EP0214542A2 - Thickener systems for functional fluids containing a large amount of water, and such functional fluids containing these thickener systems - Google Patents
Thickener systems for functional fluids containing a large amount of water, and such functional fluids containing these thickener systems Download PDFInfo
- Publication number
- EP0214542A2 EP0214542A2 EP86111729A EP86111729A EP0214542A2 EP 0214542 A2 EP0214542 A2 EP 0214542A2 EP 86111729 A EP86111729 A EP 86111729A EP 86111729 A EP86111729 A EP 86111729A EP 0214542 A2 EP0214542 A2 EP 0214542A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- weight
- mol
- combinations
- functional liquids
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000002562 thickening agent Substances 0.000 title claims abstract description 19
- 239000012530 fluid Substances 0.000 title description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 88
- 229920000570 polyether Polymers 0.000 claims abstract description 88
- 150000003077 polyols Chemical class 0.000 claims abstract description 82
- 229920005862 polyol Polymers 0.000 claims abstract description 80
- 239000004094 surface-active agent Substances 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 150000002334 glycols Chemical class 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 25
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 17
- 239000007795 chemical reaction product Substances 0.000 description 17
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 14
- -1 ether sulfates Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 235000008504 concentrate Nutrition 0.000 description 6
- 239000012973 diazabicyclooctane Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 229940055577 oleyl alcohol Drugs 0.000 description 4
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- YIDSTEJLDQMWBR-UHFFFAOYSA-N 1-isocyanatododecane Chemical compound CCCCCCCCCCCCN=C=O YIDSTEJLDQMWBR-UHFFFAOYSA-N 0.000 description 2
- GFLXBRUGMACJLQ-UHFFFAOYSA-N 1-isocyanatohexadecane Chemical compound CCCCCCCCCCCCCCCCN=C=O GFLXBRUGMACJLQ-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000005068 cooling lubricant Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229960000735 docosanol Drugs 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000005555 metalworking Methods 0.000 description 2
- CMIAIUZBKPLIOP-YZLZLFLDSA-N methyl (1r,4ar,4br,10ar)-7-(2-hydroperoxypropan-2-yl)-4a-methyl-2,3,4,4b,5,6,10,10a-octahydro-1h-phenanthrene-1-carboxylate Chemical compound C1=C(C(C)(C)OO)CC[C@@H]2[C@]3(C)CCC[C@@H](C(=O)OC)[C@H]3CC=C21 CMIAIUZBKPLIOP-YZLZLFLDSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N 1-Tetradecanol Natural products CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- ALEYBMUCCRAJEB-UHFFFAOYSA-N 2,3-bis(1-phenylethyl)phenol Chemical compound C=1C=CC(O)=C(C(C)C=2C=CC=CC=2)C=1C(C)C1=CC=CC=C1 ALEYBMUCCRAJEB-UHFFFAOYSA-N 0.000 description 1
- BITAPBDLHJQAID-KTKRTIGZSA-N 2-[2-hydroxyethyl-[(z)-octadec-9-enyl]amino]ethanol Chemical compound CCCCCCCC\C=C/CCCCCCCCN(CCO)CCO BITAPBDLHJQAID-KTKRTIGZSA-N 0.000 description 1
- YZCWXIRNXBSTTB-UHFFFAOYSA-N 2-benzyl-4-phenylphenol Chemical group OC1=CC=C(C=2C=CC=CC=2)C=C1CC1=CC=CC=C1 YZCWXIRNXBSTTB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- QZEGWNPZFAKKEM-UHFFFAOYSA-N octadecyl cyanate Chemical compound CCCCCCCCCCCCCCCCCCOC#N QZEGWNPZFAKKEM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
- C10M149/18—Polyamides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/043—Mannich bases
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/044—Polyamides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/045—Polyureas; Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/042—Metal salts thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/043—Ammonium or amine salts thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/01—Emulsions, colloids, or micelles
Definitions
- the invention relates to the use of combinations of special polymeric thickeners and surfactants as thickener systems for highly water-containing functional liquids.
- functional fluids are understood to mean hydraulic fluids, metalworking fluids (cooling lubricants) and metal hardening media.
- functional liquids are referred to as "highly water-containing", the water content of which is either more than 90% by weight, if no low-molecular glycols are used, or more than 70% by weight, preferably more than 80% by weight. -%, for the case that in addition to the water as a diluent, larger proportions of low molecular weight glycols, such as ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol, are used.
- polymeric water-soluble urethane groups have polyether polyols and in DE-PS 3 302 465 and US Pat 4,288,639 with long-chain 1,2-epoxyalkanes modified polyether monoalcohols for the stated purpose. Combinations of these modified polyether monoalcohols with acidic phosphoric acid esters of nonionic polyether monoalcohol emulsifiers are known from US Pat. Nos.
- the invention therefore relates to the use of combinations of water-soluble polymeric polyether polyols in which at least 50% of the hydroxyl end groups are blocked by reaction with a monoisocyanate having a long-chain aliphatic hydrocarbon radical, and certain surfactants as thickener systems for highly water-containing functional liquids.
- the invention further relates to highly water-containing functional liquids containing, in addition to water, combinations of water-soluble polymeric polyether polyols in which at least 50% of the hydroxyl end groups are blocked by reaction with a monoisocyanate having a long-chain aliphatic hydrocarbon radical, and certain surfactants and, if appropriate, conventionally used in functional liquids Additives.
- the capped water-soluble polymeric polyether polyols used in the thickener systems according to the invention have the advantage that they are much easier to produce are than the water-soluble polymeric polyether polyols modified by long-chain 1,2-epoxyalkanes.
- the combinations of monoisocyanate-capped water-soluble polymeric polyether polyols and certain surfactants to be used according to the invention as thickener systems contain the surfactants in such an amount that 0.1 to 3 parts by weight, preferably 0.25, of 1 to 1 part by weight of capped polyether polyol up to 2.5 parts by weight of surfactant are eliminated.
- Non-ionic and anionic surfactants are used as special surfactants.
- Nonionic or anionic surfactants with a low tendency to foam are preferred. Both individual surfactants and mixtures of different surfactants can be used.
- anionic and nonionic surfactants which can be used in the combinations to be used according to the invention are e.g. in the review "Tenside”, by K. Kosswig in Ullmann's encyclopedia of techn. Chemistry, 4th ed., Volume 22, pages 468-494 and 498.
- the anionic surfactants are carboxylates, for example carboxymethylated oxethylates and derivatives of amino acids; Sulfonates, for example alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkanesulfonates, ⁇ -olefinsulfonates, ⁇ -sulfofatty acid esters, sulfosuccinic acid esters, alkoxy, acyloxy and acylaminoalkanesulfonates; as sulfates, for example alkyl sulfates and ether sulfates, phosphonates and phosphates.
- carboxylates for example carboxymethylated oxethylates and derivatives of amino acids
- Sulfonates for example alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkanesulfonates, ⁇ -olefinsulfonates, ⁇
- Alkanesulfonates with 8 to 30 are preferred Carbon atoms, sulfosuccinic acid esters of C 12 -C 18 fatty alcohols ethoxylated with 8 to 30 moles of ethylene oxide, of C 8 -C 20 alkyl phenols reacted with 8 to 70 moles of ethylene oxide, of C 12 -C 18 ethoxylated with 8 to 30 moles of ethylene oxide -Fatty acids or C 12 -C 18 fatty alcohols; C 12 -C 18 n-alkyl sulfates; Sulphates of 8 to 30 mol E t h y-oxide ethoxylated C 12 -C 18 fatty alcohols, C 12 -C 18 fatty acids and C 8 -C 20 alkylphenols.
- Suitable nonionic surfactants are oxethylates, terminally blocked oxyethylates and fatty acid esters of polyhydroxy compounds, and also block polymers of propylene oxide and ethylene oxide.
- non-ionic surfactants with 8 to 50 moles of ethylene oxide unreacted C 12 -C 18 -Fetteäuren, with 8 to 40 moles of ethylene oxide ethoxy- l i t he e C 12 - C18 fatty acid amides with 8 to 30 moles of ethylene oxide, ethoxylated C 12 - C 18 fatty alcohols, C 8 -C 20 -alkylphenols ethoxylated with 8 to 50 moles of ethylene oxide and with 8 to 60 moles of ethylene oxide ethoxylated, styrenated or benzylated phenols.
- Nonionic surfactants with an HLB value ⁇ 18 are preferably used.
- the monoisocyanate-capped water-soluble polymeric polyether polyols to be used in the combinations to be used according to the invention are reaction products of known polymeric water-soluble polyether polyols which have an average molecular weight of 5,000 to 70,000 (determined by determining the OH-Ehd groups; the number of the OH end groups becomes that average molecular weight calculated using the following formula: have, with a long-chain aliphatic hydrocarbon radical having monoisocyanate.
- Possible long-chain aliphatic hydrocarbon radicals are especially C 12 -C 30 alkyl radicals such as the dodecyl, hexadecyl, octadecyl and behenyl radical and C 12 -C 30 alkenyl radicals such as the oleyl radical.
- These long-chain aliphatic hydrocarbon radicals do not necessarily have to be bonded directly to the isocyanate group, but can also be bonded to the isocyanate group via other groups, for example aromatic rings and / or urethane groups.
- Such monoisocyanates in which the long-chain aliphatic hydrocarbon radicals are not directly bound to the isocyanate group are, for example, the addition products from 1 mol of a C 12 -C 30 -n-alkanol, for example lauryl, myristyl, cetyl, stearyl or behenyl alcohol or of oleyl alcohol to 1 mole of an aliphatic, cycloaliphatic, aromatic or heterocyclic diisocyanate.
- the amount of monoisocyanate is dimensioned such that at least 50%, preferably 70 to 100%, particularly preferably 85 to 100% of the hydroxyl end groups present in the water-soluble polymeric polyether polyols are capped.
- the capping of the OH end groups of the polymeric water-soluble polyether polyols with the monoisocyanates having a long-chain hydrocarbon radical is a reaction which is known in principle (see, for example, Ullmann's Enzyklopadie der techn. Chemie, 4th edition, volume 19, pages 309-310).
- the end of the reaction can be determined by IR spectroscopy on the basis of the disappearance of the absorption band typical of isocyanates at about 2,270 cm -1 .
- This addition reaction can be accelerated in a known manner by using known catalysts.
- the water-soluble polymeric, optionally urethane or ester group-containing polyether polyols of average molecular weight 5,000 to 70,000 on which the blocked water-soluble polyether polyols are based are known or can be obtained by processes known per se, for example by polymerizing ethylene oxide or copolymerizing ethylene oxide with other alkylene oxides in the presence of compounds, which have at least two active hydrogen atoms, and optionally modifying the water-soluble polymeric polyether polyols thus obtained by reaction with diisocyanates or dicarboxylic acids to form water-soluble polymeric polyether polyols containing urethane or ester groups or by polymerizing ethylene oxide or copolymerizing ethylene oxide and other alkylene oxides in the presence of compounds, which have two active hydrogen atoms and implementation the water-soluble polyether diols obtained with polyisocyanates, while maintaining a ratio of isocyanate groups / OH groups of at most 0.5: 1, to water-soluble polymeric polyether polyo
- the combinations of monoisocyanate-capped water-soluble polymeric polyether polyols and surfactants to be used according to the invention are produced by mixing both components together in a liquid state to form a homogeneous liquid. Since they are often solid at room temperature, the components are generally at the melting temperature, that is from 60 to 100 . C, warmed and stirred at this temperature until a homogeneous liquid has formed.
- surfactant mixtures it may be advantageous to first mix only one surfactant with the masked polyether polyol in the liquid state and then to stir the second or the remaining surfactants into the homogeneous melt.
- the combinations of capped water-soluble polymeric polyether polyols and surfactants obtained in this way are diluted by adding water to liquid concentrates, the water content of which is approximately 30 to 70% by weight, preferably 40 to 60% by weight, for better handling in the preparation of the functional liquids , based on the weight of the concentrate.
- the ready-to-use hydraulic fluids, metalworking fluids (cooling lubricants) and metal hardening media are produced from these concentrates by further dilution with water.
- the concentrates, or the functional liquids prepared from them by dilution can also contain additives commonly used in these functional liquids, such as lubricity improvers, metal deactivators, corrosion inhibitors, defoamers, substances for adjusting or buffering certain pH values, and anti-aging agents , Biocides, colorants, etc. in the amounts customary for these additives, as well as monomeric and / or oligomeric glycols.
- additives commonly used in these functional liquids such as lubricity improvers, metal deactivators, corrosion inhibitors, defoamers, substances for adjusting or buffering certain pH values, and anti-aging agents , Biocides, colorants, etc.
- the highly water-containing functional liquids which are thickened according to the invention preferably contain 3 to 7% by weight of the combination to be used according to the invention as a thickener system and optionally additionally 0.5 to 3, preferably 1 to 3% by weight. % of the above-mentioned additives usually used in functional liquids, and optionally up to 25% by weight, for example 0.5 to 20% by weight, of monomeric and / or oligomeric glycols.
- surfactants (I) used in the examples water-soluble polymeric polyether polyols (II) capped with monoisocyanates and the water-soluble polyether polyols (III) used to prepare these capped polyether polyols.
- the polyether chain contains 25% by weight propylene oxide and 75% by weight ethylene oxide units in a statistical distribution. Average molecular weight: 22,400.
- Liquid has formed. This is again diluted by adding water to a concentrate containing 50% by weight of water.
- the concentrates obtained according to a) or b) are diluted to 100 parts by weight of solution with stirring by adding further water.
- a mixture of 80% by weight of water, 10% by weight of diethylene glycol and 10% by weight of dipropylene glycol is diluted to 100 parts by weight of solution.
- the water content of which, depending on the amount of thickener system used, is from 91 to 95.5% by weight the viscosities at 40 and 50'C and the change in viscosity Influence of shear forces (according to DIN 51 382; modification: 300 cycles instead of 30 cycles) determined.
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Abstract
Die Erfindung betrifft die Verwendung von Kombinationen aus wasserlöslichen polymeren Polyetherpolyolen, in denen mindestens 50 % der Hydroxyl-Endgruppen durch Umsetzung mit einem einen langkettigen aliphatischen Kohlenwasserstoffrest aufweisenden Monoisocyanat verkappt sind, und bestimmten Tensiden als Verdicker-Systeme für hoch wasserhaltige funktionelle Flüssigkeiten und die verdickten hoch wasserhaltigen funktionellen Flüssigkeiten.The invention relates to the use of combinations of water-soluble polymeric polyether polyols in which at least 50% of the hydroxyl end groups are blocked by reaction with a monoisocyanate containing a long-chain aliphatic hydrocarbon radical, and certain surfactants as thickener systems for highly water-containing functional liquids and the thickened high functional liquids containing water.
Description
Die Erfindung betrifft die Verwendung von Kombinationen aus speziellen polymeren Verdickungsmitteln und Tensiden als Verdickersysteme für hoch wasserhaltige funktionelle Flüssigkeiten.The invention relates to the use of combinations of special polymeric thickeners and surfactants as thickener systems for highly water-containing functional liquids.
Unter funktionellen Flüssigkeiten werden im Rahmen der vorliegenden Erfindung Hydraulikflüssigkeiten, Metallbearbeitungsflüssigkeiten (Kühlschmiermittel) und Metallhärtungsmedien verstanden. Als "hoch wasserhaltig" werden im Rahmen der vorliegenden Erfindung solche funktionellen Flüssigkeiten bezeichnet, deren Wassergehalt entweder mehr als 90 Gew.-% beträgt, falls keine niedermolekularen Glykole mitverwendet werden, oder mehr als 70 Gew.-%, bevorzugt mehr als 80 Gew.-%, beträgt für den Fall, daß neben dem Wasser als Verdünnungsmittel größere Anteile an niedermolekularen Glykolen, wie Ethylenglykol, Diethylenglykol, Propylenglykol oder Dipropylenglykol eingesetzt werden.In the context of the present invention, functional fluids are understood to mean hydraulic fluids, metalworking fluids (cooling lubricants) and metal hardening media. In the context of the present invention, functional liquids are referred to as "highly water-containing", the water content of which is either more than 90% by weight, if no low-molecular glycols are used, or more than 70% by weight, preferably more than 80% by weight. -%, for the case that in addition to the water as a diluent, larger proportions of low molecular weight glycols, such as ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol, are used.
Seit etwa 25 Jahren ist man bemüht, die bislang als funktionelle Flüssigkeiten verwendeten brennbaren Mineralöle bzw. Mineralölprodukte durch nicht brennbare wäßrige Flüssigkeiten zu ersetzen. Diese Entwicklung hat inzwischen zu wäßrigen funktionellen Flüssigkeiten geführt, deren Wassergehalt bereits über 90 Gew.-% beträgt (sog. viscous high water-based fluids). Für die Herstellung dieser hoch wasserhaltigen funktionellen Flüssigkeiten wurden als Verdickungsmittel vor allem wasserlösliche polymere Polyether(poly)ole bzw. Kombinationen dieser polymeren Polyether(poly)ple mit weiteren Hilfsmitteln vorgeschlagen. So sind z.B. in der US-PS 4 481 367, in der EP-A 1-0 031 777 und der JA-A 1-41 300181 polymere wasserlösliche Urethangruppen aufweisende Polyetherpolyole und in der DE-PS 3 302 465 und der US-PS 4 288 639 mit langkettigen 1,2-Epoxyalkanen modifizierte Polyethermonoalkohole für den genannten Zweck beschrieben. Aus den US-PS 4 310 436 und 4 395 351 sind Kombinationen dieser modifizierten Polyethermonoalkohole mit sauren Phosphorsäureestern nichtionischer Polyethermonoalkohol-Emulgatoren bekannt und in der CA-PS 1 163 041 werden Kombinationen dieser modifizierten Polyethermonoalkohole mit speziellen Polyetherestern, sauren Phosphorsäureestern nichtionischer Polyethermonoalkohol-Emulgatoren und speziellen geschwefelten Metallverbindungen beschrieben.For about 25 years, efforts have been made to replace the flammable mineral oils or mineral oil products used as functional liquids with non-flammable aqueous ones To replace liquids. This development has meanwhile led to aqueous functional liquids, the water content of which is already over 90% by weight (so-called viscous high water-based fluids). For the preparation of these highly water-containing functional liquids, water-soluble polymeric polyether (poly) oils or combinations of these polymeric polyether (poly) p le with other auxiliaries have been proposed as thickeners. For example, in US Pat. No. 4,481,367, in EP-A 1-0 031 777 and in JA-A 1-41 300181, polymeric water-soluble urethane groups have polyether polyols and in DE-PS 3 302 465 and US Pat 4,288,639 with long-chain 1,2-epoxyalkanes modified polyether monoalcohols for the stated purpose. Combinations of these modified polyether monoalcohols with acidic phosphoric acid esters of nonionic polyether monoalcohol emulsifiers are known from US Pat. Nos. 4,310,436 and 4,395,351, and combinations of these modified polyether monoalcohols with special polyetheresters, acidic phosphoric acid esters of nonionic polyether monoalcohol and emulsifier are described in CA Patent PS 1 163 041 special sulfurized metal compounds.
Mit langkettigen 1,2-Epoxyalkanen modifizierte polymere wasserlösliche Polyetherpolyole und deren Verwendung als Verdickungsmittel für hoch wasserhaltige funktionelle Flüssigkeiten sind in der EP-A 1-61 822, der WO-A1-84/00361 und in den US-PS 4 354 956 und 4 411 819 beschrieben. Kombinationen dieser modifizierten wasserlöslichen polymeren Polyetherpolyole mit weiteren Hilfsmitteln sind aus zahlreichen Patentschriften bekannt. So sind z.B. Kombinationen dieser modifizierten Polyetherpolyole mit sauren Phosphorsäureestern nichtionischer Polyethermonoalkohol-Emulgatoren in der EP-B 1-63 854, mit ethoxylierten Sorbit-monostearaten in der EP-B 1-61 823, mit Neocarbonsäuren in der US-PS 4 390 439 oder längerkettigen Fettsäuren in der US-PS 4 390 440, mit nichtionischen Tensiden bestimmter Strukturklassen in der EP-A 2-122 528, mit speziellen Aminen und sauren Phosphorsäureestern nichtionischer Polyethermonoalkohol-Emulgatoren in der US-PS 4 312 775, mit speziellen Polyetherestern, definierten geschwefelten Metallverbindungen und Korrosionsinhibitoren in der US-PS 4 312 768 und mit Schmierfähigkeitsmodifikatoren, Dispergiermitteln und bestimmten Hochdruckadditiven in der US-PS 4 481 125 beschrieben.Polymeric water-soluble polyether polyols modified with long-chain 1,2-epoxyalkanes and their use as thickeners for highly water-containing functional liquids are described in EP-A 1-61 822, WO-A1-84 / 00361 and in US Pat. Nos. 4,354,956 and 4,411,819. Combinations of these modified water-soluble polymeric polyether polyols with other auxiliaries are known from numerous patents. For example, combinations of these modified polyether polyols with acidic phosphoric acid esters of nonionic polyether monoalcohol emulsifiers in EP-B 1-63 854, with ethoxylated sorbitol monostearates in EP-B 1-61 823, with neocarboxylic acids in US Pat. No. 4,390,439 or longer-chain fatty acids in US Pat 4,390,440, with nonionic surfactants of certain structural classes in EP-A 2-122,528, with special amines and acidic phosphoric acid esters in nonionic polyether monoalcohol emulsifiers in US Pat. No. 4,312,775, with special polyetheresters, defined sulfurized metal compounds and corrosion inhibitors in the US -PS 4,312,768 and described with lubricity modifiers, dispersants and certain high pressure additives in U.S. Patent 4,481,125.
Diese bekannten, als Verdickungsmittel bzw. Verdicker- systeme für hoch wasserhaltige funktionelle Flüssigkeiten verwendeten polymeren wasserlöslichen Polyetherpolyole und deren Kombinationen mit weiteren Hilfsstoffen haben jedoch den Nachteil, daß die mit ihnen verdickten funktionellen Flüssigkeiten nicht scherstabil sind, sondern daß sich deren Viskosität bei der Einwirkung von Scherkräften (z.B. Druck) verändert. Scherstabilität ist jedoch eine der wichtigsten Eigenschaften der funktionellen Flüssigkeiten. Insbesondere bei Hydraulikflüssigkeiten ist eine von Scherkräften unabhängige Viskosität unbedingt erforderlich.However, these known polymeric water-soluble polyether polyols used as thickeners or thickener systems for highly water-containing functional liquids and their combinations with other auxiliaries have the disadvantage that the functional liquids thickened with them are not shear stable, but that their viscosity changes when exposed to Shear forces (e.g. pressure) changed. However, shear stability is one of the most important properties of functional liquids. With hydraulic fluids in particular, a viscosity that is independent of shear forces is absolutely necessary.
Überraschenderweise wurde nun gefunden, daß man hervorragend scherstabile, hoch wasserhaltige funktionelle Flüssigkeiten erhält, wenn man als Verdickersystem Kombinationen aus wasserlöslichen polymeren Polyetherpolyolen, in denen mindestens 50 % der Hydroxyl-Endgruppen durch Umsetzung mit einem einen langkettigen aliphatischen Kohlenwasserstoffrest aufweisenden Monoisocyanat verkappt sind, und bestimmten Tensiden verwendet.Surprisingly, it has now been found that excellent shear-stable, highly water-containing functional liquids are obtained if, as a thickener system, combinations of water-soluble polymeric polyether polyols in which at least 50% of the hydroxyl end groups pass through Reaction with a monoisocyanate having a long-chain aliphatic hydrocarbon radical are blocked, and certain surfactants are used.
Die Erfindung betrifft daher die Verwendung von Kombinationen aus wasserlöslichen polymeren Polyetherpolyolen, in denen mindestens 50 % der Hydroxyl-Endgruppen durch Umsetzung mit einem einen langkettigen aliphatischen Kohlenwasserstoffrest aufweisenden Monoisocyanat verkappt sind, und bestimmten Tensiden als Verdicker-Systeme für hoch wasserhaltige funktionelle Flüssigkeiten.The invention therefore relates to the use of combinations of water-soluble polymeric polyether polyols in which at least 50% of the hydroxyl end groups are blocked by reaction with a monoisocyanate having a long-chain aliphatic hydrocarbon radical, and certain surfactants as thickener systems for highly water-containing functional liquids.
Die Erfindung betrifft ferner hoch wasserhaltige funktionelle Flüssigkeiten, enthaltend außer Wasser Kombinationen aus wasserlöslichen polymeren Polyetherpolyolen, in denen mindestens 50 % der Hydroxyl-Endgruppen durch Umsetzung mit einem einen langkettigen aliphatischen Kohlenwasserstoffrest aufweisenden Monoisocyanat verkappt sind, und bestimmten Tensiden und gegebenenfalls in funktionellen Flüssigkeiten üblicherweise verwendeten Zusätzen.The invention further relates to highly water-containing functional liquids containing, in addition to water, combinations of water-soluble polymeric polyether polyols in which at least 50% of the hydroxyl end groups are blocked by reaction with a monoisocyanate having a long-chain aliphatic hydrocarbon radical, and certain surfactants and, if appropriate, conventionally used in functional liquids Additives.
Mit Hilfe der erfindungsgemäß zu verwendenden Kombinationen werden hoch wasserhaltige funktionelle Flüssigkeiten erhalten, die sich nicht nur insgesamt durch eine ausgezeichnete Beständigkeit, sondern auch durch eine hervorragende Scherstabilität auszeichnen. Außerdem haben die in den erfindungsgemäßen Verdickersystemen verwendeten verkappten wasserlöslichen polymeren Polyetherpolyole den Vorteil, daß sie wesentlich einfacher herstellbar sind, als die durch langkettige 1,2-Epoxyalkane modifizierten wasserlöslichen polymeren Polyetherpolyole.With the aid of the combinations to be used according to the invention, highly water-containing functional liquids are obtained which are not only distinguished overall by excellent resistance but also by excellent shear stability. In addition, the capped water-soluble polymeric polyether polyols used in the thickener systems according to the invention have the advantage that they are much easier to produce are than the water-soluble polymeric polyether polyols modified by long-chain 1,2-epoxyalkanes.
In den erfindungsgemäß als Verdickersysteme zu verwendenden Kombinationen aus Monoisocyanat-verkappten wasserlöslichen polymeren Polyetherpolyolen und bestimmten Tensiden sind die Tenside in einer solchen Menge enthalten, daß auf 1 Gew.-Tl verkapptes Polyetherpolyol 0,1 bis 3 Gew.-Tle, vorzugsweise 0,25 bis 2,5 Gew.-Tle Tensid entfallen.The combinations of monoisocyanate-capped water-soluble polymeric polyether polyols and certain surfactants to be used according to the invention as thickener systems contain the surfactants in such an amount that 0.1 to 3 parts by weight, preferably 0.25, of 1 to 1 part by weight of capped polyether polyol up to 2.5 parts by weight of surfactant are eliminated.
Als spezielle Tenside werden nichtionische und anionische Tenside verwendet. Bevorzugt sind nichtionische oder anionische Tenside mit geringer Schaumneigung. Es können sowohl einzelne Tenside als auch Gemische verschiedener Tenside eingesetzt werden.Non-ionic and anionic surfactants are used as special surfactants. Nonionic or anionic surfactants with a low tendency to foam are preferred. Both individual surfactants and mixtures of different surfactants can be used.
Die in den erfindungsgemäß zu verwendenden Kombinationen anwendbaren anionischen und nichtionischen Tenside sind z.B. in der Ubersichtsarbeit "Tenside", von K. Kosswig in Ullmann's Enzyklopädie der techn. Chemie, 4. Aufl., Band 22, Seite 468-494 und 498 beschrieben.The anionic and nonionic surfactants which can be used in the combinations to be used according to the invention are e.g. in the review "Tenside", by K. Kosswig in Ullmann's encyclopedia of techn. Chemistry, 4th ed., Volume 22, pages 468-494 and 498.
Als anionische Tenside kommen Carboxylate, z.B. carboxymethylierte Oxethylate und Derivate von Aminosäuren; Sulfonate, z.B. Alkylbenzolsulfonate, Alkylnaphthalin sulfonate, Alkansulfonate, α-Olefinsulfonate, a-Sulfofettsäureester, Sulfobernsteinsäureester, Alkoxy-, Acyloxy- und Acylaminoalkansulfonate; als Sulfate, z.B. Alkylsulfate und Ethersulfate, Phosphonate und Phosphate in Betracht. Bevorzugt werden Alkansulfonate mit 8 bis 30 Kohlenstoffatomen, Sulfobernsteinsäureester von mit 8 bis 30 Mol Ethylenoxid ethoxylierten C12-C18-Fettalkoholen, von mit 8 bis 70 Mol Ethylenoxid umgesetzten C8-C20-Alkyl-phenolen, von mit 8 bis 30 Mol Ethylenoxid ethoxylierten C12-C18-Fettsäuren oder C12-C18- Fettalkoholen; C12-C18-n-Alkylsulfate; Sulfate von mit 8 bis 30 Mol Ethy-lenoxid ethoxylierten C12-C18-Fettalkoholen, C12-C18-Fettsäuren und C8-C20-Alkylphenolen.The anionic surfactants are carboxylates, for example carboxymethylated oxethylates and derivatives of amino acids; Sulfonates, for example alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkanesulfonates, α-olefinsulfonates, α-sulfofatty acid esters, sulfosuccinic acid esters, alkoxy, acyloxy and acylaminoalkanesulfonates; as sulfates, for example alkyl sulfates and ether sulfates, phosphonates and phosphates. Alkanesulfonates with 8 to 30 are preferred Carbon atoms, sulfosuccinic acid esters of C 12 -C 18 fatty alcohols ethoxylated with 8 to 30 moles of ethylene oxide, of C 8 -C 20 alkyl phenols reacted with 8 to 70 moles of ethylene oxide, of C 12 -C 18 ethoxylated with 8 to 30 moles of ethylene oxide -Fatty acids or C 12 -C 18 fatty alcohols; C 12 -C 18 n-alkyl sulfates; Sulphates of 8 to 30 mol E t h y-oxide ethoxylated C 12 -C 18 fatty alcohols, C 12 -C 18 fatty acids and C 8 -C 20 alkylphenols.
Als nichtionische Tenside kommen Oxethylate, endständig blockierte Oxethylate und Fettsäureester von Polyhydroxyverbindungen, ferner Blockpolymere des Propylenoxids und Ethylenoxids in Betracht. Bevorzugt werden als nichtionische Tenside mit 8 bis 50 Mol Ethylenoxid umgesetzte C12-C18-Fetteäuren, mit 8 bis 40 Mol Ethylenoxid ethoxy- lierte C12-C18-Fettsäureamide, mit 8 bis 30 Mol Ethylenoxid ethoxylierte C12-C18-Fettalkohole, mit 8 bis 50 Mol Ethylenoxid ethoxylierte C8-C20-Alkylphenole und mit 8 bis 60 Mol Ethylenoxid ethoxylierte, styrolisierte oder benzylierte Phenole verwendet. Bevorzugt werden nichtionische Tenside mit einem HLB-Wert < 18 verwendet.Suitable nonionic surfactants are oxethylates, terminally blocked oxyethylates and fatty acid esters of polyhydroxy compounds, and also block polymers of propylene oxide and ethylene oxide. Are preferred as non-ionic surfactants with 8 to 50 moles of ethylene oxide unreacted C 12 -C 18 -Fetteäuren, with 8 to 40 moles of ethylene oxide ethoxy- l i t he e C 12 - C18 fatty acid amides with 8 to 30 moles of ethylene oxide, ethoxylated C 12 - C 18 fatty alcohols, C 8 -C 20 -alkylphenols ethoxylated with 8 to 50 moles of ethylene oxide and with 8 to 60 moles of ethylene oxide ethoxylated, styrenated or benzylated phenols. Nonionic surfactants with an HLB value <18 are preferably used.
Die in den erfindungsgemäß zu verwendenden Kombinationen einzusetzenden Monoisocyanat-verkappten wasserlöslichen polymeren Polyetherpolyole sind Umsetzungsprodukte von an sich bekannten polymeren wasserlöslichen Polyetherpolyolen, die eine mittlere Molmasse von 5.000 bis 70.000 (ermittelt durch Bestimmung der OH-Ehdgruppen; aus der Zahl der OH-Endgruppen wird die mittlere Molmasse nach folgender Formel berechnet:
Als langkettige aliphatische Kohlenwasserstoffreste kommen vor allem C12-C30- Alkylreste wie der Dodecyl-, Hexadecyl-, Octadecyl- und der Behenyl-Rest und C12-C30-Alkenylreste wie der Oleylrest in Betracht. Diese langkettigen aliphatischen Kohlenwasserstoffreste müssen nicht unbedingt unmittelbar an die Isocyanatgruppe gebunden sein, sondern können auch über andere Gruppen, z.B. aromatische Ringe und/oder Urethangruppen an die Isocyanatgruppe gebunden sein. Solche Monoisocyanate, in denen die langkettigen aliphatischen Kohlenwasserstoffreste nicht unmittelbar an die Isocyanatgruppe gebunden sind, sind beispielsweise die Additionsprodukte aus 1 Mol eines C12-C30-n-Alkanols, z.B. Lauryl-, Myristyl-, Cetyl-, Stearyl- oder Behenylalkohols oder des Oleylalkohols an 1 Mol eines aliphatischen, cycloaliphatischen, aromatischen oder heterocyclischen Diisocyanates.Possible long-chain aliphatic hydrocarbon radicals are especially C 12 -C 30 alkyl radicals such as the dodecyl, hexadecyl, octadecyl and behenyl radical and C 12 -C 30 alkenyl radicals such as the oleyl radical. These long-chain aliphatic hydrocarbon radicals do not necessarily have to be bonded directly to the isocyanate group, but can also be bonded to the isocyanate group via other groups, for example aromatic rings and / or urethane groups. Such monoisocyanates in which the long-chain aliphatic hydrocarbon radicals are not directly bound to the isocyanate group are, for example, the addition products from 1 mol of a C 12 -C 30 -n-alkanol, for example lauryl, myristyl, cetyl, stearyl or behenyl alcohol or of oleyl alcohol to 1 mole of an aliphatic, cycloaliphatic, aromatic or heterocyclic diisocyanate.
Für die Herstellung der mit den Monoisocyanaten verkappten wasserlöslichen polymeren Polyetherpolyole wird die Menge an Monoisocyanat so bemessen, daB mindestens 50 %, vorzugsweise 70 bis 100 %, besonders bevorzugt 85 bis 100 % der im Wasser löslichen polymeren Polyetherpolyole vorliegenden Hydroxyl-Endgruppen verkappt sind.For the preparation of the water-soluble polymeric polyether polyols capped with the monoisocyanates, the amount of monoisocyanate is dimensioned such that at least 50%, preferably 70 to 100%, particularly preferably 85 to 100% of the hydroxyl end groups present in the water-soluble polymeric polyether polyols are capped.
Die Verkappung der OH-Endgruppen der polymeren wasserlöslichen Polyetherpolyole mit den einen langkettigen Kohlenwasserstoffrest aufweisenden Monoisocyanaten ist eine im Prinzip bekannte Reaktion (siehe z.B. Ullmann's Enzyklopädie der techn. Chemie, 4. Aufl., Band 19, Seiten 309-310). Das Ende der Umsetzung läßt sich IR-spektroskopisch an Hand des Verschwindens der für Isocyanate typischen Absorptionsbande bei etwa 2.270 cm-1 bestimmen. Diese Additionsreaktion läßt sich in bekannter Weise durch die Mitverwendung bekannter Katalysatoren beschleunigen.The capping of the OH end groups of the polymeric water-soluble polyether polyols with the monoisocyanates having a long-chain hydrocarbon radical is a reaction which is known in principle (see, for example, Ullmann's Enzyklopadie der techn. Chemie, 4th edition, volume 19, pages 309-310). The end of the reaction can be determined by IR spectroscopy on the basis of the disappearance of the absorption band typical of isocyanates at about 2,270 cm -1 . This addition reaction can be accelerated in a known manner by using known catalysts.
Die den verkappten wasserlöslichen Polyetherpolyolen zugrunde liegenden wasserlöslichen polymeren, gegebenenfalls Urethan- oder Estergruppen aufweisenden Polyetherpolyole der mittleren Molmasse 5.000 bis 70.000 sind bekannt oder nach an sich bekannten Verfahren erhältlich, z.B. durch Polymerisation von Ethylenoxid oder Copolymerisation von Ethylenoxid mit anderen Alkylenoxiden in Gegenwart von Verbindungen, die mindestens zwei aktive Wasserstoffatome aufweisen, und gegebenenfalls Modifizierung der so erhaltenen wasserlöslichen polymeren Polyetherpolyole durch Umsetzung mit Diisocyanaten oder Dicarbonsäuren zu wasserlöslichen, Urethan- bzw. Estergruppen aufweisenden polymeren Polyetherpolyolen oder durch Polymerisation von Ethylenoxid oder Copolymerisation von Ethylenoxid und anderen Alkylenoxiden in Gegenwart von Verbindungen, die zwei aktive Wasserstoffatome aufweisen und Umsetzung der erhaltenen wasserlöslichen Polyetherdiole mit Polyisocyanaten, unter Einhaltung eines Verhältnisses von Isocyanat-Gruppen/OH-Gruppen von höchstens 0,5:1, zu wasserlöslichen polymeren Urethangruppen aufweisenden Polyetherpolyolen.The water-soluble polymeric, optionally urethane or ester group-containing polyether polyols of average molecular weight 5,000 to 70,000 on which the blocked water-soluble polyether polyols are based are known or can be obtained by processes known per se, for example by polymerizing ethylene oxide or copolymerizing ethylene oxide with other alkylene oxides in the presence of compounds, which have at least two active hydrogen atoms, and optionally modifying the water-soluble polymeric polyether polyols thus obtained by reaction with diisocyanates or dicarboxylic acids to form water-soluble polymeric polyether polyols containing urethane or ester groups or by polymerizing ethylene oxide or copolymerizing ethylene oxide and other alkylene oxides in the presence of compounds, which have two active hydrogen atoms and implementation the water-soluble polyether diols obtained with polyisocyanates, while maintaining a ratio of isocyanate groups / OH groups of at most 0.5: 1, to water-soluble polymeric polyether polyols containing urethane groups.
Die erfindungsgemäß zu verwendenden Kombinationen aus Monoisocyanat-verkappten wasserlöslichen polymeren Polyetherpolyolen und Tensiden werden hergestellt, indem man beide Komponenten in flüssigem Zustand miteinander zu einer homogenen Flüssigkeit vermischt. Da sie bei Raumtemperatur vielfach fest sind, werden die Komponenten im allgemeinen auf Schmelztemperatur, das sind Temperaturen von 60 bis 100.C, erwärmt und bei dieser Temperatur so lange verrührt, bis eine homogene Flüssigkeit entstanden ist. Bei der Verwendung von Tensid-Gemischen kann es vorteilhaft sein, zunächst nur ein Tensid mit dem verkappten Polyetherpolyol in flüssigem Zustand zu vermischen und anschließend in die homogene Schmelze das zweite bzw. die restlichen Tenside einzurühren.The combinations of monoisocyanate-capped water-soluble polymeric polyether polyols and surfactants to be used according to the invention are produced by mixing both components together in a liquid state to form a homogeneous liquid. Since they are often solid at room temperature, the components are generally at the melting temperature, that is from 60 to 100 . C, warmed and stirred at this temperature until a homogeneous liquid has formed. When using surfactant mixtures, it may be advantageous to first mix only one surfactant with the masked polyether polyol in the liquid state and then to stir the second or the remaining surfactants into the homogeneous melt.
Die so erhaltenen Kombinationen aus verkappten wasserlöslichen polymeren Polyetherpolyolen und Tensiden werden zur besseren Handhabbarkeit bei der Herstellung der funktionellen Flüssigkeiten durch Zugabe von Wasser zu flüssigen Konzentraten verdünnt, deren Wassergehalt etwa 30 bis 70 Gew.-%, vorzugsweise 40 bis 60 Gew.-X beträgt, bezogen auf das Gewicht des Konzentrates.The combinations of capped water-soluble polymeric polyether polyols and surfactants obtained in this way are diluted by adding water to liquid concentrates, the water content of which is approximately 30 to 70% by weight, preferably 40 to 60% by weight, for better handling in the preparation of the functional liquids , based on the weight of the concentrate.
Aus diesen Konzentraten werden durch weiteres Verdünnen mit Wasser die gebrauchsfertigen Hydraulikfluide, Metallbearbeitungsflüssigkeiten (Kühlschmiermittel) und Metallhärtungsmedien hergestellt.The ready-to-use hydraulic fluids, metalworking fluids (cooling lubricants) and metal hardening media are produced from these concentrates by further dilution with water.
Die Konzentrate, bzw. die aus ihnen durch Verdünnen hergestellten funktionellen Flüssigkeiten können zusätzlich zum Wasser und dem Verdicker-System noch in diesen funktionellen Flüssigkeiten üblicherweise verwendete Zusätze wie Schmierfähigkeitsverbesserer, Metalldesaktivatoren, Korrosionsinhibitoren, Entschäumer, Stoffe zum Einstellen oder Abpuffern bestimmter pH-Werte, Alterungsschutzmittel, Biozide, Kennfarbstoffe usw. in den für diese Zusätze üblichen Mengen, sowie monomere und/oder oligomere Glykole enthalten.In addition to the water and the thickener system, the concentrates, or the functional liquids prepared from them by dilution, can also contain additives commonly used in these functional liquids, such as lubricity improvers, metal deactivators, corrosion inhibitors, defoamers, substances for adjusting or buffering certain pH values, and anti-aging agents , Biocides, colorants, etc. in the amounts customary for these additives, as well as monomeric and / or oligomeric glycols.
Die erfindungsgemäß verdickten, hoch wasserhaltigen funktionellen Flüssigkeiten enthalten vorzugsweise außer Wasser und gegebenenfalls monomeren und/oder oligomeren Glykolen 3 bis 7 Gew.-% der erfindungsgemäß als Verdickersystem zu verwendende Kombination und gegebenenfalls zusätzlich 0,5 bis 3, vorzugsweise 1 bis 3 Gew.-%, der vorstehend genannten in funktionellen Flüssigkeiten üblicherweise verwendeten Zusätze, sowie gegebenenfalls bis zu 25 Gew.-%, z.B. 0,5 bis 20 Gew.-% monomere und/oder oligomere Glykole.In addition to water and optionally monomeric and / or oligomeric glycols, the highly water-containing functional liquids which are thickened according to the invention preferably contain 3 to 7% by weight of the combination to be used according to the invention as a thickener system and optionally additionally 0.5 to 3, preferably 1 to 3% by weight. % of the above-mentioned additives usually used in functional liquids, and optionally up to 25% by weight, for example 0.5 to 20% by weight, of monomeric and / or oligomeric glycols.
Beschreibung der in den Beispielen verwendeten Tenside (I), mit Monoisocyanaten verkappten wasserlöslichen polymeren Polyetherpolyole (II) und der zur Herstellung dieser verkappten Polyetherpolyole verwendeten wasserlöslichen Polyetherpolyole (III).Description of the surfactants (I) used in the examples, water-soluble polymeric polyether polyols (II) capped with monoisocyanates and the water-soluble polyether polyols (III) used to prepare these capped polyether polyols.
- Tensid A: Mit 19 Mol Ethylenoxid ethoxylierter OleylalkoholSurfactant A: Oleyl alcohol ethoxylated with 19 moles of ethylene oxide
- Tensid B: Mit 50 Mol Ethylenoxid ethoxyliertes Bis-(l-phenylelhyl)-phenolSurfactant B: Bis- (l-phenyl-ethyl) -phenol ethoxylated with 50 moles of ethylene oxide
- Tensid C: Mit 14 Mol Ethylenoxid ethoxyliertes 3-Benzyl-4-hydroxybiphenylSurfactant C: 3-benzyl-4-hydroxybiphenyl ethoxylated with 14 moles of ethylene oxide
- Tensid D: Mit 12 Mol Ethylenoxid ethoxylierter OleylalkoholSurfactant D: Oleyl alcohol ethoxylated with 12 moles of ethylene oxide
- Tensid E: N,N-Bis-(2-hydroxyethyl)-oleylaminSurfactant E: N, N-bis (2-hydroxyethyl) oleylamine
- Tensid F: Trinatriumsalz des Phosphonosuccinatesters des mit 30 Mol Ethylenoxid ethoxylierten p-NonylphenolsSurfactant F: trisodium salt of the phosphonosuccinate ester of p-nonylphenol ethoxylated with 30 mol of ethylene oxide
- Tensid G: Dinatriumsalz des Sulfosuccinatesters des mit 30 Mol Ethylenoxid ethoxylierten p-NonylphenolsSurfactant G: disodium salt of the sulfosuccinate ester of p-nonylphenol ethoxylated with 30 moles of ethylene oxide
- Tensid H: Natriumsalz des C14-C18-n-AlkylsulfonatsSurfactant H: sodium salt of C 14 -C 18 n-alkyl sulfonate
- Tensid I: Natriumsalz eines Arylalkylsulfonats mit 50 % Mono- und 50 % DisulfonatanteilSurfactant I: sodium salt of an arylalkyl sulfonate with 50% mono- and 50% disulfonate
- Tensid J: Kokosfettsäure-diethanolamidSurfactant J: coconut fatty acid diethanolamide
- Tensid K: saures Phosphat, erhalten durch Umsetzung von 1 Mol Phosphorpentoxid mit 4 Mol Octadecanol-1 und 2 Mol Octadecyl-1-deca- ethoxylat, nachträglich neutralisiert mit DiethanolaminSurfactant K: acidic phosphate, obtained by reacting 1 mol of phosphorus pentoxide with 4 mol of octadecanol-1 and 2 mol of octadecyl-1-decaethoxylate, subsequently neutralized with diethanolamine
- Tensid L: Mit 50 Mol Ethylenoxid ethoxylierter Oleylalkohol.Surfactant L: oleyl alcohol ethoxylated with 50 moles of ethylene oxide.
- II. Monoisocyanat-verkappte wasserlösliche polymere PolyetherpolyoleII. Monoisocyanate-capped water-soluble polymeric polyether polyols
Verkapptes Polyetherpolyol 1:
- Eine Mischung aus 1346,4 g Polyetherpolyol A (0,06 Mol), 0,15 g 1,4-Diazabicyclo-2,2,2-octan (DABCO) und 500 g trockenem Dioxan wird unter Rühren auf RückfluBtemperatur erhitzt. Innerhalb einer Stunde wird 50,6 g Dodecylisocyanat (0,24 Mol) zugetropft. Anschließend wird das Reaktionsgemisch solange bei Rückflußtemperatur gerührt, bis im Infrarotspektrum einer Reaktionsgemischprobe keine Isocyanatbande mehr nachweisbar ist. Nach dem Abdestillieren des Dioxans bei etwa 130°C/15 hPa bleibt ein bei erhöhten Temperaturen viskoses, bei tiefen Temperaturen erstarrendes Reaktionsprodukt zurück.
- A mixture of 1346.4 g of polyether polyol A (0.06 mol), 0.15 g of 1,4-diazabicyclo-2,2,2-octane (DABCO) and 500 g of dry dioxane is heated to the reflux temperature with stirring. 50.6 g of dodecyl isocyanate (0.24 mol) are added dropwise within one hour. The reaction mixture is then stirred at the reflux temperature until no isocyanate band can be detected in the infrared spectrum of a reaction mixture sample. After the dioxane has been distilled off at about 130 ° C./15 hPa, a reaction product which is viscous at elevated temperatures and solidifies at low temperatures remains.
Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt : 100 %.Degree of capping of the hydroxyl end groups in the reaction product: 100%.
Verkapptes Polyetherpolyol 2:
- 1346,4 g Polyetherpolyol A (0,06 Mol) werden mit 64,1 g Hexadecylisocyanat (0,24 Mol) in der in Beispiel 1 beschriebenen Weise umgesetzt.
- 1346.4 g of polyether polyol A (0.06 mol) are reacted with 64.1 g of hexadecyl isocyanate (0.24 mol) in the manner described in Example 1.
Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt : 100 %.Degree of capping of the hydroxyl end groups in the reaction product: 100%.
Verkapptes Polyetherpolyol 3:
- 897,6 g Polyetherpolyol A (0,04 Mol) werden in 500 g trockenem Dioxan mit 87,7 g (0,16 Mol) eines Behenylalkohol-Isophorondiisocyanat (IPDI) (1:1)-Adduktes solange bei Rückflußtemperatur umgesetzt, bis die Isocyanatbande im IR-Spektrum verschwunden ist. Die Aufarbeitung des Reaktionsgemisches erfolgt, wie im Beispiel 1 beschrieben. Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt : 100 %.
- 897.6 g of polyether polyol A (0.04 mol) are reacted in 500 g of dry dioxane with 87.7 g (0.16 mol) of a behenyl alcohol isophorone diisocyanate (IPDI) (1: 1) adduct at the reflux temperature until the Isocyanate band in the IR spectrum has disappeared. The reaction mixture is worked up as described in Example 1. Degree of capping of the hydroxyl end groups in the reaction product: 100%.
Verkapptes Polyetherpolyol 4:
- 897,6 g Polyetherpolyol A (0,04 Mol) werden, wie in Beispiel 3 beschrieben, mit 45,8 g (0,155 Mol) Stearylisycyanat umgesetzt.
- 897.6 g of polyether polyol A (0.04 mol) are, as described in Example 3, reacted with 45.8 g (0.155 mol) of stearyl cyanate.
Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt : 97 %.Degree of capping of the hydroxyl end groups in the reaction product: 97%.
Verkapptes Polyetherpolyol 5:
- 1240 g Polyetherpolyol B (0,08 Mol), werden wie in Beispiel 3 beschrieben (unter Verwendung von 500 g getrocknetem Dioxan), mit 94,4 g (0,32 Mol) Stearylisocyanat umgesetzt. Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt : 100 %.
- 1240 g of polyether polyol B (0.08 mol) are reacted as described in Example 3 (using 500 g of dried dioxane) with 94.4 g (0.32 mol) of stearyl isocyanate. Degree of capping of the hydroxyl end groups in the reaction product: 100%.
Verkapptes Polyetherpolyol 6:
- 775 g Polyetherpolyol B (0,05 Mol) werden, wie in Beispiel 3 beschrieben (unter Verwendung von 500 g absolutem Dioxan), mit 29,5 g Stearylisocyanat (0,1 Mol) umgesetzt. Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt : 50 %.
- 775 g of polyether polyol B (0.05 mol) are, as described in Example 3 (using 500 g of absolute dioxane), reacted with 29.5 g of stearyl isocyanate (0.1 mol). Degree of capping of the hydroxyl end groups in the reaction product: 50%.
Verkapptes Polyetherpolyol 7:
- 775 g Polyetherpolyol B (0,05 Mol) werden unter den in Beispiel 3 beschriebenen Bedingungen mit 44,3 g Stearylisocyanat (0,15 Mol) umgesetzt.
- 775 g of polyether polyol B (0.05 mol) are reacted with 44.3 g of stearyl isocyanate (0.15 mol) under the conditions described in Example 3.
Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt : 75 %.Degree of capping of the hydroxyl end groups in the reaction product: 75%.
Verkapptes Polyetherpolyol 8:
- 1346,4 g Polyetherpolyol A (0,06 Mol) werden zunächst in 500 g wasserfreiem Dioxan in Gegenwart von 0,12 g DABCO mit 5,2 g 2,4-Toluylendiisocyanat (TDI) (0,03 Mol) durch einstündiges Rühren bei Rückflußtemperatur umgesetzt (mittlere Molmasse des so erhaltenen Urethangruppenhaltigen Polyetherpolyols : 45.000). Anschließend wird das Reaktionsgemisch ebenfalls bei Rückflußtemperatur innerhalb von 1 h mit 53,1 g Stearylisocyanat (0,18 Mol) versetzt und anschließend unter Rühren weiter erhitzt, bis die Isocyanatbande im IR- Spektrum verschwunden ist. Das Reaktionsgemisch wird, wie in Beispiel 3 beschrieben, aufgearbeitet.
- 1346.4 g of polyether polyol A (0.06 mol) are first added to 500 g of anhydrous dioxane in the presence of 0.12 g of DABCO with 5.2 g of 2,4-tolylene diisocyanate (TDI) (0.03 mol) by stirring for one hour Reflux temperature implemented (average molar mass of the polyether polyol thus obtained containing urethane groups: 45,000). 53.1 g of stearyl isocyanate (0.18 mol) are then added to the reaction mixture, also at the reflux temperature, and the mixture is then heated further with stirring until the isocyanate band has disappeared in the IR spectrum. The reaction mixture is worked up as described in Example 3.
Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt : 100 %.Degree of capping of the hydroxyl end groups in the reaction product: 100%.
Verkapptes Polyetherpolyol 9:
- 897,6 g Polyol A (0,04 Mol) werden unter den in Beispiel 3 beschriebenen Reaktionsbedingungen (unter Verwendung von 500 g wasserfreiem Dioxan) mit 4,5 g IPDI (0,02 Mol) und 33,6 g Stearylisocyanat (0,114 Mol) umgesetzt. (Mittlere Molmasse des dem verkappten Polyetherpolyol zugrunde liegenden Urethangruppen-haltigen Polyetherpolyols: 45.000).
- 897.6 g of polyol A (0.04 mol) are mixed under the reaction conditions described in Example 3 (using 500 g of anhydrous dioxane) with 4.5 g of IPDI (0.02 mol) and 33.6 g of stearyl isocyanate (0.114 mol ) implemented. (Average molar mass of the polyether polyol containing urethane groups on which the blocked polyether polyol is based: 45,000).
Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt : 95 %.Degree of capping of the hydroxyl end groups in the reaction product: 95%.
Verkapptes Polyetherpolyol 10:
- 1240 g Polyol B (0,08 Mol) werden unter den in Beispiel 3 beschriebenen Bedingungen (unter Verwendung von 500 g wasserfreiem Dioxan) mit 8,9 g IPDI (0,04 Mol) und 70,8 g Stearylisocyanat (0,24 Mol) umgesetzt. (Mittlere Molmasse des dem verkappten Polyetherpolyol zugrunde liegenden Urethangruppen-haltigen Polyetherpolyols: 31.200). Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt : 100 %.
- 1240 g of polyol B (0.08 mol) are mixed under the conditions described in Example 3 (using 500 g of anhydrous dioxane) with 8.9 g of IPDI (0.04 mol) and 70.8 g of stearyl isocyanate (0.24 mol ) implemented. (Average molar mass of the urethane group-containing polyether polyol on which the blocked polyether polyol is based: 31,200). Degree of capping of the hydroxyl end groups in the reaction product: 100%.
Verkapptes Polyetherpolyol 11:
- 1300 g Polyetherpolyol C (0,234 Mol) werden bei 90 bis 100°C aufgeschmolzen und mit 73 mg Eisenacetylacetonat, gelöst in 2 ml Toluol, versetzt. Die Mischung wird bei 125 bis 130°C gleichzeitig mit 54,5 g Stearylisocyanat (0,185 Mol) und 24,4 g eines Gemisches aus 65 Gew.-% 2,4-und 35 Gew.-% 2,6-Toluylendiisocyanat (0,14 Mol) tropfenweise versetzt. (Mittlere Molmasse des dem verkappten Polyetherpolyol zugrunde liegenden Urethangruppen-haltigen Polyetherpolyols: 14.000). Nach einer Reaktionszeit von 2 h ist die Umsetzung beendet.
- 1300 g of polyether polyol C (0.234 mol) are melted at 90 to 100 ° C. and 73 mg of iron acetylacetonate, dissolved in 2 ml of toluene, are added. The mixture is at 125 to 130 ° C simultaneously with 54.5 g of stearyl isocyanate (0.185 mol) and 24.4 g of a mixture of 65 wt .-% 2.4 and 35 wt .-% 2,6-tolylene diisocyanate (0 , 14 mol) added dropwise. (Average molecular weight of the urethane group-containing polyether polyol on which the blocked polyether polyol is based: 14,000). The reaction is complete after a reaction time of 2 h.
Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt : 100 %.Degree of capping of the hydroxyl end groups in the reaction product: 100%.
Verkapptes Polyetherpolyol 12 (nicht erfindungsgemäß, Vergleichsverbindung):
- Eine Mischung aus 1346,4 g Polyetherpolyol A (0,06 Mol) und 500 g wasserfreies Dioxan werden unter Rühren auf Rückflußtemperatur (etwa 110°C) in Gegenwart von 0,15 g DABCO erhitzt. Dann tropft man innerhalb 1 h 30,0 g Cyclohexylisocyanat (0,24 Mol) zu und rührt die Reaktionsmischung solange bei Rückflußtemperatur bis im Infrarotspektrum einer Probe keine Isocyanatbande mehr nachweisbar ist. Die Reaktionsmischung wird, wie in Beispiel 1 beschrieben, aufgearbeitet.
- A mixture of 1346.4 g of polyether polyol A (0.06 mol) and 500 g of anhydrous dioxane are heated with stirring to the reflux temperature (about 110 ° C.) in the presence of 0.15 g of DABCO. 30.0 g of cyclohexyl isocyanate (0.24 mol) are then added dropwise in the course of 1 h, and the reaction mixture is stirred at the reflux temperature until no isocyanate band can be detected in the infrared spectrum of a sample. The reaction mixture is worked up as described in Example 1.
Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt 100 %.Degree of capping of the hydroxyl end groups in the reaction product 100%.
Verkapptes Polyetherpolyol 13 (nicht erfindungsgemäß, Vergleichspolyetherpolyol):
- 1346,4 g Polyetherpolyol A (0,06 Mol) werden mit 36,2 g Norborn-2-yl-methylisocyanat (0,24 Mol) unter den Polyetherpolyol 12 beschriebenen Reaktionsbedingungen umgesetzt.
- 1346.4 g of polyether polyol A (0.06 mol) are reacted with 36.2 g of norborn-2-yl-methyl isocyanate (0.24 mol) under the reaction conditions described in polyether polyol 12.
Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt : 100 %.Degree of capping of the hydroxyl end groups in the reaction product: 100%.
Umsetzungsprodukt von Pentaerythrit, Ethylenoxid und Propylenoxid. Die Polyetherkette enthält 25 Gew.-% Propylenoxid- und 75 Gew.-% Ethylenoxid-Einheiten in statistischer Verteilung. Mittlere Molmasse: 22.400.Reaction product of pentaerythritol, ethylene oxide and propylene oxide. The polyether chain contains 25% by weight propylene oxide and 75% by weight ethylene oxide units in a statistical distribution. Average molecular weight: 22,400.
Polyetherpolyol B:
- Umsetzungsprodukt von Pentaerythrit, Ethylenoxid und Propylenoxid. Die Polyetherketten enthalten 25 Gew.-% Propylenoxid- und 75 Gew.-% Ethylenoxid-Einheiten in statistischer Verteilung. Mittlere Molmasse: 15.500.
- Reaction product of pentaerythritol, ethylene oxide and propylene oxide. The polyether chains contain 25% by weight of propylene oxide and 75% by weight of ethylene oxide units in a statistical distribution. Average molecular weight: 15,500.
Polyetherpolyol C:
- Polyethylenglykol mit einer mittleren Molmasse von 5555.
- Polyethylene glycol with an average molecular weight of 5555.
Herstellung der erfindungsgemäB als Verdickersystem zu verwendenden Kombinationen aus Monoisocyanat verkapptem wasserlöslichem polymerem Polyetherpolyol und Tensid:
- a) Bei Verwendung eines Tensides: Die in der nachstehenden Tabelle angegebenen Gew.-Teile an verkapptem Polyetherpolyol und Tensid werden durch Erwärmen auf etwa 90°C verflüssigt und zu einer homogenen Flüssigkeit verrührt. Diese wird anschließend durch Zugabe von Wasser auf ein 50 Gew.-% Wasser enthaltendes Konzentrat verdünnt.
- b) Bei Verwendung von zwei oder mehr Tensiden: In diesem Fall wird die in der Tabelle angegebenen Menge an verkapptem Polyetherpolyol zunächst nur mit einem der zu verwendenden Tenside in der für dieses Tensid in der Tabelle angegebenen Menge durch Erwärmen auf etwa 90°C verflüssigt und zu einer homogenen Flüssigkeit verrührt. In diese wird anschließend ebenfalls noch bei erhöhter Temperatur das andere bzw. die anderen Tenside in der für dieses bzw. diese Tenside in der Tabelle angegebenen Menge eingerührt, bis ebenfalls wieder eine homogene
- a) When using a surfactant: The parts by weight of capped polyether polyol and surfactant given in the table below are liquefied by heating to about 90 ° C. and stirred to give a homogeneous liquid. This is then diluted by adding water to a concentrate containing 50% by weight of water.
- b) When using two or more surfactants: In this case, the amount of capped polyether polyol specified in the table is first liquefied by heating to about 90 ° C. with only one of the surfactants to be used in the amount specified for this surfactant in the table and stirred into a homogeneous liquid. The other or the other surfactants in the amount specified for this or these surfactants in the table is then also stirred into this at an elevated temperature until a homogeneous mixture is again obtained
Flüssigkeit entstanden ist. Auch diese wird wieder durch Zugabe von Wasser auf ein 50 Gew.-X Wasser enthaltendes Konzentrat verdünnt.Liquid has formed. This is again diluted by adding water to a concentrate containing 50% by weight of water.
Die nach a) oder b) erhaltenen Konzentrate werden unter Rühren durch Zugabe von weiterem Wasser auf 100 Gewichtsteile Lösung verdünnt. In einem besonders gekennzeichneten Fall wird mit einem Gemisch aus 80 Gew.-% Wasser, 10 Gew.-% Diethylenglykol und 10 Gew.-% Dipropylenglykol auf 100 Gewichtsteile Lösung verdünnt. Von den so erhaltenen verdickten wäßrigen Lösungen (funktionellen Flüssigkeiten), deren Wassergehalt in Abhängigkeit von der verwendeten Menge an Verdicker-System 91 bis 95,5 Gew.-% beträgt, werden die Viskositäten bei 40 und 50'C und die Änderung der Viskosität bei Einwirkung von Scherkräften (gemäß DIN 51 382; Abänderung: 300 Cyclen anstelle von 30 Cyclen) bestimmt. Die erhaltenen Werte und das aus den Viskositäten bei 40 und 50°C errechnete Viskositätsverhältnis sind in der nachfolgenden Tabelle zusammengestellt. Außerdem ist in der Tabelle in der Spalte "Verdickungsfaktor durch Tensid-Zusatz" der Faktor angegeben, um den die Viskosität des erfindungsgemäß verdickten Wassers höher ist als die Viskosität des nur mit dem verkappten Polyetherpolyol verdickten Wassers (aus diesem Verdickungsfaktor geht die synergistische Wirkung des Tensids in den erfindungsgemäßen Kombinationen hervor).
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3531915 | 1985-09-07 | ||
| DE19853531915 DE3531915A1 (en) | 1985-09-07 | 1985-09-07 | THICKENING SYSTEMS FOR HIGH-WATER-FUNCTIONAL LIQUIDS AND THE HIGH-WATER-FUNCTIONAL LIQUIDS CONTAINING THESE THICKENING SYSTEMS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0214542A2 true EP0214542A2 (en) | 1987-03-18 |
| EP0214542A3 EP0214542A3 (en) | 1989-05-10 |
| EP0214542B1 EP0214542B1 (en) | 1990-10-31 |
Family
ID=6280325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86111729A Expired - Lifetime EP0214542B1 (en) | 1985-09-07 | 1986-08-25 | Thickener systems for functional fluids containing a large amount of water, and such functional fluids containing these thickener systems |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4770804A (en) |
| EP (1) | EP0214542B1 (en) |
| JP (1) | JPS6259696A (en) |
| BR (1) | BR8604275A (en) |
| CA (1) | CA1288413C (en) |
| DE (2) | DE3531915A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0459282A2 (en) * | 1990-06-01 | 1991-12-04 | Bayer Ag | Improved functional fluids |
| EP0462408A2 (en) * | 1990-06-01 | 1991-12-27 | Bayer Ag | Functional aqueous liquids based on novel polyoxyalkylene polymers |
| EP2062905A3 (en) * | 2007-11-23 | 2009-12-16 | Clariant Finance (BVI) Limited | Mixture of compounds containing phosphor, method for production of same and use of same as flame-retardant material |
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| DE3905939A1 (en) * | 1989-02-25 | 1990-08-30 | Huels Chemische Werke Ag | TENSIDE COMBINATION |
| GB9003192D0 (en) * | 1990-02-13 | 1990-04-11 | Du Pont | Improvements in or relating to polymeric compounds |
| US5141662A (en) * | 1990-02-15 | 1992-08-25 | Dexheimer Edward M | Heat transfer fluids comprising oxyalkylenated polyols |
| JPH0776695A (en) * | 1993-09-07 | 1995-03-20 | Sanyo Chem Ind Ltd | Water/glycol-based hydraulic liquid |
| JP3581450B2 (en) * | 1995-09-01 | 2004-10-27 | 旭電化工業株式会社 | Emulsion paint composition |
| WO1997021743A1 (en) * | 1995-12-08 | 1997-06-19 | Henkel Corporation | Polymeric thickeners for aqueous compositions |
| US6107394A (en) * | 1995-12-08 | 2000-08-22 | Henkel Corporation | Polymeric thickeners for aqueous compositions |
| JP2000094951A (en) * | 1998-09-02 | 2000-04-04 | Webasto Thermosyst Internatl Gmbh | Ice storing element having condensed ice storing medium |
| GB0027216D0 (en) * | 2000-11-08 | 2000-12-27 | Avecia Ltd | Polyether/polyurethane association thickeners |
| JP5089179B2 (en) * | 2007-01-19 | 2012-12-05 | Ｊｘ日鉱日石エネルギー株式会社 | Cutting / grinding method with ultra-trace oil supply |
| JP6892100B2 (en) * | 2016-12-27 | 2021-06-18 | 出光興産株式会社 | Water-based quenching liquid composition and method for producing metal materials using it |
| JP6355033B1 (en) * | 2017-08-22 | 2018-07-11 | 大同化学工業株式会社 | Water-soluble heat treatment composition |
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| US4091030A (en) * | 1974-01-31 | 1978-05-23 | Air Products And Chemicals, Inc. | Protected graft copolymers of cyclic nitrogenous and ester monomers |
| EP0031777A1 (en) * | 1979-12-26 | 1981-07-08 | Union Carbide Corporation | High viscosity polyoxyalkylene glycol block copolymers and method of making the same |
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| US3813341A (en) * | 1970-03-09 | 1974-05-28 | Buemah Oil Trading Ltd | Derivatives of glycols,glycol ethers and glycol esters |
| US4257902A (en) * | 1976-08-04 | 1981-03-24 | Singer & Hersch Industrial Development (Pty.) Ltd. | Water-based industrial fluids |
| US4180491A (en) * | 1976-12-01 | 1979-12-25 | Rohm And Haas Company | Nonionic polyurethane thickener with surfactant cothickener and organic diluent, clear concentrates, aqueous print pastes, coloring compositions, methods of making and printing |
| JPS5641300A (en) * | 1979-09-12 | 1981-04-17 | Asahi Denka Kogyo Kk | Aqueous hydraulic fluid |
| US4312775A (en) * | 1979-10-22 | 1982-01-26 | Basf Wyandotte Corporation | Polyether thickeners for aqueous systems containing additives for increased thickening efficiency |
| US4411819A (en) * | 1979-10-22 | 1983-10-25 | Basf Wyandotte Corporation | Thickening aqueous compositions with polyethers modified with alpha-olefin oxides |
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| US4428860A (en) * | 1979-10-22 | 1984-01-31 | Basf Wyandotte Corporation | Polyether thickeners for aqueous systems containing additives for increased thickening efficiency |
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| US4310436A (en) * | 1979-10-22 | 1982-01-12 | Basf Wyandotte | Polyether-based thickeners with additives for increased efficiency in aqueous systems |
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- 1985-09-07 DE DE19853531915 patent/DE3531915A1/en not_active Withdrawn
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- 1986-08-25 EP EP86111729A patent/EP0214542B1/en not_active Expired - Lifetime
- 1986-08-25 US US06/900,064 patent/US4770804A/en not_active Expired - Fee Related
- 1986-08-25 DE DE8686111729T patent/DE3675302D1/en not_active Expired - Lifetime
- 1986-09-01 JP JP61203894A patent/JPS6259696A/en active Pending
- 1986-09-05 CA CA000517526A patent/CA1288413C/en not_active Expired - Lifetime
- 1986-09-05 BR BR8604275A patent/BR8604275A/en unknown
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| US4091030A (en) * | 1974-01-31 | 1978-05-23 | Air Products And Chemicals, Inc. | Protected graft copolymers of cyclic nitrogenous and ester monomers |
| EP0031777A1 (en) * | 1979-12-26 | 1981-07-08 | Union Carbide Corporation | High viscosity polyoxyalkylene glycol block copolymers and method of making the same |
| US4481125A (en) * | 1982-05-03 | 1984-11-06 | E.F. Houghton & Co. | Water-based hydraulic fluid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0459282A2 (en) * | 1990-06-01 | 1991-12-04 | Bayer Ag | Improved functional fluids |
| EP0462408A2 (en) * | 1990-06-01 | 1991-12-27 | Bayer Ag | Functional aqueous liquids based on novel polyoxyalkylene polymers |
| EP0459282A3 (en) * | 1990-06-01 | 1992-02-26 | Bayer Ag | Improved functional fluids |
| EP0462408A3 (en) * | 1990-06-01 | 1992-03-11 | Bayer Ag | Functional aqueous liquids based on novel polyoxyalkylene polymers |
| EP2062905A3 (en) * | 2007-11-23 | 2009-12-16 | Clariant Finance (BVI) Limited | Mixture of compounds containing phosphor, method for production of same and use of same as flame-retardant material |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0214542B1 (en) | 1990-10-31 |
| BR8604275A (en) | 1987-05-05 |
| DE3531915A1 (en) | 1987-03-19 |
| CA1288413C (en) | 1991-09-03 |
| US4770804A (en) | 1988-09-13 |
| DE3675302D1 (en) | 1990-12-06 |
| JPS6259696A (en) | 1987-03-16 |
| EP0214542A3 (en) | 1989-05-10 |
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