NO179481B - Use of ester polyol-containing reaction mixtures as antifoaming additives - Google Patents
Use of ester polyol-containing reaction mixtures as antifoaming additives Download PDFInfo
- Publication number
- NO179481B NO179481B NO931619A NO931619A NO179481B NO 179481 B NO179481 B NO 179481B NO 931619 A NO931619 A NO 931619A NO 931619 A NO931619 A NO 931619A NO 179481 B NO179481 B NO 179481B
- Authority
- NO
- Norway
- Prior art keywords
- carboxylic acid
- ester
- epoxidized
- reaction mixtures
- polyoline
- Prior art date
Links
- 239000011541 reaction mixture Substances 0.000 title claims abstract description 47
- 239000000654 additive Substances 0.000 title claims description 13
- -1 ester polyol Chemical class 0.000 title abstract description 7
- 229920005862 polyol Polymers 0.000 title abstract description 7
- 230000003254 anti-foaming effect Effects 0.000 title description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 32
- 150000001298 alcohols Chemical class 0.000 claims abstract description 25
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000012545 processing Methods 0.000 claims abstract description 10
- 238000000855 fermentation Methods 0.000 claims abstract description 8
- 230000004151 fermentation Effects 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000002518 antifoaming agent Substances 0.000 claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 150000003138 primary alcohols Chemical class 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 150000002118 epoxides Chemical group 0.000 claims 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 17
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 15
- 235000013305 food Nutrition 0.000 abstract description 5
- 239000003112 inhibitor Substances 0.000 abstract description 4
- 230000002452 interceptive effect Effects 0.000 abstract 1
- 150000002924 oxiranes Chemical group 0.000 description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000004593 Epoxy Chemical class 0.000 description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000003549 soybean oil Substances 0.000 description 5
- 235000012424 soybean oil Nutrition 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000944 linseed oil Substances 0.000 description 4
- 235000021388 linseed oil Nutrition 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 235000016068 Berberis vulgaris Nutrition 0.000 description 3
- 241000335053 Beta vulgaris Species 0.000 description 3
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 3
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- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- 235000021536 Sugar beet Nutrition 0.000 description 3
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- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 150000003626 triacylglycerols Chemical class 0.000 description 3
- IMYZYCNQZDBZBQ-UHFFFAOYSA-N (+-)-8-(cis-3-octyl-oxiranyl)-octanoic acid Natural products CCCCCCCCC1OC1CCCCCCCC(O)=O IMYZYCNQZDBZBQ-UHFFFAOYSA-N 0.000 description 2
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- YQEMORVAKMFKLG-UHFFFAOYSA-N 2-stearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 235000021319 Palmitoleic acid Nutrition 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 235000019486 Sunflower oil Nutrition 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 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 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012994 industrial processing Methods 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- 229960004488 linolenic acid Drugs 0.000 description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000013379 molasses Nutrition 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002600 sunflower oil Substances 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical class CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- JXNPEDYJTDQORS-HZJYTTRNSA-N (9Z,12Z)-octadecadien-1-ol Chemical compound CCCCC\C=C/C\C=C/CCCCCCCCO JXNPEDYJTDQORS-HZJYTTRNSA-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
- DJYWKXYRGAMLRE-QXMHVHEDSA-N (z)-icos-9-en-1-ol Chemical compound CCCCCCCCCC\C=C/CCCCCCCCO DJYWKXYRGAMLRE-QXMHVHEDSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- OPJWPPVYCOPDCM-UHFFFAOYSA-N 2-ethylhexyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)CCCC OPJWPPVYCOPDCM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FKLSONDBCYHMOQ-UHFFFAOYSA-N 9E-dodecenoic acid Natural products CCC=CCCCCCCCC(O)=O FKLSONDBCYHMOQ-UHFFFAOYSA-N 0.000 description 1
- YWWVWXASSLXJHU-UHFFFAOYSA-N 9E-tetradecenoic acid Natural products CCCCC=CCCCCCCCC(O)=O YWWVWXASSLXJHU-UHFFFAOYSA-N 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 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 1
- 235000013830 Eruca Nutrition 0.000 description 1
- 241000801434 Eruca Species 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- XZJZNZATFHOMSJ-KTKRTIGZSA-N cis-3-dodecenoic acid Chemical compound CCCCCCCC\C=C/CC(O)=O XZJZNZATFHOMSJ-KTKRTIGZSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000010636 coriander oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000012020 french fries Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- LQJBNNIYVWPHFW-QXMHVHEDSA-N gadoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCC(O)=O LQJBNNIYVWPHFW-QXMHVHEDSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- UPWGQKDVAURUGE-UHFFFAOYSA-N glycerine monooleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC(CO)CO UPWGQKDVAURUGE-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JXNPEDYJTDQORS-UHFFFAOYSA-N linoleyl alcohol Natural products CCCCCC=CCC=CCCCCCCCCO JXNPEDYJTDQORS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-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
- 229960002446 octanoic acid Drugs 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- ALSTYHKOOCGGFT-MDZDMXLPSA-N oleyl alcohol Chemical compound CCCCCCCC\C=C\CCCCCCCCO ALSTYHKOOCGGFT-MDZDMXLPSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 238000010915 one-step procedure Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 235000020232 peanut Nutrition 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
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001522 polyglycol ester Polymers 0.000 description 1
- 229920005903 polyol mixture Polymers 0.000 description 1
- 235000013573 potato product Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical class CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000020374 simple syrup Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Lubricants (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Vessels, Lead-In Wires, Accessory Apparatuses For Cathode-Ray Tubes (AREA)
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Abstract
Description
Oppfinnelsen angår anvendelse av esterpolyolinneholdende reaksjonsblanding, fremstilt ved ringåpnende omsetning av epoksiderende karboksylsyreestere med karboksylsyrer og/eller alkoholer, som skumdempende middel ved bearbeiding og/eller fremstilling av næringsmidler så vel som ved fermenteringsprosesser . The invention relates to the use of ester polyoline-containing reaction mixture, produced by ring-opening reaction of epoxidizing carboxylic acid esters with carboxylic acids and/or alcohols, as defoamer in the processing and/or production of foodstuffs as well as in fermentation processes.
Ved industriell bearbeiding og/eller .fremstilling av næringsmidler, er det aktuelt med bekjempelse og forebygging av skum som opptrer. Således kan det f.eks. ved industriell bearbeiding av sukkerholdige plantesafter, slik det skjer i stor målestokk ved utvinning av sukkerroer, opptre spesielle vanskeligheter ved en stor mengde skumutvikling, i klare-ringsinnretning, ved roetransport, i diffundering så vel som i karbon!seringstankene og før fordamperen. Likeledes gjelder dette .fremstilling av ferdige potetprodukter som chips eller pommes frites, ved oppnåelse av bakegjær under anvendelse av melasse og andre tekniske fermenteringsprosesser som utvinning av legemidler. In the case of industrial processing and/or production of foodstuffs, it is relevant to combat and prevent the formation of foam. Thus, it can e.g. in the industrial processing of sugar-containing plant juices, as occurs on a large scale in the extraction of sugar beet, special difficulties occur in the case of a large amount of foam development, in the clarification device, during beet transport, in diffusion as well as in the carbonation tanks and before the evaporator. This also applies to the production of finished potato products such as chips or French fries, by obtaining baker's yeast using molasses and other technical fermentation processes such as the extraction of pharmaceuticals.
Det anvendte hjelpemidlet til skumregulering innenfor næringsmiddelområdet må kunne bli fjernet ved vanlig opparbeiding fra sluttproduktet, slik at det ferdige resultatet ikke blir belastet. Videre må alle hjelpemidler, som blir anvendt ved fremstilling av næringsmidler, være luktfrie, smakfrie og naturligvis fysiologisk fullstendig godtagbare. Skumbekjempelsesmidler som kommer i avfallsvannet bør videre være biologisk godt nedbrytbare. Av økologiske og økonomiske grunner er spesielt høyvirksomme skumbekjempelsesmidler ønskelig, for at forurensninger fra næringsmiddelpro-duktene og avvannet skal holdes mest mulig lavt. For praktisk anvendelse av skumdempende midler forventer man at man med små anvendelsesmengder oppnår høy spontanvirkning og god langtidsvirkning. I tillegg skal de skumdempende tilsetningsstoffene både bekjempe opptreden av skum (avskummere) og også forhindre preventivt skum (skumhemmere). The aid used for foam control within the food area must be able to be removed from the final product during normal processing, so that the finished result is not burdened. Furthermore, all aids used in the production of foodstuffs must be odorless, tasteless and, of course, physiologically completely acceptable. Foam control agents that end up in the waste water should also be biodegradable. For ecological and economic reasons, particularly highly effective anti-foam agents are desirable, so that contamination from the food products and the wastewater is kept as low as possible. For the practical use of anti-foaming agents, it is expected that with small amounts of application, a high spontaneous effect and a good long-term effect will be achieved. In addition, the antifoam additives must both combat the appearance of foam (defoamers) and also prevent preventive foaming (foam inhibitors).
For avskumming innenfor sukker- og gjærindustrien er det for tiden i bruk fett og olje som roe-, jordnøtt-, olivenolje, så vel som helfett. Også fettsyremonoglyserider, fettsyrepoly-glykolestere, polyalkylenglykoler, etylenoksidaddukter til forgrenede alkoholer, alkylenoksidaddukter til oligosakka-rider så vel som frie fettalkoholer, er blitt foreslått til dette formål. Typiske skumbekjempelsesmidler med patent-sitater og anvendelsesområder er angitt i JUllmans encyklo-pedi med teknisk kjemi, bind A 11 (5. opplag), 1988, side 465 til 490. Selv om man med disse stoffene også kan oppnå en viss skumundertrykklng, har de enten ulempen at de ikke kan bli anvendt i mindre mengder eller de oppviser ikke en tilstrekkelig fullstendig biologisk nedbrytbarhet. En biologisk fullstendig, rask nedbrytning av klaringsanlegget er imidlertid i dag en av de viktigste kravene til hjelpemidler av nevnte type. For skimming within the sugar and yeast industry, fats and oils such as beet, peanut, olive oil, as well as whole fat are currently in use. Also fatty acid monoglycerides, fatty acid polyglycol esters, polyalkylene glycols, ethylene oxide adducts to branched alcohols, alkylene oxide adducts to oligosaccharides as well as free fatty alcohols have been proposed for this purpose. Typical foam control agents with patent citations and areas of application are indicated in JUllman's encyclopedia of technical chemistry, volume A 11 (5th edition), 1988, pages 465 to 490. Although these substances can also achieve some foam suppression, they have either the disadvantage is that they cannot be used in smaller quantities or they do not exhibit a sufficiently complete biodegradability. A biologically complete, rapid breakdown of the clarification plant is, however, today one of the most important requirements for aids of the aforementioned type.
Oppgaven til foreliggende oppfinnelse er derfor å stille til rådighet nye skumdempende tilsetningsstoffer for fremstilling, hhv. bearbeiding av næringsmidler, så vel som til fermenteringsprosesser, som allerede i mindre anvendelsesmengder bevirker spontan avskumming og bibeholder denne virkningen over et langt tidsrom. Samtidig må de skumdempende tilsetningsstoffene oppvise en rask, biologisk nedbrytbarhet. The task of the present invention is therefore to make available new anti-foam additives for production, or processing of foodstuffs, as well as for fermentation processes, which even in small application quantities cause spontaneous defoaming and maintain this effect over a long period of time. At the same time, the anti-foam additives must show rapid, biological degradability.
Gjenstand for foreliggende oppfinnelse er således anvendelse av esterpolyolinneholdende reaksjonsblandinger fremstilt ved ringåpnende omsetning av epoksiderende karboksylsyreestere med karboksylsyre og/eller alkoholer som skumdempende tilsetningsstoffer ved fremstilling og/eller bearbeiding av næringsmidler og/eller ved fermenteringsprosesser. The object of the present invention is thus the use of ester polyoline-containing reaction mixtures prepared by ring-opening reaction of epoxidizing carboxylic acid esters with carboxylic acid and/or alcohols as defoaming additives in the manufacture and/or processing of foodstuffs and/or in fermentation processes.
I forbindelse med foreliggende oppfinnelse blir begrepet esterpolyolet brukt til forbindelser som minst oppviser en karboksylsyreestergruppe og minst en hydroksylgruppe i esterpolyolmolekylet på det aktuelle stedet og ikke nød-vendigvis i nabostilling. In connection with the present invention, the term ester polyol is used for compounds which exhibit at least one carboxylic acid ester group and at least one hydroxyl group in the ester polyol molecule at the relevant location and not necessarily in a neighboring position.
I en første utførelsesform angår oppfinnelsen anvendelse av esterpolyolinneholdende reaksjonsblandinger fremstilt ved ringåpnende omsetning av epoksiderte karboksylsyreestere med alkoholer som skumdempende tilsetningsstoffer. Fremstilling av slike esterpolyolinneholdende reaksjonsblandinger er allerede kjent og kan skje ved den såkalte tildråpingsfremgangsmåten eller entrinnsfremgangsmåten. Etter tildråpingsfremgangsmåten blir de aktuelle alkoholene for omsetning blandet sammen med en sur katalysator som en sterk mineral-syre, og deretter ved en reaksjonstemperatur mellom 60 og 120°C tilsatt den epoksiderte karboksylsyresteren konti-nuerlig og porsjonsvis. Etter den såkalte entrinnsfremgangsmåten, blir alle reaksjonsdelene omsatt i nærvær av en sur katalysator ved temperaturer mellom 60 og 120°C. Videre fremgang av reaksjonen kan bli bestemt via innhold av ikke-avreagerte epoksidgrupper, som f.eks. etter titreringsmetoden til R.R. Jay, Analytische Chemie, 36, 667 (1964). Etter avsluttet omsetning kan den sure katalysatoren bli spaltet ved nøytralisasjon og eventuelt overskudd alkohol kan bli. atskilt destillativt eller ved hjelp av faseseparasjon. Naturligvis kan den sure katalysatoren også forbli i reaksjonsblandingen når ytterligere anvendelse ikke blir påvirket av dette. In a first embodiment, the invention relates to the use of ester polyoline-containing reaction mixtures produced by ring-opening reaction of epoxidized carboxylic acid esters with alcohols as antifoam additives. The production of such ester polyoline-containing reaction mixtures is already known and can take place by the so-called drop-in method or the one-step method. After the dropwise method, the relevant alcohols for reaction are mixed together with an acidic catalyst such as a strong mineral acid, and then at a reaction temperature between 60 and 120°C the epoxidized carboxylic acid ester is added continuously and in portions. Following the so-called one-step process, all the reaction parts are reacted in the presence of an acidic catalyst at temperatures between 60 and 120°C. Further progress of the reaction can be determined via the content of unreacted epoxide groups, such as e.g. according to the titration method of R.R. Jay, Analytische Chemie, 36, 667 (1964). After completion of the reaction, the acid catalyst can be split by neutralization and any excess alcohol can remain. separated by distillation or by means of phase separation. Naturally, the acid catalyst can also remain in the reaction mixture when further use is not affected by this.
Innenfor rammen av oppfinnelsen kan det som epoksiderte karboksylsyreestere bli anvendt estere av epoksiderte karboksylsyrer med alkoholer og/eller av epoksiderte alkoholer med karboksylsyrer for fremstilling av de anvendte reaksjonsblandingene ifølge oppfinnelsen. Fremstillingen av espoksiderte karboksylsyreestere foregår etter kjente fremgangsmåter som f.eks. etter EP 286 937 eller DE-PS 1 042 565, hvorved det må være gitt at de fremstilte epoksiderte karboksylsyreestrene inneholder pr. molekyl minst en epoksidgruppe i molekylet. Within the scope of the invention, esters of epoxidized carboxylic acids with alcohols and/or of epoxidized alcohols with carboxylic acids can be used as epoxidized carboxylic acid esters for the preparation of the used reaction mixtures according to the invention. The production of epoxidized carboxylic acid esters takes place according to known methods such as e.g. according to EP 286 937 or DE-PS 1 042 565, whereby it must be provided that the produced epoxidized carboxylic acid esters contain per molecule at least one epoxide group in the molecule.
For epoksiderte karboksylsyreestere av epoksiderte alkoholer er det spesielt egnet med epoksyderivater av alkoholer med 12 til 32, fortrinnsvis 22 C-atomer som epoksyderivater av oleylalkohol, elaidylalkohol, ricinolalkohol, linoleyl-alkohol, linolenylalkohol, gadoleylalkohol og/eller eruca-alkohol. Selv om også karboksylsyreestere av epoksiderte alkoholer og epoksiderte karboksylsyrer kan bli anvendt, er den foretrukne gruppen som er aktuell ifølge oppfinnelsen epoksiderte estere av epoksiderte karboksylsyrer og alifatiske, og en— og/eller flerverdige alkoholer. Spesielt er det egnet med epoksiderte karboksylsyreestere av forgrenede og/eller uforgrenede enverdige til fireverdige alkoholer med inntil 40 C-atomer, fortrinnsvis med inntil 36 C-atomer og særlig med 1 til 22 C-atomer som metanol, etanol, propanol, 2-etylheksanol, etylenglykol, butandiol, neopentylglykol, pentaerytritt og/eller glyserin. Innenfor rammen av oppfinnelsen kan det også bli anvendt epoksiderte partialkarbok-sylsyreestere av flerverdige alkoholer, dvs. epoksiderte karboksylsyreester flerfunksjonene alkoholer som minst disponerer over en fri hydroksylgruppe som partialglyserid. Under henvisning til kravene med biologisk nedbrytbarhet, er det helt spesielt foretrukket epoksiderte karboksylsyreestere der deres epoksiderte karboksylsyreandel avleder seg fra en-og/eller flere ganger umettede karboksylsyrer med 12 til 22 C-atomer og særlig av naturlig forekommende en- og/eller flere ganger umettede fettsyrer med 12 til 22 C-atomer. Tilsvarende egner det seg med umettede fettsyrer som lauroleinsyre, myristoleinsyre, palmitoleinsyre, oljesyre, petroselinsyre, gadoleinsyre, erucasyre, linolsyre og/eller linolensyre. For epoxidized carboxylic acid esters of epoxidized alcohols, epoxy derivatives of alcohols with 12 to 32, preferably 22 C atoms such as epoxy derivatives of oleyl alcohol, elaidyl alcohol, ricinol alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol and/or eruca alcohol are particularly suitable. Although carboxylic acid esters of epoxidized alcohols and epoxidized carboxylic acids can also be used, the preferred group relevant according to the invention are epoxidized esters of epoxidized carboxylic acids and aliphatic, and mono- and/or polyhydric alcohols. In particular, it is suitable with epoxidized carboxylic acid esters of branched and/or unbranched monohydric to tetrahydric alcohols with up to 40 C atoms, preferably with up to 36 C atoms and especially with 1 to 22 C atoms such as methanol, ethanol, propanol, 2-ethylhexanol , ethylene glycol, butanediol, neopentyl glycol, pentaerythritol and/or glycerin. Within the scope of the invention, epoxidized partial carboxylic acid esters of polyhydric alcohols can also be used, i.e. epoxidized carboxylic acid esters, polyfunctional alcohols which at least dispose of a free hydroxyl group as a partial glyceride. With reference to the requirements for biodegradability, epoxidized carboxylic acid esters are particularly preferred where their epoxidized carboxylic acid portion is derived from mono- and/or polyunsaturated carboxylic acids with 12 to 22 C atoms and in particular from naturally occurring mono- and/or polyunsaturated carboxylic acids unsaturated fatty acids with 12 to 22 carbon atoms. Similarly, it is suitable with unsaturated fatty acids such as lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, petroselic acid, gadoleic acid, erucic acid, linoleic acid and/or linolenic acid.
Spesielt foretrukne epoksiderte karboksylsyreestere er for det første triglyserider av epoksiderte naturlig forekommende fettsyrer som epoksidert soyabønneolje (epoksidoksygeninnhold 5,8 til 6,8 vekt-£), oljesyrerik og/eller oljesyrefattig epoksidert solsikkeolje (epoksidoksygeninnhold 4,4 til 6,6 vekt-#), epoksidert leinolje (epoksidoksygeninnhold 8,2 til 8,6 vekt-£), så vel epoksidert tranolje (epoksidoksygeninnhold 6,3 til 6,7 vekt-*). Particularly preferred epoxidized carboxylic acid esters are, firstly, triglycerides of epoxidized naturally occurring fatty acids such as epoxidized soybean oil (epoxide oxygen content 5.8 to 6.8 wt-£), oleic acid-rich and/or oleic acid-poor epoxidized sunflower oil (epoxide oxygen content 4.4 to 6.6 wt-# ), epoxidized linseed oil (epoxide oxygen content 8.2 to 8.6 wt-£), as well as epoxidized linseed oil (epoxide oxygen content 6.3 to 6.7 wt-*).
Som utgangsstoffer for epoksiderte karboksylsyreestere egner det seg med tallrike animalske og/eller plantetriglyserider som oksetalg, palmeolje, kokosolje, jordnøttolje, roeolje, bomullsfrøolje, soyabønneolje, tranolje, solsikkeolje, korrianderolje og/eller leinolje. As starting materials for epoxidized carboxylic acid esters, numerous animal and/or plant triglycerides such as beef tallow, palm oil, coconut oil, peanut oil, beet oil, cottonseed oil, soybean oil, safflower oil, sunflower oil, coriander oil and/or linseed oil are suitable.
Foretrukket på samme måte er epoksiderte karboksylsyreestere av enverdige alkoholer med naturlig forekommende epoksiderte fettsyrer som de som f.eks. kan bli oppnådd ved omestrings-reaksjon av de forannevnte epoksiderte triglyseridene med enverdige alkoholer som beskrevet i det følgende. Preferred in the same way are epoxidized carboxylic acid esters of monohydric alcohols with naturally occurring epoxidized fatty acids such as those that e.g. can be obtained by transesterification reaction of the aforementioned epoxidized triglycerides with monohydric alcohols as described below.
Ifølge en utførelsesform av foreliggende oppfinnelse blir det anvendt esterpolyolinneholdende reaksjonsblandinger, som blir fremstilt ved ringåpnende omsetning av epoksiderte karboksylsyreestere med alkoholer. Til ringåpning kan det prinsipielt bli anvendt mettede, umettede, forgrenede, uforgrenede, cykliske, aromatiske, enverdige primære alkoholer. Av disse kan det spesielt bli anvendt mettede, uforgrenede, enverdige primære alkoholer med 1 til 22 C-atomer, fortrinnsvis inntil 8 C-atomer og særlig inntil 4 C-atomer som metanol, etanol, propanol og/eller butanol. Naturligvis kan det som enverdige primære alkoholer også bli anvendt dioler, der en hydroksylgruppe er foretret hhv. forestret, som monoalkyletylenglykol. I en tilsvarende utforming av foreliggende oppfinnelse kan ringåpningsprodukter av epoksiderte karboksylsyreestere med toverdige, treverdige og/eller flerverdige alkoholer som etylenglykol, propylenglykol, propandiol, butandiol, heksandiol, trimetylolpropan, glyserin, trimetyloletan, pentaerytritt og/eller sorbitt som kondensasjonsprodukter som diglyserin, polyglyserin, polytrimetylpropan bli anvendt. Selv derivater av de nevnte flerverdige alkoholene som partialester kan bli anvendt for ringåpning så lenge de disponerer over minst en fri hydroksylgruppe som glyserin-monooleat, glyserinmonostearat, trimetylolpropanmonostearat. According to one embodiment of the present invention, ester polyoline-containing reaction mixtures are used, which are produced by ring-opening reaction of epoxidized carboxylic acid esters with alcohols. Saturated, unsaturated, branched, unbranched, cyclic, aromatic, monovalent primary alcohols can in principle be used for ring opening. Of these, saturated, unbranched, monovalent primary alcohols with 1 to 22 C atoms, preferably up to 8 C atoms and in particular up to 4 C atoms such as methanol, ethanol, propanol and/or butanol can be used in particular. Naturally, diols can also be used as monohydric primary alcohols, where a hydroxyl group is etherified or esterified, such as monoalkylethylene glycol. In a corresponding embodiment of the present invention, ring-opening products of epoxidized carboxylic acid esters with dihydric, trihydric and/or polyhydric alcohols such as ethylene glycol, propylene glycol, propanediol, butanediol, hexanediol, trimethylolpropane, glycerin, trimethylolethane, pentaerythritol and/or sorbitol as condensation products such as diglycerin, polyglycerin, polytrimethylpropane be used. Even derivatives of the mentioned polyhydric alcohols as partial esters can be used for ring opening as long as they have at least one free hydroxyl group such as glycerine monooleate, glycerine monostearate, trimethylolpropane monostearate.
Ifølge en annen utførelsesform av foreliggende oppfinnelse kan ringåpnings epoksiderte karboksylsyreestere med karboksylsyre bli anvendt som skumdempende tilsetningsstoffer. For ringåpning kan det bli anvendt syntetiske, naturlige, alifatiske, aromatiske, forgrenede og/eller uforgrenede monokarboksylsyrer med inntil 36 C-atomer, fortrinnsvis Inntil 22 C-atomer. Spesielt foretrukket er maursyre, eddiksyre, propionsyre, kaprylsyre, kaprinsyre, laurinsyre, behensyre, myristinsyre, palmitoleinsyre, oljesyre, stearin-syre, linolsyre og/eller linolensyre. Dersom det til ringåpning blir anvendt umettede karboksylsyrer, oppnår man spesielt lavviskøse esterpolyolinneholdende reaksjonsblandinger som kan være fordelaktig for enkelte anvendelsesområder . According to another embodiment of the present invention, ring-opening epoxidized carboxylic acid esters with carboxylic acid can be used as antifoam additives. For ring opening, synthetic, natural, aliphatic, aromatic, branched and/or unbranched monocarboxylic acids with up to 36 C atoms, preferably up to 22 C atoms, can be used. Particularly preferred are formic acid, acetic acid, propionic acid, caprylic acid, capric acid, lauric acid, behenic acid, myristic acid, palmitoleic acid, oleic acid, stearic acid, linoleic acid and/or linolenic acid. If unsaturated carboxylic acids are used for ring opening, particularly low-viscosity ester polyoline-containing reaction mixtures are obtained, which can be advantageous for certain areas of application.
Også ringåpningsprodukter av epoksiderte kaboksylsyreestere med karboksylsyrer er i og for seg kjente produkter og disse kan som regel bli fremstilt etter entrinnsfremgangsmåten. En nesten fullstendig ringåpning av epoksidert soyaolje med leinoljefettsyre eller dehydratisert ricinolsyre etter . entrinnsfremgangsmåten, beskriver f.eks. US 2 909 537 en delvis ringåpning av epoksiderte fett med di- og polykarbok-sylsyrer, eller deres anhydrider beskrives i US 3 180 749. Den for tiden ennå Ikke offentlige patentsøknad P 39 35 127 beskriver minst delvis ringåpning av epoksiderte estere og/eller epoksiderte alkoholer med karboksylsyrer etter tildråpingsfremgangsmåten, hvorved karboksyl syrene blandes og de epoksiderte reaktantene blir dråpevis tilsatt. Analog til de allerede kjente fremgangsmåtene kan de anvendte ester-polyol inneholdende reaksjonsblandingene ifølge oppfinnelsen bli fremstilt hvorved reaksjonstemperaturen fortrinnsvis er i området fra 80"C til 270"C. Likeledes kan, i forbindelse med foreliggende oppfinnelse, de epoksiderte karboksylsyrene bli fullstendig eller delvis ringåpnet, hvorved esterpolyolinneholdende reaksjonsblandlnger bør oppvise et absolutt restepoksidoksygeninnhold under 3 vekt-*. Ring-opening products of epoxidized carboxylic acid esters with carboxylic acids are also known products in and of themselves and these can usually be prepared according to the one-step process. An almost complete ring opening of epoxidized soybean oil with linseed oil fatty acid or dehydrated ricinoleic acid after . the one-step procedure, describes e.g. US 2 909 537 a partial ring opening of epoxidized fats with di- and polycarboxylic acids, or their anhydrides is described in US 3 180 749. The currently not yet public patent application P 39 35 127 describes at least partial ring opening of epoxidized esters and/or epoxidized alcohols with carboxylic acids according to the dropwise method, whereby the carboxylic acids are mixed and the epoxidized reactants are added dropwise. Analogous to the already known methods, the used ester-polyol containing reaction mixtures according to the invention can be prepared whereby the reaction temperature is preferably in the range from 80°C to 270°C. Likewise, in connection with the present invention, the epoxidized carboxylic acids can be completely or partially ring-opened, whereby ester polyoline-containing reaction mixtures should exhibit an absolute residual epoxide oxygen content below 3 wt-*.
For esterpolyolinneholdende reaksjonsblandlnger som blir fremstilt ved fullstendig, hhv. nesten fullstendig ringåpnende omsetning, anbefales det at de epoksiderte karboksylsyreestrene reagerer i mengder 1:1 til 1:10, fortrinnsvis 1:1 til 1:3 - beregnet som mol-* epoksid og med-hensyn til mol-* syregrupper og/eller alkoholgrupper - med de nevnte alkoholene og/eller karboksylsyrene. For ringåpning av epoksiderte karboksylsyreestere med karboksylsyrer er det spesielt egnet med mengder av epoksiderte karboksylsyreestere til karboksylsyrer på 1:1,1 - beregnet som mol-* epoksid og mol-* syregruppe. For å oppnå en nesten fullstendig ringåpning er det imidlertid videre nødvendig å la reaksjonspartnerne reagere ved de allerede nevnte temperaturene inntil det opptrer et absolutt restepoksidoksygeninnhold i reaksjonsblandingen under 0,3 vekt-*. Dersom omsetningen blir avbrutt tidligere, hhv. omsetningforholdene valgt, slik at de ligger under en fullstendig omsetning, så blir det oppnådd ester-polyol inneholdende reaksjonsblandinger som oppviser et høyere restepoksidoksygeninnhold. I forbindelse med foreliggende oppfinnelse kan det også bli anvendt esterpolyolinneholdende reaksjonsblandlnger som bare blir oppnådd ved delringåpnende omsetning og som oppviser et restepoksidoksygeninnhold som bør ligge under 3 vekt-*. For ester polyoline-containing reaction mixtures which are produced by complete, or almost complete ring-opening reaction, it is recommended that the epoxidized carboxylic acid esters react in amounts of 1:1 to 1:10, preferably 1:1 to 1:3 - calculated as mol-* epoxide and taking into account mol-* acid groups and/or alcohol groups - with the aforementioned alcohols and/or carboxylic acids. For ring opening of epoxidized carboxylic acid esters with carboxylic acids, it is particularly suitable with amounts of epoxidized carboxylic acid esters to carboxylic acids of 1:1.1 - calculated as mol-* epoxide and mol-* acid group. In order to achieve an almost complete ring opening, however, it is further necessary to allow the reaction partners to react at the already mentioned temperatures until an absolute residual epoxide oxygen content in the reaction mixture below 0.3 wt-* appears. If the turnover is interrupted earlier, or the reaction conditions chosen, so that they lie below a complete reaction, then ester-polyol containing reaction mixtures are obtained which exhibit a higher residual epoxide oxygen content. In connection with the present invention, ester polyoline-containing reaction mixtures can also be used which are only obtained by ring-opening reaction and which exhibit a residual epoxy oxygen content which should be below 3 weight-*.
I esterpolyolinneholdende reaksjonsblandinger kan eventuelt overskudd karboksylsyre og/eller alkoholer bli fjernet destillativt ved hjelp av faseseparasjon eller ved nøytral-isasjon og eventuelt etterfølgende filtrering. Dersom man eventuelt må avdestillere overskudd karboksylsyre, må man legge vekt på at temperaturen ikke må over 300°C, for å utelukke krakkprosesser. De eventuelt i reaksjonsblandingen foreliggende sure katalysatorer, kan bli atskilt ved hjelp av faseseparasjon med alkohol, nøytralisert med baser eller forbli i reaksjonsblandingen. In ester polyoline-containing reaction mixtures, any excess carboxylic acid and/or alcohols can be removed by distillation by means of phase separation or by neutralization and possibly subsequent filtration. If it is necessary to distill excess carboxylic acid, emphasis must be placed on the temperature not exceeding 300°C, in order to exclude cracking processes. Any acidic catalysts present in the reaction mixture can be separated by means of phase separation with alcohol, neutralized with bases or remain in the reaction mixture.
I forbindelse med oppfinnelsen blir esterpolyolinneholdende reaksjonsblandlnger foretrukket som ved romtemperatur foreligger som væske. Naturligvis kan også faste esterpolyolinneholdende reaksjonsblandlnger bli anvendt som skumdempende tilsetningsmiddel. f.eks. i form av en oppløsning, emulsjon eller dispersjon. For dosering og for en optimal gjennom-blanding med den avskummede massen så <y>el som en god fuktgjøring av allerede opptrådte skumblærer, egner alltid væsker seg bedre. In connection with the invention, reaction mixtures containing ester polyoline are preferred which are liquid at room temperature. Naturally, solid ester polyoline-containing reaction mixtures can also be used as antifoam additives. e.g. in the form of a solution, emulsion or dispersion. Liquids are always better for dosing and for an optimal thorough mixing with the skimmed mass as well as a good moistening of foam blisters that have already appeared.
De ifølge oppfinnelsen anvendte esterpolyolinneholdende reaksjonsblandingene kan etter behov bli anvendt i vide mengdeforhold. Den viser allerede ved tilsetning av små mengder, fortrinnsvis i mengder under 1 vekt-* og særlig i mengder fra 20 til 50 ppm, med hensyn til avskummende masse, god virkning, en øvre grense for tilsetningsmengden er ikke resultat av esterpolyolinneholdende reaksjonsblanding. Av økonomiske grunner tilsetter imidlertid teknikere så lite som mulig skumdempende tilsetninger til den avskummende massen, og som for det meste ligger unde.r 1 vekt-*. Naturligvis kan de esterpolyolinneholdende reaksjonsblandingene bli anvendt med handelsvanlige avskummere og/eller skumhemmere, fortrinnsvis slike som er flytende ved romtemperatur. The esterpolyoline-containing reaction mixtures used according to the invention can be used in wide proportions as required. It already shows a good effect when adding small amounts, preferably in amounts below 1 weight-* and especially in amounts from 20 to 50 ppm, with regard to defoaming mass, an upper limit for the amount of addition is not the result of an ester polyoline-containing reaction mixture. However, for economic reasons, technicians add as little anti-foaming additives as possible to the defoaming mass, which is mostly below 1 weight-*. Naturally, the ester polyoline-containing reaction mixtures can be used with commercially available defoamers and/or foam inhibitors, preferably those which are liquid at room temperature.
De ifølge oppfinnelsen anvendte esterpolyolinneholdende reaksjonsblandingene virker både som skumhemmere og også som avskummere og kan på tilsvarende måte bli tilsatt før eller etter opptreden av skum. De viser god spontan- og langtidsvirkning over et samlet pH-område både ved høyere og lavere temperaturer. I tillegg kan de uten problemer bli atskilt fra det avskummende gods slik at de på grunn av deres lukt-, smakløshet og deres fysiologiske forlikelighet i næringsmiddelindustrien, bli anvendt som hjelpestoff. Helt spesielt gode resultater blir oppnådd når man anvender de esterpolyolinneholdende reaksjonsblandingene som skumdempende tilsetninger ved bearbeiding av sukkerroer, i potetbearbeidende industri og/eller ved fermenteringsprosesser som ved oppnåelse av bakegjær under anvendelse av melasse og/eller ved fremstilling av legemidler. Ved bearbeiding av sukkerroer kan de esterpolyolinneholdende reaksjonsblandingene bli anvendt både i utedrift, dvs. ved transport, rensing og lagring, og også i innvendig drift for ekstraksjon av sukker med vann til skumdamping. The ester polyoline-containing reaction mixtures used according to the invention act both as foam inhibitors and also as defoamers and can be added in a similar way before or after the appearance of foam. They show good spontaneous and long-term effects over an overall pH range at both higher and lower temperatures. In addition, they can be easily separated from the defoaming material so that, due to their odorlessness, tastelessness and their physiological compatibility in the food industry, they are used as excipients. Particularly good results are achieved when using the ester polyoline-containing reaction mixtures as anti-foam additives in the processing of sugar beet, in the potato processing industry and/or in fermentation processes such as in the production of baker's yeast using molasses and/or in the manufacture of pharmaceuticals. When processing sugar beet, the esterpolyolin-containing reaction mixtures can be used both in outdoor operation, i.e. in transport, cleaning and storage, and also in indoor operation for the extraction of sugar with water for foam steaming.
Eksempler Examples
A) Fremstilling av avskummende tilsetninger A) Production of defoaming additives
Eksempel 1 Example 1
234 g proprionsyre, med hensyn på syretall tilsvarer 3,15 mol, ble oppvarmet i reaksjonsapparatur under omrøring ved 140°C. Til dette ble 713 g soyaoljeepoksid (epoksidoksygeninnhold 6,73 vekt-*, tilsvarer 3, 0 mol med hensyn på epoksidinnhold, dråpevis tilsatt i løpet av 80 minutter. Etter avsluttet tilsetning lar man reaksjonsblandingen avreagere i_5 timer ved 140°C (restepoksidoksygeninnhold under 0,18 vekt-*). Deretter ble det avdestillert i vakuum (0,02 mbar) den uomsatte propionsyre (114 g) inntil 190°C. Man får esterpolyolblandingen som en klar, mørkegul væske med gjenkjenningstallene OHZ = 129; VZ = 277,5; JZ = 4,3; SZ = 2,1. 234 g of proprionic acid, with regard to the acid number corresponding to 3.15 mol, was heated in a reaction apparatus with stirring at 140°C. To this, 713 g of soybean oil epoxide (epoxide oxygen content 6.73 wt-*, corresponding to 3.0 mol with regard to epoxide content) was added dropwise over the course of 80 minutes. After completion of the addition, the reaction mixture is allowed to react for 5 hours at 140°C (residual epoxide oxygen content below 0 .18 weight-*). The unreacted propionic acid (114 g) was then distilled off in vacuum (0.02 mbar) up to 190° C. The ester polyol mixture is obtained as a clear, dark yellow liquid with the identification numbers OHZ = 129; VZ = 277, 5; JZ = 4.3; SZ = 2.1.
Eksempel 2 Example 2
2360 g epoksidert soyaolje (epoksidoksygeninnhold 6,78 vekt-*), tilsvarer 10 mol med hensyn på epoksidinnhold, ble dråpevis tilsatt under omrøring til den under tilbakestrøm kokende oppløsningen med 9 g konsentrert svovelsyre, tilsvarende 0,9 mol med hensyn på epoksidinnhold, i 960 g metanol, tilsvarende 30 mol med hensyn på epoksidinnhold. Etter avsluttet tilsetning av epoksidert soyaolje lar man reaksjonsblandingen avreagere i ca. 6 timer. Deretter ble In 960 g of methanol, corresponding to 30 mol with regard to epoxide content. After the addition of epoxidized soybean oil is finished, the reaction mixture is allowed to react for approx. 6 hours. Then became
reaksjonsblandingen avkjølt, nøytralisert med dletyletanol-amin og overskudd metanol ble fjernet 1 vakuum. Man oppnår en klar gul væske med gjenkjenningstallene OHZ = 185; VZ = 163; JZ = 19,4; SZ - 1,6. the reaction mixture cooled, neutralized with dletylethanolamine and excess methanol was removed under vacuum. A clear yellow liquid with the recognition numbers OHZ = 185 is obtained; VZ = 163; JZ = 19.4; SZ - 1.6.
Eksempel 3 Example 3
100 kg epoksystearinsyremetylester (epoksidoksygeninnhold 4,95 vekt-*), tilsvarer 309 mol med hensyn på epoksidinnhold, og 38,3 kg etylenglykol, tilsvarer 618 mol med hensyn på epoksidinnhold, ble i nærvær av 34 g konsentrert saltsyre oppvarmet under omrøring til 90°C. Den til å begynne med sterke eksoterme reaksjonen ble avsluttet etter 1,5 timer (restepoksidoksygeninnhold 0,03 vekt-*). Reaksjonsblandingen ble avkjølt og nøytralisert med 160 g 30 vekt-* metanolisk natriummetylatoppløsning. I vakuum (0,02 mbar) ble den uomsatte etylenglykol (27,7 kg) destillert inntil 200°C. Man oppnår en klar, gul væske med gjenkjenningstallene OHZ = 234,6; VZ = 162,1; JZ - 6,9; SZ = 0,7. 100 kg of epoxy stearic acid methyl ester (epoxy oxygen content 4.95 wt-*), corresponding to 309 mol with respect to epoxide content, and 38.3 kg of ethylene glycol, corresponding to 618 mol with respect to epoxide content, were heated in the presence of 34 g of concentrated hydrochloric acid with stirring to 90° C. The initially strongly exothermic reaction was terminated after 1.5 hours (residual epoxide oxygen content 0.03 wt-*). The reaction mixture was cooled and neutralized with 160 g of 30 wt.* methanolic sodium methylate solution. In vacuum (0.02 mbar) the unreacted ethylene glycol (27.7 kg) was distilled up to 200°C. A clear, yellow liquid with the recognition numbers OHZ = 234.6 is obtained; VZ = 162.1; JZ - 6.9; SZ = 0.7.
Eksempel 4 Example 4
1019 g epoksystearinsyremetylester (epoksidoksygeninnhold 4,95 vekt-*), tilsvarer 3 mol med hensyn på epoksidinnhold, 552 g glyserin, tilsvarer 6 mol med hensyn på epoksidinnhold, og 2,1 g svovelsyre ble blandet i en rørebeholder og oppvarmet under omrøring til ca. 100°C. Etter ca. 2 timer oppviser reaksjonsblandingen et epoksidoksygeninnhold under 0,1 vekt-*. Reaksjonsblandingen ble avkjølt og nøytralisert med 7 g dietyletanolamin. Overskuddet glyserin kan bli adskilt som øvre fase fra reaksjonsblandingen ved hjelp av faseseparasjon. Man får 1257 g av en gul, lett seig væske med gjenkjenningstallene OHZ = 334; SZ = 0,3. 1019 g of epoxy stearic acid methyl ester (epoxy oxygen content 4.95 wt-*), corresponding to 3 mol with respect to epoxide content, 552 g glycerin, corresponding to 6 mol with respect to epoxide content, and 2.1 g of sulfuric acid were mixed in a mixing vessel and heated with stirring to approx. . 100°C. After approx. After 2 hours, the reaction mixture has an epoxide oxygen content of less than 0.1% by weight. The reaction mixture was cooled and neutralized with 7 g of diethylethanolamine. The excess glycerin can be separated as the upper phase from the reaction mixture by means of phase separation. You get 1257 g of a yellow, slightly viscous liquid with the identification numbers OHZ = 334; SZ = 0.3.
Eksempel 5 Example 5
1260 g epoksystearinsyre-2-etylheksylester (epoksidoksygeninnhold 3,81 vekt-*), tilsvarende 3 mol med hensyn på epoksidinnhold, 552 g glyserin, tilsvarende 6 mol med hensyn på epoksidinnhold, og 2,1 g konsentrert svovelsyre ble under omrøring oppvarmet til 100°C. Etter ca. 5 timer oppviste reaksjonsblandingen et restepoksidoksygeninnhold under 0,1 vekt-*. Opparbeidingen av reaksjonsblandingen foregår analog til eksempel 4. Man får 1361 g av en gul, lett seig væske med gjenkjenningstallene OHZ = 131, SZ = 0,6. 1260 g of epoxy stearic acid-2-ethylhexyl ester (epoxy oxygen content 3.81 wt-*), corresponding to 3 mol with regard to epoxide content, 552 g glycerin, corresponding to 6 mol with regard to epoxide content, and 2.1 g of concentrated sulfuric acid were heated to 100 with stirring °C. After approx. After 5 hours, the reaction mixture showed a residual epoxide oxygen content below 0.1 wt-*. The reaction mixture is worked up analogously to example 4. 1361 g of a yellow, slightly viscous liquid with the identification numbers OHZ = 131, SZ = 0.6 is obtained.
B) Anvendelsesprøvlng B) Application testing
En 2 1 målsylinder ble fylt med 110 g sukkersirup (Riiben-kraut) og 420 ml vann. Ved hjelp av en Laborsch-pumpe med en tilførselsytelse på 3 1 pr. minutt ble oppløsningen suget av med et glassrør på gulvet av målesylinderen. Tilbakeføringen av væsken foregikk over et annet rør, hvis nedre ende lå i høyde med øvre kant til målesylinder. Straks skum og væske sammen hadde nådd dette volum på 200 ml, ble 50 ppm av de forskjellige skumdempende tilsetningsstoffene tilsatt med en mikropipette og etter 0,5; 1; 2; 3; 5; 10; 20 og 30 minutter ble det samlede volumet av skumhøyde og væske avlest. På denne måte ble det prøvet forskjellige pH-verdier, som ble innstilt ved tilsetning av kalsiumhydroksid, og ved forskjellige temperaturer, esterpolyoler fra eksempel 1, 2, 3 og 4. A 2 1 measuring cylinder was filled with 110 g of sugar syrup (Riiben-kraut) and 420 ml of water. Using a Laborsch pump with a delivery performance of 3 1 per minute, the solution was sucked off with a glass tube on the floor of the measuring cylinder. The return of the liquid took place over another pipe, the lower end of which lay at the height of the upper edge of the measuring cylinder. As soon as the foam and liquid together had reached this volume of 200 ml, 50 ppm of the various anti-foam additives were added with a micropipette and after 0.5; 1; 2; 3; 5; 10; At 20 and 30 minutes, the total volume of foam height and liquid was read. In this way, different pH values were tested, which were adjusted by adding calcium hydroxide, and at different temperatures, ester polyols from examples 1, 2, 3 and 4.
Claims (9)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4038608A DE4038608A1 (en) | 1990-12-04 | 1990-12-04 | USE OF ESTER POLYOLE-CONTAINING REACTION MIXTURES AS FOAM-ABSORBING ADDITIVES |
PCT/EP1991/002210 WO1992010266A1 (en) | 1990-12-04 | 1991-11-25 | Use of ester-polyol-containing reaction mixtures as foam-inhibiting additives |
Publications (4)
Publication Number | Publication Date |
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NO931619L NO931619L (en) | 1993-05-04 |
NO931619D0 NO931619D0 (en) | 1993-05-04 |
NO179481B true NO179481B (en) | 1996-07-08 |
NO179481C NO179481C (en) | 1996-10-16 |
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Application Number | Title | Priority Date | Filing Date |
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NO931619A NO179481C (en) | 1990-12-04 | 1993-05-04 | Use of ester polyol-containing reaction mixtures as antifoaming additives |
Country Status (10)
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EP (1) | EP0561814B1 (en) |
JP (1) | JPH06502991A (en) |
AT (1) | ATE116865T1 (en) |
CA (1) | CA2097829A1 (en) |
DE (2) | DE4038608A1 (en) |
DK (1) | DK0561814T3 (en) |
ES (1) | ES2066490T3 (en) |
FI (1) | FI932539A (en) |
NO (1) | NO179481C (en) |
WO (1) | WO1992010266A1 (en) |
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DE4331228A1 (en) * | 1993-09-15 | 1995-03-16 | Henkel Kgaa | Ester group-containing block polymers as defoamers for aqueous systems |
DE4331229A1 (en) * | 1993-09-15 | 1995-03-16 | Henkel Kgaa | Ester group-containing block polymers as defoamers for aqueous systems |
CA2202552A1 (en) * | 1994-10-13 | 1996-04-25 | John J. Palmer | Defoamer composition and method of using the same |
DE19503062A1 (en) * | 1995-02-01 | 1996-08-08 | Henkel Kgaa | Use of alkoxylation products of epoxidized fatty substances as defoamers |
DE69806244T2 (en) * | 1997-05-27 | 2002-11-07 | Unichema Chemie Bv | FAT-Oligomers |
CN114479057B (en) * | 2021-12-27 | 2023-08-29 | 科之杰新材料集团有限公司 | Ester monomer, polycarboxylate water reducer and preparation method thereof |
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US3066159A (en) * | 1960-11-29 | 1962-11-27 | Petrolite Corp | Reaction product of polyols and epoxidized fatty compounds |
DE1965639A1 (en) * | 1969-12-31 | 1971-07-08 | Henkel & Cie Gmbh | Low-foaming detergent, cleaning agent and depilatory agent |
IE42854B1 (en) * | 1975-06-13 | 1980-11-05 | Ciba Geigy Ag | Process for removing foam from aqueous systems |
CH637304A5 (en) * | 1978-11-03 | 1983-07-29 | Ciba Geigy Ag | FOAM ABSORBENT FOR AQUEOUS SYSTEMS. |
DE2925628A1 (en) * | 1979-06-26 | 1981-01-22 | Huels Chemische Werke Ag | CONNECTIONS SUITABLE FOR LOWING THE INTERFACE VOLTAGE OF OILY PHASES AGAINST WATER |
-
1990
- 1990-12-04 DE DE4038608A patent/DE4038608A1/en not_active Withdrawn
-
1991
- 1991-11-25 CA CA002097829A patent/CA2097829A1/en not_active Abandoned
- 1991-11-25 DE DE59104273T patent/DE59104273D1/en not_active Expired - Fee Related
- 1991-11-25 JP JP4500031A patent/JPH06502991A/en active Pending
- 1991-11-25 DK DK91920148.3T patent/DK0561814T3/en active
- 1991-11-25 WO PCT/EP1991/002210 patent/WO1992010266A1/en active IP Right Grant
- 1991-11-25 EP EP91920148A patent/EP0561814B1/en not_active Expired - Lifetime
- 1991-11-25 ES ES91920148T patent/ES2066490T3/en not_active Expired - Lifetime
- 1991-11-25 AT AT91920148T patent/ATE116865T1/en not_active IP Right Cessation
-
1993
- 1993-05-04 NO NO931619A patent/NO179481C/en unknown
- 1993-06-03 FI FI932539A patent/FI932539A/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
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WO1992010266A1 (en) | 1992-06-25 |
JPH06502991A (en) | 1994-04-07 |
NO931619L (en) | 1993-05-04 |
ATE116865T1 (en) | 1995-01-15 |
EP0561814A1 (en) | 1993-09-29 |
FI932539A0 (en) | 1993-06-03 |
NO179481C (en) | 1996-10-16 |
DK0561814T3 (en) | 1995-06-26 |
DE4038608A1 (en) | 1992-06-11 |
FI932539A (en) | 1993-06-03 |
NO931619D0 (en) | 1993-05-04 |
EP0561814B1 (en) | 1995-01-11 |
ES2066490T3 (en) | 1995-03-01 |
DE59104273D1 (en) | 1995-02-23 |
CA2097829A1 (en) | 1992-06-05 |
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