WO1998000387A1 - Mixture of esters and use thereof - Google Patents
Mixture of esters and use thereof Download PDFInfo
- Publication number
- WO1998000387A1 WO1998000387A1 PCT/GB1997/001741 GB9701741W WO9800387A1 WO 1998000387 A1 WO1998000387 A1 WO 1998000387A1 GB 9701741 W GB9701741 W GB 9701741W WO 9800387 A1 WO9800387 A1 WO 9800387A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alcohol
- maleate
- succinate
- catalyst
- stage
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 150000002148 esters Chemical class 0.000 title claims description 22
- 239000003085 diluting agent Substances 0.000 claims abstract description 75
- 239000003973 paint Substances 0.000 claims abstract description 71
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 54
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 34
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 12
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000009472 formulation Methods 0.000 claims description 38
- 229920000180 alkyd Polymers 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- -1 alkaline earth metal alkoxide Chemical class 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011976 maleic acid Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000001530 fumaric acid Substances 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- 125000000746 allylic group Chemical group 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 6
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 5
- 241000088844 Nothocestrum Species 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- GVSHQHKVTMIMCE-UHFFFAOYSA-N 4-butoxybut-2-en-1-ol Chemical compound CCCCOCC=CCO GVSHQHKVTMIMCE-UHFFFAOYSA-N 0.000 claims description 2
- SAOXPNBHKSWHGW-UHFFFAOYSA-N 4-methylpent-3-en-2-ol Chemical compound CC(O)C=C(C)C SAOXPNBHKSWHGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- AYQPVPFZWIQERS-UHFFFAOYSA-N oct-2-en-1-ol Chemical compound CCCCCC=CCO AYQPVPFZWIQERS-UHFFFAOYSA-N 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- LDRWAWZXDDBHTG-UHFFFAOYSA-N 3,5,5-trimethylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CC(C)(C)C1 LDRWAWZXDDBHTG-UHFFFAOYSA-N 0.000 claims 1
- MHOHVJSBYNCTJW-UHFFFAOYSA-N 4-[(2-methylpropan-2-yl)oxy]but-2-en-1-ol Chemical compound CC(C)(C)OCC=CCO MHOHVJSBYNCTJW-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 238000010533 azeotropic distillation Methods 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 238000005502 peroxidation Methods 0.000 claims 1
- 239000008199 coating composition Substances 0.000 abstract description 3
- 238000010586 diagram Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000010408 film Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 25
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000012074 organic phase Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000008346 aqueous phase Substances 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- HZYABSBSRWFZEG-BSWSSELBSA-N (1E,3E)-octa-1,3-dien-1-ol Chemical compound CCCC\C=C\C=C\O HZYABSBSRWFZEG-BSWSSELBSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000004448 titration Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 150000002596 lactones Chemical class 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 241000894007 species Species 0.000 description 6
- YHYGSIBXYYKYFB-VOTSOKGWSA-N (2e)-octa-2,7-dien-1-ol Chemical compound OC\C=C\CCCC=C YHYGSIBXYYKYFB-VOTSOKGWSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- BXQNVUBLDKGZKV-UHFFFAOYSA-N bis(octa-2,7-dienyl) butanedioate Chemical compound C=CCCCC=CCOC(=O)CCC(=O)OCC=CCCCC=C BXQNVUBLDKGZKV-UHFFFAOYSA-N 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 230000035772 mutation Effects 0.000 description 5
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000002924 oxiranes Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- IZGSWAXFIAPWJQ-IFOVKSSTSA-N 1-o-methyl 4-o-octa-1,3-dienyl (z)-but-2-enedioate Chemical compound CCCCC=CC=COC(=O)\C=C/C(=O)OC IZGSWAXFIAPWJQ-IFOVKSSTSA-N 0.000 description 3
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000004808 allyl alcohols Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- DMIKZTFGGJBMHQ-QXBWTDKZSA-N bis(octa-2,7-dienyl) (Z)-but-2-enedioate Chemical compound C=CCCCC=CCOC(=O)\C=C/C(=O)OCC=CCCCC=C DMIKZTFGGJBMHQ-QXBWTDKZSA-N 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 241000448280 Elates Species 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 101100443626 Mus musculus Dner gene Proteins 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- VSMOENVRRABVKN-UHFFFAOYSA-N oct-1-en-3-ol Chemical compound CCCCCC(O)C=C VSMOENVRRABVKN-UHFFFAOYSA-N 0.000 description 2
- 229940099990 ogen Drugs 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 150000003900 succinic acid esters Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- STGNLGBPLOVYMA-KDTZGSNLSA-N (z)-but-2-enedioic acid;(e)-but-2-enedioic acid Chemical compound OC(=O)\C=C\C(O)=O.OC(=O)\C=C/C(O)=O STGNLGBPLOVYMA-KDTZGSNLSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
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- ACRMIBFELABVHW-IPBYNONMSA-N 1-o-methyl 4-o-octa-2,7-dienyl (e)-but-2-enedioate Chemical compound COC(=O)\C=C\C(=O)OCC=CCCCC=C ACRMIBFELABVHW-IPBYNONMSA-N 0.000 description 1
- JSRFYJBJQPGAAA-UHFFFAOYSA-N 2-ethylhex-2-en-1-ol Chemical compound CCCC=C(CC)CO JSRFYJBJQPGAAA-UHFFFAOYSA-N 0.000 description 1
- YDXQPTHHAPCTPP-UHFFFAOYSA-N 3-Octen-1-ol Natural products CCCCC=CCCO YDXQPTHHAPCTPP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 201000004384 Alopecia Diseases 0.000 description 1
- 241000744472 Cinna Species 0.000 description 1
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 101100289061 Drosophila melanogaster lili gene Proteins 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
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- 241000738583 Senna artemisioides Species 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
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- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
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- DMIKZTFGGJBMHQ-DABSYIHCSA-N bis(octa-2,7-dienyl) (E)-but-2-enedioate Chemical compound C=CCCCC=CCOC(=O)\C=C\C(=O)OCC=CCCCC=C DMIKZTFGGJBMHQ-DABSYIHCSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AIXMJTYHQHQJLU-UHFFFAOYSA-N chembl210858 Chemical compound O1C(CC(=O)OC)CC(C=2C=CC(O)=CC=2)=N1 AIXMJTYHQHQJLU-UHFFFAOYSA-N 0.000 description 1
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- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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- 239000000194 fatty acid Substances 0.000 description 1
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- 238000013467 fragmentation Methods 0.000 description 1
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- 230000003676 hair loss Effects 0.000 description 1
- XXYOEHRZCDHOOF-UHFFFAOYSA-N hept-1-en-2-ol Chemical compound CCCCCC(O)=C XXYOEHRZCDHOOF-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-L mesaconate(2-) Chemical compound [O-]C(=O)C(/C)=C/C([O-])=O HNEGQIOMVPPMNR-NSCUHMNNSA-L 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
Definitions
- This invention i elates to a compositioncharing a mixture of esters denvable h orn maleic and/oi tumai ic acid, anhydndes and alkyl esters thereof, a pi ocess lot pioducing said mixtui e of estei s and use of said ether esters as diluents m paint and polymei formulations
- One of the pi ocesses used hitherto to pioduce 2-subst ⁇ tuted succinate esters is the combined tianseste ⁇ fication and Michael addition reaction of an alcohol 01 a monoethei of a polyoxyalkylene glycol as described in GB-A-552715 m which ethei esteis of hydioxysuccinic acid and unsatutated alcohols are prepared by l eading in a single step u dei anhydtous conditions an alkyl ester of maleic acid with an unsatiiiated alcohol in the presence of
- R' R and R" is H oi an alky! oi an alkylene gi oup having 1 to 2 carbon atoms and, each of a and b is same oi difret ent and has a value oC 0 or is an integer from 1 -6
- R'O[CHR" CH 2 O] ⁇ H whei e x is 0 or an integer from 1 -6 which is used for making the MOE and can be an allylic hydrocarbyl or an allylic hydrocarbyloxy alkylene group
- the first reactant alcohol may be an allylic alcohol and includes mtei alia 2-ethyl-hex-2-en- l -ol (which compound will hereaftei be l efen
- the l eactant R'0[CHR" CH 2 Oj ⁇ H whei e A- is 0 01 an integer from 1 -6 can be prepared in several ways known to those skilled in the art
- the i cactant alcohol, eg an allylic alcohol, used to produce the MOE of the present invention can be pi oduced by the 1 eduction of the co ⁇ esponding ⁇ , ⁇ -unsaturated aldehyde eg by hydi ogenation, which will genei ate a mixture of the allylic alcohol and its satui ated analogue
- Some othei allylic alcohols may be produced from conjugated diene via the well known addition reactions
- Furthermoi e other allylic alcohols may be pi oduced by initially foi ming an unsaturated ester from an olefin and a cai boxyhc acid followed by hydi olysis of the ester to a mixture of isomeric ally
- the catalyst can be heterogeneous or homogeneous
- the epoxidation step is suitably carried out in the presence of a base catalyst
- base catalysts that may be used include alkali metal hydroxides such as sodium oi potassium hydroxide and other metal salts such as potassium acetate
- the alkoxylation reaction to form the hydroxy ether of the allylic alcohol can be cai ⁇ ed out using one oi moie of the epoxides which include inter alia ethylene oxide, piopylene oxide, butene oxide and butadiene mono-oxide
- the amount of epoxide used for thi step would depend upon the number of alkoxy groups desired in the hydioxy ethei 1 he amount of epoxide used is suitably in the range fiom 01 to 20 moles, piefeiably fiom 1 to 5 moles based on the allylic alcohol leactant
- 1 he alkoxylation leaction is suitably earned out at a temperature in the range fiom 50 to 180 ⁇ C , piefeiably fi m 60-l40°C
- the leaction pressure for this step is suitably autogenous but is piefeiably fiom 100 to 700 KPa
- the hydioxy ethei foimed in this step is suitably separated from the leaction mixtuie by neutialisation using eg magnesium silicate, then filtered to remove the neutralising agent and the salt of neutialisation so formed to leave behind a filti te comp ⁇ sing the desued hydioxy ethei
- the hydioxy ethei so pioduced can be used either as such without memeification, oi, optionally, aftei memeif ⁇ cation (eg by distillation) for the este ⁇ fication stage
- the MOE of toimula (I) in the compositions according to the piesent invention can be piepaied by a single-stage oi two stage reaction
- the dicaiboxylic compound and the reactant alcohol R'O[CHR" CH 2 O] H wheie v is 0 oi an integei fiom 1-6 are reacted at a temperatuie in the la ge fiom 80-l4()°C in theistnce of the catalyst (a), le zinc acetate
- the alcohol leactant is used in a molar excess, suitably using latio of alcohol to dicaiboxylic compound in the region of 2- 41, prefeiably 25 1
- Such a leaction is deemed to be complete when the level of half estei in the leaction mixtuie falls below about 05% w/w, preferably below 03% w/w 1 his can be monitoied by analysing samples withdrawn from the reaction
- the unreacted materials are stripped out by steam stripping oi by azeotiopic distillation eg using an azeotroping agent such as eg cyclohexane
- the catalyst may then be neutralised or removed as appi op ⁇ ate, the solids filtei ed and the MOE in the filti ate lecovered
- the MOE from this initial step is then further reacted in a second step with the catalyst component (b2), an alkaline earth metal alkoxide, in the presence of a further aliquot of the l eactant alcohol to enhance the 2-allyloxy succinate ester content thereof
- the alkaline earth metal in the alkoxide is suitably magnesium
- the pressures used are prefeiably in the lange iom atmospheiic to 50 Kpa, more preferably from atmospheric to 5 KPa
- a feature of the two-stage pi cess of the present invention is that it uses telatively milder conditions than a conventional Michael addition reaction For instance, no l eflux conditions need be used din ing this step Furthermore, the present process enables the proportion of the 2-substituted succinate ester in the reaction product to be enhanced considerably without leading to undesirable polymer formation or increasing the colouration of the ester product. Moreover, the present process not only gives better yields of the desired 2-substituted succinate ester.
- the MOE of the present invention have low volatility and relatively low viscosity suitably below 1500 mPa.s, thereby rendering them a suitable solvent component for curable paint and varnish formulations. These MOEs are especially suitable as the so called “reactive dilutents" for paint formulations and in particular those containing alkyd resins.
- Reactive diluents are usually compounds or mixtures of compounds of relatively low viscosity, a relatively high boiling point (or low saturated vapour pressure) which act as solvents during the formulation and processing of the coatin
- An advantage of reactive diluents is that such diluents can copolymerise with components of the alkyd resi
- reactive diluents may be used to replace part or all of the traditional solvents normally used in such formulations thereby reducing losses of the solvent to atmosphere on drying of the coating
- Use of reactive diluents comprising esters of p ⁇ lyhydric alcohols which have been partially etherified with allyl alcohol are described in EP-A-0 253 474.
- Alkyd resins are well known components of decorative paints (see, for example, "The Technology of Paints, Varnishes and Lacquers” by C R Martens (Ed ), published by Robert Krieger Publishing ( 1 974) and can be prepared from polybasic acids or anhydrides, polyhy ⁇ e alcohols and fatty acids or oils. US-A-3 8 19 720 describes methods of preparing such alkyd formulations. Alkyd coating compositions usually contain large amounts of solvents (eg mineral spirits and aromatic hydrocarbons).
- solvents eg mineral spirits and aromatic hydrocarbons
- compositions of the pi esent invention are highly suitable for use as reactive diluents.
- the relative ratios of reactive diluent to the alkyd resin in a formulation can be derived from the ranges quoted in published EP-A-0 305 006.
- the ratio of reactive diluent to alkyd resin is suitably in the range from 1 -50 : 99-50 parts by weight, eg 5-50 : 95-50 parts by weight, preferably from 5-25 : 95-75 and more preferably from 5- 1 5 : 95-85 parts by weight
- a diluent can replace all or part of a traditional solvent such as white spirit
- the formulations may contain further components such as catalyst, drier, aniiskinning agent, pigments, pigment stabilisers, rheology conti ilers (e g for sag control), UV and oxidation stabilisers, flow additives, microgels (e g to enhance hardness) and other additives
- the formulations may also need to include water scavengers such as trialkyl orthoformates, molecular sieves or zeolites where the reactive diluent used is susceptible to hydrolysis such
- a feature of the pi esent invention is that ethei estei s of formula (1) when used as r eactive diluents in paint oi coating formulations, especially those compr ising alkyd l esins, enhance the peifoi mance of these formulations
- a further aspect of the present invention is that such esters when used in
- the molecules of this invention include the partial or total replacement of ti aditional hydi ocai bon-based solvents in solvent-borne alkyd paints used foi p ⁇ mei , undei coat and topcoat decoi ative applications as well as in lndust ⁇ al applications such as alkyd pnmei and UV-cui e
- the molecules of this invention ai e also suitable for use as co-monomers, foi example in vinyl acetate-based polymei used in emulsion paints
- the molecules of this invention impart a temporar y plasticisation to the paint film, befote air-cui ing to a hai d finish They can, thei efoi e, facilitate the partial or total replacement of coalescent solvents
- the molecules could be used in watei -based paints based on acrylic and alkyd l esins, in addition to oi instead of, coalescent solvents
- the pr esent invention is fui thei lliusti ated with l efei ence to the following Examples
- the mixture was then heated in stages to 130°C (ie 80°C for 10 minutes, then 100°C for 10 minutes and then 120°C for 10 minutes).
- the progress of the reaction was monitored by the methanol collected in the Dean and Stark apparatus When 90% of the predicted methanol had been collected, the reaction mixture was sampled hourly and analysed by GC The reaction was adjudged complete when the level of the "half ester" (methyl octadienyl maleate/fumarate) fell to below 0.3% w/w, this took approximately 8 hours. At this point the heating was switched off and the reaction mixture allowed to cool to room temperature.
- the product from the reaction was then decanted from any solids in the reaction flask This product was then charged to a heated decanter (40°C) with an equal volume of 5% w/w aqueous sodium hydroxide solution. The mixture was stirred for 20 minutes and then allowed to separate and the lower aqueous phase decanted.
- the base wash was then repeated and the remaining organic phase was washed with satui ated brine until the aqueous phase r eached a steady pH
- the organic phase was then heated ( l ()0°C) under reduced pressure ( ⁇ 500 Pa ( ⁇ 5 mBar)) on a rotatory evaporator to remove residual water and the majority of the excess octadienol
- the product was filtered and transferred to a 5- litre three necked round bottomed quickfit flask This flask was equipped with a still head condenser and receiver flask (Perkin triangle), a thermocouple, a steam inlet pipe, and a eurotherm controlled heating mantle.
- the apparatus was evacuated to 4000 Pa (40 mBar) and the product heated to I 20°C. The supply of steam was then connected and the residual traces of octadienol were removed. The purification was judged complete when the volume of the heads product aqueous phase increased to more than 5 times that of the organic phase After cooling down, the product was then treated with activated carbon ( l %w/w, 100°C 2Hrs, ⁇ 500 Pa ( ⁇ 5 mBar)) on a rotatory evaporator. The cooled mixture was filtered through dried celite to obtain the final product which had the following analyses
- Fumaric acid - l Oppm (HPLC) Zinc - 5ppm (atomic absorption, detection limit) sodium - 30ppm ( atomic absorption) chlorine - - lOppm (atomic absorption detection limit)
- e flanged flask with an insert pipe foi a nitiogen sparge, a thermowell for thermocouple, and a Dean and Stark apparatus with double-walled condenser.
- the flask was heated with an electric heating mantle which was controlled with a eurotherm controller connected to the thermocouple.
- the nitrogen sparge pipe was inserted so that the nitrogen flow agitated the flask contents and provided mixing during the course of the reaction. The nitrogen flow also served to entrain out the liberated methanol and force the reaction to completion.
- the reaction was adjudged complete, when the level of the "half ester" (methyl octadienyl maleate/fumarate) fell to below 0.3% w/w and this took approximately 72 hours. At this point the heating was switched off and the reaction mixture allowed to cool to room temperature The product from the reaction was then decanted from any solids in the reaction flask. This product was then charged to a heated decanter (40"C) with an equal volume of 5% w/w aqueous sodium hydroxide solution The mixture was stirred for 20 minutes and then allowed to separate and the lower aqueous phase decanted.
- a heated decanter 40"C
- This llask was equipped with a still head condenser and receiver flask (Perkin triangle), a thermocouple, a steam inlet pipe, and a eurotherm controlled heating mantle
- the apparatus was evacuated to 4000 Pa (40 mBar) and the product heated u> 120°( ⁇ )
- the supply of steam was then connected and the residual traces of octadienol were removed.
- the purification was judged complete when the volume of the heads product aqueous phase increased more than 5 times that of th organic phase.
- Fuma ⁇ c acid - l Oppm HPLC tin - 5ppm (atomic absorption, detection limit) sodium - 20ppm ( atomic absorption, detection limit) chlorine - - 1 Oppm (atomic absoiption detection limit)
- a five-htie flanged flask with an insert pipe foi a nitrogen sparge, a thermowell for thei mocouple, and a Dean and Stai k appaiatus with double- walled condenser
- the flask was heated with ⁇ I ⁇ elect! IC heating mantle which was controlled with a eui othei m conttollei connected to the theimocouple
- the nitrogen sparge pipe was inserted so that the nitiogen flow agitated the flask contents and provided mixing din ing the coui e of the leaction
- the nitiogen flow also served to entrain out the hbei ted methanol and foice the l eaction to completion
- the organic phase was then heated ( 100°C) under reduced pressure ( - 500 Pa (- 5 mBar)) on a rotatory evaporator to remove residual water and the majority of the excess octadienol. After cooling, the product was filtered and transferred to a 5-litre three-necked round-bottomed quickfit flask .
- This flask was equipped with a still-head condenser and reciever flask (Perkin triangle), a thermocouple, a steam inlet pipe, and a eurotherm controlled heating mantle.
- the appai atus was evacuated to 4000 Pa (40 mBar) and the product heated to 120°C The supply of steam was then connected and the residual traces of octadienol were removed The purification was judged complete when the volume of the heads product aqueous phase increased more than 5 times that of the organic phase After cooling down the product was then treated with activated carbon ( l %w/w, 100 'C 2 hrs, 500 Pa ( •' 5 mBar)) on a rotatory evaporator The cooled mixture was filtered through dried celite to obtain the final product which had the following analyses. OH number - 4 mg KOH/g (titration) total acid - 46 ppm KOH/g (titration) maleic acid / anhydride - l Oppm ( HPLC)
- Example S4 The process of Example S I was repeated to give a product with the following analysis:
- Zinc ppm (atomic absorption, detection limit) sodium 20ppm ( atomic absorption) chlorine l ppm (atomic absorption detection limit)
- a one-litre flanged flask with an insert pipe for a nitrogen sparge, a thermowell for thermocouple ⁇ magnetic follower, and a double-walled condenser was heated with an electric heating mantle which was controlled with a eurotherm controller connected to the thermocouple.
- the nitrogen sparge pipe was inserted so that the flask and contents could be purged of air prior to the reaction and the pipe raised to provide a top cover during the course of the reaction, the reactor contents were stirred with the polytetrailuoroethylene coated magnetic follower.
- the reaction was judged complete after I 6Hrs.
- the heating was switched offand the mixture allowed to cool
- the mixture was then washed repeatedly with an equla volume of de-ionised water t, at room remperature for 20 minutes, to remove the magnesium catalyst. This was judged complete when the pH of the lower aqueous phase remained steady. This took three washes.
- the organic phase was then heated ( 100°C) under reduced pressure (- ⁇ 500 Pa (- 5 mBar)) on a rotatory evaporator to remove residual water and the majority of the excess octadienol After cooling, the product was filtered and transferred to a 1 -litre three-necked round-bottomed quickfit flask .
- This flask was equipped with a still head condenser and receiver flask (Perkin triangle), a thermocouple, a steam inlet pipe, and a eurotherm controlled heating mantle.
- the apparatus was evacuated to 4000 Pa (40 mBar) and the product heated to 120°C. The supply of steam was then connected and the residual traces of octadienol were removed. The purification was judged complete when the volume of the heads pi oduct aqueous phase increased moi e than 5 times that of the organic phase.
- Table 2 demonsti ates that the cstei s/i eactive diluents of this invention have relatively low viscosity ( '200 mPa s) and are suitable for use as reactive diluents 3. Examples of the use of the reactive diluents in paint formulations
- Reactive diluents such as those of the piesent invention, must meet a range of criteria including low odoui and low toxicity, low viscosity and the ability to "cut" the viscosity of the paint to facilitate application on the surface to be coated therewith Fuithei moi e, the diluent should not have a markedly adverse effect on the properties of the paint film such as di ying speed, haidness and degree of wrinkling
- the l eactive diluents descnbed above have thei efore been tested in paint applications using both cleai and pigmented paints
- the diluents have been compared with paints foi mulated using white spirit, a conventional thinner
- % leactive diluent refers to the ratio of reactive diluent to alkyd (e g 30% reactive diluent implies 30g diluent to every 70g alkyd)
- Coating viscosity was measured in accordance with the IC1 Cone & Plate method (IS02884) at 10,000 s- l , 23 ⁇ C, 50% RH (Pa s)
- K ⁇ nig hardness (ISO 1 522 ) was measured at 23°C, 50% RFI (s) of a coating film applied with a 100 mm applicator on a glass substrate.
- the Fischer spherical indention test is based on 1S06441 (um) and was performed on a coating film applied with a 1 00 mm applicator on a glass substrate. Drying performance was determined at I °C, 85% RH with a Beck-Koller drying recorder (hours) under daylight lamps Films were applied to glass substrates using a 90 mm applicato
- the measurements quoted (in hours) are : a) For high solids alkyd resin-based pigmented paints : "phase 1 ", the dust drying time, b) For conventional alkyd resin-based pigmented paints : "phase 2"
- Example T l Paints containing 30% reactive diluent were prepared from the diluents
- Tables 8 and 9 summai i.se the diymg and hardness test data from the pigmented paint foi mutations based on conventional alkyd l esins
- the drying data in Table 8 show that the paints based on the leactive diluents of this invention dry in a period acceptable to the mdustiy, even aftei storage at 35°C for two weeks Furthei moie, the bal dness of the pamt films is excellent
- Diying performance was measured using films applied to 30 cm x 2 5 cm glass strips and BK diying recorders.
- the BK recorders were enclosed in a Fisons controlled temperature and humidity cabinet so that the drying experiment could be performed at 10°C and at 70% relative humidity.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/011,949 US6130275A (en) | 1996-06-28 | 1997-06-27 | Mixture of esters and use thereof |
AU33501/97A AU3350197A (en) | 1996-06-28 | 1997-06-27 | Mixture of esters and use thereof |
DE69706128T DE69706128T2 (en) | 1996-06-28 | 1997-06-27 | ESTER MIXTURE AND THEIR USE |
JP50391898A JP4105232B2 (en) | 1996-06-28 | 1997-06-27 | Ester mixture and method of using the same |
CA002230223A CA2230223C (en) | 1996-06-28 | 1997-06-27 | Mixture of esters and use thereof |
EP97929379A EP0847380B1 (en) | 1996-06-28 | 1997-06-27 | Mixture of esters and use thereof |
DK97929379T DK0847380T3 (en) | 1996-06-28 | 1997-06-27 | Mixture of esters and their use |
NO980811A NO980811L (en) | 1996-06-28 | 1998-02-26 | Mixture of esters and their use |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9613675.9 | 1996-06-28 | ||
GBGB9613675.9A GB9613675D0 (en) | 1996-06-28 | 1996-06-28 | Mixtures of esters and use thereof |
GB9624679.8 | 1996-11-27 | ||
GBGB9624679.8A GB9624679D0 (en) | 1996-11-27 | 1996-11-27 | Mixtures of esters and use thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998000387A1 true WO1998000387A1 (en) | 1998-01-08 |
Family
ID=26309597
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1997/001741 WO1998000387A1 (en) | 1996-06-28 | 1997-06-27 | Mixture of esters and use thereof |
Country Status (9)
Country | Link |
---|---|
US (1) | US6130275A (en) |
EP (1) | EP0847380B1 (en) |
JP (1) | JP4105232B2 (en) |
AU (1) | AU3350197A (en) |
CA (1) | CA2230223C (en) |
DE (1) | DE69706128T2 (en) |
DK (1) | DK0847380T3 (en) |
NO (1) | NO980811L (en) |
WO (1) | WO1998000387A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1120826C (en) * | 2000-01-21 | 2003-09-10 | 浙江省化工研究院 | Process for preparation of 1,1,1,3,3-pentafluoropropane |
US8124688B2 (en) | 2006-03-30 | 2012-02-28 | Akzo Novel Coatings International B.V. | Coating composition comprising a reactive diluent of malonate |
US8486187B2 (en) | 2006-01-18 | 2013-07-16 | Basf Se | Multipurpose additive for low VOC solvent based coatings |
US8829151B2 (en) | 2006-03-30 | 2014-09-09 | Akzo Nobel Coatings International B.V. | Coating composition comprising a reactive diluent of polyunsaturated alcohol ester |
US12054630B2 (en) | 2019-02-14 | 2024-08-06 | The University Of Akron | Modified cardanol as the reactive diluents for alkyd coating |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020151629A1 (en) * | 2001-02-08 | 2002-10-17 | Buffkin Halbert C. | Protective coating |
CA2521629A1 (en) * | 2003-05-08 | 2004-11-18 | The University Of Southern Mississippi Research Foundation | Reactive diluents |
JP2006525402A (en) * | 2003-05-08 | 2006-11-09 | ザ ユニバーシティ オブ サザン ミシシッピ リサーチ ファンデーション | Reactive diluents in paint formulations |
DE102009060813A1 (en) * | 2009-12-30 | 2011-07-07 | Emery Oleochemicals GmbH, 40589 | Catalyst system for the preparation of an ester and this ester using methods |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997002229A1 (en) * | 1995-06-30 | 1997-01-23 | Bp Chemicals Limited | Reactive diluents |
WO1997002230A1 (en) * | 1995-06-30 | 1997-01-23 | Bp Chemicals Limited | Reactive diluents |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB552715A (en) * | 1941-09-19 | 1943-04-21 | Du Pont | Manufacture of ether-esters of hydroxysuccinic acid and polymers derived therefrom |
-
1997
- 1997-06-27 CA CA002230223A patent/CA2230223C/en not_active Expired - Fee Related
- 1997-06-27 EP EP97929379A patent/EP0847380B1/en not_active Expired - Lifetime
- 1997-06-27 US US09/011,949 patent/US6130275A/en not_active Expired - Lifetime
- 1997-06-27 WO PCT/GB1997/001741 patent/WO1998000387A1/en active IP Right Grant
- 1997-06-27 DE DE69706128T patent/DE69706128T2/en not_active Expired - Fee Related
- 1997-06-27 DK DK97929379T patent/DK0847380T3/en active
- 1997-06-27 AU AU33501/97A patent/AU3350197A/en not_active Abandoned
- 1997-06-27 JP JP50391898A patent/JP4105232B2/en not_active Expired - Fee Related
-
1998
- 1998-02-26 NO NO980811A patent/NO980811L/en not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997002229A1 (en) * | 1995-06-30 | 1997-01-23 | Bp Chemicals Limited | Reactive diluents |
WO1997002230A1 (en) * | 1995-06-30 | 1997-01-23 | Bp Chemicals Limited | Reactive diluents |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1120826C (en) * | 2000-01-21 | 2003-09-10 | 浙江省化工研究院 | Process for preparation of 1,1,1,3,3-pentafluoropropane |
US8486187B2 (en) | 2006-01-18 | 2013-07-16 | Basf Se | Multipurpose additive for low VOC solvent based coatings |
US8124688B2 (en) | 2006-03-30 | 2012-02-28 | Akzo Novel Coatings International B.V. | Coating composition comprising a reactive diluent of malonate |
US8829151B2 (en) | 2006-03-30 | 2014-09-09 | Akzo Nobel Coatings International B.V. | Coating composition comprising a reactive diluent of polyunsaturated alcohol ester |
US12054630B2 (en) | 2019-02-14 | 2024-08-06 | The University Of Akron | Modified cardanol as the reactive diluents for alkyd coating |
Also Published As
Publication number | Publication date |
---|---|
DE69706128T2 (en) | 2002-04-25 |
US6130275A (en) | 2000-10-10 |
CA2230223C (en) | 2007-06-05 |
NO980811D0 (en) | 1998-02-26 |
JP4105232B2 (en) | 2008-06-25 |
JPH11514697A (en) | 1999-12-14 |
NO980811L (en) | 1998-04-03 |
AU3350197A (en) | 1998-01-21 |
EP0847380B1 (en) | 2001-08-16 |
DE69706128D1 (en) | 2001-09-20 |
DK0847380T3 (en) | 2001-11-26 |
EP0847380A1 (en) | 1998-06-17 |
CA2230223A1 (en) | 1998-01-08 |
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