WO1994007840A1 - Internally stable mixed hydroxyethers - Google Patents
Internally stable mixed hydroxyethers Download PDFInfo
- Publication number
- WO1994007840A1 WO1994007840A1 PCT/EP1993/002601 EP9302601W WO9407840A1 WO 1994007840 A1 WO1994007840 A1 WO 1994007840A1 EP 9302601 W EP9302601 W EP 9302601W WO 9407840 A1 WO9407840 A1 WO 9407840A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxides
- carbon atoms
- fatty acid
- formula
- ring opening
- Prior art date
Links
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 title abstract 2
- 150000002170 ethers Chemical class 0.000 claims abstract description 24
- -1 unsaturated fatty-acid esters Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 12
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 229920000151 polyglycol Polymers 0.000 claims abstract description 10
- 239000010695 polyglycol Substances 0.000 claims abstract description 10
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 150000002118 epoxides Chemical class 0.000 claims abstract 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000004593 Epoxy Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 claims description 2
- 239000010893 paper waste Substances 0.000 claims description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 238000005187 foaming Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 239000011343 solid material Substances 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 150000002924 oxiranes Chemical class 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 239000003245 coal Substances 0.000 description 8
- QYDYPVFESGNLHU-KHPPLWFESA-N Methyl oleate Natural products CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000003549 soybean oil Substances 0.000 description 4
- 235000012424 soybean oil Nutrition 0.000 description 4
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N alpha-tetradecene Natural products CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- CFOQKXQWGLAKSK-KTKRTIGZSA-N (13Z)-docosen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCO CFOQKXQWGLAKSK-KTKRTIGZSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- IKYKEVDKGZYRMQ-PDBXOOCHSA-N (9Z,12Z,15Z)-octadecatrien-1-ol Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCCO IKYKEVDKGZYRMQ-PDBXOOCHSA-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
- DJYWKXYRGAMLRE-QXMHVHEDSA-N (z)-icos-9-en-1-ol Chemical compound CCCCCCCCCC\C=C/CCCCCCCCO DJYWKXYRGAMLRE-QXMHVHEDSA-N 0.000 description 1
- TVPWKOCQOFBNML-SEYXRHQNSA-N (z)-octadec-6-en-1-ol Chemical compound CCCCCCCCCCC\C=C/CCCCCO TVPWKOCQOFBNML-SEYXRHQNSA-N 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- CFOQKXQWGLAKSK-UHFFFAOYSA-N 13-docosen-1-ol Natural products CCCCCCCCC=CCCCCCCCCCCCCO CFOQKXQWGLAKSK-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- LQJBNNIYVWPHFW-QXMHVHEDSA-N gadoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCC(O)=O LQJBNNIYVWPHFW-QXMHVHEDSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000021281 monounsaturated fatty acids Nutrition 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- ALSTYHKOOCGGFT-MDZDMXLPSA-N oleyl alcohol Chemical compound CCCCCCCC\C=C\CCCCCCCCO ALSTYHKOOCGGFT-MDZDMXLPSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- LBIYNOAMNIKVKF-FPLPWBNLSA-N palmitoleyl alcohol Chemical compound CCCCCC\C=C/CCCCCCCCO LBIYNOAMNIKVKF-FPLPWBNLSA-N 0.000 description 1
- LBIYNOAMNIKVKF-UHFFFAOYSA-N palmitoleyl alcohol Natural products CCCCCCC=CCCCCCCCCO LBIYNOAMNIKVKF-UHFFFAOYSA-N 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- CNVZJPUDSLNTQU-SEYXRHQNSA-N petroselinic acid Chemical compound CCCCCCCCCCC\C=C/CCCCC(O)=O CNVZJPUDSLNTQU-SEYXRHQNSA-N 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 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
- 239000010499 rapseed oil Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
Definitions
- the invention relates to internal hydroxy mixed ethers which are obtained by ring opening epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers, a process for their preparation and their use as auxiliaries in solids dewatering.
- the invention relates to internal hydroxy mixed ethers which are obtained by epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers of the formula (I),
- R ⁇ represents a linear or branched, aliphatic hydrocarbon radical having 4 to 22 carbon atoms and R- ⁇ represents hydrogen or a methyl group, is subjected to a ring opening.
- the internal hydroxy mixed ethers according to the invention have significantly better cold behavior, in particular lower pour points, compared to the known terminal hydroxy mixed ethers of DE-A-39 18 274, with comparatively good, e.g. T. even have slightly improved application engineering properties.
- Another object of the invention relates to a process for the preparation of internal hydroxy mixed ethers, in which Epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers of the formula (I),
- R 1 is a linear or branched, aliphatic hydrocarbon radical having 4 to 22 carbon atoms and R 2 is hydrogen or a methyl group, is subjected to a ring opening.
- Epoxides of unsaturated fatty acid esters are, for example, addition products of oxygen to the double bonds of mono- or polyunsaturated fatty acid lower alkyl esters of the formula (II),
- R ⁇ CO stands for an unsaturated acyl radical with 16 to 22 carbon atoms and R ⁇ stands for a linear or branched alkyl radical with 1 to 4 carbon atoms.
- Typical examples are epoxidized methyl, ethyl, propyl or butyl esters of palmoleic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, gadoleic acid and erucic acid and their technical mixtures.
- the epoxides used can be completely epoxidized, but they can also contain double bonds; the degree of epoxidation, based on the double bonds available, is preferably 50 to 100% and in particular 70 to 95%.
- the preferred feed is oleic acid methyl ester epoxide with an epoxy oxygen content of 4.5 to 5.1% by weight.
- epoxidized unsaturated fatty acid glycerol esters of the formula (III) are also suitable as starting materials,
- R ⁇ CO, R ⁇ CO and R ⁇ CO independently of one another represent unsaturated acyl radicals having 16 to 24 carbon atoms.
- Typical examples are epoxides of unsaturated triglycerides of plant or animal origin, such as soybean oil, rape oil, olive oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, beef tallow or fish oil.
- These feedstocks can also contain saturated portions; Usually, however, epoxides of such fatty acid glycerol esters are used which have an iodine number in the range from 50 to 150, preferably up to 115. As already described, both completely and partially epoxidized esters can be used as starting materials.
- the preferred feedstock is epoxidized Soybean oil with an epoxy content of 4.5 to 6.5% by weight.
- Fatty alcohol polyglycol ethers of the formula (I) are suitable as the nucleophile for the ring opening of the insert epoxides mentioned.
- Typical examples are adducts of 1 to 30, preferably 2 to 10, moles of ethylene and / or propylene oxide with butanol, pentanol, capro alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, isotridecyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostyl alcohol ,
- Elaidyl alcohol petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol, and their technical mixtures, such as those obtained in the hydrogenation of Fettsron fatty acid methyl ester fractions or aldehydes from Roelen's oxosynthesis.
- the epoxides and the fatty alcohol polyglycol ethers can usually be used in a molar ratio of 1: 0.5 to 1: 1.5, preferably 1: 0.9 to 1: 1.1, based on the epoxy content.
- the internal hydroxy mixed ethers to be used according to the invention support the dewatering of solid suspensions, are readily biodegradable and are characterized by low pour points.
- Another object of the invention therefore relates to their use as auxiliaries for the dewatering of finely divided solid suspensions, such as iron ore concentrates, quartz sand, hard coal or coke.
- Another important area of application is the use of the internal hydroxy mixed ethers to be used according to the invention as auxiliaries in the dewatering of solid suspensions which are used in waste paper processing, e.g. B. in the de-inking process or filler flotation.
- the internal hydroxy mixed ethers according to the invention can be used individually; for the dewatering of certain solids, however, it can be advantageous to combine products of different chain lengths or different degrees of alkoxylation with one another in order to exploit synergies in their physicochemical properties. In the same way, it can be advantageous to use combinations of the internal hydroxy mixed ethers with other already known ionic or nonionic drainage aids. According to an advantageous embodiment of the process according to the invention, the internal hydroxy mixed ethers are used in amounts of 10 to 500, preferably 50 to 300 and in particular 150 to 250 g, based on solids content, per ton of solid.
- Viscosity (according to Höppler) 60 mPa.s hydroxyl number 81
- Residual epoxy oxygen content 0.1% by weight viscosity (Höppler) 33 mPa.s hydroxyl number 131
- Products A) and B) are inventive, product C) is used for comparison.
- Quartz sand of the following grain size was used for the drainage tests:
- the tests were carried out in a cup centrifuge, with which centrifuge parameters from 15 to 2000 can be achieved.
- Perforated plates with sieve openings of 0.1 x 2 mm were used as the sieve covering.
- the drainage aids were used in aqueous solutions; all concentration data are based on the solid.
- the operational filter application of an iron ore concentrate was used for the drainage tests.
- the tests were carried out in a pressure filter (60 cm 2 ) at a pressure difference of 2 bar.
- the filter feed had a solids content of 65% by weight and the sample amount was 120 ml.
- the drainage aids were again used in aqueous solutions; all concentration data are based on the solid.
- After dewatering, the moist solids were weighed out, dried to constant weight at 100 ° C and the residual moisture in% rel. certainly. All test results represent means of duplicate determinations. The results are summarized in Table 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Innenständige Hydroxymischether Internal hydroxy mixed ethers
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft innenständige Hydroxymischether, die man durch Ringöffnung von Epoxiden ungesättigter Fettsäure¬ ester mit Fettalkoholpolyglycolethern erhält, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung als Hilfsmittel bei der Feststoffentwässerung.The invention relates to internal hydroxy mixed ethers which are obtained by ring opening epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers, a process for their preparation and their use as auxiliaries in solids dewatering.
Stand der TechnikState of the art
In zahlreichen Industriezweigen, z.B. im Bergbau oder in Klärwerken, fallen große Mengen an stark wasserhaltigen, feinteiligen Feststoffen an, die vor der Weiterverarbeitung oder Deponierung entwässert werden müssen. So ist z.B. die Entwässerung von Steinkohle bzw. Koks ein zentraler Prozeß innerhalb der Aufbereitung von Brennstoffen auf Kohlebasis. Dabei können die vom Markt geforderten oberen Grenzwerte für den Wassergehalt dieser Materialien oft nur schwer eingehal¬ ten werden, da z.B. geförderte Steinkohle aufgrund der weit¬ gehenden Mechanisierung des untertägigen Kohleabbaus sehr feinkörnig anfällt. Zur Zeit bestehen etwa 38 % der Rohför¬ derung aus Feinkohle mit einem Teilchendurchmesser im Bereich von 0,5 bis 10 mm; weitere 14 % bestehen aus Feinstkohle mit einem darunter liegenden Teilchendurchmesser.In numerous branches of industry, for example in mining or sewage treatment plants, large amounts of highly water-containing, fine-particle solids are produced, which have to be dewatered before further processing or landfilling. For example, the drainage of hard coal or coke is a central process in the processing of coal-based fuels. The upper limit values for the water content of these materials required by the market can often be adhered to only with difficulty since, for example, mined coal is very fine-grained due to the extensive mechanization of underground coal mining. Around 38% of the raw material currently consists of fine coal with a particle diameter in the range from 0.5 to 10 mm; a further 14% consist of fine coal with an underlying particle diameter.
Es ist bekannt, daß als Hilfsmittel zur Entwässerung von was¬ serhaltigen feinteiligen FeststoffSuspensionen, insbesondere Eisenerzkonzentraten oder Steinkohlen, durch die die Rest¬ feuchte herabgesetzt werden kann, manche Tenside geeignet sind. Als tensidische Entwässerungshilfsmittel der vorstehend genannten Art sind beispielsweise Dialkylsulfosuccinate [US-2 266 954] und nichtionische Tenside vom Typ der Fettalkohol- polyglycolether [Erzmetall 30, 292 (1977)] beschrieben wor¬ den. Diese Tenside sind jedoch mit dem Nachteil einer erheb¬ lichen Schaumbildung behaftet, die insbesondere bei der üb¬ licherweise angewendeten Kreislaufführung des Wassers in den Aufbereitungsbetrieben zu erheblichen Problemen führt.It is known that some surfactants are suitable as auxiliaries for dewatering finely divided solid suspensions containing water, in particular iron ore concentrates or hard coal, by means of which the residual moisture can be reduced. Dialkyl sulfosuccinates [US Pat. No. 2,266,954] and nonionic surfactants of the fatty alcohol polyglycol ether type [Erzmetall 30, 292 (1977)] have been described, for example, as surfactant dewatering aids of the type mentioned above. However, these surfactants have the disadvantage of considerable foam formation, which leads to considerable problems in the treatment plants, in particular when water is circulated in the treatment plants.
Aus der Deutschen Offenlegungsschrift DE-Al-39 18 274 (Hen¬ kel) sind Alkyl-endgruppenverschlossene ß-Hydroxyalkylether, sogenannte Hydroxymischether, bekannt, die durch Ringöffnung von alpha-Olefinepoxiden mit Fettalkoholethoxylaten herge¬ stellt und als schaumarme Hilfsmittel in der Entwässerung von FeststoffSuspensionen eingesetzt werden. Obschon mit diesen Mitteln in der Feststoffentwässerung gute Ergebnisse erzielt werden, weisen sie den Nachteil eines unbefriedigenden Käl¬ teverhaltens auf. Insbesondere bei Außenlagerung kann es schon bei Temperaturen von 10 bis 15°C zur Bildung von Kri¬ stallen kommen, wodurch das Pump- und Fließverhalten dieser Produkte und damit ihre bestimmungsgemäße Verwendung erheb¬ lich beeinträchtigt wird. Die Aufgabe der Erfindung bestand somit darin, neuartige Hy¬ droxymischether zur Verfügung zu stellen, die bei gleicher anwendungstechnischer Leistung über ein verbessertes Kälte¬ verhalten verfügen.From German published patent application DE-Al-39 18 274 (Hen¬ kel), alkyl-end group-capped β-hydroxyalkyl ethers, so-called hydroxy mixed ethers, are known, which are produced by ring opening of alpha-olefin epoxides with fatty alcohol ethoxylates and as low-foam auxiliaries in the dewatering of solid suspensions be used. Although good results are achieved in the dewatering of solids with these agents, they have the disadvantage of unsatisfactory cold behavior. Particularly when stored outdoors, crystals can form even at temperatures of 10 to 15 ° C., as a result of which the pumping and flow behavior of these products and thus their intended use is considerably impaired. The object of the invention was therefore to provide novel hydroxy mixed ethers which, with the same application performance, have improved cold behavior.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung sind innenständige Hydroxymisch¬ ether, die man dadurch erhält, daß man Epoxide von ungesät¬ tigten Fettsäureestern mit Fettalkoholpolyglycolethern der Formel (I),The invention relates to internal hydroxy mixed ethers which are obtained by epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers of the formula (I),
R2 SI -3i rR 2 SI -3i r
II.
R10-(CH2CHO)nH _- (I)R 1 0- (CH 2 CHO) n H _- (I)
in der R^ für einen linearen oder verzweigten, aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen und R-~ für Wasserstoff oder eine Methylgruppe steht, einer Ringöff¬ nung unterwirft.in which R ^ represents a linear or branched, aliphatic hydrocarbon radical having 4 to 22 carbon atoms and R- ~ represents hydrogen or a methyl group, is subjected to a ring opening.
Überraschenderweise wurde gefunden, daß die erfindungsgemäßen innenständigen Hydroxymischether gegenüber den bekannten endständigen Hydroxymischethern der DE-A-39 18 274 ein deut¬ lich besseres Kälteverhalten, insbesondere niedrigere Stock¬ punkte, bei vergleichbar guten, z. T. sogar leicht verbes¬ serten anwer ingstechnischen Eigenschaften aufweisen.Surprisingly, it was found that the internal hydroxy mixed ethers according to the invention have significantly better cold behavior, in particular lower pour points, compared to the known terminal hydroxy mixed ethers of DE-A-39 18 274, with comparatively good, e.g. T. even have slightly improved application engineering properties.
Ein weiterer Gegenstand der Erfindung betrifft ein Verfahren zur Herstellung innenständiger Hydroxymischether, bei dem man Epoxide von ungesättigten Fettsäureestern mit Fettalkohol¬ polyglycolethern der Formel (I),Another object of the invention relates to a process for the preparation of internal hydroxy mixed ethers, in which Epoxides of unsaturated fatty acid esters with fatty alcohol polyglycol ethers of the formula (I),
R2R2
I R10-(CH2CHO)nH (I)IR 1 0- (CH 2 CHO) n H (I)
in der Rl für einen linearen oder verzweigten, aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen und R2 für Wasserstoff oder eine Methylgruppe steht, einer Ringöff¬ nung unterwirft.in which R 1 is a linear or branched, aliphatic hydrocarbon radical having 4 to 22 carbon atoms and R 2 is hydrogen or a methyl group, is subjected to a ring opening.
Unter Epoxlden ungesättigter Fettsäureester sind beispiels¬ weise Anlagerungsprodukte von Sauerstoff an die Doppelbin¬ dungen einfach oder mehrfach ungesättigter Fettsäureniedrig- alkylester der Formel (II) zu verstehen,Epoxides of unsaturated fatty acid esters are, for example, addition products of oxygen to the double bonds of mono- or polyunsaturated fatty acid lower alkyl esters of the formula (II),
R3CO-OR4 (II)R 3 CO-OR 4 (II)
in der R-^CO für einen ungesättigten Acylrest mit 16 bis 22 Kohlenstoffatomen und R^ für einen linearen oder verzweigten Alkylrest mit 1 bis 4 Kohlenstoffatomen steht. Typische Bei¬ spiele sind epoxidierte Methyl-, Ethyl-, Propyl- oder Butylester von Palmoleinsäure, ölsäure, Elaidinsäure, Petro- εelinsäure, Linolsäure, Linolensäure, Gadoleinsäure und Erucasäure sowie deren technischen Mischungen. Die einge¬ setzten Epoxide können vollständig epoxidiert vorliegen, sie können jedoch auch noch Doppelbindungen enthalten; vorzugs¬ weise liegt der Epoxidierungsgrad - bezogen auf die zur Ver¬ fügung stehenden Doppelbindungen - bei 50 bis 100 und ins¬ besondere 70 bis 95 %. Da zur Herstellung der epoxidierten Fettsäureester üblicherweise technische Schnitte ungesättig¬ ter Fettsaureniedrigalkylester herangezogen werden, die noch gesättigte Anteile enthalten, können die Einsatzepoxide folglich ebenfalls geringe Anteile gesättigter Fettsaure¬ niedrigalkylester aufweisen. Das bevorzugte Einsatzmaterial ist ölsäuremethylesterepoxid mit einem Epoxidsauerstoffgehalt von 4,5 bis 5,1 Gew.-%.in which R ^ CO stands for an unsaturated acyl radical with 16 to 22 carbon atoms and R ^ stands for a linear or branched alkyl radical with 1 to 4 carbon atoms. Typical examples are epoxidized methyl, ethyl, propyl or butyl esters of palmoleic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, gadoleic acid and erucic acid and their technical mixtures. The epoxides used can be completely epoxidized, but they can also contain double bonds; the degree of epoxidation, based on the double bonds available, is preferably 50 to 100% and in particular 70 to 95%. Because to manufacture the epoxidized Fatty acid esters, usually technical sections of unsaturated lower fatty acid alkyl esters that still contain saturated portions, can consequently also contain small amounts of saturated fatty acid lower alkyl esters. The preferred feed is oleic acid methyl ester epoxide with an epoxy oxygen content of 4.5 to 5.1% by weight.
Neben den Epoxiden ungesättigter Fettsaureniedrigalkylester kommen als Einsatzstoffe auch epoxidierte ungesättigte Fett- ßäureglycerinester der Formel (III) in Betracht,In addition to the epoxides of unsaturated fatty acid lower alkyl esters, epoxidized unsaturated fatty acid glycerol esters of the formula (III) are also suitable as starting materials,
CH2O-COR4 CH2O-COR 4
I CH-O-COR5 (III)I CH-O-COR 5 (III)
I CH2O-COR6 I CH2O-COR 6
in der R-^CO, R-^CO und R^CO unabhängig voneinander für unge¬ sättigte Acylreste mit 16 bis 24 Kohlenstoffatomen stehen.in which R ^ CO, R ^ CO and R ^ CO independently of one another represent unsaturated acyl radicals having 16 to 24 carbon atoms.
Typische Beispiele sind Epoxide von ungesättigten Triglyce- riden pflanzlicher oder tierischer Herkunft, wie etwa Sojaöl, Rüböl, Olivenöl, Sonnenblumenöl, Baumwollsaatöl, Erdnußöl, Leinöl, Rindertalg oder Fischöl. Auch diese Einsatzstoffe können gesättigte Anteile enthalten; üblicherweise werden jedoch Epoxide sol her Fettsäureglycerinester eingesetzt, die eine Iodzahl im Bereich von 50 bis 150, vorzugsweise bis 115 aufweisen. Wie schon zuvor geschildert, kommen als Ein¬ satzstoffe sowohl vollständig, wie auch partiell epoxidierte Ester in Betracht. Bevorzugter Einsatzstoff ist epoxidiertes Sojaöl mit einem Epoxidsauersto fgehalt von 4,5 bis 6,5 Gew.-%.Typical examples are epoxides of unsaturated triglycerides of plant or animal origin, such as soybean oil, rape oil, olive oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, beef tallow or fish oil. These feedstocks can also contain saturated portions; Usually, however, epoxides of such fatty acid glycerol esters are used which have an iodine number in the range from 50 to 150, preferably up to 115. As already described, both completely and partially epoxidized esters can be used as starting materials. The preferred feedstock is epoxidized Soybean oil with an epoxy content of 4.5 to 6.5% by weight.
Als Nucleophil für die Ringöffnung der genannten Einsatz- epoxide kommen Fettalkoholpolyglycolether der Formel (I) in Betracht. Typische Beispiele sind Anlagerungsprodukte von 1 bis 30, vorzugsweise 2 bis 10 Mol Ethylen- und/oder Propy- lenoxid an Butanol, Pentanol, Capronalkohol, Caprylalkohol, Caprinalkohol, Laurylalkohol, Myristylalkohol, Isotridecyl- alkohol, Cetylalkohol, Palmitoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroseli- nylalkohol, Linolylalkohol, Linolenylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol und Erucylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hy¬ drierung Λron Fettsauremethylesterfraktionen oder Aldehyden aus der Roelen'sehen Oxosynthese anfallen. Vorzugsweise wer¬ den Anlagerungsprodukte von 2 bis 8 Mol Ethylenoxid an Butanol sowie technische C12 14- bzw. Ci2/ιg-Kokosfettalko- holschnitte eingesetzt.Fatty alcohol polyglycol ethers of the formula (I) are suitable as the nucleophile for the ring opening of the insert epoxides mentioned. Typical examples are adducts of 1 to 30, preferably 2 to 10, moles of ethylene and / or propylene oxide with butanol, pentanol, capro alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, isotridecyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostyl alcohol , Elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol, and their technical mixtures, such as those obtained in the hydrogenation of Fettsron fatty acid methyl ester fractions or aldehydes from Roelen's oxosynthesis. Addition products of 2 to 8 moles of ethylene oxide with butanol as well as technical C12 14 or Ci2 / ιg coconut fatty alcohol cuts are preferably used.
Üblicherweise können die Epoxide und die Fettalkoholpolygly¬ colether im molaren Verhältnis von 1 : 0,5 bis 1 : 1,5, vor¬ zugsweise 1 : 0,9 bis 1 : 1,1 - bezogen auf den Epoxidgehalt - eingesetzt werden.The epoxides and the fatty alcohol polyglycol ethers can usually be used in a molar ratio of 1: 0.5 to 1: 1.5, preferably 1: 0.9 to 1: 1.1, based on the epoxy content.
Im Hinblick auf eine möglichst kurze Reaktionszeit empfiehlt es sich, die Ringöffnungsreaktion in Gegenwart basischer Ka¬ talysatoren, wie beispielsweise Natriummethylat durchzufüh¬ ren, die in Mengen von 0,1 bis 5 Gew.-% - bezogen auf das Epoxid - eingesetzt werden können. In gleicher Weise ist es vorteilhaft, die Ringöffnungεreaktion bei Temperaturen von 80 bis 150, vorzugsweise 100 bis 130°C durchzuführen.In view of the shortest possible reaction time, it is advisable to carry out the ring opening reaction in the presence of basic catalysts, such as, for example, sodium methylate, which can be used in amounts of 0.1 to 5% by weight, based on the epoxide. In the same way it is advantageous to carry out the ring opening reaction at temperatures of 80 to 150, preferably 100 to 130 ° C.
Gewerbliche AnwendbarkeitIndustrial applicability
Die erfindungsgemäß einzusetzenden innenständigen Hydroxy¬ mischether unterstützen die Entwässerung von FeststoffSus¬ pensionen, sind biologisch leicht abbaubar und zeichnen sich durch niedrige Stockpunkte aus.The internal hydroxy mixed ethers to be used according to the invention support the dewatering of solid suspensions, are readily biodegradable and are characterized by low pour points.
Ein weiterer Gegenstand der Erfindung betrifft daher ihre Verwendung als Hilfsmittel zur Entwässerung von feinteiligen FeststoffSuspensionen, wie beispielsweise Eisenerzkonzentra¬ ten, Quarzsand, Steinkohle oder Koks. Ein weiteres wichtiges Einsatzgebiet stellt die Verwendung der erfindungsgemäß ein¬ zusetzenden innenständigen Hydroxymischether als Hilfsmittel bei der Entwässerung von FeststoffSuspensionen dar, die bei der Altpapieraufbereitung, z. B. beim De-inking-Prozeß oder der Füllstoffflotation anfallen.Another object of the invention therefore relates to their use as auxiliaries for the dewatering of finely divided solid suspensions, such as iron ore concentrates, quartz sand, hard coal or coke. Another important area of application is the use of the internal hydroxy mixed ethers to be used according to the invention as auxiliaries in the dewatering of solid suspensions which are used in waste paper processing, e.g. B. in the de-inking process or filler flotation.
Die erfindungsgemäßen innenständigen Hydroxymischether können einzeln eingesetzt werden; für die Entwässerung bestimmter Feststoffe kann es jedoch vorteilhaft sein, Produkte unter¬ schiedlicher Kettenlänge bzw. unterschiedlichen Alkoxylie- rungsgrades miteinander zu kombinieren, um Synergien ihrer physikochemisehen Eigenschaften auszunutzen. In gleicher Weise kann es vorteilhaft sein, Kombinationen der innenstän¬ digen Hydroxymischether mit anderen schon bekannten ionischen oder nichtionischen Entwässerungshilfsmittei einzusetzen. Gemäß einer vorteilhaften Ausführungsform des erfindungsge¬ mäßen Verfahrens setzt man die innenständigen Hydroxymisch¬ ether in Mengen von 10 bis 500, vorzugsweise 50 bis 300 und insbesondere 150 bis 250 g - bezogen auf Feststoffgehalt - pro Tonne Feststoff ein.The internal hydroxy mixed ethers according to the invention can be used individually; for the dewatering of certain solids, however, it can be advantageous to combine products of different chain lengths or different degrees of alkoxylation with one another in order to exploit synergies in their physicochemical properties. In the same way, it can be advantageous to use combinations of the internal hydroxy mixed ethers with other already known ionic or nonionic drainage aids. According to an advantageous embodiment of the process according to the invention, the internal hydroxy mixed ethers are used in amounts of 10 to 500, preferably 50 to 300 and in particular 150 to 250 g, based on solids content, per ton of solid.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. The following examples are intended to explain the subject matter of the invention in more detail without restricting it.
BeispieleExamples
I. HerstellungsbeispieleI. Manufacturing examples
A) Hydroxymischether auf Basis ölsäuremethylesterepoxld.A) Hydroxy mixed ether based on oleic acid methyl ester epoxy.
374 g (1 mol) Butyldiglycol-5 EO-ether und 5 g Natrium- methylat (30 %ige Lösung in Methanol) wurden zur Entfer¬ nung des mit dem Katalysator eingebrachten Methanols im Vakuum auf 60°C erwärmt. Nach Zugabe von 312 g (1 mol) ölsäuremethylesterepoxld (Edenor(R) MeTiOs-Epoxid, Fa. Henkel KGaA, Düsseldorf/FRG) wurde 130 min auf 160°C erhitzt. Der Hydroxymischether wurde in praktisch quan¬ titativer Ausbeute als klare Flüssigkeit erhalten.374 g (1 mol) of butyl diglycol 5 EO ether and 5 g of sodium methylate (30% solution in methanol) were heated to 60 ° C. in vacuo in order to remove the methanol introduced with the catalyst. After adding 312 g (1 mol) of oleic acid methyl ester epoxy (Edenor ( R ) MeTiOs epoxy, from Henkel KGaA, Düsseldorf / FRG), the mixture was heated to 160 ° C. for 130 minutes. The hydroxy mixed ether was obtained as a clear liquid in practically quantitative yield.
Kenndaten des Produktes;Product characteristics;
Stockpunkt 9 °CPour point 9 ° C
Viskosität (nach Höppler) 60 mPa.s Hydroxylzahl 81Viscosity (according to Höppler) 60 mPa.s hydroxyl number 81
Verseifungszahl 88Saponification number 88
Iodzahl 15,2Iodine number 15.2
Säurezahl 1,1Acid number 1.1
Rest-Epoxidsauerεtoffgehalt 0,1 Gew.-% Residual epoxy acid content 0.1% by weight
Hydroxymischether auf Basis Sojaölepoxid.Hydroxy mixed ether based on soybean oil epoxide.
Analog Beispiel A) wurden 748 g (2 mol) Butyldiglycol-5 EO-ether und 5 g Natriummethylat (30 %ige Lösung in Me¬ thanol) zur Entfernung des mit dem Katalysator einge¬ brachten Methanols im Vakuum auf 60°C erwärmt. Nach Zu¬ gabe von 929 g (1 mol) Sojaölepoxid (Edenor(R) D81, Epoxidsauerεtoffgehalt 6,5 Gew.-%, Fa.Henkel KGaA, Düsseldorf/FRG) wurde 130 min auf 160°C erhitzt. Der Hydroxymischether wurde in praktisch quantitativer Aus¬ beute als klare Flüssigkeit erhalten.Analogously to Example A), 748 g (2 mol) of butyl diglycol-5 EO ether and 5 g of sodium methylate (30% solution in methanol) were heated to 60 ° C. in vacuo in order to remove the methanol introduced with the catalyst. After the addition of 929 g (1 mol) of soybean oil epoxide (Edenor ( R ) D81, epoxy acid content 6.5% by weight, from Henkel KGaA, Düsseldorf / FRG), the mixture was heated to 160 ° C. for 130 minutes. The hydroxy mixed ether was obtained in practically quantitative yield as a clear liquid.
Kenndaten des Produktes;Product characteristics;
Stockpunkt -7 °CPour point -7 ° C
Rest-Epoxidsauerstoffgehalt 0,1 Gew.-% Viskosität (Höppler) 33 mPa.s Hydroxy1zahl 131 Residual epoxy oxygen content 0.1% by weight viscosity (Höppler) 33 mPa.s hydroxyl number 131
C) Hydroxymischether auf Basis alpha-Tetradecenepoxid.C) Hydroxy mixed ether based on alpha-tetradecene epoxide.
Analog Beispiel A) wurden 374 g (1 mol) Butyldiglycol-5 EO-ether und 5 g Natriummethylat (30 %ige Lösung in Me¬ thanol) zur Entfernung des mit dem Katalysator einge¬ brachten Methanols im Vakuum auf 60°C erwärmt. Nach Zu¬ gabe von 212 g (1 mol) alpha-Tetradecenepoxid wurde 130 min auf 160°C erhitzt. Der Hydroxymischether wurde in praktisch quantitativer Ausbeute als trübe Flüssigkeit erhalten.Analogously to Example A), 374 g (1 mol) of butyl diglycol-5 EO ether and 5 g of sodium methylate (30% solution in methanol) were heated to 60 ° C. in vacuo in order to remove the methanol introduced with the catalyst. After addition of 212 g (1 mol) of alpha-tetradecene epoxide, the mixture was heated to 160 ° C. for 130 minutes. The hydroxy mixed ether was obtained in virtually quantitative yield as a cloudy liquid.
Kenndaten des Produktes;Product characteristics;
StockpunktPour point
Viskosität (nach Höppler)Viscosity (according to Höppler)
Hydroxy1zah1Hydroxy1zah1
Rest-Epoxidsauerstoffgehalt Residual epoxy oxygen content
Die Produkte A) und B) sind erfinderisch, Produkt C) dient dem Vergleich. Products A) and B) are inventive, product C) is used for comparison.
II. Entwässerung von OuarzsandII. Drainage of Ouarzsand
Für die Entwässerungsversuche wurde Quarzsand der folgenden Körnung verwendet:Quartz sand of the following grain size was used for the drainage tests:
< 125 um : 2,8 Gew.-%<125 µm: 2.8% by weight
125 bis 200 um : 26,4 Gew.-%125 to 200 µm: 26.4% by weight
200 bis 315 um : 60,1 Gew.-%200 to 315 µm: 60.1% by weight
> 315 um : 10,7 Gew.-%> 315 µm: 10.7% by weight
Durchgeführt wurden die Versuche in einer Becherzentrifuge, mit der Zentrifugenkennwerte von 15 bis 2000 realisierbar sind. Als Siebbelag wurden Lochplatten mit Sieböffnungen von 0,1 x 2 mm verwendet. Die Entwässerungshilfsmittel wurden in wäßrigen Lösungen eingesetzt; alle Konzentrationsangaben verstehen sich bezogen auf den Feststoff.The tests were carried out in a cup centrifuge, with which centrifuge parameters from 15 to 2000 can be achieved. Perforated plates with sieve openings of 0.1 x 2 mm were used as the sieve covering. The drainage aids were used in aqueous solutions; all concentration data are based on the solid.
Nach Einwaage des Quarzsandes in die Zentrifugenbecher wurden die wäßrigen Lösungen der Entwässerungshilfsmittel über die Schüttung gegossen. Nach einer Abtropfzeit von 1 min wurde der Feststoff über einen Zeitraum von 30 s bei einer Drehzahl von 500 Upm entwässert. Anschließend wurden die feuchten Feststoffe ausgewogen, bei 100°C bis zur Gewichtskonstanz getrocknet und die Restfeuchte sowie die Restfeuchte-Reduk- tion in %-rel. bestimmt. Alle Versuchsergebnisse stellen Mittel von Doppelbestimmungen dar. Die Ergebnisse sind in Tab.1 zusammengefaßt. Tab.1; Entwässerung von QuarzsandAfter the quartz sand had been weighed into the centrifuge beaker, the aqueous solutions of the drainage aids were poured over the bed. After a draining time of 1 min, the solid was dewatered over a period of 30 s at a speed of 500 rpm. The moist solids were then weighed out, dried to constant weight at 100 ° C. and the residual moisture and the residual moisture reduction in% rel. certainly. All test results represent means of duplicate determinations. The results are summarized in Tab. 1. Tab. 1; Drainage of quartz sand
Legende; HM = HilfsmittelLegend; HM = aids
El - Einwaage 150 g Hilfsmittel/t FeststoffEl - Weight 150 g auxiliary / t solids
E2 = Einwaage 250 g Hilfsmittel/t FeststoffE2 = initial weight 250 g auxiliary / t solids
E3 = Einwaage 350 g Hilfsmittel/t Feststoff E3 = initial weight 350 g auxiliary / t solids
III. Entwässerung von EisenerzkonzentratIII. Drainage of iron ore concentrate
Für die Entwässerungsversuche wurde die betriebliche Filter¬ aufgabe eines Eisenerzkonzentrates eingesetzt. Durchgeführt wurden die Versuche in einem Druckfilter (60 cm2) bei einer Druckdifferenz von 2 bar. Die Filteraufgabe besaß einen Feststoffgehalt von 65 Gew.-%, die Probenmenge betrug 120 ml. Die Entwässerungshilfsmittel wurden wiederum in wäßrigen Lö¬ sungen eingesetzt; alle Konzentrationsangaben verstehen sich bezogen auf den Feststoff. Nach der Entwässerung wurden die feuchten Feststoffe ausgewogen, bei 100°C bis zur Gewichts- konstanz getrocknet und die Restfeuchte in %-rel. bestimmt. Alle Versuchsergebnisse stellen Mittel von Doppelbestimmungen dar. Die Ergebnisse sind in Tab.2 zusammengefaßt. The operational filter application of an iron ore concentrate was used for the drainage tests. The tests were carried out in a pressure filter (60 cm 2 ) at a pressure difference of 2 bar. The filter feed had a solids content of 65% by weight and the sample amount was 120 ml. The drainage aids were again used in aqueous solutions; all concentration data are based on the solid. After dewatering, the moist solids were weighed out, dried to constant weight at 100 ° C and the residual moisture in% rel. certainly. All test results represent means of duplicate determinations. The results are summarized in Table 2.
Tab.2; Entwässerung von EisenerzkonzentratTab. 2; Drainage of iron ore concentrate
Legende; HM = HilfsmittelLegend; HM = aids
El = Einwaage 100 g Hilfsmittel/t FeststoffEl = weight 100 g auxiliary / t solids
E2 = Einwaage 150 g Hilfsmittel/t FeststoffE2 = initial weight 150 g auxiliary / t solids
E3 = Einwaage 200 g Hilfsmittel/t Feststoff E3 = initial weight 200 g auxiliary / t solids
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93920819A EP0662947A1 (en) | 1992-10-02 | 1993-09-24 | Internally stable mixed hydroxyethers |
FI951552A FI951552L (en) | 1992-10-02 | 1995-03-31 | Internal hydroxy mixed ethers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4233219.2 | 1992-10-02 | ||
DE4233219A DE4233219A1 (en) | 1992-10-02 | 1992-10-02 | Internal hydroxymix ethers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994007840A1 true WO1994007840A1 (en) | 1994-04-14 |
Family
ID=6469525
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1993/002601 WO1994007840A1 (en) | 1992-10-02 | 1993-09-24 | Internally stable mixed hydroxyethers |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0662947A1 (en) |
CA (1) | CA2146236A1 (en) |
DE (1) | DE4233219A1 (en) |
FI (1) | FI951552L (en) |
WO (1) | WO1994007840A1 (en) |
ZA (1) | ZA937314B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19622967C1 (en) * | 1996-06-07 | 1998-01-29 | Henkel Kgaa | Aqueous pearlescent concentrates |
WO2001000567A1 (en) * | 1999-06-29 | 2001-01-04 | Akzo Nobel Nv | Compounds from epoxidised nitriles, process for their production and use as cleaning agents |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19526501A1 (en) * | 1995-07-20 | 1997-01-23 | Basf Ag | Hydroxy mixed ethers by ring opening of epoxides of unsaturated fatty acid esters with polyglycol ethers and their use as biodegradable defoamers |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0127810A1 (en) * | 1983-05-21 | 1984-12-12 | Henkel Kommanditgesellschaft auf Aktien | Hydroxyalkoxycarboxylic acids and their salts, their preparation and use |
WO1991011424A1 (en) * | 1990-01-26 | 1991-08-08 | Henkel Kommanditgesellschaft Auf Aktien | Alkoxylated compounds produced from epoxylated carboxylic acid derivatives |
WO1992019577A1 (en) * | 1991-05-08 | 1992-11-12 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing epoxy open ring products with a defined residual epoxy oxygen content |
-
1992
- 1992-10-02 DE DE4233219A patent/DE4233219A1/en not_active Withdrawn
-
1993
- 1993-09-24 WO PCT/EP1993/002601 patent/WO1994007840A1/en not_active Application Discontinuation
- 1993-09-24 EP EP93920819A patent/EP0662947A1/en not_active Withdrawn
- 1993-09-24 CA CA002146236A patent/CA2146236A1/en not_active Abandoned
- 1993-10-01 ZA ZA937314A patent/ZA937314B/en unknown
-
1995
- 1995-03-31 FI FI951552A patent/FI951552L/en not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0127810A1 (en) * | 1983-05-21 | 1984-12-12 | Henkel Kommanditgesellschaft auf Aktien | Hydroxyalkoxycarboxylic acids and their salts, their preparation and use |
WO1991011424A1 (en) * | 1990-01-26 | 1991-08-08 | Henkel Kommanditgesellschaft Auf Aktien | Alkoxylated compounds produced from epoxylated carboxylic acid derivatives |
WO1992019577A1 (en) * | 1991-05-08 | 1992-11-12 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing epoxy open ring products with a defined residual epoxy oxygen content |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19622967C1 (en) * | 1996-06-07 | 1998-01-29 | Henkel Kgaa | Aqueous pearlescent concentrates |
WO2001000567A1 (en) * | 1999-06-29 | 2001-01-04 | Akzo Nobel Nv | Compounds from epoxidised nitriles, process for their production and use as cleaning agents |
US6770679B1 (en) | 1999-06-29 | 2004-08-03 | Akzo Nobel N.V | Compounds from epoxidised nitriles, process for their production and use as cleaning agents |
Also Published As
Publication number | Publication date |
---|---|
FI951552A0 (en) | 1995-03-31 |
ZA937314B (en) | 1994-04-05 |
DE4233219A1 (en) | 1994-04-07 |
EP0662947A1 (en) | 1995-07-19 |
FI951552L (en) | 1995-03-31 |
CA2146236A1 (en) | 1994-04-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0264826B1 (en) | Fatty acid esters of polyglycerinpolyglycol ethers, their production and their use | |
DE69318958T2 (en) | Composition containing surfactants and glycolipids and method for decontaminating contaminated porous medium | |
EP0324887A2 (en) | Compositions for freeing stuck drill pipes | |
WO1992000268A1 (en) | Process for producing fatty acid esters of lower alcohols | |
EP1406722A1 (en) | Aqueous preparations | |
EP0231890A2 (en) | Method for the purification of alkyl glycosides, the products so obtained and their use | |
EP0595942B1 (en) | Method of preparing polyol compounds | |
EP0642650A1 (en) | Process for dehydrating finely divided solid suspensions | |
EP0180081B1 (en) | Application of alkoxylated fatty alcohol or alkyl phenol containing locked end groups for the prevention of foaming in the sugar and yeast industries | |
EP0642651B1 (en) | Process for dehydrating finely divided solid suspensions | |
EP0281960B1 (en) | Dispersants and their use in aqueous coal suspensions | |
EP0662947A1 (en) | Internally stable mixed hydroxyethers | |
EP0475969A1 (en) | Used of mixed hydroxy ethers as aids for drying solids materials. | |
DE2748126A1 (en) | NON-ionogenic surfactants | |
WO2006134145A1 (en) | Aminocarboxylic acid esters having eo/po/buo-blockpolymers and use thereof as demulsifiers | |
DE3837947A1 (en) | NEW FATTY ALCOHOL MIXTURES AND THEIR ETHOXYLATE WITH IMPROVED COLD BEHAVIOR | |
EP0457965B1 (en) | Low foaming washing-machine detergents | |
EP0065267A2 (en) | Process for the preparation of carboxylic esters of anhydrohexitols | |
EP0041626B1 (en) | Defoamer mixture of alkali salts of the dialkyl esters of sulfosuccinic acid and long-chained aliphatic alcohols and use of this mixture for skimming acid decomposition materials | |
EP0702074B1 (en) | Mixtures containing acetals based on dialdehydes | |
EP0626004B1 (en) | Method of stabilizing aqueous zeolite suspensions | |
DE4038608A1 (en) | USE OF ESTER POLYOLE-CONTAINING REACTION MIXTURES AS FOAM-ABSORBING ADDITIVES | |
DE19611508C1 (en) | Alkoxylated fatty acid alkyl ester preparation with optimum washing power at low temperature | |
DE19848548C2 (en) | Process for processing contaminated fatty alcohol mixtures | |
DE2558907A1 (en) | PROCESS FOR PRODUCING A SURFACE-ACTIVE, BIODEGRADABLE CHEMICAL COMPOUND AND THE USE OF IT |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA FI US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES 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: 1993920819 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 951552 Country of ref document: FI |
|
ENP | Entry into the national phase |
Ref country code: CA Ref document number: 2146236 Kind code of ref document: A Format of ref document f/p: F Ref country code: US Ref document number: 1995 411722 Date of ref document: 19950403 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2146236 Country of ref document: CA |
|
WWP | Wipo information: published in national office |
Ref document number: 1993920819 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1993920819 Country of ref document: EP |