfield Viscosity, M4 / 10rpm / 23 ° C 6000 Cps
Viscosité Brookfield à J+1 , M4 / 10rpm / 23°C 6700 Cps Brookfield Viscosity at D + 1, M4 / 10rpm / 23 ° C 6700 Cps
Brillance / 60° / 150μΓΠ, Carte BYK - PA-2810 25 Brightness / 60 ° / 150μΓΠ, BYK Card - PA-2810 25
Contrast Ratio / 150μηι, Carte BYK - PA-2810 97,5 Contrast Ratio / 150μηι, BYK Card - PA-2810 97.5
Densité 1 ,345 Kg/L Density 1, 345 Kg / L
Extrait sec 52,4 % Dry extract 52.4%
VOC 0,0 g/i VOC 0.0 g / i
Dureté Persoz / 100μηη / j+1 76 Hardness Persoz / 100μηη / d + 1 76
Dureté Persoz / 10Ομηι / j+28 250 Hardness Persoz / 10Ομηι / day + 28 250
Pigment 28,98 Pigment 28.98
Charges 5,78 Charges 5.78
Liant sec 16,31 Dry binder 16,31
Solvant 0,00 Solvent 0.00
Eau 47,61 Water 47.61
Additifs 1 ,32 Additives 1, 32
TOTAL 100,00
Formule 3 : TOTAL 100,00 Formula 3:
La peinture obtenue présente les caractéristiques suivantes : The resulting paint has the following characteristics:
Viscosité ICI, 10000s-1 /25°C 1,6 Poises Viscosity ICI, 10000s-1/25 ° C 1.6 Poises
Viscosité Brookfield, M4 / 10rpm / 23°C 8400 Cps Brookfield Viscosity, M4 / 10rpm / 23 ° C 8400 Cps
Viscosité Brookfield à J+1, M4/ 10rpm/23°C 9400 CpsBrookfield Viscosity at D + 1, M4 / 10rpm / 23 ° C 9400 Cps
Contrast Ratio / 150μηι, Carte BYK - PA-Contrast Ratio / 150μηι, BYK Card - PA-
96,8 96.8
2810 2810
Brillance / 60° / 150μΓη, Carte BYK - PA-2810 2,6 Brightness / 60 ° / 150μΓη, BYK Card - PA-2810 2,6
Brillance / 85° / 150 m,Carte BYK - PA-2810 5,1
Densité 1,581 Kg/LBrightness / 85 ° / 150 m, BYK Card - PA-2810 5.1 Density 1,581 Kg / L
Extrait sec 59,3 %Dry extract 59,3%
VOC 0,0 g/i VOC 0.0 g / i
Pigment 22,25 Pigment 22.25
Charges 31,25 Charges 31.25
Liant sec 4,11 Dry binder 4.11
Solvant 0,00 Solvent 0.00
Eau 40,69 Water 40.69
Additifs 1,70 Additives 1.70
TOTAL 100,00
TOTAL 100,00
Claims
1 . Résine alkyde présentant une masse moléculaire moyenne allant de 15 000 à 100 000 g/mol et susceptible d'être obtenue par polycondensation à partir d'un mélange comprenant : 1. An alkyd resin having an average molecular weight ranging from 15,000 to 100,000 g / mol and obtainable by polycondensation from a mixture comprising:
un acide gras comprenant au moins une double liaison carbone-carbone et/ou un ester d'acide gras comprenant au moins une double liaison carbone-carbone et au moins un groupe hydroxyle; a fatty acid comprising at least one carbon-carbon double bond and / or a fatty acid ester comprising at least one carbon-carbon double bond and at least one hydroxyl group;
- un polyol ; a polyol;
un polyacide et/ou un anhydride cyclique, et a polyacid and / or a cyclic anhydride, and
de l'acide abiétique polymérisé. polymerized abietic acid.
2. Résine selon la revendication 1 , comprenant un second acide gras comprenant au moins une double liaison carbone-carbone et/ou un second ester d'acide gras comprenant au moins une double liaison carbone-carbone et un groupe hydroxyle. 2. Resin according to claim 1, comprising a second fatty acid comprising at least one carbon-carbon double bond and / or a second fatty acid ester comprising at least one carbon-carbon double bond and a hydroxyl group.
3. Résine selon la revendication 1 ou la revendication 2, dans laquelle l'acide gras est choisi parmi le groupe constitué par les acides gras comprenant des doubles liaisons carbone-carbone conjuguées. The resin of claim 1 or claim 2, wherein the fatty acid is selected from the group consisting of fatty acids comprising conjugated carbon-carbon double bonds.
4. Résine selon l'une quelconque des revendications 1 à 3, dans laquelle le(s)dit(s) acide gras est/sont compris dans une/des huile(s) d'origine végétale, éventuellement hydrolysée(s) et/ou alcoolysée(s). 4. Resin according to any one of claims 1 to 3, wherein the (s) said (s) fatty acid is / are included in oil (s) of plant origin, optionally hydrolyzed (s) and / or or alcoholic (s).
5. Résine selon l'une quelconque des revendications précédentes, dans laquelle le polyol est choisi parmi le groupe constitué par le xylose, le sucrose, le lactose, le sorbose, le sorbitol, le glycérol, les polyglycérols, l'acide saccharique, l'érythritol, le glucose, le xylitol, le maltose, le mannitol, le pentaérythritol, le di-pentaérythritol, tri-pentaérythritol, le mannose, le 1 ,2- propanediol, le 1 ,3-propanediol, l'isosorbide, leurs dérivés et leurs mélanges. The resin according to any one of the preceding claims, wherein the polyol is selected from the group consisting of xylose, sucrose, lactose, sorbose, sorbitol, glycerol, polyglycerols, saccharic acid, erythritol, glucose, xylitol, maltose, mannitol, pentaerythritol, di-pentaerythritol, tri-pentaerythritol, mannose, 1,2-propanediol, 1,3-propanediol, isosorbide, their derivatives and their mixtures.
6. Résine selon l'une quelconque des revendications précédentes, dans laquelle le polyacide est choisi parmi le groupe constitué par les oligomères d'acides gras, les diacides, les triacides ou leurs mélanges. 6. A resin according to any one of the preceding claims, wherein the polyacid is selected from the group consisting of oligomers of fatty acids, diacids, triacids or mixtures thereof.
7. Résine alkyde selon l'une quelconque des revendications précédentes, présentant une masse moléculaire moyenne allant de 16 000 et 60 000 g/mol. An alkyd resin according to any one of the preceding claims, having an average molecular weight of from 16,000 to 60,000 g / mol.
8. Résine alkyde selon l'une quelconque des revendications précédentes, dans laquelle l'acide abiétique polymérisé comprend un trimère d'acide abiétique.An alkyd resin according to any one of the preceding claims, wherein the polymerized abietic acid comprises an abietic acid trimer.
9. Résine alkyde selon la revendication 8, caractérisée en ce que l'acide abiétique polymérisé est compris dans un mélange comprenant: de 30 à 50% en poids d'acide abiétique, 9. Alkyd resin according to claim 8, characterized in that the polymerized abietic acid is included in a mixture comprising: from 30 to 50% by weight of abietic acid,
de 34 à 70% en poids de dimère d'acide abiétique, et from 34 to 70% by weight of abietic acid dimer, and
de 4 à 10% en poids de trimères d'acide abiétique, from 4 to 10% by weight of abietic acid trimers,
les pourcentages en poids étant donnés sur le poids total dudit mélange d'acide abiétique. the percentages by weight being given on the total weight of said mixture of abietic acid.
10. Procédé de préparation d'une résine alkyde selon l'une quelconque des revendications 1 à 9, comportant une étape de mélange des produits suivants : au moins un acide gras comprenant au moins une insaturation carbone- carbone et/ou un ester d'acide gras comprenant au moins un insaturation carbone-carbone et un groupe hydroxyle, 10. Process for the preparation of an alkyd resin according to any one of claims 1 to 9, comprising a step of mixing the following products: at least one fatty acid comprising at least one carbon-carbon unsaturation and / or an ester of fatty acid comprising at least one carbon-carbon unsaturation and one hydroxyl group,
un polyol, a polyol,
un polyacide et/ou un anhydride cyclique, et a polyacid and / or a cyclic anhydride, and
de l'acide abiétique polymérisé. polymerized abietic acid.
1 1. Utilisation de la résine alkyde selon l'une quelconque des revendications 1 à 9 pour la fabrication de liant. 1. Use of the alkyd resin according to any one of claims 1 to 9 for the manufacture of binder.
12. Emulsion aqueuse comprenant une résine alkyde selon l'une quelconque des revendications 1 à 9. An aqueous emulsion comprising an alkyd resin according to any one of claims 1 to 9.
13. Emulsion aqueuse selon la revendication 12, comprenant en outre : The aqueous emulsion of claim 12, further comprising:
un tensioactif non ionique et/ou un tensioactif ionique, et a nonionic surfactant and / or an ionic surfactant, and
- un neutralisant. - a neutralizer.
14. Procédé de préparation d'une émulsion selon la revendication 12 ou la revendication 13, comportant le mélange, sous agitation, des produits suivants : 14. Process for the preparation of an emulsion according to claim 12 or claim 13, comprising the mixture, with stirring, of the following products:
une résine alkyde selon l'une quelconque des revendications 1 à 8, an alkyd resin according to any one of claims 1 to 8,
- un tensioactif non ionique et/ou un tensioactif ionique, a nonionic surfactant and / or an ionic surfactant,
de l'eau, et water, and
un neutralisant. a neutralizer.
15. Utilisation d'une émulsion selon la revendication 12 ou la revendication 13 pour la préparation d'encres et de revêtements, en particulier de vernis et de peintures. 15. Use of an emulsion according to claim 12 or claim 13 for the preparation of inks and coatings, in particular varnishes and paints.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1251916A FR2987623B1 (en) | 2012-03-01 | 2012-03-01 | ALKYD RESIN IN AQUEOUS EMULSION, PARTICULARLY OF VEGETABLE ORIGIN |
| PCT/FR2013/050422 WO2013128132A1 (en) | 2012-03-01 | 2013-02-28 | Alkyd resin in aqueous emulsion, in particular of vegetable origin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2820064A1 true EP2820064A1 (en) | 2015-01-07 |
Family
ID=47913467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP13711078.9A Withdrawn EP2820064A1 (en) | 2012-03-01 | 2013-02-28 | Alkyd resin in aqueous emulsion, in particular of vegetable origin |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2820064A1 (en) |
| FR (1) | FR2987623B1 (en) |
| WO (1) | WO2013128132A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574599B (en) * | 2019-01-29 | 2021-11-26 | 宁波盈峰新型建材有限公司 | Environment-friendly durable building material |
| EP3953414B1 (en) * | 2019-04-08 | 2023-06-07 | Palsgaard A/S | Novel nanoemulsions, methods of their production and related uses and products |
| CN115651173B (en) * | 2022-11-15 | 2024-02-06 | 亚士创能科技(乌鲁木齐)有限公司 | Bio-based water-based alkyd resin and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2094747A5 (en) * | 1970-08-10 | 1972-02-04 | Scm Corp | |
| US3980630A (en) * | 1974-08-26 | 1976-09-14 | Harima Chemicals Inc. | Method for preparation of emulsifier for emulsion polymerization |
| JP4214593B2 (en) * | 1999-01-25 | 2009-01-28 | 東洋インキ製造株式会社 | Resin and printing ink |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2791568A (en) * | 1952-02-02 | 1957-05-07 | Armour & Co | Non-yellowing baking finish |
| FR1478892A (en) * | 1965-05-06 | 1967-07-17 | ||
| AU4675900A (en) * | 1999-05-04 | 2000-11-17 | Flint Ink Corporation | Polyester based varnish for uv curable inks |
| US20070179277A1 (en) * | 2006-02-02 | 2007-08-02 | Dallavia Anthony J | Rosin ester with low color and process for preparing same |
| FR2951730B1 (en) * | 2009-10-26 | 2012-05-11 | Centre Nat Rech Scient | NATURAL ALKYDE RESIN AND AQUEOUS EMULSION OF SUCH A RESIN |
| FR2955586B1 (en) * | 2010-01-28 | 2013-02-08 | Eurovia | SYNTHETIC BINDER ESSENTIALLY BASED ON MATERIALS RESULTING FROM RENEWABLE RESOURCES, ESPECIALLY OF VEGETABLE ORIGIN, AND ITS APPLICATIONS IN ROAD TECHNOLOGY |
| WO2012005645A1 (en) * | 2010-07-07 | 2012-01-12 | Perstorp Ab | Alkyd resin |
| FR2965267B1 (en) * | 2010-09-27 | 2013-11-15 | Cray Valley Sa | POLYESTER RESINS BASED ON SHORT OIL LENGTH FATTY ACIDS, AQUEOUS DISPERSIONS AND RELATED COATINGS |
-
2012
- 2012-03-01 FR FR1251916A patent/FR2987623B1/en active Active
-
2013
- 2013-02-28 WO PCT/FR2013/050422 patent/WO2013128132A1/en active Application Filing
- 2013-02-28 EP EP13711078.9A patent/EP2820064A1/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2094747A5 (en) * | 1970-08-10 | 1972-02-04 | Scm Corp | |
| US3980630A (en) * | 1974-08-26 | 1976-09-14 | Harima Chemicals Inc. | Method for preparation of emulsifier for emulsion polymerization |
| JP4214593B2 (en) * | 1999-01-25 | 2009-01-28 | 東洋インキ製造株式会社 | Resin and printing ink |
Non-Patent Citations (1)
| Title |
|---|
| See also references of WO2013128132A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2987623B1 (en) | 2015-04-10 |
| WO2013128132A1 (en) | 2013-09-06 |
| FR2987623A1 (en) | 2013-09-06 |
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