WO1996040619A1 - Process for preparing amides of n-alkyl polyhydroxyalkyl amines - Google Patents
Process for preparing amides of n-alkyl polyhydroxyalkyl amines Download PDFInfo
- Publication number
- WO1996040619A1 WO1996040619A1 PCT/US1996/007124 US9607124W WO9640619A1 WO 1996040619 A1 WO1996040619 A1 WO 1996040619A1 US 9607124 W US9607124 W US 9607124W WO 9640619 A1 WO9640619 A1 WO 9640619A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fatty acid
- reaction
- color
- alkylamino
- ion exchange
- Prior art date
Links
- 150000001412 amines Chemical class 0.000 title claims abstract description 58
- 150000001408 amides Chemical class 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 108
- 238000006243 chemical reaction Methods 0.000 claims abstract description 99
- 239000003054 catalyst Substances 0.000 claims abstract description 88
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 73
- 239000000194 fatty acid Substances 0.000 claims abstract description 73
- 229930195729 fatty acid Natural products 0.000 claims abstract description 73
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 59
- -1 amine amides Chemical class 0.000 claims abstract description 58
- 239000002904 solvent Substances 0.000 claims abstract description 46
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 32
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000011282 treatment Methods 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000000344 soap Substances 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 238000002834 transmittance Methods 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 125000001924 fatty-acyl group Chemical group 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 65
- 230000008569 process Effects 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000000203 mixture Substances 0.000 claims description 47
- 229920005862 polyol Polymers 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 41
- 239000004094 surface-active agent Substances 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 33
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 238000005984 hydrogenation reaction Methods 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- 239000003599 detergent Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000007844 bleaching agent Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229960004592 isopropanol Drugs 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000003791 organic solvent mixture Substances 0.000 claims description 2
- 239000010414 supernatant solution Substances 0.000 claims description 2
- 150000001450 anions Chemical group 0.000 claims 4
- 150000002190 fatty acyls Chemical group 0.000 claims 4
- 230000001172 regenerating effect Effects 0.000 claims 2
- MBBZMMPHUWSWHV-BDVNFPICSA-N N-methylglucamine Chemical compound CNC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO MBBZMMPHUWSWHV-BDVNFPICSA-N 0.000 abstract description 32
- 230000015572 biosynthetic process Effects 0.000 abstract description 27
- 150000004702 methyl esters Chemical group 0.000 abstract description 13
- 125000004122 cyclic group Chemical group 0.000 abstract description 11
- 125000000129 anionic group Chemical group 0.000 abstract description 8
- 125000002091 cationic group Chemical group 0.000 abstract description 7
- 238000009895 reductive bleaching Methods 0.000 abstract description 5
- 150000003973 alkyl amines Chemical class 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 37
- 235000000346 sugar Nutrition 0.000 description 36
- 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 description 30
- 239000008103 glucose Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 27
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 24
- 239000000376 reactant Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 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 description 18
- 239000011541 reaction mixture Substances 0.000 description 18
- 230000005540 biological transmission Effects 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229960004063 propylene glycol Drugs 0.000 description 12
- 150000008163 sugars Chemical class 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 235000013772 propylene glycol Nutrition 0.000 description 9
- 235000020357 syrup Nutrition 0.000 description 9
- 239000006188 syrup Substances 0.000 description 9
- 150000003626 triacylglycerols Chemical class 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 239000003086 colorant Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 239000003125 aqueous solvent Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007868 Raney catalyst Substances 0.000 description 5
- 229910000564 Raney nickel Inorganic materials 0.000 description 5
- 240000008042 Zea mays Species 0.000 description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 5
- 235000005822 corn Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 5
- 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 description 4
- 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 description 4
- 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 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 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 description 4
- 229920001429 chelating resin Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 4
- 235000019645 odor Nutrition 0.000 description 4
- 239000003346 palm kernel oil Substances 0.000 description 4
- 235000019865 palm kernel oil Nutrition 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229930091371 Fructose Natural products 0.000 description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 3
- 239000005715 Fructose Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000010923 batch production Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 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 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 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 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 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 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 235000019486 Sunflower oil Nutrition 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000000828 canola oil Substances 0.000 description 2
- 235000019519 canola oil Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 150000002194 fatty esters Chemical class 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000008101 lactose Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000006268 reductive amination reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 239000002600 sunflower oil Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- QVEUDPHFUKJQHH-SGIHWFKDSA-N (2r,3r,4r,5s)-6-(butylamino)hexane-1,2,3,4,5-pentol Chemical compound CCCCNC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO QVEUDPHFUKJQHH-SGIHWFKDSA-N 0.000 description 1
- IKXCHOUDIPZROZ-LXGUWJNJSA-N (2r,3r,4r,5s)-6-(ethylamino)hexane-1,2,3,4,5-pentol Chemical compound CCNC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO IKXCHOUDIPZROZ-LXGUWJNJSA-N 0.000 description 1
- XMWZOWQYICPGNI-JQCXWYLXSA-N (2r,3r,4r,5s)-6-(propan-2-ylamino)hexane-1,2,3,4,5-pentol Chemical compound CC(C)NC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO XMWZOWQYICPGNI-JQCXWYLXSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 1
- 240000003133 Elaeis guineensis Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 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 1
- 239000005639 Lauric acid Substances 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 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
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 229920001273 Polyhydroxy acid Polymers 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- TUTWLYPCGCUWQI-UHFFFAOYSA-N decanamide Chemical compound CCCCCCCCCC(N)=O TUTWLYPCGCUWQI-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000012470 diluted sample Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical class CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 235000019534 high fructose corn syrup Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical class [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940116335 lauramide Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- QEALYLRSRQDCRA-UHFFFAOYSA-N myristamide Chemical compound CCCCCCCCCCCCCC(N)=O QEALYLRSRQDCRA-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- CKQVRZJOMJRTOY-UHFFFAOYSA-N octadecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCCCC(O)=O CKQVRZJOMJRTOY-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000020374 simple syrup Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
Definitions
- the present invention relates to an improved process for preparing amides of N-alkyl polyhydroxyalkyl amines, especially ones having good color and low levels of undesirable by-products.
- N-alkyl polyhydroxyalkyl amines such as N-methylglucamine
- fatty acid amides thereof have been known for many years, and such materials are available commercially.
- N-alkyl polyhydroxy amines e.g., in reactions with, e.g., fatty acid esters to prepare fatty acid polyhydroxy amide detersive surfactants for use in cleaning products. It has been determined that care must be taken in preparing N- alkyl polyhydroxy amines and amides to provide the amides with the best color.
- the present invention affords access to high quality polyhydroxy fatty acid amide surfactants.
- the present invention provides means for preparing N-alkyl polyhydroxy amine amides which are almost water white, especially amides of N- methylglucamine, in high yields, and more especially, amides of N-methylglucamine containing low levels of cyclic materials as hereinafter disclosed.
- the condensation product prepared at about 160°C, is said to be "predominantly, if not exclusively, an amide" and is assertedly of the formula R-CO-NR ⁇ -CH2-(CHOH)4- CH2OH wherein R is an alkyl radical containing at least 3 carbon atoms, while R j is hydrogen or an alkyl radical.
- N- monoalkylglucamines can be reacted with fatty alkyl esters by heating at 140°C-230° C, preferably 160°C-180°C at normal, reduced or superatmospheric pressures for a period "somewhat in excess of one hour" during which time two initially immiscible phases merge to form a product said to be a useful detergent.
- Suitable N-monoalkylglucamines are illustrated by N-methylglucamine, N- ethylglucamine, N-isopropylglucamine and N-butylglucamine.
- Suitable fatty alkyl esters are illustrated by the product of reacting a C6-C30 fatty acid with an aliphatic alcohol, e.g., methyl ester of lauric acid.
- compositions comprising the amide compounds of this invention are included in the above-identified disclosure of improved thickeners. See EP-A 285,768. See also H. Kelkenberg, Tenside Surfactants Detergents 25 (1988) 8-13, inter alia for additional disclosures of processes for making N- alkylglucamines. All of the above patents and publications are incorporated herein by reference.
- N-alkyl polyhydroxy amines N-alkylamino polyols
- Both the N-alkyl polyhydroxy amines and the source of fatty acyl groups, e.g., esters, used to form the amides are selected to have good color, the reaction conditions are selected to avoid the formation of color materials and precursors for color materials; and or the amide product is treated with an ion exchange resin, mixtures of ion exchange resins, or combinations thereof, and/or a reducing "bleach" to prepare the best color amides.
- the invention provides a process for preparing polyhydroxy fatty acid amide surfactants, comprising reacting a member selected from the group consisting of fatty acids, fatty acid anhydrides and fatty acid esters, especially fatty acid esters, having greater than 98% transmittance at 460nm with an N-alkylamino polyol having a Gardner Color of less than 1 ( ⁇ 0.1 absorbence at 440nm), e.g., methyl esters or triglycerides.
- N-alkylamino polyol Crystallization of said N-alkylamino polyol can be used to provide the appropriate purity and color.
- N-alkylamino polyol with this Gardner Color is “stable” for three hours at 130°C.
- the N-alkylamino polyol is considered stable if it has a Gardner Color of 4, or less, after three hours under these conditions. A less pure N- alkylamino polyol will be a dark brown after three hours under these conditions.
- the dehydration of N-alkylamino polyol should be carried out at between about 110°C and about 160°C for a period of time of less than about three hours, more preferably at a temperature of from about 120°C to about 140°C for a period of time of less than about one and a half hours and even more preferably at a temperature of from about 130°C to about 135°C for a period of time of less than about one hour.
- good results can be obtained with dehydration times of from about four to about eight hours, preferably from about five to about six hours, to accommodate commercial equipment limitations.
- a more pure N-alkylamino polyol can be achieved by crystallization from an aqueous solution, either with, or without, an organic solvent present.
- the dehydrated N-alkylamino polyol is then reacted with, e.g., fatty acid esters and especially triglycerides, to form fatty acid polyhydroxy amide surfactants.
- the resulting polyhydroxy fatty acid amide surfactant is then post treated with an ion exchange resin, mixture of ion exchange resins, or combinations of ion exchange resins, and/or reducing bleach such as NaBH4, etc., or hydrogenation over a catalyst, as taught hereinafter, and, optionally, combinations of treatments.
- a particularly effective post treatment is the hydrogenation of a solution of the polyhydroxy fatty acid amide surfactant over a hydrogenation catalyst like nickel, palladium, copper chromite, etc.
- the fatty acid ester is a CJQ-CIS alkyl or alkenyl fatty acid methyl ester, or, triglyceride
- the N-alkylamino polyol is selected from N- methyl glucamine, N-methyl fructamine, N-methyl maltamine and N-methyl glycerol amine.
- the processes of this invention employ selected reactants, N-alkylamino polyols and sources of fatty acyl groups, with good color, especially color that is heat stable.
- the "color” referred to herein is the Gardner Color, e.g., of the N-alkylamino polyol, the N-alkylamino fatty acid amide, etc.
- Gardner Color is the standard Gardner measurement known in the art. A Gardner Color reading near zero (solution) represents a nearly colorless (“water-white”) solution. Gardner Colors below about 1 are required for the N-alkylamino polyol reactants, and it is preferred to have Gardner Colors close to 0.
- Gardner Color is determined by A.O.C.S. (American Oil Chemists Society) Official Method to la-64, entitled COLOR Gardner 1963 (Glass Standards) established 1978 and revised 1982.
- the equipment and standards for determining Gardner Color can be purchased from Delta Scientific, Box 5728, Long Island, New York 20014, or from Gardner Laboratory, Silver Spring, Maryland, U.S.A.
- Gardner Color limits typically refer to the color resulting from the color bodies that are present, or which are the result of the described reactions, and not to deliberately added color materials.
- the odor characters of the N-alkylamino polyol reactant, and its amide are substantially free of amine or "fish" type odor (once any excess N-alkylamine is removed) and also substantially free of typical browning sugar odors.
- Suitable N-alkylamino polyols can be prepared by processes similar to those described in copending U. S. Patent Application Serial No. 07/907,382, filed July 8, 1992, in the name of Junan Kao et al. for PROCESS FOR PREPARING N- ALKYLAMINES IN AQUEOUS HYDROXY SOLVENTS, said application being incorporated herein by reference, especially page 6, line 4, to page 23, line 3 and EXAMPLES I - VI, and K - XiV.
- the polyhydroxy amine used to form the polyhydroxy acid amide can be made by any process that will provide the desired color.
- N-alkylamino polyols with good color are achieved by careful selection of reaction conditions.
- N-alkylamino polyols also referred to herein as "polyhydroxyamines” or “N-alkyl polyhydroxy amine”
- R-l The reaction for the preparation of the N-alkylamino polyols (also referred to herein as "polyhydroxyamines" or “N-alkyl polyhydroxy amine”) herein can be termed the “R-l” reaction, and is illustrated by the formation of N-methylglucamine, wherein R 1 is methyl.
- the process involves pre-reacting the amine and reducing sugar to form an adduct.
- water and/or organic solvent e.g., methanol R!NH2 + glucose — Adduct + H2O
- the Adduct has the formula (I) as follows:
- the reactants, solvents and catalysts used in the R-l reaction are all well- known materials, although not usually used in such purified form for making detergent surfactants, and are available, at least in some form, from a variety of commercial sources.
- the following are nonlimiting examples of materials which can be used herein.
- N-alkylamines used to form the N-alkylamino polyols include primary amines of the formula R 1 NH2, wherein R* is, for example, alkyl, e.g., Cj-Cig, especially C1-C4 alkyl, or the corresponding hydroxyalkyls, e.g., Cj- C4 hydroxyalkyl. Examples include methyl, ethyl, propyl, hydroxyethyl, and the like.
- Nonlimiting examples of amines useful herein include methyl amine, ethyl amine, propyl amine, butyl amine, 2-hydroxypropyl amine, 2-hydroxymethylpropyl, 2- hydroxyethyl amine; 1-methoxypropyl, and methyl amine.
- the C1-C3 alkylamines are preferred, and N-methylamine is most preferred. All such amines are jointly referred to herein as "N-alkyl amines.”
- the amine can be either anhydrous or in a solvent, e.g., aqueous solvent, of a concentration of from about 30% to about 90%, preferably from about 40% to about 70%.
- Polyhydroxy Material - A preferred source of polyhydroxy materials useful in all of the R-l reactions comprise reducing sugars or reducing sugar derivatives.
- reducing sugars such as glucose, fructose, mannose, lactose, maltose, xylose and the like.
- the term “sugars” herein also includes glyceraldehyde.
- Such "sugars” can include materials which break down to form sugars, such as plant syrups such as cane syrups, corn syrups, potato starch-derived sugar syrups, hydrolyzed wood pulp-derived sugars and the like. High fructose, high glucose and high maltose syrups are economical and preferred, especially if their Gardner Color is satisfactory.
- the reactant sugar material comprises, for this first variation, an adduct with the amine such as methylamine.
- the species are determined (measured) by g.c. analysis, (gas-liquid chromatography or "g.l.c.") using Hewlett-Packard 5890 Series 2 on column injection using DB1 15 meter 0.25 m film thickness ID 250 m.
- a particular advantage of the "Adduct” process is that the “Adduct” can be formed in the presence of water. Accordingly, raw materials such as corn syrup, and the like, can be used as the sugar source.
- the sugar solution can be prepared from granular, powdered, etc., sugar by dissolving the sugar in the solvent, preferably aqueous solvent. Concentrations of sugar in the solvent, e.g., water, are typically from about 40% to about 90%, preferably from about 50% to about 70% (Typically, 71% is the upper limit.) It is highly important that the color of the starting sugar material, for preparing all N-akylamino polyols, be less than about one on the Gardner Color scale, preferably less than about Gardner 0+, and more preferably about water white.
- Typical color materials that are present in the starting sugar materials negatively affect the catalyst and the reaction yield. These color materials also contribute to the eventual color of the N-alkylamino polyols. Such colors can be removed, if present, by procedures such as "carbon bleaching," in which the color materials are adsorbed.
- the sugar material is preferably handled without excessive heating and/or under non-oxidizing conditions to prevent degradation.
- N-alkylamino polyols having desirably low Gardner Colors will be produced.
- low (0-1) Gardner Color sugars preferably white solids or water-white solutions
- use of the reaction sequence disclosed herein results in low Gardner Color N- alkylamino polyols.
- Catalyst - A variety of hydrogenation catalysts can be used in the R-l reaction. Included among such catalysts are nickel (preferred when treated as discussed hereinafter), platinum, palladium, iron, cobalt, tungsten, various hydrogenation alloys, and the like.
- the catalyst used in the hydrogenation step is preferably a particulate nickel catalyst, Raney nickel, nickel, other nickel catalysts affixed to substrate materials such as silica or alumina. Catalysts which are easier to remove (e.g., by filtration) are preferred.
- Highly preferred catalysts herein comprise "United Catalyst G49B,” “United Catalyst G96,” and “UCI C46" particulate Ni catalysts supported on silica, available from United Catalysts, Inc., Louisville, Kentucky, and Raney nickel type catalysts from W.R Grace & Co., of Baltimore, Maryland, such as RA4200 and RA3100.
- Achieving good color also requires optimizing and maintaining the activity of the preferred nickel catalysts including any of the conventional Raney nickel or "supported” nickel catalysts well-known in the art.
- Conventional nickel under the trademark RANEY NICKEL 4200 and 3200 (Grace Chemicals) are quite suitable for use herein.
- UCI United Catalyst, Inc.
- G-96B and G-49B and G-49C are also suitable.
- removing oxides of nickel from the catalyst prevents or impedes dissolution of nickel ions into the reaction milieu, and thus results in the formation of reaction products having a desirable low nickel content.
- nickel catalyst pre ⁇ treated and preferably post-treated with pressurized hydrogen can be re-used in multiple subsequent reactions, thereby yielding a substantial overall cost savings.
- nickel catalysts such as those that are commercially available, typically are contaminated with, e.g., oxides of nickel, organic materials, excess caustic, and/or alumina fines, especially after shipping and storage.
- the nickel catalysts that are used in the processes herein are preferably free of catalytic activity inhibiting quantities of nickel oxides, organic materials, caustic, alumina fines, etc.
- the catalyst it is desirable to wash the catalyst with one, or more, solvents to effect removal of organics and/or water-soluble materials, to preferably lower the pH, and/or treat the catalyst with a strong reducing agent, e.g., hydrogen gas under high pressure and/or temperature conditions, to destroy, or remove, the nickel oxides.
- a strong reducing agent e.g., hydrogen gas under high pressure and/or temperature conditions
- the catalyst is desirably maintained under non-reactive atmosphere, e.g., nitrogen gas, or, more desirably, a reducing gas, e.g., hydrogen. Any exposure to the normal atmosphere should desirably occur for only short periods of time and while the temperature is low
- the activity of the catalyst can be increased substantially by the reduction, or removal, of these impurities, even when they are present in very small amounts.
- the resulting catalyst also provides amines, and therefore amides, with good color.
- a high hydrogen pressure e.g., from about 100 psig to about 3500 psig, preferably from about 500 psig to about 1500 psig, and a temperature of from about 20°C to about 135°C, preferably from about 40°C to about 85°C, will reduce the level of nickel ion dissolved in the N-alkyl polyhydroxyalkyl amine, and, by depositing the nickel back onto the catalyst, regenerate its activity.
- a combination of hydrogen gas and selected pressure/temperature conditions can reduce this solubilization and, in fact, reverse the process to deposit nickel and regenerate the catalyst.
- the temperature should be less than about 135°C, preferably less than about 85°C, and the separation, typically filtration, should be accomplished under hydrogen pressure.
- N-alkylamino polyol reactant herein which is "substantially free of nickel" contains no more than about 20 parts per million (ppm) nickel, and preferably less than about 5 ppm nickel ( t* ).
- Nickel can be conveniently measured by conventional atomic absorption spectroscopy, using diluted samples (5/1 dilution to minimize interference).
- Solvent - Formation of the adduct in the R-l process is conveniently carried out in water and/or organic solvent, especially polar, most preferably hydroxy solvents.
- Typical examples of organic solvents useful herein in the formation of the amine- sugar adduct include methanol (preferred), ethanol, 1-propanol, iso-propanol, the butanols, ethylene glycol, 1,2-propylene glycol (preferred), 1,3-propylene glycol, glycerol and the like.
- the amine itself can also function as a solvent, typically at mole ratios of amine: sugar of from about 4:1 to about 30:1.
- the hydrogenation reaction of the R-l reaction can also be carried out in the presence of an organic or aqueous solvent which dissolves the adduct.
- Hydrogenation solvents are, conveniently, polar, especially hydroxy, solvents, i.e., of the same type as those mentioned above for use in the formation of the adduct.
- substantially anhydrous organic solvent is used, the unreacted amine is removed with the water after the adduct formation step.
- an aqueous solvent is used, the amine and solvent are not removed until the catalyst removal step.
- Water is the preferred solvent for the hydrogenation reaction.
- Methanol is a preferred organic solvent for use in the hydrogenation reaction.
- Step (a) - Adduct formation - Step (a) of the process is preferably carried out at a temperature of from about 0°C to about 80°C, preferably from about 10°C to about 60°C, for processes utilizing organic hydroxy solvent and below about 70°C, preferably less than about 50°C, more preferably less than about 30°C, more preferably from about 15°C to about 25°C, for aqueous solvents.
- the reaction time used for adduct formation will typically be on the order of from a few minutes to about 20 hours, depending somewhat on the reaction temperature chosen and/or the ratio of amine to sugar.
- reaction temperatures in the range of 0°C-80°C require longer reaction times, and vice-versa.
- good adduct yields e.g., more than about 90%, preferably more than about 95%, are achieved in 1-10 hours for the organic solvent.
- the reaction time can also be as much as 10 hours, but, typically, equilibrium is substantially reached within about four hours or less, especially with higher amine: sugar ratios.
- the temperature and reaction time are selected to give an adduct with a Gardner Color of preferably less than about 1.
- adduct color is necessary for obtaining good reactions and color in any subsequent hydrogenation reaction and maintaining catalyst activity. Below a Gardner Color of about 1, the resulting N-alkyl polyhydroxy amine, and consequently the resulting amide, has good color.
- the color bodies can be removed by, e.g., carbon bleaching as used for the sugar solution.
- the adduct also has a very low level of glucose.
- the glucose level, as a percentage of the adduct is preferably less than about 1%, and more preferably less than about one-half of one percent.
- Glucose interferes with the hydrogen reaction step to form the N-alkyl polyhydroxy amine. Excess amine can also help reduce the glucose level and minimize formation of sorbitol during hydrogenation.
- the temperature will rise during adduct formation since the reaction is exothermic. Therefore, maintaining temperatures below about 30°C, as required in batch processes, involves providing cooling for the reactants and/or the reaction mix. Temperatures above about 50°C require reaction times of less than about 10 minutes to avoid excessive color formation. Such short times are normally not feasible except in a continuous reaction. Even with such a continuous reaction, back-mixing should be minimized, e.g., by use of plug flow conditions, to avoid excessive exposure of the adduct to higher temperatures. Ideally, the adduct is promptly reacted with hydrogen to form the corresponding N-alkyl polyhydroxy amine to minimize degradation. However, temperatures below about 30°C, preferably less than about 20°C, allow one to handle and/or store the adduct for at least several hours, which facilitates the use of batch processes. At 0°C, the adduct is stable for 24 hours.
- Typical reactant concentrations in the water and/or hydroxy solvent are in the 10-80%, typically 40-50% (wt.) range.
- Adduct formation can be carried out at atmospheric or superatmospheric pressures.
- Step (b) Reaction with Hydrogen - Step (b) should be accomplished so as to avoid the prolonged exposure of the adduct to the catalyst when the hydrogen pressure is less than about 500 psig, and preferably the hydrogen pressure should be at least about 1000, and more preferably at least about 1500 psig. Keeping this time below about one hour, and preferably below about a half hour, minimizes the amount of catalyst metal, e.g., nickel, that is converted to water soluble ion. Such ions are undesirable for a variety of reasons including their affect on color formation, incompatibility with other materials, safety, etc.
- catalyst metal e.g., nickel
- Step (b) can be carried out in either a slurry process or a fixed bed.
- Step (b) is preferably carried out at a temperature of from about 20°C to about 120°C, preferably from about 50°C to about 100°C for organic hydroxy solvent processes.
- Step (b) is preferably carried out in two stages for aqueous solvent processes. The first stage is at a temperature that is low enough to avoid formation of the corresponding reduced sugar, e.g., sorbitol in the case of glucose, and other unwanted byproducts. Typically this is from about 20°C to about 70°C, more preferably from about 40°C to about 65°C, and even more preferably from about 50°C to about 60°C.
- the temperature is raised to at least about 75°C, preferably at least about 80°C, and up to about 135°C, preferably 130°C, so that the remaining adduct and any other materials that may form color bodies are minimized and the adduct is at least about 95%, preferably at least about 98%, more preferably at least about 99.9% converted to the corresponding N-alkyl amino polyol.
- This second stage is essential to the preparation of N-alkyl polyhydoxy amine with good stable color upon heating. Heat stability is improved for the N-alkylamino polyol by using excess amine in the preparation step and a higher temperature at the heat treatment step.
- Step (b) it is highly preferred to avoid localized overheating, e.g., at the surface of the heating element or heat exchanger.
- Such surface or “skin” temperatures should be below about 180°C, preferably below about 100°C, and even more preferably less than about 70°C, during the first stage and less than about 100°C during the second stage.
- the reaction with hydrogen is preferably carried out with limited initial water when the solvent is an organic hydroxy solvent, although even then, water (e.g., up to 1:1 wt. H2 ⁇ :alcohol) can be present.
- Optional water removal from the adduct prepared in Step (a) can be effected by use of drying agents, or by simply stripping water and solvent from the adduct, and then redissolving the adduct in fresh water- free solvent.
- the hydrogen reaction can typically be run, for example, at temperatures of 20°C-120°C at 50-1,000 psi or, for example, at 50°C-90°C at 100- 500 psi for periods of 0.1-35 hours, generally 0.5-8 hours, typically 1-3 hours when the organic solvent is used.
- the hydrogenation reaction is done in two stages as discussed before.
- the adduct/solvent solution used in the hydrogen reaction is typically at a 10- 80%, typically 40-50%, (wt.) solute level.
- the hydrogen pressure preferably should be above about 500, preferably 1000, more preferably about 1500, psig when the adduct and the catalyst, especially the preferred nickel catalyst, are both present.
- Use of lower pressures down to about 100 psig will require either a separate step to remove Ni ion, or more prolonged post treatment, as discussed hereinafter, to achieve very low Ni content.
- Hydrogen reaction catalyst levels are typically from about 1% to about 100%, preferably from about 2% (preferably about 5%) to about 30% (preferably 20%) more preferably from about 5% (preferably 10%) to about 15% (preferably about 20%) solids by weight, calculated based on wt. catalyst:wt. reducing sugar substituent.
- Step (c) Finishing - The catalyst is then separated from the product after the reaction is completed. The catalyst is removed from the product of Step (c) which is then preferably dried by crystallization, or by solvent/water stripping, or by means of effective drying agents. This helps prevent reversion to the sugar starting material.
- Step (c), when it involves solvent/water stripping, is preferably done in a wiped film evaporator.
- Steps (a)-(c) of the R-l process are preferably conducted under non-oxidizing conditions (e.g., H2 or inert gas) to provide good color.
- Catalyst removal in the Step (c) process is done preferably under hydrogen pressure to prevent Ni (catalyst) dissolution or at least under inert conditions.
- Another suitable process for preparing the polyhydroxy amine utilizes glucose addition (The "Glucose Addition” process) after premixing the catalyst and amine in a simplified reaction which can achieve good results so long as the glucose is added under a hydrogen pressure of at least about 100 psig, preferably at least about 500 psig, and more preferably at least about 1000 psig, at a temperature of less than about 80°C, preferably less than about 70°C, most preferably less than about 60°C.
- the materials and the conditions for the remainder of the reaction are the same as detailed above for the adduct process.
- the preparation of the N-alkylaminol polyols by either of the processes can be conducted in any well-stirred pressure vessel suitable for conducting hydrogenation reactions.
- a pressure reactor with a separate storage reservoir is employed.
- the reservoir (which, itself, can be pressurized) communicates with the reactor via suitable pipes, or the like.
- a stirred slurry of the nickel catalyst is first "cleaned," including being treated with hydrogen to remove traces of nickel oxides. This can be conveniently done in the reactor. (Alternatively, if the manufacturer has access to an oxide-free source of nickel catalyst, pretreatment with H2 is unnecessary.
- the N-alkyl amine is introduced into the reactor. Thereafter, the sugar is introduced from the storage reservoir into the reactor either under hydrogen pressure or by means of a high pressure pumping system, and the reaction is allowed to proceed. The progress of the reaction can be monitored by periodically removing samples of the reaction mixture and analyzing for unreacted sugar using gas chromatography ("g.c"), or by heating the sample to about 100°C for 30-60 minutes in a sealed vial to check for color stability. Typically, for a reaction of about 8 liters (ca.
- the color quality, stability, and/or purity of the N-alkylamino polyol can be further improved by a process of crystallization of the N-alkylamino polyol from an aqueous solution or water/organic solvent mixture. Crystallization is carried out by cooling the aqueous mixture of the N-alkylamino polyol from Step (b) to 0-10°C, or more, preferably by concentrating the aqueous mixture to about 70% solids prior to cooling, and most preferably by adding from about 10 to about 200 parts of an organic solvent, e.g., methanol, acetone, etc. either to the aqueous feed solution, or, most preferably, to the concentrated solution.
- an organic solvent e.g., methanol, acetone, etc.
- N-alkylamino polyol compounds prepared by either of the above reactions and having the required Gardner Color can be used in an overall process for preparing polyhydroxy fatty acid amide surfactants which includes an amide-forming reaction comprising reacting a source of fatty acyl groups such as fatty acids, fatty acid anhydrides and fatty acid esters, especially fatty acid esters, having greater than 98% transmittance at 460nm with an N-alkylamino polyol having a Gardner Color of less than 1 ( ⁇ 0.1 abs.
- esters which have been distilled in the presence of from about 0.05% to about 2% alkali metal oxide, e.g., those prepared in the foregoing manner, in an organic hydroxy solvent in the presence of base catalyst are preferably esters which have been distilled in the presence of from about 0.05% to about 2% alkali metal oxide, e.g., those prepared in the foregoing manner, in an organic hydroxy solvent in the presence of base catalyst.
- the formation of such surfactants with high purity and low color is an especially beneficial result of such a process when an organic hydroxy solvent is used, since the detergent formulator can pump and/or incorporate the polyhydroxy fatty acid amide reaction product plus the reaction solvent such as 1,2-propane diol, (propylene glycol), glycerol, or alcohol (e.g., in liquid detergents) directly into the final detergent formulation.
- This offers economic advantages in that a final solvent removal step is rendered unnecessary, particularly where anhydrous glycols or ethanol are used.
- R-2 amide- forming reaction
- Base catalyst e.g., methoxide
- R 2 C(O)N(R 3 )CH 2 (CHOH)4CH 2 OH + MeOH wherein each R 2 is C10-C20 alkyl and each R 3 is C1-C4 alkyl, C1-C4 alkoxyalkyl, or hydroxyalkyl group.
- the process herein can encompass an overall process for preparing polyhydroxy fatty acid amide surfactant optionally comprising an R-l process as described above and then reacting the polyhydroxyamine having a color of less than Gardner 1 with a fatty acid ester having at least 98% transmittance at 460nm in an organic hydroxy solvent (preferably, methanol) in the presence of a base catalyst to form the polyhydroxy fatty acid amide surfactant (at a temperature of from about 40°C to about 135°C for a time of less than about three hours, more preferably at a temperature of from about 40°C to about 100°C, and even more preferably at a temperature of from about 50°C to about 80°C for a time of less than about 2 hours,); and optionally, removing said solvent.
- the resulting amide product is treated with ion exchange resin, more preferably a mixture of acid and base resins, or, optionally, with reducing bleach to provide a product that is essentially "water white".
- the amide surfactant is treated first with acid ion exchange resin to convert any soap to fatty acid and remove any residual amine that has not been converted to amide. Then the amide surfactant is treated with base ion exchange resin to remove the fatty acid. Both resins remove part of any color bodies that have already formed.
- R-2 or the combination of R-l and R-2 reactions herein, can be used to prepare polyhydroxy fatty acid amide surfactants of the formula (TJ) as follows:
- each R* is H, C1-C4 hydrocarbyl, C1-C4 alkoxyalkyl, or hydroxyalkyl, e.g., 2-hydroxyethyl, 2-hydroxypropyl, etc., preferably C1-C4 alkyl, more preferably C or C2 alkyl, most preferably Cj alkyl (i e., methyl) or methoxyalkyl; and R 2 is a C5-C31 hydrocarbyl moiety, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C ⁇ ⁇ - C17 alkyl or alkenyl, or mixture thereof, and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably e
- Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety.
- Z preferably will be selected from the group consisting of -CH 2 -(CHOH) n -CH2OH, -CH(CH 2 OH)-(CHOH) n -CH2OH, -CH 2 - (CHOH)2(CHOR')(CHOH)-CH2OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof.
- Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2 ⁇ .
- R 1 can be, for example, N-methyl, N-ethyl, N-propyl, N- isopropyl, N-butyl, N-isobuty N-2-hydroxyethyl, N-1-methoxypropyl, or N-2- hydroxypropyl.
- R 2 -CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
- Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1- deoxygalactityL, l-deoxymannityl, 1-deoxymaltotriotityl, etc.
- the polyhydroxyamine reactants include reactants available from the above-described R-l reaction, such as N-alkyl and N-hydroxyalkyl polyhydroxyamines with the N-substituent group such as CH3-, C2H5-, C3H7-, HOCH2CH2-, and the like.
- Polyhydroxyamines available from the R-l reaction are preferably not contaminated by the presence of residual amounts of metallo hydrogenation catalysts, although a few parts per million [e.g., 10-20 ppm] can be present.) Mixtures of the ester and mixtures of the polyhydroxyamine reactants can also be used.
- Catalysts - The catalysts used in the R-2 reaction are basic materials such as the alkoxides (preferred), hydroxides (less preferred due to possible hydrolysis reactions), carbonates, and the like.
- Preferred alkoxide catalysts include the alkali metal C1-C4 alkoxides such as sodium methoxide, potassium ethoxide, and the like.
- the catalysts can be prepared separately from the reaction mixture, or can be generated in situ using an alkali metal such as sodium. For in situ generation, e.g., sodium metal in the methanol solvent, it is preferred that the other reactants not be present until catalyst generation is complete.
- the catalyst typically is used at a level of about 5-8 mole % of the ester reactant.
- Solvents The organic hydroxy solvents used in the R-2 reaction include, for example, methanol, ethanol, propanol, iso-propanol, the butanols, glycerol, 1,2- propylene glycol, 1,3-propylene glycol, and the like. Methanol is a preferred alcohol solvent and 1,2-propylene glycol is a preferred diol solvent. Mixtures of solvents can also be used.
- reaction temperatures below about 135°C, typically in the range of from about 40°C to about 100°C, preferably 50°C to 80°C, are used to achieve this objective, especially in batch processes where reaction times are typically on the order of about 0.5-2 hours, or even up to 6 hours. Somewhat higher temperatures can be tolerated in continuous processes, where residence times can be shorter.
- the polyhydroxy fatty acid amide surfactant prepared by the processes herein is very pure and has good color. However, for products that are not colored, or which are clear, even purer, less colored surfactants are required. Accordingly, the polyhydroxy fatty acid amide surfactant is preferably post treated with an ion exchange resin, mixture of ion exchange resins, or combinations of ion exchange resins, and/or reducing bleach such as NaBHj, etc., or hydrogenation over a catalyst.
- Treatment with ion exchange resins can be very effective if the treatment is carefully carried out. Since the minor contaminants present are both cationic in nature, e.g., amines, and/or anionic in nature, e.g., soaps and/or fatty acids, it is desirable to treat with both anionic and cationic (acidic and basic) ion exchange resins.
- a particularly effective treatment is to treat a solution of the polyhydroxy fatty acid amide surfactant first with acid ion exchange resin to remove the amine and convert any fatty acid soap to fatty acid and then treat with base ion exchange resin to remove the fatty acid.
- Another particularly effective post treatment is the hydrogenation of a solution of the polyhydroxy fatty acid amide surfactant over a hydrogenation catalyst like nickel, palladium, copper chromite, etc.
- the hydrogenation is effective in eliminating color bodies and color body precursors without adversely affecting the structure of the surfactant.
- the hydrogenation is typically carried out in a batch reactor.
- a catalyst typically of either nickel or palladium, is slurried in a solution of the polyhydroxy fatty acid amide surfactant and reacted under conditions that will achieve the desired improvement.
- Typical reaction conditions are hydrogen pressure of from about 150 to about 1000, preferably from about 300 to about 500, psi; temperature of from about 50 to about 120, preferably from about 50 to about 65, °C, to limit potential soap formation; and reaction time of from about one to about four, preferably from about one to about two hours.
- the color of the surfactant is measured as % transmission at 420 nanometers, against a 50/50 ⁇ iixture, by weight, of methanol/distilled water blank.
- the surfactant is diluted to 50% by weight with the blank solution and read in a spectrophotometer.
- Typical color of commercial production varies from about 55% to about 70% transmission, as measured above. For clear products, the n ⁇ iimum transmission should be at least about 70%.
- the catalyst loading to achieve 70% transmission depends on the type of catalyst used, and the desired level of color improvement.
- the loading ranges from about 2% to about 10%, preferably from about 2% to about 5%, expressed as weight of catalyst based upon the surfactant in solution. These levels of catalyst will raise the transmission from about 40%-48% to about 70% with 2% catalyst and to about 80-85% with 10% catalyst.
- Post hydrogenation with palladium catalyst produces superior color with less catalyst.
- Palladium catalyst usage ranges from about 0.005% to about 0.15% with resulting transmissions of from about 85% to about 90% when starting with colors having transmissions of about 60%.
- a transmission of about 42% was raised to about 75% by nickel catalyst and to about 93% by palladium catalyst, using conditions of about 120°C and about 360 psi hydrogen.
- Another optional reductive bleaching step utilizes a reducing material such as;
- the pH should be from about 10 to about 10.9, preferably from about 10.1 to about 10.6, more preferably about 10.4.
- This pH range provides excellent bleaching at a good rate without excessive creation of fatty acid soap by hydrolysis of the amide.
- the following examples are intended to illustrate the practice of the R-2 reaction using the N-polyhydroxyamines prepared by the above-disclosed R-l reaction (with H2O having been removed). It is desirable to use concentration ranges of the reactants and solvent to provide a "70% concentrated" (with respect to reactants) reaction mixture. This 70% concentrated mixture provides excellent results, in that high yields of the desired polyhydroxy fatty acid amide product are secured rapidly.
- a reaction mixture consisting of about 214 g Cj2 fatty acid methyl ester (Procter & Gamble methyl ester CE1295); about 195 g N-methyl-D-glucamine, dry powder, about 10.8 g 25% sodium methylate; and about 37.7 g propylene glycol as a solvent is used.
- the reaction vessel comprises a one liter, four neck, round-bottom flask reactor; one 300 mm coiled condenser, one 250 ml round-bottom flask; several adaptors; one agitator with a variable speed motor; one mantle connected to a Therm- O-Watch® for temperature control; and a vacuum water aspirator for vacuum.
- the methyl ester is added to the reactor and, with agitation, is heated to about 60°C.
- the propylene glycol and the N-methyl glucamine (powdered), are added with sufficient agitation to keep the solids suspended.
- the temperature is raised to about 80°C and a vacuum of about 100 mmHg abs. is created, if more than about 0.1% moisture is present, to eliminate the moisture.
- the pressure is raised with nitrogen and the sodium methylate is added.
- the temperature is set at about 80°C and the time is set at zero.
- the pressure is reduced approximately every thirty minutes from, approximately, 500 to 350 to 200 to 100 mmHg.
- the pressure is again raised with nitrogen and a sample is taken for GC analysis.
- the level of cyclic is 250 ppm while the percent conversion is 91%; lowering the reaction temperature to about 70°C lowers the cyclic level to about 80 ppm and the conversion to about 88%; lowering the reaction time to about one hour decreases the cyclic materials to about 50 ppm and the conversion to about 89%; cutting the catalyst level in half reduces the cyclic materials to about 90 ppm and raises the conversion to about 93%; removing the methanol in 30 minutes reduces the cyclic materials to less than about 50 ppm and raises the conversion to about 90%; and reducing the vacuum to a maximum of about 200 mmHg reduces the cyclic materials to about 40 ppm while reducing the conversion to about 87%.
- Color improvement is obtained by using reactants with better color.
- the methyl ester and polyhydroxy amine should both have a Gardner color of less than about 1, the amine being the most important.
- Using an excess of amine in the R-l reaction, e.g., about 100% excess and/or higher heat treatment temperatures provide improved amine color.
- Use of a crystallization step improves the color even more.
- the amide is preferably treated with an ion exchange resin, or, more preferably, with both anionic and cationic ion exchange resins, to remove color bodies. This treatment is accomplished as follows.
- a reaction mixture consisting of about 84.87 g Cj2 fatty acid methyl ester (Procter & Gamble methyl ester CE1270), about 75 g N-methyl polyhydroxyamine per Example L above, about 1.04 g sodium methoxide and a total of about 39.96 g methyl alcohol (ca. 20% by wt. of reaction mixture) is used.
- the reaction vessel comprises a standard reflux set-up fitted with a drying tube, condenser and mechanical stirring blade.
- the N-methylglucamine/methanol is heated with stirring under nitrogen (reflux). After the solution has reached the desired temperature, the ester and sodium methoxide catalyst are added.
- the reaction mixture is maintained at reflux for about 6 hours.
- the reaction is essentially complete in about 1.5 hours.
- the recovered product weighs about 105.57 grams. Chromatography indicates the presence of only traces of undesired ester-amide by ⁇ products, and no detectable cyclized by-product.
- N-methyl polyhydroxy amines such as N-methylglucamine
- fatty acid amide derivatives using fatty methyl esters variations are available which do not depart from the spirit and scope of this invention.
- reducing sugars such as fructose, galactose, mannose, maltose and lactose, as well as sugar sources such as high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup, and the like, can be used to prepare the polyhydroxyamine material (i.e., to replace glucamine) of the reaction.
- fats and oils can be used herein in place of the fatty esters exemplified above and can provide an unobvious improvement in the degree of completeness.
- fats and oils such as soybean oil, cottonseed oil, sunflower oil, tallow, lard, safflower oil, corn oil, canola oil, peanut oil, fish oil, rapeseed oil, and the like, or hardened (hydrogenated) forms thereof, can be used as the source of triglyceride esters for use in the present process.
- the reaction proceeds to be closer to completion and there are less by-products to be removed. Specifically, greater than about 95% completion is possible.
- Preferred triglycerides are palm kernel oil, coconut oil, palm oil, and tallow. Purification
- the surfactants produced by the processes disclosed above are surprisingly pure. However, for preparation of very clear products, even greater purity is required. Therefore, it has been found necessary to treat the surfactant product herein by at least one of treatments selected from the group consisting of reductive bleaching and ion exchange treatments.
- Reductive bleaching is well known as a method of reducmg eliminating color bodies and/or color body precursors that are converted to color bodies later by action of light, oxygen, interaction with other materials, etc.
- N-alkyl polyhydroxy amine amide surfactant herein, it is necessary to take precautions to avoid soap formation, as disclosed hereinafter
- the use of hydrogen and hydrogenation catalyst can also provide good reductive bleaching without excessive soap formation although this technique usually is more complicated and requires special equipment.
- Preferred hydrogenation catalysts are those described hereinbefore. It will be appreciated that the manufacture of detersive surfactants from such renewable resources is an important advantage of the present process.
- the present process is particularly useful when preparing the longer-chain (e.g., Cig) and unsaturated fatty acid polyhydroxy amides, since the relatively mild reaction temperatures and conditions herein afford the desired products with minimal by- product formation.
- a pre-formed portion of the polyhydroxy fatty acid amide surfactant can be used to assist initiation of the R-2 amide-forming reaction when triglycerides or the longer-chain methyl esters are used as reactants.
- N-methyl glucamine Purification of N-methyl glucamine proceeds as follows. Approximately 2500 g of aqueous solution containing about 45% by weight commercial grade N-methyl glucamine is charged to a rotary evaporator where it is heated to about 71°C under about 27.5' of Hg vacuum until about 957 g of condensate is collected corresponding to a solids concentration in the evaporator residue of about 75%. The residue is mixed with about 660 g of anhydrous methanol and cooled rapidly to about 1-2°C using an ice bath whereupon N-methyl glucamine crystallizes yielding a white slurry.
- the following table illustrates the color and heat stability improvement generated by this procedure.
- the purified crystals are dissolved in distilled water to yield the same concentration of solids as the original feed. Color is measured on the samples as percent transmittance using a Milton Roy Spectronic 2 ID spectrometer in an about 21 cm cell at about 420 nm.
- the samples are also tested for heat stability by subjecting the material to about 180°C in an oil bath under an inert atmosphere for about 1 hour. The treated samples are re-diluted to about 50% concentration to make up for any water lost during heat treatment and the subsequent colors are read.
- aqueous solution (about 332.62 g) of commercial grade N-methyl glucamine containing about 54% by weight solids is charged to a standard one liter reaction flask set up comprising a mechanical stirring blade, condenser and receiver. Over the course of about one hour and twenty minutes, the solution is gradually heated to about 132°C and the pressure is reduced to about 66 cm Hg vacuum to remove the water which is condensed and collected in the receiver.
- Example IV-B Amide Crystallization with Crystallized Amine
- a reaction mixture consisting of about 121.0 g of purified N-methyl glucamine filter cake from Example in (about 16% volatiles), about 112.1 g of Procter & Gamble CE-1295 methyl ester and about 19.7 g propylene glycol are charged to a one liter reaction vessel equipped with mechanical stirring blade, condenser and receiver. The mixture is heated with stirring to about 80°C and held under a slight vacuum for about 30 minutes to remove any residual moisture and methanol from the filter cake. After breaking vacuum with nitrogen, about 8.4 g of about 25% sodium methoxide solution is charged to the reactor and the time recorded. Methanol is allowed to distill off and is collected in the receiver.
- EXAMPLE V The regeneration of strong base anionic ion exchange resin after exhaustion by polyhydroxy amide elution is conducted as follows.
- Ethanolic HCl solution is prepared by adding about 27.4 g of concentrated (about 36.5 wgt%) HCl to about 972.6 g 3A ethanol.
- About four hundred-fifty ml. of exhausted Amberlite IRA-410 resin is packed in a 500 ml graduated dispensing cylinder and is washed with about one liter warm distilled water to remove residual amide.
- the resin is washed with about one liter of about 5% ethanolic HCl solution (prepared as described above) to acidify, followed by washing with about one liter of ethanol to complete the removal of fatty acid.
- the resin is then washed with about one liter of warm distilled water to rehydrate the resin.
- the resin is then regenerated by slowly eluting about 11/2 liters of about 5% aqueous NaOH solution through the resin.
- the resin is then washed with distilled water until the pH is about 8.
- the resin is acidified by eluting about one liter of ethanolic HCl and is then washed with warm distilled water to rehydrate the resin.
- Ethanolic HCl solution is prepared by adding about 27.4 of concentrated (about 36.5 wgt %) HCl to about 972.6 g 3A ethanol.
- a dilute solution of about 7 mole ethoxylated lauryl alcohol is prepared by dissolving about 9 g of ethoxylate in about 9 g of ethanol and about 1482 g of warm, distilled water.
- the resin is then regenerated by slowing eluting about 11/2 liters of about 5% aqueous NaOH solution through the resin.
- the resin is then washed with distilled water until the pH is about 8.
- the cationic resin is regenerated in the same manner as described in Example v ⁇ .
- EXAMPLE Vm N-methyl glucamine with good color stability and which subsequently produces good quality glucose amide is prepared in the following manner.
- Approximately a two gallon autoclave is charged with about 360g of Grace 4200 Raney nickel catalysts as a 50% suspension in water, about 920g of 50% methyl amine and about lOOOg water.
- the reactor is pressurized to about 1500 psig with hydrogen.
- the reactor contents are heated to about 50°C while stirring.
- To this is charged about 2600g of ClearSweat ⁇ u 99DE corn syrup and the contents are reacted at about 50°C for about two hours.
- Fresh hydrogen is added to maintain the pressure as it is consumed by the reaction.
- the reaction mixture remaining in the autoclave is now subjected to a temperature increase from about 50°C to about 100°C over the course of about 60 minutes while hydrogen pressure was maintained at about 1500 psig.
- the reactor is quickly cooled under hydrogen pressure by introducing cooling water to the reactor coil.
- the material is discharged from the reactor. Its composition is approximately:
- n-methyl glucamine crystals purified in accordance with Example Hi are dissolved in water to produce about 375.0 g of aqueous solution.
- This solution is charged to a standard one liter reaction flask set up comprising a mechanical stirring blade, condenser,, and receiver. Over the course of about two hours and forty minutes, the solution is gradually heated to about 130°C and the pressure is reduced to about 26 inches of Hg vacuum to remove the water which is condensed and collected in the receiver.
- n-methyl glucamine To the dehydrated n-methyl glucamine is added about 195.9 g of the distilled methyl laurate described above and about 36.5 g of propylene glycol. After stirring, about 14.5 g of sodium methoxide solution (about 25% by weight in methanol) is added to the reactor and the time is recorded. The mixture is allowed to cool to about 85°C as methanol is distilled off under atmospheric pressure. After about 30 minutes no more methanol is visibly distilling so vacuum is slowly applied to the reaction vessel to strip out the remaining methanol and drive the reaction to completion. When the vacuum reaches about 25 inches of Hg without excessive foaming the reaction is complete. After breaking the vacuum with nitrogen, about 123.0 g water and about 72.3 g ethanol are added to the mixture. The resulting glucose amide solution is * water white' in color and measures as 95% Transmission at 420nm.
- Triglyceride reactants include CRISCO® oil, palm oil, sunflower oil, canola oil, rapeseed oil, coconut oil palm stearine, and the corresponding hydrogenated oils.
- the catalysts are alkali metal salts of monohydric alcohols, or polyhydroxy alcohols, e.g., sodium methoxide.
- the reaction medium is a nonionic surfactant, e.g., NEODOL® 10-8 or 23-3, or GENAPOL 26-L-5.
- the reaction is conducted in a melt.
- the N-methylglucamine at a mole ratio of from about 2.3:1 to about 2.9:1 based upon the triglyceride, nonionic surfactant and triglyceride are co-melted at about 120-140°C under vacuum in about 30 minutes.
- About 7.5 mole%, based upon the N-methyl glucamine, of sodium methoxide is added to the reaction mixture.
- the reaction mixture becomes homogeneous in seconds.
- the reaction mixture is immediately cooled to about 85°C.
- the reaction mixture is maintained under vacuum for about 1-2 hours and is complete at this point.
- the N-methylglucamine is mixed at room temperature with the nonionic surfactant, triglyceride, and catalyst.
- the mixture is heated to 85- 90°C under, alternatively, vacuum and nitrogen.
- the reaction mixtures become clear in one to one and a half hours.
- the reaction mixtures are maintained at about 85°C for about 2-3 hours.
- N-methylglucamine powder is added to a 500 ml three-necked, round-bottom, flask equipped with an internal thermometer, vacuum line, nitrogen line, and mechanical stirrer.
- the N-methylglucamine is melted at about 130-140°C and dried under vacuum.
- Hardened palm kernel oil (about 156.41 g) is added to a separate 500 ml three-necked, round-bottom, flask equipped with an internal thermometer and a vacuum line.
- the hardened palm kernel oil is melted at about 130-140°C and dried under vacuum.
- the dried hardened palm kernel oil and about 31.54 g propylene glycol are added to the N-methylglucamine with mixing.
- the water level is less than about 0.1%.
- the temperature is raised to, and maintained at, about 38°C throughout the treatment period.
- About 1.23 g of commercial sodium borohydride and about 0.20 g of powdered sodium borohydride are added to the reactor.
- There is about 0.49 g of sodium hydroxide in the borohydride which raises the pH from about 8.7 to about 10.4.
- the starting color of the amide is about 54% transmission at 420 nanometers and after about two hours of treatment the transmission is about 76%.
- the final pH of the solution is lowered to about 8 with 31% hydrochloric acid.
- the pH of 10.4 results in increased production of soap, but a pH of more than about 10 is required for borohydride stability.
- Untreated N-methylglucamine amide typically has a soap content of about 3.09.
- the pH/soap content of borohydride treated N-methylglucamine amide varies approximately as follows: 10.1/3.14; 10.3 3.16; 10.6/3.17; and 11.0/3.41. As a result, the pH should be less than about 10.9 during treatment.
- EXAMPLE XU Polyhydroxy fatty acid amide surfactant solution as in Example II before purification, having a % transmission below about 70%, is treated with hydrogen in a high pressure stirred reactor, heated by an internal coil connected to a steam/water mixing apparatus.
- the surfactant solution contains, approximately: 60% surfactant, 22% water, 12% ethanol, and 6% propylene glycol.
- About 1000 g of the solution is slurried with about 1.2 g of palladium catalyst (5% palladium on carbon) wetted to about 50% moisture.
- the reactor is sealed and the agitator started at about 500 rpm.
- the reactor is repeatedly (five times) slowly pressurized to about 200 psi and then slowly vented.
- the reactor is then pressurized to about 400 psi and the agitator increased to about 1200 rpm.
- the temperature is raised to about 66°C and the reaction carried out for about two hours and the product filtered under hydrogen pressure to remove catalyst.
- the % transmission is now more than about 80%.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9500594A JPH11509526A (en) | 1995-06-07 | 1996-05-17 | Method for producing amide of N-alkyl polyhydroxyalkylamine |
EP96914677A EP0830339A1 (en) | 1995-06-07 | 1996-05-17 | Process for preparing amides of n-alkyl polyhydroxyalkyl amines |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US48380295A | 1995-06-07 | 1995-06-07 | |
US47208395A | 1995-06-07 | 1995-06-07 | |
US08/483,802 | 1995-06-07 | ||
US08/474,857 | 1995-06-07 | ||
US08/472,083 | 1995-06-07 | ||
US08/474,857 US5723673A (en) | 1995-06-07 | 1995-06-07 | Process for preparing amides of N-alkyl polyhydroxyalkyls |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996040619A1 true WO1996040619A1 (en) | 1996-12-19 |
Family
ID=27413197
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/007124 WO1996040619A1 (en) | 1995-06-07 | 1996-05-17 | Process for preparing amides of n-alkyl polyhydroxyalkyl amines |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0830339A1 (en) |
JP (1) | JPH11509526A (en) |
CA (1) | CA2223981A1 (en) |
WO (1) | WO1996040619A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005049551A1 (en) | 2003-11-12 | 2005-06-02 | Chemtura Corporation | Method of purifying hydroxyalkyl amide |
CN103842489A (en) * | 2011-07-28 | 2014-06-04 | 荷兰联合利华有限公司 | Fatty acyl amido based surfactant concentrates |
CN103857653A (en) * | 2011-07-28 | 2014-06-11 | 荷兰联合利华有限公司 | General method for preparing fatty acyl amido based surfactants |
EP2736877B1 (en) | 2011-07-28 | 2015-09-16 | Unilever PLC, a company registered in England and Wales under company no. 41424 | Amino acid salt containing compositions |
US20220041957A1 (en) * | 2018-12-21 | 2022-02-10 | Clariant International Ltd. | Glucamide-based surfactants |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8822711B2 (en) * | 2011-07-28 | 2014-09-02 | Conopco, Inc. | Method for preparing fatty acyl amido carboxylic acid based surfactants |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3373174A (en) * | 1964-12-17 | 1968-03-12 | Armour & Co | A method for improving color and the color and odor stability of fatty amides |
JPS4928484B1 (en) * | 1970-05-27 | 1974-07-26 | ||
FR2278830A1 (en) * | 1974-04-24 | 1976-02-13 | Centre Tech Teinture Nettoyage | Fatty acid cpds removal from textile cleaning solvents - using anionic exchange |
US4988737A (en) * | 1985-12-30 | 1991-01-29 | The Dow Chemical Company | Process for regenerating ion exchange resins loaded with naphthenic and other organic acids |
WO1992006073A1 (en) * | 1990-09-28 | 1992-04-16 | The Procter & Gamble Company | Preparation of polyhydroxy fatty acid amides in the presence of solvents |
WO1992006070A1 (en) * | 1990-09-28 | 1992-04-16 | The Procter & Gamble Company | High catalyst process for glucamide detergents |
-
1996
- 1996-05-17 JP JP9500594A patent/JPH11509526A/en not_active Withdrawn
- 1996-05-17 EP EP96914677A patent/EP0830339A1/en not_active Withdrawn
- 1996-05-17 WO PCT/US1996/007124 patent/WO1996040619A1/en not_active Application Discontinuation
- 1996-05-17 CA CA002223981A patent/CA2223981A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3373174A (en) * | 1964-12-17 | 1968-03-12 | Armour & Co | A method for improving color and the color and odor stability of fatty amides |
JPS4928484B1 (en) * | 1970-05-27 | 1974-07-26 | ||
FR2278830A1 (en) * | 1974-04-24 | 1976-02-13 | Centre Tech Teinture Nettoyage | Fatty acid cpds removal from textile cleaning solvents - using anionic exchange |
US4988737A (en) * | 1985-12-30 | 1991-01-29 | The Dow Chemical Company | Process for regenerating ion exchange resins loaded with naphthenic and other organic acids |
WO1992006073A1 (en) * | 1990-09-28 | 1992-04-16 | The Procter & Gamble Company | Preparation of polyhydroxy fatty acid amides in the presence of solvents |
WO1992006070A1 (en) * | 1990-09-28 | 1992-04-16 | The Procter & Gamble Company | High catalyst process for glucamide detergents |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Week 7434, Derwent World Patents Index; Class E16, AN 74-60784V, XP002015195 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005049551A1 (en) | 2003-11-12 | 2005-06-02 | Chemtura Corporation | Method of purifying hydroxyalkyl amide |
US7312346B2 (en) | 2003-11-12 | 2007-12-25 | Crompton Corporation | Method of purifying hydroxyalkyl amide |
CN103842489A (en) * | 2011-07-28 | 2014-06-04 | 荷兰联合利华有限公司 | Fatty acyl amido based surfactant concentrates |
CN103857653A (en) * | 2011-07-28 | 2014-06-11 | 荷兰联合利华有限公司 | General method for preparing fatty acyl amido based surfactants |
EP2736877B1 (en) | 2011-07-28 | 2015-09-16 | Unilever PLC, a company registered in England and Wales under company no. 41424 | Amino acid salt containing compositions |
EP2736879B1 (en) | 2011-07-28 | 2015-11-18 | Unilever PLC, a company registered in England and Wales under company no. 41424 of | General method for preparing fatty acyl amido based surfactants |
CN103857653B (en) * | 2011-07-28 | 2016-08-17 | 荷兰联合利华有限公司 | Prepare surfactant conventional method based on fatty acyl amino |
CN103842489B (en) * | 2011-07-28 | 2016-08-17 | 荷兰联合利华有限公司 | Surfactant concentrate based on fatty acyl amino |
EP2736879B2 (en) † | 2011-07-28 | 2019-07-03 | Unilever PLC, a company registered in England and Wales under company no. 41424 of | General method for preparing fatty acyl amido based surfactants |
US20220041957A1 (en) * | 2018-12-21 | 2022-02-10 | Clariant International Ltd. | Glucamide-based surfactants |
Also Published As
Publication number | Publication date |
---|---|
JPH11509526A (en) | 1999-08-24 |
CA2223981A1 (en) | 1996-12-19 |
EP0830339A1 (en) | 1998-03-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5625098A (en) | Process for preparing N-alkyl polyhydroxyalkyl amines in aqueous/hydroxy solvents | |
US5194639A (en) | Preparation of polyhydroxy fatty acid amides in the presence of solvents | |
US5620952A (en) | Fluid compositions containing polyhydroxy fatty acid amides | |
EP0558515B1 (en) | Process for preparing n-alkyl polyhydroxy amines and fatty acid amides therefrom in hydroxy solvents | |
US5380891A (en) | Phase transfer assisted process for glucamide detergents | |
US5723673A (en) | Process for preparing amides of N-alkyl polyhydroxyalkyls | |
JPH06501473A (en) | Process for producing N-alkyl polyhydroxyamines and fatty acid amides therefrom in amines and amine/aqueous solvents | |
EP0550651B1 (en) | Improved catalyzed process for glucamide detergents | |
US5777165A (en) | Process for preparing amides of N-alkyl polyhydroxyalkyl amines | |
US5298636A (en) | Process for reducing the levels of unreacted amino polyol contaminants in polyhydroxy fatty acid amide surfactants | |
EP0830339A1 (en) | Process for preparing amides of n-alkyl polyhydroxyalkyl amines | |
MXPA97009529A (en) | Process for preparing amidas in n-alkyl polyhydroxylamilic ami | |
MXPA97009528A (en) | Process for preparing amidas n-rent polyhydroxyalylamine amines comprising a process to regenerate an ionic exchange resin of base fue | |
KR100274687B1 (en) | Process for preparing amides of n-alkyl polyhydroxyalkyl amines |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA JP KR MX |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1996914677 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/1997/009529 Country of ref document: MX |
|
ENP | Entry into the national phase |
Ref document number: 2223981 Country of ref document: CA Ref country code: CA Ref document number: 2223981 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1019970709111 Country of ref document: KR |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 1997 500594 Kind code of ref document: A Format of ref document f/p: F |
|
WWP | Wipo information: published in national office |
Ref document number: 1996914677 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1019970709111 Country of ref document: KR |
|
WWG | Wipo information: grant in national office |
Ref document number: 1019970709111 Country of ref document: KR |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1996914677 Country of ref document: EP |