EP1404726A2 - Low-molecular and high-molecular emulsifiers, particularly based on polyisobutylene, and mixtures thereof - Google Patents
Low-molecular and high-molecular emulsifiers, particularly based on polyisobutylene, and mixtures thereofInfo
- Publication number
- EP1404726A2 EP1404726A2 EP02750949A EP02750949A EP1404726A2 EP 1404726 A2 EP1404726 A2 EP 1404726A2 EP 02750949 A EP02750949 A EP 02750949A EP 02750949 A EP02750949 A EP 02750949A EP 1404726 A2 EP1404726 A2 EP 1404726A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- general formula
- compound
- group
- compounds
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 41
- 229920002367 Polyisobutene Polymers 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 111
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 12
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 12
- 125000001424 substituent group Chemical group 0.000 claims abstract description 12
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 12
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims abstract description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 5
- 239000000839 emulsion Substances 0.000 claims description 56
- 239000000446 fuel Substances 0.000 claims description 35
- -1 oligoalcohols Polymers 0.000 claims description 24
- 239000003921 oil Substances 0.000 claims description 23
- 239000000654 additive Substances 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000012141 concentrate Substances 0.000 claims description 15
- 239000000314 lubricant Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 229920000768 polyamine Polymers 0.000 claims description 14
- 239000002816 fuel additive Substances 0.000 claims description 13
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 12
- 238000005260 corrosion Methods 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 10
- 230000002401 inhibitory effect Effects 0.000 claims description 9
- 239000003879 lubricant additive Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 239000002283 diesel fuel Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 235000000346 sugar Nutrition 0.000 claims description 5
- ZLYYJUJDFKGVKB-UPHRSURJSA-N (z)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C/C(Cl)=O ZLYYJUJDFKGVKB-UPHRSURJSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 239000004435 Oxo alcohol Substances 0.000 claims description 4
- 239000003139 biocide Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000002537 cosmetic Substances 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- 229940015043 glyoxal Drugs 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- ZLYYJUJDFKGVKB-OWOJBTEDSA-N (e)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C\C(Cl)=O ZLYYJUJDFKGVKB-OWOJBTEDSA-N 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000001720 carbohydrates Chemical class 0.000 claims description 3
- 235000014633 carbohydrates Nutrition 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 150000008163 sugars Chemical class 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001593 sorbitan monooleate Substances 0.000 claims description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 2
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 235000012907 honey Nutrition 0.000 claims 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid group Chemical group C(CCC(=O)O)(=O)O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 16
- 229920002266 Pluriol® Polymers 0.000 description 13
- 229920001223 polyethylene glycol Polymers 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000002199 base oil Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- 239000002202 Polyethylene glycol Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 150000003443 succinic acid derivatives Chemical group 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 235000011044 succinic acid Nutrition 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- 239000001384 succinic acid Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 229920002368 Glissopal ® Polymers 0.000 description 5
- 229920001983 poloxamer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical group ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 229940014800 succinic anhydride Drugs 0.000 description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- 238000006418 Brown reaction Methods 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- 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 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 3
- 229960001231 choline Drugs 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229960002920 sorbitol Drugs 0.000 description 3
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 2
- NKRVGWFEFKCZAP-UHFFFAOYSA-N 2-ethylhexyl nitrate Chemical compound CCCCC(CC)CO[N+]([O-])=O NKRVGWFEFKCZAP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007962 solid dispersion Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- RIJVOTKRVIPNIZ-UHFFFAOYSA-N 1-[4-(2-aminoethyl)piperazin-1-yl]propan-2-ol Chemical compound CC(O)CN1CCN(CCN)CC1 RIJVOTKRVIPNIZ-UHFFFAOYSA-N 0.000 description 1
- HIZLKTYBQGWVMQ-UHFFFAOYSA-N 1-amino-2-methylbut-3-en-2-ol Chemical compound NCC(O)(C)C=C HIZLKTYBQGWVMQ-UHFFFAOYSA-N 0.000 description 1
- ICVIFRMLTBUBGF-UHFFFAOYSA-N 2,2,6,6-tetrakis(hydroxymethyl)cyclohexan-1-ol Chemical compound OCC1(CO)CCCC(CO)(CO)C1O ICVIFRMLTBUBGF-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GKVINAFHJXHVDS-UHFFFAOYSA-N 2-[1-(3-aminopropyl)piperidin-4-yl]ethanol Chemical compound NCCCN1CCC(CCO)CC1 GKVINAFHJXHVDS-UHFFFAOYSA-N 0.000 description 1
- WVMWULRIHKUMRY-UHFFFAOYSA-N 2-[2-(2-aminoethylamino)ethoxy]ethanol Chemical compound NCCNCCOCCO WVMWULRIHKUMRY-UHFFFAOYSA-N 0.000 description 1
- CYOIAXUAIXVWMU-UHFFFAOYSA-N 2-[2-aminoethyl(2-hydroxyethyl)amino]ethanol Chemical compound NCCN(CCO)CCO CYOIAXUAIXVWMU-UHFFFAOYSA-N 0.000 description 1
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 1
- IOAOAKDONABGPZ-UHFFFAOYSA-N 2-amino-2-ethylpropane-1,3-diol Chemical compound CCC(N)(CO)CO IOAOAKDONABGPZ-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 1
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- ANHQLUBMNSSPBV-UHFFFAOYSA-N 4h-pyrido[3,2-b][1,4]oxazin-3-one Chemical group C1=CN=C2NC(=O)COC2=C1 ANHQLUBMNSSPBV-UHFFFAOYSA-N 0.000 description 1
- LQGKDMHENBFVRC-UHFFFAOYSA-N 5-aminopentan-1-ol Chemical compound NCCCCCO LQGKDMHENBFVRC-UHFFFAOYSA-N 0.000 description 1
- LREQLEBVOXIEOM-UHFFFAOYSA-N 6-amino-2-methyl-2-heptanol Chemical compound CC(N)CCCC(C)(C)O LREQLEBVOXIEOM-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 108010053481 Antifreeze Proteins Proteins 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 description 1
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N Putrescine Natural products NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
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Classifications
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- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
- C08F110/10—Isobutene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- C09K23/16—Amines or polyamines
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- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
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- C10L1/00—Liquid carbonaceous fuels
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- C10L1/14—Organic compounds
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- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
- C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
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- C10L1/00—Liquid carbonaceous fuels
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
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Definitions
- Low and high molecular weight emulsifiers especially those based on polyisobutylene, and their mixtures
- the present invention relates to low and high molecular weight compounds, in particular based on polyisobutylene, and mixtures thereof, which are suitable as emulsifiers for water-in-oil emulsions, processes for the preparation of such compounds and the emulsions themselves.
- the invention also relates to the use of such compounds as additives for fuels and lubricants, and as a corrosion-inhibiting additive in water-containing liquids, and also fuels, lubricants, fuel and lubricant additive concentrates and water-containing liquids containing the compounds according to the invention.
- US Pat. No. 4,225,447 describes water-in-oil emulsions which are used as lubricants and a succinic anhydride substituted with an alkylenyl group (such as a polyisobutylenyl group), preferably with a number average molecular weight M n of 300 to 3000 g / mol Contain (earth) alkali metal salt of a succinic acid substituted with an alkenyl group or a succinic acid amide substituted with an alkenyl group as an emulsifier, optionally in combination with the salt of a resin acid.
- an alkylenyl group such as a polyisobutylenyl group
- EP-A 0 156 572 describes the use of surface-active substances based on succinic acid derivatives substituted with polyisobutylenyl groups, preferably with a cell-average molecular weight M n of 400 to 5000, with an anionic group for the preparation of water-in-oil or oil -in water emulsions.
- Suitable anionic groups are phosphate, phosphonate, sulfate, sulfonate and carboxymethyl groups.
- the applicant's German application filed on January 25, 2000 with the file number 100 03 105.6 describes the use of alkoxylated polyisobutylenes as emulsifiers in water-in-fuel emulsions.
- R is a polyisobutylene with a weight average molecular weight of 300 to 2300, preferably 500 to 2000.
- A is an alkylene radical with 2 to 8 carbon atoms.
- the number m is a number from 1 to 200, which is chosen so that the alkoxylated polyisobutylene contains 0.2 to 1.5 alkylene oxide units per C 4 unit, preferably 0.5 alkylene oxide units per C unit; n is either 0 or 1.
- R 1 is derived, inter alia, from a poly-1-butylene, -2-butylene or -to-butylene or mixtures thereof, and R 2 can be a polyalkylenepolyarnine or a polyalkylenimine radical.
- WO 00/15740 discloses water-in-fuel emulsions which contain, as emulsifiers, two succinic acid derivatives which are linked via a linker such as alkanolamine, polyamine or polyol and which are substituted by hydrocarbon radicals such as polyisobutylenyl groups, in one embodiment the one succinic acid derivative being a polyisobutylenyl group with 8 to 25 carbon atoms and the other succinic acid derivative contains a polyisobutylenyl group with 50 to 400 carbon atoms.
- a linker such as alkanolamine, polyamine or polyol and which are substituted by hydrocarbon radicals such as polyisobutylenyl groups
- drilling fluids which contain both graft or block copolymers of polycarboxylic acids and polyethylene glycol and also compounds which consist of a succinic anhydride substituted with a polyisobutylenyl group, preferably with a number average molecular weight M n of 400 to 5000, and polyols, Polyamines, hydroxycarboxylic acids or amino alcohols are produced.
- No. 4,708,753 discloses water-in-fuel emulsions which contain, inter alia, mono- or disalts of succinic acid with amines or amine salts of succinic acid monoesters as emulsifiers. These salts are formed by reacting alkanolamines, polyamines, oligoalcohols or polyols with succinic anhydrides which are substituted with C 2 o-C5 ⁇ ö hydrocarbon radicals such as polyisobutylenyl groups. In The examples only describe the salts of succinic acids or their monoesters which carry a polyisobutylenyl group with a number average molecular weight of 950 or 1700.
- Friction-reducing additives for fuels and lubricants as well as emulsifiers are already known from the prior art.
- US Pat. No. 5,858,029 describes friction-reducing additives for fuels and lubricants, in particular compounds of the formula R 1 (-OR -) a NH (CO) -R 3 -OH being used as friction-reducing additives, wherein R 1 is for a C] - bis C ⁇ so- alkyl radical, R is a C to C 4 alkylene radical, a is an integer from 1 to 12 and R is Ci to C alkylene or substituted alkylene or cycloalkylene.
- Succinimides substituted with polyisobutylenyl groups may also be present as dispersants and polyalkylene amines such as polyisobutylene amines may be present as surfactants.
- the object of the present invention is to provide further compounds which can be used as emulsifiers in water-in-oil emulsions.
- L a stands for a polyisobutylenyl group with a number average molecular weight M n of 300 to 1000
- L b represents a polyisobutylenyl group with a number average molecular weight M n of 2,000 to 20,000
- -A- stands for -O- -N (H) - or -N (R ') -
- M + stands for H 1 " , an alkali metal ion, 0.5 alkaline earth metal ions or NH, where one or more H in NH + can be replaced by alkyl radicals,
- R represents a linear or branched saturated hydrocarbon radical which bears at least one substituent selected from the group OH, NH 2 or NH 3 + and optionally one or more C (O) H groups and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, and wherein in the NH 2 - or NH 3 + groups one or more H may be replaced by alkyl radicals, and R 1 represents a linear or branched saturated hydrocarbon radical, which optionally has one or carries several substituents selected from the group OH, NH 2 , NH 3 + or C (O) H and optionally contains one or more non-adjacent -O- and / or secondary amines and / or tertiary amines, and wherein in the NH 2 - or NH 3 + groups one or more H may be replaced by alkyl radicals, and
- the proportion of A-R in the compound of the general formula (Ia) or (Ib) is at least 20% by weight.
- the compounds according to the invention can be used both individually and in a mixture as emulsifiers in water-in-oil emulsions. More stable emulsions can be produced than when using conventional emulsifiers.
- the compounds of the general formula (Ib) can be regarded as diblock emulsifiers linked via a linker, the lipophilic block L a or L b via a covalent CC bond and the hydrophilic block R or R 1 via an ester or amide bond is linked to the left succinic acid.
- Preferred compounds of the general formula (Ia) are those in which
- - L a stands for a polyisobutylenyl group with a number average molecular weight M n from 350 to 950, in particular from 350 to 650, and / or
- L a stands for a polyisobutylenyl group which has a polydispersity ⁇ 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2.0, and / or
- A-R in the compound of general formula (Ia) is at least 25% by weight, in particular 35 to 60% by weight, and / or
- R is composed of [-CH 2 -CH 2 -X] -, [-CH (CH 3 ) -CH 2 -X] - and / or [-CH 2 -CH (CH 3 ) -X] units, with X - O or NH.
- Preferred compounds of the general formula (Ib) are those in which
- L stands for a polyisobutylenyl group with a number average molecular weight from 2000 to 12000, in particular from 2300 to 5000, and / or
- L b stands for a polyisobutylenyl group which has a polydispersity 3,0 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2.0, and / or
- Particularly preferred are compounds of the general formula (Ia) or (Ib) in which A -O- and R is a monovalent radical of an oligomer or polymer of ethylene and / or propylene oxide or a monovalent radical of a block copolymer of ethylene and propylene oxide ,
- Particularly effective emulsifiers are compounds of the general formula (Ia) in which L a stands for a polyisobutylenyl group with a number average molecular weight M n of 350 to 950, in particular 350 to 650, this polyisobutylenyl group optionally having a polydispersity 3,0 3.0 from 1.1 to 2.5, particularly preferably from 1.1 to 2.0.
- L a is a polyisobutylenyl group with a number average molecular weight M n of 300 to 1000 and L b is a polyisobutylenyl group with a number average molecular weight M n of 2000 to 20,000,
- -A- stands for -O- -N (H) - or -N (R ! ) -
- M * stands for Ff 1 " , an alkali metal ion, 0.5 alkaline earth metal ions or NELt 4" , it being possible for one or more H in NHt + to be replaced by alkyl radicals,
- R represents a linear or branched saturated hydrocarbon radical which bears at least one substituent selected from the group OH, NH 2 or NH 3 + and optionally one or more C (O) H groups and optionally one or more non-adjacent -O- and / or contains secondary amines and or tertiary amines, and wherein one or more H in the NH 2 - or NH 3 + groups can be replaced by alkyl radicals, and
- R 1 stands for a linear or branched saturated hydrocarbon radical which optionally carries one or more substituents selected from the group OH, NH 2 , NH 3 + or C (O) H and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, and wherein one or more H in the NH 2 - or NH 3 + groups can be replaced by alkyl radicals, and
- the proportion of A - R in the compound of the general formula (Ia) is at least 10% by weight and in the compound of the general formula (Ib) at least 20
- Effective emulsifier mixtures are obtained not only when using compounds of the general formula (Ia) with hydrophilic parts of at least 20% by weight, but also when using compounds of the general formula (Ia) with hydrophilic parts of at least 10% by weight.
- n is from 350 to 950, in particular from 350 to 650, and / or the proportion of AR in the connection of the general formula (Ia) is at least 15% by weight, preferably at least 20% by weight, particularly preferably at least 25% by weight, very particularly preferably 35 to 60% by weight.
- L b is a polyisobutylenyl group with a number average molecular weight M n of 2000 to 12000, in particular from 2300 to 5000, and or the proportion of AR in the compound of the general formula (Ib) is at least 25% by weight, in particular 35 to 60% by weight.
- the present invention also relates to processes for the preparation of the compounds of the general formula (Ia) or (Ib).
- polyisobutylene with fumaric acid dichloride, fumaric acid, maleic acid dichloride, maleic anhydride or maleic acid preferably with maleic anhydride or maleic acid dichloride, particularly preferably with maleic anhydride
- the reaction is carried out by the processes known to the person skilled in the art and, for example, analogously to the processes for the reaction of polyisobutylenes with maleic anhydride described in German Offenlegungsschriften DE-A 195 19 042, DE-A 43 19 671 and DE-A 43 19 672.
- the number average molecular weight M n of the resulting succinic anhydride derivative, which is substituted by a polyisobutylenyl group can be characterized by the saponification number [mg KOH / g substance].
- R is a linear or branched saturated hydrocarbon radical which has at least one substituent selected from the group OH, NH 2 or NH 3 + and optionally one or more C (O) H groups and optionally contains one or more non-adjacent -O- and / or secondary amines and / or tertiary amines, and wherein in the NH 2 - or NH + groups one or more H may be replaced by alkyl radicals, and
- R 1 stands for a linear or branched saturated hydrocarbon radical which optionally carries one or more substituents selected from the group OH, NH 2 , NH 3 + or C (O) H and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, and one or more H in the NH - or NH + groups can be replaced by alkyl radicals.
- alkyl radicals that can replace the H atoms are - - alkyl radicals.
- Suitable polar reactants ROH and RR ⁇ H are alkanolamines, polyamines, oligoalcohols, polyols, oligoalkylene glycols, polyalkylene glycols as well as carbohydrates and sugar.
- Polar reactants can also be ethylene oxide and / or propylene oxide. The reaction with polyethylene glycol, polypropylene glycol, their (block) copolymers, ethylene oxide or propylene oxide is preferred.
- reaction with alkanolamines such as di- / triethanolamine, tris (hydroxymethyl) aminomethane and their salts, oligoalcohols such as sorbitol and pentaerythritol or carbohydrates and sugars is also preferred.
- alkanolamines such as di- / triethanolamine, tris (hydroxymethyl) aminomethane and their salts, oligoalcohols such as sorbitol and pentaerythritol or carbohydrates and sugars is also preferred.
- the reaction with tris (hydroxymethyl) aminomethane, choline, sugars and polyethylene glycol is particularly preferred for the preparation of compounds of the general formula (Ia).
- the amount of polar reactant is chosen so that the proportion of the hydrophilic radical AR in the compound of general formula (Ia) or (Ib) is at least 20 % By weight, preferably 25% by weight, particularly preferably 35 to 60% by weight.
- Compounds of the general formula (Ia) in which the hydrophilic content is 10 to 20% by weight can also be prepared by the processes described.
- the conversion ratio of the substituted succinic acid derivatives (Ha), (üb) or (IIc) to the alkanolamines, polyamines, oligoalcohols, polyols, oligoalkylene glycols or polyalkylene glycols is generally 1: (0.75 to 2), preferably 1: (0.8 to 1.2), particularly preferably 1: 1.
- the amount of ethylene and / or propylene oxide is selected in accordance with the desired chain length of the hydrophilic radical AR.
- succinic acid semiesters or half amides are obtained.
- alkanolamines the hydroxyl and / or amino groups react, so that mixtures of succinic acid and succinic acid halamides are generally obtained.
- maleic or fumaric acid dichloride is used as the starting material, the C (O) Cl group still present after the reaction steps mentioned is hydrolyzed to the CO 2 H group.
- the free CO 2 H group present in the succinic acid semiesters and half amides can then be reacted with NH 3 , amines, alkali metal or alkaline earth metal salts to give the corresponding A 1, alkali metal or alkaline earth metal salts.
- salts are compounds of the general formula (Ia) or (Ib) in which M * "is an alkali metal ion, 0.5 alkaline earth metal ion or NEU, where one or more H in NELi * can be replaced by alkyl radicals
- Suitable amines for salt formation are primary, secondary and tertiary amines which carry linear C 1 -C 4 or branched C 3 -C 6 alkyl groups.These alkyl groups can also be substituted by one or more hydroxyl groups.
- suitable alkyl amines are Diethylamine, diisopropylamine, trimethylamine, mono-, di- and triethanolamine and tris (hydroxymethyl) aminomethane.
- polyisobutylenes with a number average molecular weight M n of 300 to 1000, preferably from 350 to 950, particularly preferably from 350 to 650, are used to prepare the compounds of the general formula (Ia).
- polyisobutylenes with a number average molecular weight M n of 2,000 to 20,000, preferably from 2,000 to 12,000, particularly preferably from 2,300 to 5,000, are generally used.
- polyisobutylenes with a number-average molecular weight M n in the ranges mentioned preference is given to those which have a high content of vinylidene groups.
- Polyisobutylenes which have a number-average molecular weight M n in the abovementioned ranges, a high content of vinylidene groups and a uniform polymer skeleton structure are particularly preferably used.
- polyisobutylenes with a number-average molecular weight M n in the ranges mentioned, a high content of vinylidene groups and a uniform structure, which have a polydispersity pers 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2.0.
- Polydispersity means the quotient M w / M n from the weight-average molecular weight M w and the number-average molecular weight M n .
- Polyisobutylenes with a number average molecular weight M n in the ranges mentioned, which are essentially composed of isobutylene units and have a high content of vinylidene groups, are available, for example, from BASF AG under the trade name Glissopal®, such as Glissopal® 1000 with an M n of 1000 , Glissopal® V 33 with an M n of 550 and Glissopal® 2300 with an M n of 2300.
- Glissopal® such as Glissopal® 1000 with an M n of 1000
- Glissopal® V 33 with an M n of 550 and Glissopal® 2300 with an M n of 2300.
- suitable alkanolamines, polyamines, oligoalcohols, polyols and polyalkylene glycols which can be used for the preparation of the compounds according to the invention are described in WO 00/15740.
- alkanolamines are monoethanolamine, diethanolamine, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl- 1,3-propanediol, N- (2-hydroxypropyl) -N '- (2-aminoethyl) piperazine, tris (hydroxymethyl) amino-methane, 2-amino-1-butanol, ß- (2-hydroxyethoxy) ethylamine, glucamine , Glucosamine, 4-amino-3-hydroxy-3-methyl-1-butene, N- (3-aminopropyl) -4- (2-hydroxyethyl) piperidine, 2-amino-6-methyl-6-heptanol, 5- Amino-1-pentanol, N- (2-hydroxyethyl) -l, 3-diaminopropane
- the salts of the alkanolamines mentioned can also be used.
- one or more of the H atoms bound to N atoms can optionally be replaced by linear d-C ⁇ -alkyl or branched C 3 -C 6 -alkyl groups.
- Choline may be mentioned as an example.
- polyalkylene polyamines such as polymethylene polyamines, polyethylene polyamines, polypropylene polyamines, polybutylene polyamines and polypentylene polyamines; see also “Ethylene Amines” in Kirk Othmer's “Encyclopedia of Chemical Technology", 2nd Edition, Volume 7, pp. 22-37, Interscience Publishers, New York 1965.
- oligoalcohols and polyols examples include 1,2-butanediol, 2,3-dimethyl-2,3-butanediol, 2,3-hexanediol, 1,2-cyclohexanediol, (mono-, di-) - pentaerythritol, 1.7 - and 2,4- heptanediol, 1,2,3-, 1,2,4-, 1,2,5- and 2,3, 4-hexanetriol, 1,2,3- and 1,2,4- Butanetriol, 2,2,6,6-tetrakis (hydroxymethyl) cyclohexanol, 1,10-decanediol, 2-hydroxymethyl-2-methyl-1,3-propanediol, 2-hydroxymethyl-2-ethyl-1,3-propanediol, Sorbitol, mannitol and inositol.
- C 5 and C 6 sugars such as glucose and fructose are also
- Examples of (oligo) alkylene glycols are (tri, tetra, penta-, hexa-) ethylene glycol, (tri-, tetra-, penta-, hexa-) propylene glycol and (tri-, tetra-, penta-, hexa-) butylene glycol.
- Examples of polyalkylene glycols are polytetrahydrofuran, polyethylene glycol and polypropylene glycol.
- Preferred polyalkylene glycols are polyethylene glycol and polypropylene glycol.
- Polyethylene glycol and polypropylene glycol and their block copolymers are particularly preferred which have a number average molecular weight M n of 300 to 5000, preferably 300 to 2000, particularly preferably 500 to 1500.
- Such polyethylene glycols are available, for example, under the trade name Pluriol® E from BASF AG, such as Pluriol® E 300 with an M n of 300, Pluriol® E 600 with an M "of 600, Pluriol® E 4000 with an M" of 4000 and Pluriol® E 5000 with an M n of 5000.
- Polyethylene-polypropylene glycol block copolymers are available, for example, from BASF AG under the trade name Pluronic® PE, such as Pluronic® PE 3500 with an M n of 1900 and an ethylene oxide content of 50% by weight.
- the compounds according to the invention and or the mixtures according to the invention are used in oil-in-water emulsions, stable vesicles can be produced. This can be done, for example, by the action of ultrasound.
- the compounds of the invention and / or the mixtures of the invention can also be used in a variety of ways, e.g. B. as additives in fuels and lubricants, as a corrosion-inhibiting additive in water-containing liquids and as dispersants for inorganic and organic solid dispersions.
- the compounds according to the invention and / or the mixtures according to the invention can also be used as surfactants for washing and cleaning formulations.
- the high-molecular compounds of the general formula (Ib) which contain a monovalent residue of a polyethylene glycol as a hydrophilic block are particularly suitable for stabilizing inorganic and organic solid dispersions.
- the compounds according to the invention and / or mixtures according to the invention are also suitable as emulsifiers for water-in-oil emulsions in which the oil phase is formed from a vegetable, animal or synthetic oil or fat.
- emulsifiers for water-in-oil emulsions in which the oil phase is formed from a vegetable, animal or synthetic oil or fat.
- oils or fats are triglycerides and glycol esters of lauric acid, myristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid and linolenic acid.
- the compounds and / or mixtures according to the invention are particularly advantageously used as emulsifiers for water-in-oil emulsions, in which the oil phase is formed by a fuel, light or heavy heating oil.
- a fuel light or heavy heating oil.
- All common types of fuel can be used, for example diesel fuel, petrol and kerosene. Diesel fuel is preferably used.
- Water-in-oil emulsions according to the invention generally contain 95 up to 60% by weight of oil, 3 to 35% by weight of water and 0.2 to 10% by weight of at least one compound according to the invention and / or a mixture according to the invention.
- Water-in-fuel emulsions according to the invention can also contain one or more C 4 alcohols and / or monoethylene glycol, in particular monoethylene glycol.
- the amount of C 1 -C 4 alcohol and / or monoethylene glycol used is from 5 to 50% by weight, based on the amount of water.
- the temperature range in which the emulsion is stable can be broadened.
- the water-in-fuel emulsions according to the invention have high stability and good combustion efficiency. Good exhaust gas values can still be obtained, the emission of soot and NO x being significantly reduced, particularly in the case of diesel engines. A largely complete and residue-free combustion can be achieved without deposits on the assemblies of the combustion apparatus, for example injection nozzles, pistons, annular grooves, valves and cylinder head.
- the water-in-fuel emulsions according to the present invention can have further components in addition to the components mentioned above. These are, for example, other emulsifiers such as sodium lauryl sulfate, quaternary ammonium salts such as
- Sorbitan monooleate, C 13 oxo alcohol ethoxylates and alkylphenol ethoxylates, for example octyl and nonylphenol ethoxylates, are preferably used as further emulsifiers.
- a combination of one or more of the above-mentioned further emulsifiers together with the compounds according to the invention and / or mixtures thereof is preferably used for the water-in-fuel emulsions according to the invention.
- these further emulsifiers are used, this is done in amounts of 0.5 to 5% by weight, preferably 1 to 2.5% by weight, based on the overall composition.
- the amount of this further emulsifier is chosen so that the total amount of emulsifier does not exceed the amount of 0.2 to 10% by weight given for the compounds according to the invention and their mixtures alone.
- the compounds and / or mixtures according to the invention are mixed with the oil, the water and the further, optionally usable components and emulsified in a manner known per se.
- the emulsification can be carried out in a rotor mixer, by means of a mixing nozzle or by an ultrasound probe. Particularly good results were achieved when a mixing nozzle of the type used as disclosed in German application, file number: 198 56 604 by the applicant on December 8, 1998 was used.
- Water-in-oil emulsions for the cosmetics sector can be produced as well as water-in-fuel emulsions.
- the compounds and / or mixtures according to the invention also have a lubricity-improving and corrosion-inhibiting effect. They also improve the wear protection behavior of liquids.
- the compounds and / or mixtures according to the invention are therefore used as additives for lubricants, fuels and water-containing liquids such as coolant liquids or drilling and cutting liquids. This use is also the subject of the present invention.
- the compounds and / or mixtures according to the invention can be added directly to the fuels and lubricants — together with other components.
- the compounds according to the invention and or mixtures according to the invention can first be mixed with other components to give fuel or lubricant additive concentrates.
- These fuel or lubricant additive concentrates according to the invention can be added to the fuels or lubricants undiluted or diluted with one or more solvents or carrier oils. The addition in dilute form is preferred.
- the fuels, lubricants, fuel additive and lubricant additive concentrates, and also water-containing liquids which contain the compounds and / or mixtures according to the invention are likewise the subject of the present invention and are to be explained in more detail below.
- Fuels according to the invention generally contain - in addition to conventional components - at least one compound according to the invention and / or a mixture according to the invention in an amount of 10 to 5000 ppm, preferably in an amount of 20 to 2000 ppm, based on the total amount.
- Lubricants according to the invention generally contain between 90 and 99.9% by weight, preferably between 95 and 99.5% by weight, of a liquid, semi-solid or solid lubricant and between 0.1 and 10% by weight, preferably between 0 , 5 and 5 wt .-% of at least one compound according to the invention and / or a mixture according to the invention, based on the total amount.
- Fuel additive and lubricant additive concentrates according to the invention contain - in addition to conventional components - at least one compound according to the invention and / or a mixture according to the invention in proportions of 0.1 to 80% by weight, in particular 0.5 to 60% by weight, based on the total weight of the concentrate.
- Typical components for fuels or fuel additive concentrates are, for example, additives with detergent action, as described in the applicant's German application, file number 100 36 956.1, dated July 28, 2000 (page 14 ff.), In the applicant's German application, file number 100 03 105.6, dated 25.1.2000 and in the PCT application of the applicant with the file number PCT / EP / 01/00496.
- the additives mentioned there and other fuel additives described there with polar Generations are part of the present application and are incorporated by reference.
- the fuels and fuel additive concentrates according to the invention can also contain fuel additives as described, for example, in European patent applications EP-A 0 277 345, 0 356 725, 0 476 485, 0 484 736, 0 539 821, 0 543 225, 0 548 617, 0 561 214, 0 567 810, 0 568 873, German patent applications DE-A 39 42 860, 43 09 074, 43 09 271, 43 13 088, 44 12 489, 44 25 834, 195 25 938, 196 06 845, 196 06 846, 196 15 404, 196 06 844, 196 16 569, 196 18 270, 196 14 349, and WO-A 96/03479.
- biocides such as glutardialdehyde or glyoxal.
- the biocides are usually used in an amount of 0.01 to 3% by weight, based on the total weight of the concentrate.
- further corrosion-inhibiting additives are those based on ammonium salts of organic carboxylic acids, which tend to form films, or on heterocyclic aromatics in the case of non-ferrous metal corrosion protection.
- stabilizers are those based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or on phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid.
- organometallic compounds examples include ferrocene or methylcyclopentadienylmanganese tricarbonyl.
- cetane number improvers are organic C -C 10 nitrates such as 2-ethylhexyl nitrate, and inorganic cetane number improvers for the aqueous phase such as ammonium nitrate. 2-Ethylhexyl nitrate and ammonium nitrate are preferably used.
- the cetane number improvers are usually used in an amount of 0.05 to 5% by weight, based on the total weight of the concentrate.
- Solvents for the fuel and lubricant additive concentrates according to the invention are aliphatic and aromatic hydrocarbons such as solvent naphtha, isododecane, mihagol (a technical mixture of the fuels and lubricants themselves as well as carrier oils.
- Carrier oils which also serve to dilute the fuel and lubricant additive concentrates, are, for example, mineral carrier oils (base oils), in particular those of the viscosity class "Solvent Neutral (SN) 100 to 500", as well as synthetic carrier oils based on polyolefins, (poly) esters, ( Alkylphenol-started) polyethers, (aliphatic) (alkylphenol-started) polyetheramines, and carrier oils based on alkoxylated long-chain alcohols or phenols.
- base oils mineral carrier oils
- base oils in particular those of the viscosity class "Solvent Neutral (SN) 100 to 500”
- synthetic carrier oils based on polyolefins polyolefins
- poly poly esters
- Alkylphenol-started polyethers Alkylphenol-started polyethers
- aliphatic alkylphenol-started polyetheramines
- carrier oils based on alkoxylated long-chain alcohols or phenols.
- Polyethylene oxides, polypropylene oxides, polybutene oxides and mixtures thereof are also suitable carrier oils. Further suitable carrier oils and carrier oil mixtures are described, for example, in the publications DE-A 38 38 918, DE-A 38 26 608, DE-A 41 42241, DE-A 43 09074, US 4,877,416 and EP-A 0452 328.
- Water-containing liquids according to the invention contain the compounds and / or mixtures according to the invention, if appropriate in combination with other customary corrosion-inhibiting additives, generally in a proportion of about 1 to 10% by weight, based on the total amount.
- composition of the compounds produced can be found in Table 1.
- Glissopal® from BASF AG with a number average molecular weight M n of 380 to 8400 and a proportion of vinylidene end groups of> 70 was used as polyisobutylene
- Pluriol® E from BASF AG with a number average molecular weight M n of 300 to 5000 was used as the polyethylene glycol.
- Pluronic® PE 3500 from BASF AG with a number-average molecular weight M n of 1900 and an ethylene oxide content of 50% by weight was used as the polyethylene / polypropylene-glycol block copolymer.
- Heptane Mihagol, a mixture of C 10 -C 12 paraffins from Wintershall, and Solvesso® 150, a mixture of aromatic hydrocarbons from ExxonMobil Chemical, were used as solvents.
- Clariant commercially available under the name Ambossol®, was used as the ion exchanger.
- the compounds obtained were characterized via the acid number, the OH number, the viscosity and / or the IR spectra.
- the OH number was determined using solvent when using high-boiling solvents, i. H. that the OH number of the compounds in the respective solvent was measured and then extrapolated to the pure substance.
- high-boiling solvents i. H. that the OH number of the compounds in the respective solvent was measured and then extrapolated to the pure substance.
- low-boiling solvents such as heptane
- the solvent was removed by distillation and the OH number was determined from the pure substance.
- Table 1 Composition of the compounds of the general formula (Ia) or (Ib)
- An 11 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 250 g PIBSA 550 and heated to 90 ° C. 67 g of diethanolamine are metered in via a dropping funnel within 5 minutes. The mixture is gradually heated to 130 ° C or 170 ° C. After 2 hours at 170 ° C, the brown reaction product is filtered at 100 ° C.
- An 11 four-necked flask with stirrer, distillation bridge and thermocouple is filled with 310 g PIBSA 750 and 60 g D-sorbitol.
- the mixture is gradually heated to 160 ° C or 220 ° C. Released water is removed using a stream of nitrogen; after 3 hours at 220 ° C, diluted with 200 g of Mihagol and filtered hot. A yellow, viscous product solution (65%) is obtained.
- a 21 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 350 g Pluriol® E 300 and degassed at 90 ° C for 30 minutes in a vacuum.
- a solution of 650 g of PIBSA 380 in 350 g of heptane is metered into a dropping funnel at 80 ° C. in the course of 5 minutes. The mixture is gradually heated to 110 ° C or 140 ° C. Heptane is distilled off under reduced pressure (350 mbar).
- a 21 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 300 g Pluriol® E 300 and degassed at 90 ° C for 30 minutes in a vacuum.
- a solution of 750 g of PIBSA 550 in 450 g of heptane is metered into a dropping funnel at 80 ° C. within 5 minutes. The mixture is gradually heated to 110 ° C or 140 ° C. Heptane is distilled off under reduced pressure (350 mbar). After 3 hours at 140 ° C, 105 g of diethanolamine are added in portions at 95 ° C. After a further 20 minutes at 95 ° C, the orange-brown product is filtered hot. OH number: 55; IR: intense band at 1736 cm "1 (ester).
- a 21 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 400 g Pluriol® E 600 and degassed in a vacuum at 90 ° C for 30 minutes.
- a solution of 790 g of PIBSA 1000 in 450 g of heptane is metered in at 80 ° C. in the course of 5 minutes.
- the mixture is gradually heated to 110 ° C or 140 ° C.
- Heptane is distilled off under reduced pressure (350 mbar). After 3 hours at 140 ° C., a yellow product with a viscosity of 1650 mm 2 / s (100 ° C.) is obtained.
- An 11 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 150 g Pluriol® E 4000 and degassed in a vacuum at 90 ° C for 30 minutes.
- a solution of 250 g PIBSA 5200 in 300 g Mihagol is dosed within 5 minutes at 80 ° C using a dropping funnel.
- the mixture is gradually heated to 110 ° C or 140 ° C. After 3 hours at 140 ° C, a beige wax is obtained.
- the product is isolated as a cream-colored wax (60% in Mihagol); IR: 1737 cm “1 .
- the product is isolated as an orange-yellow, highly viscous liquid. Viscosity: 2100 mm / s; 100 ° C.
- An 11 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 75 g of a 45% methanolic solution of choline from Fluka and 150 g of Mihagol. Methanol is then removed at 50 ° C and reduced pressure (50 mbar) (45 minutes). 200 g of PIBSA 550 are added to this suspension and the mixture is heated to 90 ° C. in the course of 15 minutes. After 60 minutes, the temperature is raised to 170 ° C. and the mixture is stirred for a further two hours. The brown reaction product is filtered at 100 ° C.
- An 11 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 300 g PIBSA 2300, 200 g PIBSA 1000 and 200 g Mihagol and heated to 95 ° C. 17.2 g of ethylene glycol are metered in at 95.degree. The mixture is heated to 130 ° C. and stirred at this temperature for three hours. The brown reaction product is filtered at 100 ° C.
- the emulsifier of comparative example 2 was produced according to the principle of WO 00/15740 according to example C-1, p. 34.
- a 21 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 100 g Pluriol® E 200 and degassed in a vacuum at 90 ° C for 30 minutes.
- a solution of 590 g of PIBSA 1000 in 450 g of heptane is metered into a dropping funnel at 80 ° C. within 5 minutes.
- the mixture is gradually heated to 110 ° C or 140 ° C.
- Heptane is distilled off under reduced pressure (350 mbar). After 3 hours at 140 ° C., an amber-colored product with a viscosity of 1450 mm 2 / s (100 ° C.) is obtained.
- the hydrophilic or water-soluble components were previously dissolved in the aqueous phase, lipophilic components in the diesel oil.
- an Ultra-Turrax® (Jahnke and Kunkel laboratory device T25) 500 g of this mixture were homogenized with 100 ml water for 15 minutes at a speed of 24000 / min.
- the emulsion was produced on an industrial scale and the motor tests were carried out analogously to DE-A 198 56 604 by the applicant (registered on December 8, 1998), with a mixing nozzle described there.
- the pressure in the mixing apparatus was 50 to 200 bar (in front of the orifice), preferably 120 bar, with a conversion of (total) 12 kg / h.
- Example 3 Studies on the stability of the water-in-fuel emulsions
- the size of the water drops was physically determined by laser diffraction (X3, 2 values) using a Malvem Mastersizer 2000 from Malvem Instruments GmbH. The measurement method is described, for example, in Terence Allen, Particle Size Measurement, Volume 1, 5 ft Edition, Kluwer Academic Publishers, Dordrecht, Netherlands 1999. Depending on the actual size distribution, there are other methods besides laser light diffraction such as: B. the dynamic light scattering, single particle counter and ultrasonic extinction in question.
- the size of the water drops is a measure of the quality of the emulsion.
- the corresponding values for the drop size (the X3, 2 values) are summarized in Table 3.
- Table 3 the emulsions using the compounds according to the invention and also the mixtures according to the invention sometimes have significantly smaller drop sizes than the comparison emulsions.
- the fact that the drop size is really a measure of the stability of the emulsion at room temperature is shown by the stability values determined by storage tests.
- the emulsions with larger droplet sizes also have poorer storage stability.
- the stability of the emulsions was checked in a static storage test at 20 ° C (for 12 weeks) and additionally under changing temperatures (-20 ° C and 70 ° C, each for 1 week).
- the emulsion was filled into a scaled 100 ml standing cylinder and its quality was assessed visually in accordance with the specified conditions.
- the storage tests at -20 ° C were then assessed at room temperature.
- the emulsion according to Example 2 is comparatively homogeneous even without the addition of anti-freeze (e.g. monoethylene glycol). Otherwise, phase separation, a so-called "breaking" of the emulsion, took place after or even when heated.
- anti-freeze e.g. monoethylene glycol
- Example 4 Use of the compounds of the general formula (I) according to the invention as rust protection and wear protection additives
- a 20 x 40 mm sheet of iron is blasted with 40 ⁇ m glass beads and then - based on ASTM D-665 - immersed in the emulsions prepared in Example 2 and stored at 40 ⁇ 1 ° C for 24 hours. After 24 hours, the iron sheet is examined for rust formation.
- ASTM D-665 - immersed in the emulsions prepared in Example 2 and stored at 40 ⁇ 1 ° C for 24 hours. After 24 hours, the iron sheet is examined for rust formation.
- Example 5 Use of the compounds of the general formula (I) according to the invention in fuels and their wear protection behavior
- the connections listed in the table were solved in an unadditized diesel fuel (Miro, Düsseldorf).
- the concentration of additive in the diesel fuel was 75 ppm.
- the wear protection behavior was assessed using the HFRR test (High Frequency Roller Rig Test), which was carried out in accordance with ISO 12156-1.
- the length of the resulting grooves was measured and used as a measure of wear. The shorter the scoring, the better the wear protection of the additive added. Unaddivated diesel fuel was used for comparison.
- Table 4 the compounds according to the invention protected against wear.
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Abstract
The invention relates to low-molecular and high-molecular diblock emulsifiers, particularly based on polyisobutylene, of general formulas (Ia) and (Ib), and to mixtures thereof, whereby: La represents a polyisobutylene group having a numerical average molecular weight M¿n? ranging from 300 to 1000; L?b¿ represents a polyisobutylene group having a numerical average molecular weight M¿n? ranging from 2000 to 20000; -A- represents -O-, -N(H)- or N(R?1)-; M+¿ represents H+, an alkali metal ion, 0.5 alkaline-earth metal ions or NH¿4?+, whereby in NH¿4?+, one or more H's can be substituted by alkyl radicals; R represents a linear or branched saturated hydrocarbon radical, which supports at least one substituent selected from the group consisting of OH, NH¿2? or NH3?+¿ and optionally supports one or more C(O)H groups while optionally containing one or more non-adjacent -O- and/or secondary amines and/or tertiary amines and, in the NH¿2? or NH3?+¿ groups, one or more H's can be substituted by alkyl radicals, and; R1 represents a linear or branched saturated hydrocarbon radical, which optionally supports one or more substituents selected from the group consisting of OH, NH¿2, NH3?+ or C(O)H while optionally containing one or more non-adjacent -O- and/or secondary amines and/or tertiary amines and, in the NH¿2? or NH3?+¿ groups, one or more H's can be substituted by alkyl radicals, and the proportion of A-R on the compound of general formula (Ib) equals at least 20 wt. %.
Description
Nieder- und hochmolekulare Emulgatoren, insbesondere auf Basis von Polyisobutylen, sowie deren Mischungen Low and high molecular weight emulsifiers, especially those based on polyisobutylene, and their mixtures
Die vorliegende Erfindung betrifft nieder- und hochmolekulare Verbindungen, insbesondere auf Basis von Polyisobutylen, sowie deren Mischungen, welche als Emulgatoren für Wasser-in-Öl-Emulsionen geeignet sind, Verfahren zur Herstellung solcher Verbindungen sowie die Emulsionen selbst.The present invention relates to low and high molecular weight compounds, in particular based on polyisobutylene, and mixtures thereof, which are suitable as emulsifiers for water-in-oil emulsions, processes for the preparation of such compounds and the emulsions themselves.
Gegenstand der Erfindung ist außerdem die Verwendung solcher Verbindungen als Additive für Kraftstoffe und Schmierstoffe, sowie als korrosionsinhibierender Zusatz in wasserhaltigen Flüssigkeiten, sowie Kraftstoffe, Schmierstoffe, Kraftstoff- und Schmier- stoffadditiv-Konzentrate und wasserhaltige Flüssigkeiten enthaltend die erfindungsgemäßen Verbindungen.The invention also relates to the use of such compounds as additives for fuels and lubricants, and as a corrosion-inhibiting additive in water-containing liquids, and also fuels, lubricants, fuel and lubricant additive concentrates and water-containing liquids containing the compounds according to the invention.
Aus dem Stand der Technik sind Verbindungen verschiedenen Typs mit Emulgiereigen- schaften bekannt. Unter anderem werden Derivate des mit einer Polyisobutylenylgruppe substituierten Bernsteinsäureanhydrids in verschiedenen Anwendungen eingesetzt.Compounds of various types with emulsifying properties are known from the prior art. Among others, derivatives of the succinic anhydride substituted with a polyisobutylenyl group are used in various applications.
So beschreibt beispielsweise die US-A 4,225,447 Wasser-in-Öl-Emulsionen, welche als Schmiermittel eingesetzt werden und ein mit einer Alkylenylgruppe (wie einer Polyisobutylenylgruppe) substituiertes Bernsteinsäureanhydrid, vorzugsweise mit einem zahlenmittleren Molekulargewicht Mn von 300 bis 3000 g/mol, ein (Erd) Alkalimetallsalz einer mit einer Alkenylgruppe substituierten Bernsteinsäure oder ein mit einer Alkenylgruppe substituiertes Bernsteinsäureamid als Emulgator enthalten, gegebenenfalls in Kombination mit dem Salz einer Harzsäure.For example, US Pat. No. 4,225,447 describes water-in-oil emulsions which are used as lubricants and a succinic anhydride substituted with an alkylenyl group (such as a polyisobutylenyl group), preferably with a number average molecular weight M n of 300 to 3000 g / mol Contain (earth) alkali metal salt of a succinic acid substituted with an alkenyl group or a succinic acid amide substituted with an alkenyl group as an emulsifier, optionally in combination with the salt of a resin acid.
Die EP-A 0 156 572 beschreibt die Verwendung von oberflächenaktiven Substanzen auf der Basis von mit Polyisobutylenylgruppen substituierten Bernsteinsäurederivaten, vorzugsweise mit einem zal lenmittleren Molekulargewicht Mn von 400 bis 5000, mit einer anionischen Gruppe zur Herstellung von Wasser-in-Öl- oder Öl-in- Wasser-Emulsionen. Als anionische Gruppen kommen Phosphat-, Phosphonat-, Sulfat-, Sulfonat- und Carboxymethylgruppen in Betracht.
Die am 25.1.2000 eingereichte Deutsche Anmeldung der Anmelderin mit dem Aktenzeichen 100 03 105.6 beschreibt den Einsatz von alkoxylierten Polyisobutylenen als Emulgatoren in Wasser-in-Kraftstoff-Emulsionen. Diese alkoxylierten Polyisobutylene können durch die allgemeine Formel R-(CH2)n-(O-A)m-OH beschrieben werden. R ist dabei ein Polyisobutylen mit einer gewichtsmittleren Molmasse von 300 bis 2300, vorzugsweise 500 bis 2000. A ist ein Alkylenrest mit 2 bis 8 Kohlenstoffatomen. Die Zahl m ist eine Zahl von 1 bis 200, die so gewählt ist, daß das alkoxylierte Polyisobutylen 0,2 bis 1,5 Alkylenoxid-Einheiten pro C4-Einheit, vorzugsweise 0,5 Alkylenoxid-Einheiten pro C -Einheit, enthält; n ist entweder 0 oder 1.EP-A 0 156 572 describes the use of surface-active substances based on succinic acid derivatives substituted with polyisobutylenyl groups, preferably with a cell-average molecular weight M n of 400 to 5000, with an anionic group for the preparation of water-in-oil or oil -in water emulsions. Suitable anionic groups are phosphate, phosphonate, sulfate, sulfonate and carboxymethyl groups. The applicant's German application filed on January 25, 2000 with the file number 100 03 105.6 describes the use of alkoxylated polyisobutylenes as emulsifiers in water-in-fuel emulsions. These alkoxylated polyisobutylenes can be described by the general formula R- (CH 2 ) n - (OA) m -OH. R is a polyisobutylene with a weight average molecular weight of 300 to 2300, preferably 500 to 2000. A is an alkylene radical with 2 to 8 carbon atoms. The number m is a number from 1 to 200, which is chosen so that the alkoxylated polyisobutylene contains 0.2 to 1.5 alkylene oxide units per C 4 unit, preferably 0.5 alkylene oxide units per C unit; n is either 0 or 1.
Die am 28.7.2000 eingereichte Deutsche Anmeldung der Anmelderin mit dem Aktenzeichen 100 36 956.1 beschreibt u. a. die Verwendung von Amiden der allgemeinen Formel R!R2NR3 als Emulgatoren in Wasser-in-Öl-Emulsionen, wobei R3 für einenThe applicant's German application filed on July 28, 2000 with the file number 100 36 956.1 describes, inter alia, the use of amides of the general formula R ! R 2 NR 3 as emulsifiers in water-in-oil emulsions, where R 3 for one
Acylrest einer Mono- oder Polycarbonsäure steht, und R1 u. a. von einem Poly-1-Butylen, - 2-Butylen oder -tso-Butylen oder Gemischen davon abgeleitet und R2 ein Polyalkylenpolyarnin- oder ein Polyalkyleniminrest sein kann.Is an acyl radical of a mono- or polycarboxylic acid, and R 1 is derived, inter alia, from a poly-1-butylene, -2-butylene or -to-butylene or mixtures thereof, and R 2 can be a polyalkylenepolyarnine or a polyalkylenimine radical.
Die WO 00/15740 offenbart Wasser-in-Kraftstoff-Emulsionen, die als Emulgatoren zwei über einen Linker wie Alkanolamin, Polyamin oder Polyol verknüpfte Bernsteinsäure- derivate enthalten, die mit Kohlenwasserstoffresten wie Polyisobutylenylgruppen substituiert sind, wobei in einem Ausführungsbeispiel das eine Bernsteinsäurederivat eine Polyisobutylenylgruppe mit 8 bis 25 C-Atomen und das andere Bernsteinsäurederivat eine Polyisobutylenylgruppe mit 50 bis 400 C-Atomen enthält.WO 00/15740 discloses water-in-fuel emulsions which contain, as emulsifiers, two succinic acid derivatives which are linked via a linker such as alkanolamine, polyamine or polyol and which are substituted by hydrocarbon radicals such as polyisobutylenyl groups, in one embodiment the one succinic acid derivative being a polyisobutylenyl group with 8 to 25 carbon atoms and the other succinic acid derivative contains a polyisobutylenyl group with 50 to 400 carbon atoms.
Aus der GB-A 2,157,744 sind Bohrflüssigkeiten bekannt, die sowohl Pfropf- oder Blockcopolymere von Polycarbonsäuren und Polyethylenglykol, als auch Verbindungen enthalten, die aus einem mit einer Polyisobutylenylgruppe substituierten Bernsteinsäureanhydrid, vorzugsweise mit einem zahlenmittleren Molekulargewicht Mn von 400 bis 5000, und Polyolen, Polyaminen, Hydroxycarbonsäuren oder Aminoalkoholen hergestellt werden.From GB-A 2,157,744 drilling fluids are known which contain both graft or block copolymers of polycarboxylic acids and polyethylene glycol and also compounds which consist of a succinic anhydride substituted with a polyisobutylenyl group, preferably with a number average molecular weight M n of 400 to 5000, and polyols, Polyamines, hydroxycarboxylic acids or amino alcohols are produced.
Die US 4,708,753 offenbart Wasser-in-Kraftstoff-Emulsionen, die unter anderem als Emulgatoren Mono- oder Disalze von Bernsteinsäure mit Aminen oder Aminsalze von Bernsteinsäuremonoestern enthalten. Diese Salze entstehen durch Umsetzung von Alkanolaminen, Polyaminen, Oligoalkoholen oder Polyolen mit Bernsteinsäureanhydriden, die mit C2o-C5θö-Kohlenwasserstoffresten wie Polyisobutylenylgruppen substituiert sind. In
den Beispielen werden nur die Salze von Bernsteinsäuren oder deren Monoestem beschrieben, die eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht von 950 bzw. 1700 tragen.No. 4,708,753 discloses water-in-fuel emulsions which contain, inter alia, mono- or disalts of succinic acid with amines or amine salts of succinic acid monoesters as emulsifiers. These salts are formed by reacting alkanolamines, polyamines, oligoalcohols or polyols with succinic anhydrides which are substituted with C 2 o-C5θö hydrocarbon radicals such as polyisobutylenyl groups. In The examples only describe the salts of succinic acids or their monoesters which carry a polyisobutylenyl group with a number average molecular weight of 950 or 1700.
Reibungsvermindemde Additive für Kraft- und Schmierstoffe sind ebenso wie Emulgatoren bereits aus dem Stand der Technik bekannt.Friction-reducing additives for fuels and lubricants as well as emulsifiers are already known from the prior art.
So beschreibt die US 5,858,029 reibungsvermindemde Additive für Kraft- und Schmierstoffe, wobei insbesondere Verbindungen der Formel R1(-OR -)aNH(CO)-R3-OH als reibungsvermindemde Additive verwendet werden, worin R1 für einen C]- bis C<so- Alkylrest, R für einen C bis C4-Alkylenrest, a für eine ganze Zahl von 1 bis 12 und R für Ci- bis C -Alkylen oder substituiertes Alkylen oder Cycloalkylen stehen. Zusätzlich können als Dispergiermittel mit Polyisobutylenylgruppen substituierte Succinimide und als Tenside Polyalkylenamine wie Polyisobutylenamine enthalten sein.For example, US Pat. No. 5,858,029 describes friction-reducing additives for fuels and lubricants, in particular compounds of the formula R 1 (-OR -) a NH (CO) -R 3 -OH being used as friction-reducing additives, wherein R 1 is for a C] - bis C <so- alkyl radical, R is a C to C 4 alkylene radical, a is an integer from 1 to 12 and R is Ci to C alkylene or substituted alkylene or cycloalkylene. Succinimides substituted with polyisobutylenyl groups may also be present as dispersants and polyalkylene amines such as polyisobutylene amines may be present as surfactants.
Die oben genannten, aus dem Stand der Technik bekannten Verbindungen weisen hinsichtlich Herstellung und/oder Produkteigenschaften verschiedene Nachteile auf. Bei einigen Verbindungen fallen bei der Synthese in unterschiedlicher Ausbeute Nebenprodukte an, die - wenn sie nicht entfernt werden - die Einstellung einer gleich- bleibenden Viskosität des Emulgators erschweren können. Nachteile können sich auch bei der Herstellung von Emulsionen ergeben: häufig weisen die Emulsionen nur eine ungenügende Stabilität auf, so dass bei der Lagerung eine Phasentrennung auftritt. Die verwendeten Emulgatoren müssen deshalb in hohen Konzentrationen eingesetzt werden, um die Ausbildung einer stabilen Emulsion zu ermöglichen.The above-mentioned compounds known from the prior art have various disadvantages with regard to production and / or product properties. With some compounds, by-products are obtained in the synthesis in different yields, which - if they are not removed - can make it difficult to set a constant viscosity of the emulsifier. Disadvantages can also arise in the production of emulsions: the emulsions often have insufficient stability, so that phase separation occurs during storage. The emulsifiers used must therefore be used in high concentrations to enable the formation of a stable emulsion.
Daher besteht ein Bedarf an Verbindungen, die als Emulgatoren eingesetzt werden können und die genannten Nachteile nicht aufweisen. Vor allem im Bereich der Wasser-inKraftstoff-Emulsionen werden Emulgatoren benötigt, die relativ stabile Emulsionen erzeugen und zudem eine möglichst vollständige und weitgehend rückstandsfreie Verbrennung des Kraftstoffs ermöglichen.There is therefore a need for compounds which can be used as emulsifiers and which do not have the disadvantages mentioned. Especially in the field of water-in-fuel emulsions, emulsifiers are needed that produce relatively stable emulsions and also enable the most complete and largely residue-free combustion of the fuel.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, weitere Verbindungen bereitzustellen, welche als Emulgatoren in Wasser-in-Öl-Emulsionen eingesetzt werden können.The object of the present invention is to provide further compounds which can be used as emulsifiers in water-in-oil emulsions.
Die obige Aufgabe wird gelöst durch Verbindungen der allgemeinen Formel (Ia) und (Ib)
The above object is achieved by compounds of the general formulas (Ia) and (Ib)
wobei La für eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 300 bis 1000 steht,where L a stands for a polyisobutylenyl group with a number average molecular weight M n of 300 to 1000,
Lb für eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 2000 bis 20000 steht,L b represents a polyisobutylenyl group with a number average molecular weight M n of 2,000 to 20,000,
-A- für -O- -N(H)- oder -N(R')- steht,-A- stands for -O- -N (H) - or -N (R ') -,
M+ für H1", ein Alkalimetallion, 0,5 Erdalkalimetallionen oder NH steht, wobei in NH + ein oder mehrere H durch Alkylreste ersetzt sein können,M + stands for H 1 " , an alkali metal ion, 0.5 alkaline earth metal ions or NH, where one or more H in NH + can be replaced by alkyl radicals,
R für einen linearen oder verzweigten gesättigten Kohlenwasserstoffrest steht, der mindestens einen Substituenten ausgewählt aus der Gruppe OH, NH2 oder NH3 + und gegebenenfalls ein oder mehrere C(O)H-Gruppen trägt und gegebenenfalls ein oder mehrere nicht-benachbarte -O- und/oder sekundäre Amine und/oder tertiäre Amine enthält, und wobei in den NH2- oder NH3 +-Gruppen ein oder mehrere H durch Alkylreste ersetzt sein können, und R1 für einen linearen oder verzweigten gesättigten Kohlenwasserstoffrest steht, der gegebenenfalls einen oder mehrere Substituenten ausgewählt aus der Gruppe OH, NH2, NH3 + oder C(O)H trägt und gegebenenfalls ein oder mehrere nichtbenachbarte -O- und/oder sekundäre Amine und/oder tertiäre Amine enthält, und wobei in den NH2- oder NH3 +-Gruppen ein oder mehrere H durch Alkylreste ersetzt sein können, undR represents a linear or branched saturated hydrocarbon radical which bears at least one substituent selected from the group OH, NH 2 or NH 3 + and optionally one or more C (O) H groups and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, and wherein in the NH 2 - or NH 3 + groups one or more H may be replaced by alkyl radicals, and R 1 represents a linear or branched saturated hydrocarbon radical, which optionally has one or carries several substituents selected from the group OH, NH 2 , NH 3 + or C (O) H and optionally contains one or more non-adjacent -O- and / or secondary amines and / or tertiary amines, and wherein in the NH 2 - or NH 3 + groups one or more H may be replaced by alkyl radicals, and
der Anteil von A-R an der Verbindung der allgemeinen Formel (Ia) bzw. (Ib) mindestens 20 Gew.-% beträgt.the proportion of A-R in the compound of the general formula (Ia) or (Ib) is at least 20% by weight.
Verbindungen der allgemeinen Formel (Ia), in denen der Anteil des hydrophilen Restes A- R bei niedrigeren Werten wie 5,2 bis 15,2 Gew.-% liegt, sind an sich bekannt und werden in GB-A 2,157,744 und US 4,708,753 beschrieben. Es werden darin jedoch nicht die
vorteilhaften Eigenschaften als Emulgator erkannt, die bei den erfindungsgemäßen Verbindungen mit einem A-R-Anteil von ≥ 20 Gew.-% eintreten.Compounds of the general formula (Ia) in which the proportion of the hydrophilic radical A-R is at lower values such as 5.2 to 15.2% by weight are known per se and are described in GB-A 2,157,744 and US 4,708,753 , However, it does not include the advantageous properties recognized as emulsifiers which occur in the compounds according to the invention with an AR content of ≥ 20% by weight.
Die erfindungsgemäßen Verbindungen können sowohl einzeln als auch im Gemisch als Emulgatoren in Wasser-in-Öl-Emulsionen verwendet werden. Es lassen sich stabilere Emulsionen erzeugen als bei Verwendung herkömmlicher Emulgatoren. Insbesondere die Verbindungen der allgemeinen Formel (Ib) können als über einen Linker verknüpfte Diblockemulgatoren aufgefasst werden, wobei der lipophile Block La bzw. Lb über eine kovalente C-C-Bindung und der hydrophile Block R bzw. R1 über eine Ester- oder Amidbindung an den Linker Bernsteinsäure geknüpft ist.The compounds according to the invention can be used both individually and in a mixture as emulsifiers in water-in-oil emulsions. More stable emulsions can be produced than when using conventional emulsifiers. In particular, the compounds of the general formula (Ib) can be regarded as diblock emulsifiers linked via a linker, the lipophilic block L a or L b via a covalent CC bond and the hydrophilic block R or R 1 via an ester or amide bond is linked to the left succinic acid.
Bevorzugt sind solche Verbindungen der allgemeinen Formel (Ia), in denenPreferred compounds of the general formula (Ia) are those in which
- La für eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 350 bis 950, insbesondere von 350 bis 650, steht, und/oder- L a stands for a polyisobutylenyl group with a number average molecular weight M n from 350 to 950, in particular from 350 to 650, and / or
- La für eine Polyisobutylenylgruppe steht, die eine Polydispersität ≤ 3,0, bevorzugt von 1,1 bis 2,5, besonders bevorzugt von 1,1 bis 2,0, aufweist, und/oderL a stands for a polyisobutylenyl group which has a polydispersity ≤ 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2.0, and / or
- der Anteil von A-R an der Verbindung der allgemeinen Formel (Ia) mindestens 25 Gew.-%, insbesondere 35 bis 60 Gew.-% beträgt, und/oder- The proportion of A-R in the compound of general formula (Ia) is at least 25% by weight, in particular 35 to 60% by weight, and / or
- R aus [-CH2-CH2-X]-, [-CH(CH3)-CH2-X]- und/oder [-CH2-CH(CH3)-X] -Einheiten aufgebaut ist, mit X - O oder NH.R is composed of [-CH 2 -CH 2 -X] -, [-CH (CH 3 ) -CH 2 -X] - and / or [-CH 2 -CH (CH 3 ) -X] units, with X - O or NH.
Bevorzugt sind solche Verbindungen der allgemeinen Formel (Ib), in denenPreferred compounds of the general formula (Ib) are those in which
- L für eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht von 2000 bis 12000, insbesondere von 2300 bis 5000 steht, und/oderL stands for a polyisobutylenyl group with a number average molecular weight from 2000 to 12000, in particular from 2300 to 5000, and / or
- Lb für eine Polyisobutylenylgruppe steht, die eine Polydispersität ≤ 3,0, bevorzugt von 1,1 bis 2,5, besonders bevorzugt von 1,1 bis 2,0, aufweist, und/oderL b stands for a polyisobutylenyl group which has a polydispersity 3,0 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2.0, and / or
- der Anteil von A-R an der Verbindung der allgemeinen Formel (Ib) mindestens 25 Gew.-%, insbesondere 35 bis 60 Gew.-% beträgt, und/oder
- R aus [-CH2-CH2-X]-, [-CH(CH3)-CH2-X]- und/oder [-CH2-CH(CH3)-X]-Einheiten aufgebaut ist, mit X = O oder NH.- The proportion of AR in the compound of general formula (Ib) is at least 25% by weight, in particular 35 to 60% by weight, and / or R is composed of [-CH 2 -CH 2 -X] -, [-CH (CH 3 ) -CH 2 -X] - and / or [-CH 2 -CH (CH 3 ) -X] units, with X = O or NH.
Besonders bevorzugt sind Verbindungen der allgemeinen Formel (Ia) oder (Ib), in denen A = -O- und R ein monovalenter Rest eines Oligomeren oder Polymeren von Ethylen- und/oder Propylenoxid oder ein monovalenter Rest eines Blockcopolymeren von Ethylen- und Propylenoxid ist.Particularly preferred are compounds of the general formula (Ia) or (Ib) in which A = -O- and R is a monovalent radical of an oligomer or polymer of ethylene and / or propylene oxide or a monovalent radical of a block copolymer of ethylene and propylene oxide ,
Besonders effektive Emulgatoren sind Verbindungen der allgemeinen Formel (Ia), in denen La für eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 350 bis 950, insbesondere von 350 bis 650, steht, wobei diese Polyisobutylenylgruppe gegebenenfalls eine Polydispersität ≤ 3,0, bevorzugt von 1,1 bis 2,5, besonders bevorzugt von 1,1 bis 2,0, hat.Particularly effective emulsifiers are compounds of the general formula (Ia) in which L a stands for a polyisobutylenyl group with a number average molecular weight M n of 350 to 950, in particular 350 to 650, this polyisobutylenyl group optionally having a polydispersity 3,0 3.0 from 1.1 to 2.5, particularly preferably from 1.1 to 2.0.
Es hat sich gezeigt, daß die Gesamtmenge an Emulgator zur Herstellung stabiler Emulsionen gesenkt werden kann, wennIt has been shown that the total amount of emulsifier for the preparation of stable emulsions can be reduced if
als Emulgator eine Mischung eingesetzt wird enthaltenda mixture is used as an emulsifier containing
(a) höchstens 99 Gew.-%, bevorzugt von 98 bis 80 Gew.-%, besonders bevorzugt von 97 bis 85 Gew.-%, mindestens einer Verbindung der allgemeinen Formel (Ia),(a) at most 99% by weight, preferably from 98 to 80% by weight, particularly preferably from 97 to 85% by weight, of at least one compound of the general formula (Ia),
(Ia) (Ib)(Ia) (Ib)
(b) mindestens 1 Gew.-%, bevorzugt 2 bis 20 Gew.-%, besonders bevorzugt 3 bis 15 Gew.-%, mindestens einer Verbindung der allgemeinen Formel (Ib),(b) at least 1% by weight, preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight, of at least one compound of the general formula (Ib),
wobei La eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 300 bis 1000 und Lb eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 2000 bis 20000 ist,where L a is a polyisobutylenyl group with a number average molecular weight M n of 300 to 1000 and L b is a polyisobutylenyl group with a number average molecular weight M n of 2000 to 20,000,
-A- für -O- -N(H)- oder -N(R!)- steht,
M* für Ff1", ein Alkalimetallion, 0,5 Erdalkalimetallionen oder NELt4" steht, wobei in NHt+ ein oder mehrere H durch Alkylreste ersetzt sein können,-A- stands for -O- -N (H) - or -N (R ! ) -, M * stands for Ff 1 " , an alkali metal ion, 0.5 alkaline earth metal ions or NELt 4" , it being possible for one or more H in NHt + to be replaced by alkyl radicals,
R für einen linearen oder verzweigten gesättigten Kohlenwasserstoffrest steht, der mindestens einen Substituenten ausgewählt aus der Gruppe OH, NH2 oder NH3 + und gegebenenfalls ein oder mehrere C(O)H-Gruppen trägt und gegebenenfalls ein oder mehrere nicht-benachbarte -O- und/oder sekundäre Amine und oder tertiäre Amine enthält, und wobei in den NH2- oder NH3 +-Gruppen ein oder mehrere H durch Alkylreste ersetzt sein können, undR represents a linear or branched saturated hydrocarbon radical which bears at least one substituent selected from the group OH, NH 2 or NH 3 + and optionally one or more C (O) H groups and optionally one or more non-adjacent -O- and / or contains secondary amines and or tertiary amines, and wherein one or more H in the NH 2 - or NH 3 + groups can be replaced by alkyl radicals, and
R1 für einen linearen oder verzweigten gesättigten Kohlenwasserstoffrest steht, der gegebenenfalls einen oder mehrere Substituenten ausgewählt aus der Gruppe OH, NH2, NH3 + oder C(O)H trägt und gegebenenfalls ein oder mehrere nicht- benachbarte -O- und/oder sekundäre Amine und/oder tertiäre Amine enthält, und wobei in den NH2- oder NH3 +-Gruppen ein oder mehrere H durch Alkylreste ersetzt sein können, undR 1 stands for a linear or branched saturated hydrocarbon radical which optionally carries one or more substituents selected from the group OH, NH 2 , NH 3 + or C (O) H and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, and wherein one or more H in the NH 2 - or NH 3 + groups can be replaced by alkyl radicals, and
der Anteil von A— R an der Verbindung der allgemeinen Formel (Ia) mindestens 10 Gew.-% beträgt und an der Verbindung der allgemeinen Formel (Ib) mindestens 20the proportion of A - R in the compound of the general formula (Ia) is at least 10% by weight and in the compound of the general formula (Ib) at least 20
Gew.-% beträgt.% By weight.
Effektive Emulgatormischungen werden nicht nur bei Einsatz von Verbindungen der allgemeinen Formel (Ia) mit hydrophilen Anteilen von mindestens 20 Gew.-%, sondern auch bei Einsatz von Verbindungen der allgemeinen Formel (Ia) mit hydrophilen Anteilen von mindestens 10 Gew.-% erhalten.Effective emulsifier mixtures are obtained not only when using compounds of the general formula (Ia) with hydrophilic parts of at least 20% by weight, but also when using compounds of the general formula (Ia) with hydrophilic parts of at least 10% by weight.
Bevorzugt sind erfindungsgemäße Mischungen, welche - neben mindestens einer Verbindung der allgemeinen Formel (Ib) -Mixtures according to the invention which, in addition to at least one compound of the general formula (Ib), are preferred
höchstens 99 Gew.-%, bevorzugt von 98 bis 80 Gew.-%, besonders bevorzugt von 97 bis 85 Gew.-%, mindestens einer Verbindung der allgemeinen Formel (Ia) enthalten, in der La eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 350 bis 950, insbesondere von 350 bis 650, ist und/oder der Anteil von A-R an der Verbindung der
allgemeinen Formel (Ia) mindestens 15 Gew.-%, bevorzugt mindestens 20 Gew.-%, besonders bevorzugt mindestens 25 Gew.-%, ganz besonders bevorzugt 35 bis 60 Gew.-%, beträgt.contain at most 99% by weight, preferably from 98 to 80% by weight, particularly preferably from 97 to 85% by weight, of at least one compound of the general formula (Ia) in which L a is a polyisobutylenyl group with a number-average molecular weight M. n is from 350 to 950, in particular from 350 to 650, and / or the proportion of AR in the connection of the general formula (Ia) is at least 15% by weight, preferably at least 20% by weight, particularly preferably at least 25% by weight, very particularly preferably 35 to 60% by weight.
Bevorzugt sind auch erfindungsgemäße Mischungen, welche neben mindestens einer Verbindung der allgemeinen Formel (Ia) -Mixtures according to the invention which, in addition to at least one compound of the general formula (Ia) -
mindestens 1 Gew.-%, bevorzugt 2 bis 20 Gew.-%, besonders bevorzugt 3 bis 15 Gew.-%, mindestens einer Verbindung der allgemeinen Formel (Ib) enthalten, in denen Lb eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 2000 bis 12000, insbesondere von 2300 bis 5000, ist und oder der Anteil von A-R an der Verbindung der allgemeinen Formel (Ib) mindestens 25 Gew.-%, insbesondere 35 bis 60 Gew.-%, beträgt.contain at least 1% by weight, preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight, of at least one compound of the general formula (Ib) in which L b is a polyisobutylenyl group with a number average molecular weight M n of 2000 to 12000, in particular from 2300 to 5000, and or the proportion of AR in the compound of the general formula (Ib) is at least 25% by weight, in particular 35 to 60% by weight.
Die vorliegende Erfindung betrifft ebenfalls Verfahren zur Herstellung der Verbindungen der allgemeinen Formel (Ia) bzw. (Ib). Hierbei wird Polyisobutylen mit Furnarsäuredichlorid, Fumarsäure, Maleinsäuredichlorid, Maleinsäureanhydrid oder Maleinsäure, bevorzugt mit Maleinsäureanhydrid oder Maleinsäuredichlorid, besonders bevorzugt mit Maleinsäureanhydrid, zu Bemsteinsäurederivaten der allgemeinen Formel (Ha), (Ilb) oder (IIc) umgesetzt, wobei La eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 300 bis 1000 und Lb eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 2000 bis 20000 ist.The present invention also relates to processes for the preparation of the compounds of the general formula (Ia) or (Ib). Here, polyisobutylene with fumaric acid dichloride, fumaric acid, maleic acid dichloride, maleic anhydride or maleic acid, preferably with maleic anhydride or maleic acid dichloride, particularly preferably with maleic anhydride, is converted to succinic acid derivatives of the general formula (Ha), (Ilb) or (IIc) with one poly, where L a is a group number average molecular weight M n of 300 to 1000 and L b is a polyisobutylenyl group with number average molecular weight M n of 2000 to 20,000.
(Ha) (Ilb) (IIc)(Ha) (Ilb) (IIc)
Die Umsetzung erfolgt nach den dem Fachmann bekannten Verfahren und beispielsweise analog zu den in den deutschen Offenlegungsschriften DE-A 195 19 042, DE-A 43 19 671 und DE-A 43 19 672 beschriebenen Verfahren zur Umsetzung von Polyisobutylenen mit Maleinsäureanhydrid.
Das zahlenmittlere Molekulargewicht Mn des entstandenen - mit einer Polyisobutylenylgruppe substituierten - Bemsteinsäureanhydridderivats kann über die Verseifungszahl [mg KOH/g Substanz] charakterisiert werden.The reaction is carried out by the processes known to the person skilled in the art and, for example, analogously to the processes for the reaction of polyisobutylenes with maleic anhydride described in German Offenlegungsschriften DE-A 195 19 042, DE-A 43 19 671 and DE-A 43 19 672. The number average molecular weight M n of the resulting succinic anhydride derivative, which is substituted by a polyisobutylenyl group, can be characterized by the saponification number [mg KOH / g substance].
Die substituierten Bernsteinsäurederivate der allgemeinen Formel (Ha) und (Hb) werden anschließend nach dem Fachmann bekannten Verfahren mit polaren Reaktionspartnern ROH oder RR NH umgesetzt, wobei R für einen linearen oder verzweigten gesättigten Kohlenwasserstoffrest steht, der mindestens einen Substituenten ausgewählt aus der Gruppe OH, NH2 oder NH3 + und gegebenenfalls ein oder mehrere C(O)H-Gruppen trägt und gegebenenfalls ein oder mehrere nicht-benachbarte -O- und/oder sekundäre Amine und/oder tertiäre Amine enthält, und wobei in den NH2- oder NH +-Gruppen ein oder mehrere H durch Alkylreste ersetzt sein können, undThe substituted succinic acid derivatives of the general formulas (Ha) and (Hb) are then reacted with polar reaction partners ROH or RR NH by processes known to those skilled in the art, where R is a linear or branched saturated hydrocarbon radical which has at least one substituent selected from the group OH, NH 2 or NH 3 + and optionally one or more C (O) H groups and optionally contains one or more non-adjacent -O- and / or secondary amines and / or tertiary amines, and wherein in the NH 2 - or NH + groups one or more H may be replaced by alkyl radicals, and
R1 für einen linearen oder verzweigten gesättigten Kohlenwasserstoffrest steht, der gegebenenfalls einen oder mehrere Substituenten ausgewählt aus der Gruppe OH, NH2, NH3 + oder C(O)H trägt und gegebenenfalls ein oder mehrere nicht-benachbarte -O- und/oder sekundäre Amine und/oder tertiäre Amine enthält, und wobei in den NH - oder NH +-Gruppen ein oder mehrere H durch Alkylreste ersetzt sein können.R 1 stands for a linear or branched saturated hydrocarbon radical which optionally carries one or more substituents selected from the group OH, NH 2 , NH 3 + or C (O) H and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, and one or more H in the NH - or NH + groups can be replaced by alkyl radicals.
Bei den Alkylresten, die die H-Atome ersetzen können, handelt es sich um - - Alkylreste.The alkyl radicals that can replace the H atoms are - - alkyl radicals.
Beispiele für geeignete polare Reaktionspartner ROH und RR^H sind Alkanolamine, Polyamine, Oligoalkohole, Polyole, Oligoalkylenglykole, Polyalkylenglykole sowie Kohlenhydrate und Zucker. Polare Reaktionspartner können ebenfalls Ethylenoxid und/oder Propylenoxid sein. Die Umsetzung mit Polyethylenglykol, Polypropylenglykol, deren (Block)Copolymeren, Ethylenoxid oder Propylenoxid ist bevorzugt. Zur Herstellung von niedermolekularen Verbindungen der allgemeinen Formel (Ia) ist darüber hinaus auch die Umsetzung mit Alkanolaminen wie Di-/Triethanolamin, Tris(hydroxymethyl)amino- methan und deren Salzen, Oligoalkoholen wie Sorbit und Pentaerithrit bzw. Kohlenhydraten und Zuckern bevorzugt. Besonders bevorzugt für die Herstellung von Verbindungen der allgemeinen Formel (Ia) ist die Umsetzung mit Tris(hydroxymethyl)- aminomethan, Cholin, Zuckern und Polyethylenglykol.Examples of suitable polar reactants ROH and RR ^ H are alkanolamines, polyamines, oligoalcohols, polyols, oligoalkylene glycols, polyalkylene glycols as well as carbohydrates and sugar. Polar reactants can also be ethylene oxide and / or propylene oxide. The reaction with polyethylene glycol, polypropylene glycol, their (block) copolymers, ethylene oxide or propylene oxide is preferred. For the preparation of low molecular weight compounds of the general formula (Ia), reaction with alkanolamines such as di- / triethanolamine, tris (hydroxymethyl) aminomethane and their salts, oligoalcohols such as sorbitol and pentaerythritol or carbohydrates and sugars is also preferred. The reaction with tris (hydroxymethyl) aminomethane, choline, sugars and polyethylene glycol is particularly preferred for the preparation of compounds of the general formula (Ia).
Die Menge des polaren Reaktionspartners wird so gewälilt, daß der Anteil des hydrophilen Restes A-R an der Verbindung der allgemeinen Formel (Ia) bzw. (Ib) mindestens 20
Gew.-%, bevorzugt 25 Gew.-%, besonders bevorzugt 35 bis 60 Gew.-%, beträgt. Auch Verbindungen der allgemeinen Formel (Ia), in denen der hydrophile Anteil 10 bis 20 Gew.-% liegt, lassen sich nach den geschilderten Verfahren herstellen. Das Umsetzungsverhältnis der substituierten Bemsteinsäurederivate (Ha), (üb) bzw. (IIc) zu den Alkanolaminen, Polyaminen, Oligoalkoholen, Polyolen, Oligoalkylenglykolen oder Polyalkylenglykolen beträgt im allgemeinen 1 : (0,75 bis 2), bevorzugt 1:(0,8 bis 1,2), besonders bevorzugt 1:1. Bei der Umsetzung mit Ethylenoxid und/oder Propylenoxid wird die Menge an Ethylen- und/oder Propylenoxid entsprechend der gewünschten Kettenlänge des hydrophilen Restes A-R gewählt.The amount of polar reactant is chosen so that the proportion of the hydrophilic radical AR in the compound of general formula (Ia) or (Ib) is at least 20 % By weight, preferably 25% by weight, particularly preferably 35 to 60% by weight. Compounds of the general formula (Ia) in which the hydrophilic content is 10 to 20% by weight can also be prepared by the processes described. The conversion ratio of the substituted succinic acid derivatives (Ha), (üb) or (IIc) to the alkanolamines, polyamines, oligoalcohols, polyols, oligoalkylene glycols or polyalkylene glycols is generally 1: (0.75 to 2), preferably 1: (0.8 to 1.2), particularly preferably 1: 1. In the reaction with ethylene oxide and / or propylene oxide, the amount of ethylene and / or propylene oxide is selected in accordance with the desired chain length of the hydrophilic radical AR.
Verbindungen der allgemeinen Formel (Ia) oder (Ib), in denen A = -O- und R ein monovalenter Rest eines Oligomeren oder Polymeren von Ethylen- und/oder Propylenoxid oder ein monovalenter Rest eines Blockcopolymeren von Ethylen- und Propylenoxid ist, lassen sich sowohl durch Umsetzung von Polyethylenglykol, Polypropylenglykol oder deren (Block)Copolymeren mit den substituierten Bemsteinsäurederivaten (Ha), (Ilb) oder (IIc) erhalten, als auch durch Umsetzung von Ethylenoxid und oder Propylenoxid mit den substituierten Bemsteinsäurederivaten (Ha), (Ilb) oder (IIc).Compounds of the general formula (Ia) or (Ib) in which A = -O- and R are a monovalent radical of an oligomer or polymer of ethylene and / or propylene oxide or a monovalent radical of a block copolymer of ethylene and propylene oxide can be used obtained both by reacting polyethylene glycol, polypropylene glycol or their (block) copolymers with the substituted succinic acid derivatives (Ha), (Ilb) or (IIc), and also by reacting ethylene oxide and or propylene oxide with the substituted succinic acid derivatives (Ha), (Ilb) or (IIc).
Durch die Umsetzung der substituierten Bemsteinsäurederivate (Ha), (Ilb) oder (IIc) mit den genannten polaren Reaktionspartnem werden Bemsteinsäurehalbester oder -halbamide erhalten. Beim Einsatz von Alkanolaminen reagieren die Hydroxy- und/oder Aminogruppen, so daß im allgemeinen Gemische von Bernsteinsäurehalbestem und Bemsteinsäurehalbamiden erhalten werden. Wird Malein- oder Fumarsäuredichlorid als Ausgangsmaterial eingesetzt, so wird die nach den genannten Reaktionsschritten noch vorhandene C(O)Cl-Gruppe zur CO2H-Gruppe hydrolysiert. Die vorhandene freie CO2H- Gruppe in den Bernsteinsäurehalbestem und -halbamiden kann anschließend mit NH3, Aminen, Alkalimetall- oder Erdalkalimetallsalzen zu den entsprechenden A in-, Alkalimetall- bzw. Erdalkalimetall-Salzen umgesetzt werden. Bei diesen Salzen handelt es sich um Verbindungen der allgemeinen Formel (Ia) bzw. (Ib), in denen M*" für ein Alkalimetallion, 0,5 Erdalkalimetallionen oder NEU steht, wobei in NELi* ein oder mehrere H durch Alkylreste ersetzt sein können. Geeignete Amine für die Salzbildung sind primäre, sekundäre und tertiäre Amine, die lineare C1-C4- oder verzweigte C3-C6- Alkylgruppen tragen. Diese Alkylgruppen können auch mit einer oder mehreren Hydroxygruppen substituiert sein. Beispiele für geeignete Alkylamine sind Diethylamin, Diisopropylamin, Trimethylamin, Mono-, Di- und Triethanolamin und Tris(hydroxymethyl)aminomethan.
Im allgemeinen werden zur Herstellung der Verbindungen der allgemeinen Formel (Ia) Polyisobutylene mit einem zahlenmittleren Molekulargewicht Mn von 300 bis 1000, bevorzugt von 350 bis 950, besonders bevorzugt von 350 bis 650, eingesetzt.By reacting the substituted succinic acid derivatives (Ha), (Ilb) or (IIc) with the polar reaction partners mentioned, succinic acid semiesters or half amides are obtained. When alkanolamines are used, the hydroxyl and / or amino groups react, so that mixtures of succinic acid and succinic acid halamides are generally obtained. If maleic or fumaric acid dichloride is used as the starting material, the C (O) Cl group still present after the reaction steps mentioned is hydrolyzed to the CO 2 H group. The free CO 2 H group present in the succinic acid semiesters and half amides can then be reacted with NH 3 , amines, alkali metal or alkaline earth metal salts to give the corresponding A 1, alkali metal or alkaline earth metal salts. These salts are compounds of the general formula (Ia) or (Ib) in which M * "is an alkali metal ion, 0.5 alkaline earth metal ion or NEU, where one or more H in NELi * can be replaced by alkyl radicals Suitable amines for salt formation are primary, secondary and tertiary amines which carry linear C 1 -C 4 or branched C 3 -C 6 alkyl groups.These alkyl groups can also be substituted by one or more hydroxyl groups.Examples of suitable alkyl amines are Diethylamine, diisopropylamine, trimethylamine, mono-, di- and triethanolamine and tris (hydroxymethyl) aminomethane. In general, polyisobutylenes with a number average molecular weight M n of 300 to 1000, preferably from 350 to 950, particularly preferably from 350 to 650, are used to prepare the compounds of the general formula (Ia).
Zur Herstellung der Verbindungen der allgemeinen Formel (Ib) werden im allgemeinen Polyisobutylene mit einem zahlenmittleren Molekulargewicht Mn von 2000 bis 20000, bevorzugt von 2000 bis 12000, besonders bevorzugt von 2300 bis 5000, eingesetzt.To prepare the compounds of the general formula (Ib), polyisobutylenes with a number average molecular weight M n of 2,000 to 20,000, preferably from 2,000 to 12,000, particularly preferably from 2,300 to 5,000, are generally used.
Von den Polyisobutylenen mit einem zahlenmittleren Molekulargewicht Mn in den genannten Bereichen werden bevorzugt diejenigen eingesetzt, die einen hohen Gehalt an Vinylidengruppen haben. Darunter versteht man im Rahmen der vorliegenden Erfindung einen Anteil an Vinylidengruppen von ≥ 70 Mol-%, bevorzugt von ≥ 80 Mol-%, besonders bevorzugt von ≥ 85 Mol-%.Of the polyisobutylenes with a number-average molecular weight M n in the ranges mentioned, preference is given to those which have a high content of vinylidene groups. In the context of the present invention, this means a proportion of vinylidene groups of 70 70 mol%, preferably ≥ 80 mol%, particularly preferably ≥ 85 mol%.
Besonders bevorzugt werden solche Polyisobutylene eingesetzt, die ein zahlenmittleres Molekulargewicht Mn in den oben genannten Bereichen, einen hohen Gehalt an Vinylidengruppen und eine einheitliche Polymergerüststruktur haben. Darunter werden im Rahmen der vorliegenden Erfindung Polyisobutylene verstanden, die zu mindestens 80 Gew.-%, bevorzugt zu mindestens 90 Gew.-%, besonders bevorzugt zu mindestens 95 Gew.-% aus Isobutyleneinheiten aufgebaut sind.Polyisobutylenes which have a number-average molecular weight M n in the abovementioned ranges, a high content of vinylidene groups and a uniform polymer skeleton structure are particularly preferably used. In the context of the present invention, this means polyisobutylenes which are composed of at least 80% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, of isobutylene units.
Ganz besonders bevorzugt sind Polyisobutylene mit einem zahlenmittleren Molekulargewicht Mn in den genannten Bereichen, einem hohen Gehalt an Vinylidengruppen und einheitlicher Gerüststruktur, die eine Polydispersität ≤ 3,0, bevorzugt von 1,1 bis 2,5, besonders bevorzugt von 1,1 bis 2,0, aufweisen. Unter Polydispersität versteht man den Quotienten Mw/Mn aus gewichtsmittlerem Molekulargewicht Mw und zahlenmittlerem Molekulargewicht Mn.Very particularly preferred are polyisobutylenes with a number-average molecular weight M n in the ranges mentioned, a high content of vinylidene groups and a uniform structure, which have a polydispersity pers 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2.0. Polydispersity means the quotient M w / M n from the weight-average molecular weight M w and the number-average molecular weight M n .
Polyisobutylene mit einem zahlenmittleren Molekulargewicht Mn in den genannten Bereichen, die im wesentlichen aus Isobutyleneinheiten aufgebaut sind und einen hohen Gehalt an Vinylidengruppen aufweisen, sind beispielsweise unter der Handelsbezeichnung Glissopal® von der BASF AG erhältlich, wie Glissopal® 1000 mit einem Mn von 1000, Glissopal® V 33 mit einem Mn von 550 und Glissopal® 2300 mit einem Mn von 2300.
Beispiele für geeignete Alkanolamine, Polyamine, Oligoalkohole, Polyole und Polyalkylenglykole, die zur Herstellung der erfmdungsgemäßen Verbindungen verwendet werden können, sind in der WO 00/15740 beschrieben.Polyisobutylenes with a number average molecular weight M n in the ranges mentioned, which are essentially composed of isobutylene units and have a high content of vinylidene groups, are available, for example, from BASF AG under the trade name Glissopal®, such as Glissopal® 1000 with an M n of 1000 , Glissopal® V 33 with an M n of 550 and Glissopal® 2300 with an M n of 2300. Examples of suitable alkanolamines, polyamines, oligoalcohols, polyols and polyalkylene glycols which can be used for the preparation of the compounds according to the invention are described in WO 00/15740.
Beispiele für Alkanolamine sind Monoethanolamin, Diethanolamin, 2-Amino-l-butanol, 2- Amino-2-methyl- 1 -propanol, 2- Amino-2-methyl- 1 ,3 -propandiol, 2- Amino-2-ethyl- 1,3- propandiol, N-(2-Hydroxypropyl)-N'-(2-aminoethyl)piperazin, Tris(hydroxymethyl)amino- methan, 2-Amino-l-butanol, ß-(2-Hydroxyethoxy)ethylamin, Glucamin, Glucosamin, 4- Amino-3-hydroxy-3-methyl-l-buten, N-(3-Aminopropyl)-4-(2-hydroxyethyl)piperidin, 2- Amino-6-methyl-6-heptanol, 5-Amino-l-pentanol, N-(2-Hydroxyethyl)-l,3- diaminopropan, l,3-Diamino-2-hydroxypropan, N-(2-Hydroxyethyl)ethylendiamin, N,N- Bis(2-hydroxyethyl)ethylendiamin, N-(2-Hydroxyethoxyethyl)ethylendiamin, 1 -(2- Hydroxyethyl)piperazin, monohydroxypropyl-substituiertes Diethylentriamin, dihydroxy- propyl-substituiertes Tetaethylenpentamin und N-(3-Hydroxybutyl)tetramethylendiamin.Examples of alkanolamines are monoethanolamine, diethanolamine, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl- 1,3-propanediol, N- (2-hydroxypropyl) -N '- (2-aminoethyl) piperazine, tris (hydroxymethyl) amino-methane, 2-amino-1-butanol, ß- (2-hydroxyethoxy) ethylamine, glucamine , Glucosamine, 4-amino-3-hydroxy-3-methyl-1-butene, N- (3-aminopropyl) -4- (2-hydroxyethyl) piperidine, 2-amino-6-methyl-6-heptanol, 5- Amino-1-pentanol, N- (2-hydroxyethyl) -l, 3-diaminopropane, 1,3-diamino-2-hydroxypropane, N- (2-hydroxyethyl) ethylenediamine, N, N-bis (2-hydroxyethyl) ethylenediamine , N- (2-hydroxyethoxyethyl) ethylenediamine, 1 - (2-hydroxyethyl) piperazine, monohydroxypropyl-substituted diethylene triamine, dihydroxy-propyl substituted tetaethylene pentamine and N- (3-hydroxybutyl) tetramethylene diamine.
Es können auch die Salze der genannten Alkanolamine eingesetzt werden. In diesen Salzen können gegebenenfalls ein oder mehrere der an N-Atome gebundenen H-Atome durch lineare d-Cβ-Alkyl- oder verzweigte C3-C6-Alkylgruppen ersetzt sein. Beispielhaft sei Cholin erwähnt.The salts of the alkanolamines mentioned can also be used. In these salts, one or more of the H atoms bound to N atoms can optionally be replaced by linear d-Cβ-alkyl or branched C 3 -C 6 -alkyl groups. Choline may be mentioned as an example.
Beispiele für geeignete Polyamine sind Polyalkylenpolyamine wie Polymethylen- polyamine, Polyethylenpolyamine, Polypropylenpolyamine, Polybutylenpolyamine und Polypentylenpolyamine; siehe auch "Ethylene Amines" in Kirk Othmer's "Encyclopedia of Chemical Technology", 2te Auflage, Band 7, S. 22-37, Interscience Publishers, New York 1965.Examples of suitable polyamines are polyalkylene polyamines such as polymethylene polyamines, polyethylene polyamines, polypropylene polyamines, polybutylene polyamines and polypentylene polyamines; see also "Ethylene Amines" in Kirk Othmer's "Encyclopedia of Chemical Technology", 2nd Edition, Volume 7, pp. 22-37, Interscience Publishers, New York 1965.
Beispiele für geeignete Oligoalkohole und Polyole sind 1,2-Butandiol, 2,3-Dimethyl-2,3- butandiol, 2,3-Hexandiol, 1,2-Cyclohexandiol, (Mono-, Di-)-Pentaerythritol, 1,7- und 2,4- Heptandiol, 1,2,3-, 1,2,4-, 1,2,5- und 2,3 ,4-Hexantriol, 1,2,3- und 1,2,4-Butantriol, 2,2,6,6- Tetrakis(hydroxymethyl)cyclohexanol, 1,10-Decandiol, 2-Hydroxymethyl-2-methyl-l,3- propandiol, 2-Hydroxymethyl-2-ethyl- 1,3 -propandiol, Sorbit, Mannit und Inosit. Femer sind auch C5- und C6-Zucker wie Glucose und Fructose geeignet.Examples of suitable oligoalcohols and polyols are 1,2-butanediol, 2,3-dimethyl-2,3-butanediol, 2,3-hexanediol, 1,2-cyclohexanediol, (mono-, di-) - pentaerythritol, 1.7 - and 2,4- heptanediol, 1,2,3-, 1,2,4-, 1,2,5- and 2,3, 4-hexanetriol, 1,2,3- and 1,2,4- Butanetriol, 2,2,6,6-tetrakis (hydroxymethyl) cyclohexanol, 1,10-decanediol, 2-hydroxymethyl-2-methyl-1,3-propanediol, 2-hydroxymethyl-2-ethyl-1,3-propanediol, Sorbitol, mannitol and inositol. C 5 and C 6 sugars such as glucose and fructose are also suitable.
Beispiele für (Oligo)Alkylenglykole sind (Tri-, Tetra-, Penta-, Hexa-)Ethylenglykol, (Tri-, Tetra-, Penta-, Hexa-)Propylenglykol und (Tri-, Tetra-, Penta-, Hexa-)Butylenglykol.
Beispiele für Polyalkylenglykole sind Polytetrahydrofuran, Polyethylenglykol und Polypropylenglykol. Bevorzugte Polyalkylenglykole sind Polyethylenglykol und Polypropylenglykol. Besonders bevorzugt werden Polyethylenglykol und Polypropylenglykol und deren Blockcopolymere eingesetzt, die ein zahlenmittleres Molekulargewicht Mn von 300 bis 5000, bevorzugt von 300 bis 2000, besonders bevorzugt von 500 bis 1500, aufweisen.Examples of (oligo) alkylene glycols are (tri, tetra, penta-, hexa-) ethylene glycol, (tri-, tetra-, penta-, hexa-) propylene glycol and (tri-, tetra-, penta-, hexa-) butylene glycol. Examples of polyalkylene glycols are polytetrahydrofuran, polyethylene glycol and polypropylene glycol. Preferred polyalkylene glycols are polyethylene glycol and polypropylene glycol. Polyethylene glycol and polypropylene glycol and their block copolymers are particularly preferred which have a number average molecular weight M n of 300 to 5000, preferably 300 to 2000, particularly preferably 500 to 1500.
Solche Polyethylenglykole sind beispielsweise unter der Handelsbezeichnung Pluriol® E von der BASF AG erhältlich, wie Pluriol® E 300 mit einem Mn von 300, Pluriol® E 600 mit einem M„ von 600, Pluriol® E 4000 mit einem M„ von 4000 und Pluriol® E 5000 mit einem Mn von 5000. Polyethylen-Polypropylenglykol-Blockcopolymere sind beispielsweise unter der Handelsbezeichnung Pluronic® PE von der BASF AG erhältlich, wie Pluronic® PE 3500 mit einem Mn von 1900 und einem Ethylenoxidanteil von 50 Gew.-%.Such polyethylene glycols are available, for example, under the trade name Pluriol® E from BASF AG, such as Pluriol® E 300 with an M n of 300, Pluriol® E 600 with an M "of 600, Pluriol® E 4000 with an M" of 4000 and Pluriol® E 5000 with an M n of 5000. Polyethylene-polypropylene glycol block copolymers are available, for example, from BASF AG under the trade name Pluronic® PE, such as Pluronic® PE 3500 with an M n of 1900 and an ethylene oxide content of 50% by weight. ,
Werden die erfindungsgemäßen Verbindungen und oder die erfindungsgemäßen Mischungen in Öl-in- Wasser-Emulsionen eingesetzt, so lassen sich stabile Vesikel erzeugen. Dies kann beispielsweise durch Einwirkung von Ultraschall erfolgen. Die erfindungsgemäßen Verbindungen und/oder die erfindungsgemäßen Mischungen sind zudem in vielfältiger Weise anwendbar, z. B. als Additive in Kraftstoffen und Schmierstoffen, als korrosionsinhibierender Zusatz in wasserhaltigen Flüssigkeiten sowie als Dispergatoren für anorganische und organische Feststoffdispersionen. Die erfindungsgemäßen Verbindungen und/oder die erfindungsgemäßen Mischungen lassen sich zudem als Tenside für Wasch- und Reinigungsformulierungen einsetzen. Zur Stabilisierung von anorganischen und organischen Feststoffdispersionen sind besonders die hochmolekularen Verbindungen der allgemeinen Formel (Ib) geeignet, die einen monovalenten Rest eines Polyethylenglykols als hydrophilen Block enthalten.If the compounds according to the invention and or the mixtures according to the invention are used in oil-in-water emulsions, stable vesicles can be produced. This can be done, for example, by the action of ultrasound. The compounds of the invention and / or the mixtures of the invention can also be used in a variety of ways, e.g. B. as additives in fuels and lubricants, as a corrosion-inhibiting additive in water-containing liquids and as dispersants for inorganic and organic solid dispersions. The compounds according to the invention and / or the mixtures according to the invention can also be used as surfactants for washing and cleaning formulations. The high-molecular compounds of the general formula (Ib) which contain a monovalent residue of a polyethylene glycol as a hydrophilic block are particularly suitable for stabilizing inorganic and organic solid dispersions.
Die erfindungsgemäßen Verbindungen und/oder erfindungsgemäßen Mischungen eignen sich auch als Emulgatoren für Wasser-in-Öl-Emulsionen, bei denen die Öl-Phase von einem pflanzlichen, tierischen oder synthetischen Öl oder Fett gebildet wird. Derartige Emulsionen werden im Kosmetik- oder pharmazeutischen Bereich verwendet. Beispiele für solche Öle oder Fette sind Triglyceride und Glykolester der Laurinsäure, Myristinsäure, Stearinsäure, Palmitinsäure, Ölsäure, Linolsäure und Linolensäure.The compounds according to the invention and / or mixtures according to the invention are also suitable as emulsifiers for water-in-oil emulsions in which the oil phase is formed from a vegetable, animal or synthetic oil or fat. Such emulsions are used in the cosmetic or pharmaceutical field. Examples of such oils or fats are triglycerides and glycol esters of lauric acid, myristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid and linolenic acid.
Besonders vorteilhaft werden die erfindungsgemäßen Verbindungen und/oder erfindungsgemäßen Mischungen als Emulgatoren für Wasser-in-Öl-Emulsionen eingesetzt,
bei denen die Öl-Phase von einem Kraftstoff, leichtem oder schwerem Heizöl gebildet wird. Es können alle gängigen Kraftstoffarten eingesetzt werden, beispielsweise Dieselkraftstoff, Ottokraftstoff und Kerosin. Bevorzugt wird Dieselkraftstoff verwendet.The compounds and / or mixtures according to the invention are particularly advantageously used as emulsifiers for water-in-oil emulsions, in which the oil phase is formed by a fuel, light or heavy heating oil. All common types of fuel can be used, for example diesel fuel, petrol and kerosene. Diesel fuel is preferably used.
Generell ist eine Aufreinigung der erfindungsgemäßen Verbindungen und ihrer Zwischenprodukte nicht notwendig; lediglich bei bestimmten Anwendungen, beispielsweise bei Verwendung dieser Verbindungen als Emulgatoren für Wasser-in-Öl- Emulsionen im Kosmetik- oder pharmazeutischen Bereich, kann gegebenenfalls eine Aufreinigung nötig sein.In general, it is not necessary to purify the compounds according to the invention and their intermediates; only in certain applications, for example when using these compounds as emulsifiers for water-in-oil emulsions in the cosmetics or pharmaceutical field, may purification be necessary.
Die Verwendung erfindungsgemäßer Verbindungen und/oder erfindungsgemäßer Mischungen als Emulgatoren bei der Herstellung von Wasser-in-Öl-Emulsionen ist ebenso Gegenstand der Erfindung wie die Wasser-in-Öl-Emulsionen selbst. Erfindungsgemäße Wasser-in-Öl-Emulsionen enthalten im allgemeinen 95 bis 60 Gew.-% Öl, 3 bis 35 Gew.- % Wasser und 0,2 bis 10 Gew.-% mindestens einer erfindungsgemäßen Verbindung und/oder einer erfindungsgemäßen Mischung.The use of compounds according to the invention and / or mixtures according to the invention as emulsifiers in the production of water-in-oil emulsions is just as much a subject of the invention as the water-in-oil emulsions themselves. Water-in-oil emulsions according to the invention generally contain 95 up to 60% by weight of oil, 3 to 35% by weight of water and 0.2 to 10% by weight of at least one compound according to the invention and / or a mixture according to the invention.
Erfindungsgemäße Wasser-in-Kraftstoff-Emulsionen können auch einen oder mehrere - C4-Alkohole und/oder Monoethylenglykol, insbesondere Monoethylenglykol, enthalten. Die verwendete Menge an C1-C4- Alkohol und/oder Monoethylenglykol liegt bei Werten von 5 bis 50 Gew.-%, bezogen auf die Menge an Wasser. Durch die Zugabe von einem oder mehreren C1-C4- Alkoholen und/oder Monoethylenglykol kann beispielsweise der Temperaturbereich, in dem die Emulsion stabil ist, verbreitert werden.Water-in-fuel emulsions according to the invention can also contain one or more C 4 alcohols and / or monoethylene glycol, in particular monoethylene glycol. The amount of C 1 -C 4 alcohol and / or monoethylene glycol used is from 5 to 50% by weight, based on the amount of water. By adding one or more C 1 -C 4 alcohols and / or monoethylene glycol, for example, the temperature range in which the emulsion is stable can be broadened.
Die erfindungsgemäßen Wasser-in-Kraftstoff-Emulsionen weisen eine hohe Stabilität sowie einen guten Wirkungsgrad bei der Verbrennung auf. Es lassen sich weiterhin gute Abgaswerte erhalten, wobei, insbesondere bei Dieselmotoren, die Emission von Ruß und NOx signifikant vermindert wird. Es läßt sich eine weitgehend vollständige und rückstandsfreie Verbrennung ohne Ablagerungen auf den Baugruppen des Verbrennungs- apparates, beispielsweise Einspritzdüsen, Kolben, Ringnuten, Ventilen und Zylinderkopf, erreichen.The water-in-fuel emulsions according to the invention have high stability and good combustion efficiency. Good exhaust gas values can still be obtained, the emission of soot and NO x being significantly reduced, particularly in the case of diesel engines. A largely complete and residue-free combustion can be achieved without deposits on the assemblies of the combustion apparatus, for example injection nozzles, pistons, annular grooves, valves and cylinder head.
Die Wasser-in-Kraftstoff-Emulsionen nach der vorliegenden Erfindung können neben den oben erwähnten Bestandteilen noch weitere Komponenten aufweisen. Dies sind zum Beispiel weitere Emulgatoren wie Natriumlaurylsulfat, quaternäre Ammoniumsalze wieThe water-in-fuel emulsions according to the present invention can have further components in addition to the components mentioned above. These are, for example, other emulsifiers such as sodium lauryl sulfate, quaternary ammonium salts such as
Ammoniumnitrat, Alkylglykoside, Lecithine, Polyethylenglykolether und -ester,
Sorbitanoleate, -stearate und -ricinolate, C13-Oxoalkoholethoxylate und Alkyl- phenolethoxylate, sowie Blockcopolymere aus Ethylenoxid und Propylenoxid, wie die Pluronic®-Typen der BASF AG. Bevorzugt werden als weitere Emulgatoren Sorbitan- monooleat, C13-Oxoalkoholethoxylate und Alkylphenolethoxylate, beispielsweise Octyl- und Nonylphenolethoxylate, verwendet.Ammonium nitrate, alkyl glycosides, lecithins, polyethylene glycol ethers and esters, Sorbitan oleates, stearates and ricinolates, C 13 oxo alcohol ethoxylates and alkyl phenol ethoxylates, as well as block copolymers of ethylene oxide and propylene oxide, such as the Pluronic® types from BASF AG. Sorbitan monooleate, C 13 oxo alcohol ethoxylates and alkylphenol ethoxylates, for example octyl and nonylphenol ethoxylates, are preferably used as further emulsifiers.
Bevorzugt wird für die erfindungsgemäßen Wasser-in-Kraftstoff-Emulsionen eine Kombination aus einem oder mehreren der oben genannten weiteren Emulgatoren zusammen mit den erfindungsgemäßen Verbindungen und/oder deren Mischungen verwendet.A combination of one or more of the above-mentioned further emulsifiers together with the compounds according to the invention and / or mixtures thereof is preferably used for the water-in-fuel emulsions according to the invention.
Werden diese weiteren Emulgatoren eingesetzt, so geschieht dies in Mengen von 0,5 bis 5 Gew.-%, vorzugsweise 1 bis 2,5 Gew.-%, bezogen auf die Gesamtzusammensetzung. Die Menge dieses weiteren Emulgators wird dabei so gewählt, daß die Gesamtmenge an Emulgator die für die erfindungsgemäßen Verbindungen und oder deren Mischungen alleine angegebene Menge von 0,2 bis 10 Gew.-% nicht überschreitet.If these further emulsifiers are used, this is done in amounts of 0.5 to 5% by weight, preferably 1 to 2.5% by weight, based on the overall composition. The amount of this further emulsifier is chosen so that the total amount of emulsifier does not exceed the amount of 0.2 to 10% by weight given for the compounds according to the invention and their mixtures alone.
Zur Herstellung der erfindungsgemäßen Wasser-in-Öl-Emulsionen werden die erfindungsgemäßen Verbindungen und/oder erfindungsgemäßen Mischungen mit dem Öl, dem Wasser und den weiteren, optional verwendbaren Komponenten vermischt und in an sich bekannter Weise emulgiert. Beispielsweise kann die Emulgierung in einem Rotormischer, per Mischdüse oder per Ultraschallsonde erfolgen. Besonders gute Ergebnisse wurden erzielt, wenn eine Mischdüse des Typs verwendet wurde, wie sie in der Deutschen Anmeldung, Aktenzeichen: 198 56 604 der Anmelderin vom 08.12.1998 offenbart wird. Wasser-in-Öl-Emulsionen für den Kosmetikbereich lassen sich ebenso herstellen wie Wasser-in-Kraftstoff-Emulsionen.To prepare the water-in-oil emulsions according to the invention, the compounds and / or mixtures according to the invention are mixed with the oil, the water and the further, optionally usable components and emulsified in a manner known per se. For example, the emulsification can be carried out in a rotor mixer, by means of a mixing nozzle or by an ultrasound probe. Particularly good results were achieved when a mixing nozzle of the type used as disclosed in German application, file number: 198 56 604 by the applicant on December 8, 1998 was used. Water-in-oil emulsions for the cosmetics sector can be produced as well as water-in-fuel emulsions.
Die erfindungsgemäßen Verbindungen und/oder erfindungsgemäßen Mischungen weisen neben ihren oberflächenaktiven, grenzflächenaktiven und emulgierenden Eigenschaften auch eine schmierfahigkeitsverbessemde und korrosionsinhibierende Wirkung auf. Zudem verbessern sie das Verschleißschutzverhalten von Flüssigkeiten. Daher werden die erfindungsgemäßen Verbindungen und/oder erfindungsgemäßen Mischungen als Additive für Schmierstoffe, Kraftstoffe und wasserhaltige Flüssigkeiten wie Kühlerflüssigkeiten oder Bohr- und Schneidflüssigkeiten verwendet. Diese Verwendung ist ebenfalls Gegenstand der vorliegenden Erfindung.
Den Kraftstoffen und Schmierstoffen können die erfindungsgemäßen Verbindungen und/oder erfindungsgemäßen Mischungen direkt - zusammen mit anderen Komponenten - zugegeben werden. Alternativ können die erfindungsgemäßen Verbindungen und oder erfindungsgemäßen Mischungen zuerst mit anderen Komponenten zu Kraftstoff- bzw. Schmierstoffadditivkonzentraten vermischt werden. Diese erfindungsgemäßen Kraftstoff- bzw. Schmierstoffadditivkonzentrate können unverdünnt oder verdünnt mit einem oder mehreren Lösungsmitteln oder Trägerölen den Kraftstoffen oder Schmierstoffen zugegeben werden. Bevorzugt ist die Zugabe in verdünnter Form.In addition to their surface-active, surface-active and emulsifying properties, the compounds and / or mixtures according to the invention also have a lubricity-improving and corrosion-inhibiting effect. They also improve the wear protection behavior of liquids. The compounds and / or mixtures according to the invention are therefore used as additives for lubricants, fuels and water-containing liquids such as coolant liquids or drilling and cutting liquids. This use is also the subject of the present invention. The compounds and / or mixtures according to the invention can be added directly to the fuels and lubricants — together with other components. Alternatively, the compounds according to the invention and or mixtures according to the invention can first be mixed with other components to give fuel or lubricant additive concentrates. These fuel or lubricant additive concentrates according to the invention can be added to the fuels or lubricants undiluted or diluted with one or more solvents or carrier oils. The addition in dilute form is preferred.
Die Kraftstoffe, Schmierstoffe, Kraftstoffadditiv- und Schmierstoffadditiv-Konzentrate, sowie wasserhaltige Flüssigkeiten, die die erfindungsgemäßen Verbindungen und/oder erfindungsgemäßen Mischungen enthalten, sind ebenfalls Gegenstand der vorliegenden Erfindung und sollen im folgenden näher erläutert werden.The fuels, lubricants, fuel additive and lubricant additive concentrates, and also water-containing liquids which contain the compounds and / or mixtures according to the invention are likewise the subject of the present invention and are to be explained in more detail below.
Erfindungsgemäße Kraftstoffe enthalten im allgemeinen - neben üblichen Komponenten - wenigstens eine erfindungsgemäße Verbindung und/oder eine erfindungsgemäße Mischung in einer Menge von 10 bis 5000 ppm, bevorzugt in einer Menge von 20 bis 2000 ppm, bezogen auf die Gesamtmenge.Fuels according to the invention generally contain - in addition to conventional components - at least one compound according to the invention and / or a mixture according to the invention in an amount of 10 to 5000 ppm, preferably in an amount of 20 to 2000 ppm, based on the total amount.
Erfindungsgemäße Schmierstoffe enthalten im allgemeinen zwischen 90 und 99,9 Gew.-%, bevorzugt zwischen 95 und 99,5 Gew.-%, eines flüssigen, halbfesten oder festen Schmierstoffes und zwischen 0,1 und 10 Gew.-% , bevorzugt zwischen 0,5 und 5 Gew.-% mindestens einer erfindungsgemäßen Verbindung und/oder einer erfindungsgemäßen Mischung, bezogen auf die Gesamtmenge.Lubricants according to the invention generally contain between 90 and 99.9% by weight, preferably between 95 and 99.5% by weight, of a liquid, semi-solid or solid lubricant and between 0.1 and 10% by weight, preferably between 0 , 5 and 5 wt .-% of at least one compound according to the invention and / or a mixture according to the invention, based on the total amount.
Erfindungsgemäße Kraftstoffadditiv- und Schmierstoffadditiv-Konzentrate enthalten - neben üblichen Komponenten - wenigstens eine erfindungsgemäße Verbindung und/oder eine erfindungsgemäße Mischung in Anteilen von 0,1 bis 80 Gew.-%, insbesondere von 0,5 bis 60 Gew.-%, bezogen auf das Gesamtgewicht des Konzentrats.Fuel additive and lubricant additive concentrates according to the invention contain - in addition to conventional components - at least one compound according to the invention and / or a mixture according to the invention in proportions of 0.1 to 80% by weight, in particular 0.5 to 60% by weight, based on the total weight of the concentrate.
Übliche Komponenten für Kraftstoffe bzw. Kraftstoffadditiv-Konzentrate sind beispielsweise Additive mit Detergenswirkung, wie sie in der Deutschen Anmeldung der Anmelderin, Aktenzeichen 100 36 956.1, vom 28.7.2000 (Seite 14 ff.), in der Deutschen Anmeldung der Anmelderin, Aktenzeichen 100 03 105.6, vom 25.1.2000 und in der PCT- Anmeldung der Anmelderin mit dem Aktenzeichen PCT/EP/01/00496 beschrieben sind. Die dort genannten Additive und weitere dort beschriebene Kraftstoffadditive mit polaren
Gmppierungen sind Bestandteil der vorliegenden Anmeldung und durch Bezugnahme eingeschlossen.Typical components for fuels or fuel additive concentrates are, for example, additives with detergent action, as described in the applicant's German application, file number 100 36 956.1, dated July 28, 2000 (page 14 ff.), In the applicant's German application, file number 100 03 105.6, dated 25.1.2000 and in the PCT application of the applicant with the file number PCT / EP / 01/00496. The additives mentioned there and other fuel additives described there with polar Generations are part of the present application and are incorporated by reference.
In den erfindungsgemäßen Kraftstoffen und Kraftstoffadditiv-Konzentraten können auch Kraftstoffadditive enthalten sein, wie sie beispielsweise beschrieben sind in den europäischen Patentanmeldungen EP-A 0 277 345, 0 356 725, 0 476 485, 0 484 736, 0 539 821, 0 543 225, 0 548 617, 0 561 214, 0 567 810, 0 568 873, den deutschen Patentanmeldungen DE-A 39 42 860, 43 09 074, 43 09 271, 43 13 088, 44 12 489, 44 25 834, 195 25 938, 196 06 845, 196 06 846, 196 15 404, 196 06 844, 196 16 569, 196 18 270, 196 14 349, sowie der WO-A 96/03479.The fuels and fuel additive concentrates according to the invention can also contain fuel additives as described, for example, in European patent applications EP-A 0 277 345, 0 356 725, 0 476 485, 0 484 736, 0 539 821, 0 543 225, 0 548 617, 0 561 214, 0 567 810, 0 568 873, German patent applications DE-A 39 42 860, 43 09 074, 43 09 271, 43 13 088, 44 12 489, 44 25 834, 195 25 938, 196 06 845, 196 06 846, 196 15 404, 196 06 844, 196 16 569, 196 18 270, 196 14 349, and WO-A 96/03479.
Weitere übliche Komponenten sind beispielsweise weitere korrosionsinhibierende Zusätze, Antioxidantien, Stabilisatoren, Antistatikmittel, metallorganische Verbindungen, Verschleißschutz-Additive, Farbstoffe und Cetanzahl-Verbesserer, Flow-Improver, Biozide wie Glutardialdehyd oder Glyoxal. Die Biozide werden üblicherweise in einer Menge von 0,01 bis 3 Gew.-%, bezogen auf das Gesamtgewicht des Konzentrats, eingesetzt.Other common components are, for example, other corrosion-inhibiting additives, antioxidants, stabilizers, antistatic agents, organometallic compounds, wear protection additives, dyes and cetane number improvers, flow improvers, biocides such as glutardialdehyde or glyoxal. The biocides are usually used in an amount of 0.01 to 3% by weight, based on the total weight of the concentrate.
Beispiele für weitere korrosionsinhibierende Zusätze sind solche auf Basis von zur Filmbildung neigenden Ammoniumsalzen organischer Carbonsäuren oder von heterocyclischen Aromaten bei Buntmetallkorrosionsschutz.Examples of further corrosion-inhibiting additives are those based on ammonium salts of organic carboxylic acids, which tend to form films, or on heterocyclic aromatics in the case of non-ferrous metal corrosion protection.
Beispiele für Stabilisatoren sind solche auf Basis von Aminen wie p-Phenylendiamin, Dicyclohexylamin oder Derivaten hiervon oder von Phenolen wie 2,4-Di-tert.-Butylphenol oder 3,5-Di-tert.-butyl-4-hydroxyphenylpropionsäure.Examples of stabilizers are those based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or on phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid.
Beispiele für metallorganische Verbindungen sind Ferrocen oder Methylcyclo- pentadienylmangantricarbonyl.Examples of organometallic compounds are ferrocene or methylcyclopentadienylmanganese tricarbonyl.
Beispiele für Cetanzahl-Verbesserer sind organische C -C10-Nitrate wie 2-Ethylhexylnitrat, sowie anorganische Cetanzahl-Verbesserer für die wäßrige Phase wie Arnmoniumnitrat. Bevorzugt werden 2-Ethylhexylnitrat und Ammoniumnitrat eingesetzt. Die Cetanzahl- Verbesserer werden üblicherweise in einer Menge von 0,05 bis 5 Gew.-%, bezogen auf das Gesamtgewicht des Konzentrats, eingesetzt.
Als Lösungsmittel für die erfindungsgemäßen Kraftstoff- und Schmierstoffadditivkonzentrate kommen aliphatische und aromatische Kohlenwasserstoffe wie Solventnaphtha, Isododecan, Mihagol (ein technisches Gemisch von
die Kraft- und Schmierstoffe selbst sowie Trägeröle in Betracht.Examples of cetane number improvers are organic C -C 10 nitrates such as 2-ethylhexyl nitrate, and inorganic cetane number improvers for the aqueous phase such as ammonium nitrate. 2-Ethylhexyl nitrate and ammonium nitrate are preferably used. The cetane number improvers are usually used in an amount of 0.05 to 5% by weight, based on the total weight of the concentrate. Solvents for the fuel and lubricant additive concentrates according to the invention are aliphatic and aromatic hydrocarbons such as solvent naphtha, isododecane, mihagol (a technical mixture of the fuels and lubricants themselves as well as carrier oils.
Trägeröle, die ebenfalls zur Verdünnung der Kraftstoff- und Schmierstoffadditivkonzentrate dienen, sind beispielsweise mineralische Trägeröle (Grundöle), insbesondere solche der Viskositätsklasse "Solvent Neutral (SN) 100 bis 500", sowie synthetische Trägeröle auf Basis von Polyolefinen, (Poly)Estem, (Alkylphenol-gestarteten) Polyethem, (aliphatischen) (Alkylphenol-gestarteten) Polyetheraminen, und Trägeröle auf Basis alkoxylierter langkettiger Alkohole oder Phenole. Beispiele für besonders geeignete synthetische Trägeröle sind solche auf Basis von Polyolefinen, bevorzugt auf Basis von Polyisobutylen sowie von Poly-α-olefinen, mit einem zahlenmittleren Molekulargewicht M„ von 400 bis 1800. Auch Polyethylenoxide, Polypropylenoxide, Polybutenoxide und deren Mischungen sind geeignete Trägeröle. Weitere geeignete Trägeröle und Trägerölgemische sind beispielsweise beschrieben in den Druckschriften DE-A 38 38 918, DE-A 38 26 608, DE-A 41 42241, DE-A 43 09074, US 4,877,416 und EP-A 0452 328.Carrier oils, which also serve to dilute the fuel and lubricant additive concentrates, are, for example, mineral carrier oils (base oils), in particular those of the viscosity class "Solvent Neutral (SN) 100 to 500", as well as synthetic carrier oils based on polyolefins, (poly) esters, ( Alkylphenol-started) polyethers, (aliphatic) (alkylphenol-started) polyetheramines, and carrier oils based on alkoxylated long-chain alcohols or phenols. Examples of particularly suitable synthetic carrier oils are those based on polyolefins, preferably based on polyisobutylene and poly-α-olefins, with a number average molecular weight M "from 400 to 1800. Polyethylene oxides, polypropylene oxides, polybutene oxides and mixtures thereof are also suitable carrier oils. Further suitable carrier oils and carrier oil mixtures are described, for example, in the publications DE-A 38 38 918, DE-A 38 26 608, DE-A 41 42241, DE-A 43 09074, US 4,877,416 and EP-A 0452 328.
Erfindungsgemäße wasserhaltige Flüssigkeiten enthalten die erfindungsgemäßen Verbindungen und/oder erfindungsgemäßen Mischungen gegebenenfalls in Kombination mit weiteren üblichen korrosionsinhibierenden Zusätzen, im allgemeinen in einem Anteil von etwa 1 bis 10 Gew.-% - bezogen auf die Gesamtmenge.Water-containing liquids according to the invention contain the compounds and / or mixtures according to the invention, if appropriate in combination with other customary corrosion-inhibiting additives, generally in a proportion of about 1 to 10% by weight, based on the total amount.
Die Erfindung wird nun in den nachfolgenden Beispielen näher erläutert.The invention will now be explained in more detail in the following examples.
Ausführungsbeispieleembodiments
Beispiel 1: Herstellung der Verbindungen der allgemeinen Formel (Ia) und (Tb)Example 1: Preparation of the compounds of the general formulas (Ia) and (Tb)
Die Zusammensetzung der hergestellten Verbindungen findet sich in Tabelle 1.The composition of the compounds produced can be found in Table 1.
Als Polyisobutylen wurde Glissopal® der BASF AG mit einem zahlenmittleren Molekulargewicht Mn von 380 bis 8400, einem Anteil an Vinylidenendgrappen von > 70Glissopal® from BASF AG with a number average molecular weight M n of 380 to 8400 and a proportion of vinylidene end groups of> 70 was used as polyisobutylene
Mol.-%, einer Polydispersität Mw/Mn im Bereich von 1,15 bis 1,8 und einer
Polymergerüststruktur mit mehr als 85% Isobutylen-Einheiten verwendet. Dieses Polyisobutylen diente als Ausgangsmaterial für die Synthese von mit einer Polyisobutylenyl-Gruppe substituiertem Be steinsäureanhydrid (PIBSA; = polyisobutylene succinic anhydride).Mol .-%, a polydispersity M w / M n in the range of 1.15 to 1.8 and one Polymer scaffold structure with more than 85% isobutylene units used. This polyisobutylene served as a starting material for the synthesis of succinic anhydride (PIBSA) substituted with a polyisobutylenyl group.
Als Polyethylenglykol wurde Pluriol® E der BASF AG mit einem zahlenmittleren Molekulargewicht Mn von 300 bis 5000 eingesetzt. Als Polyethylen-/Polypropylen-glykol- Blockcopolymer wurde Pluronic® PE 3500 der BASF AG mit einem zahlenmittleren Molekulargewicht Mn von 1900 und einem Ethylenoxidanteil von 50 Gew.-% eingesetzt.Pluriol® E from BASF AG with a number average molecular weight M n of 300 to 5000 was used as the polyethylene glycol. Pluronic® PE 3500 from BASF AG with a number-average molecular weight M n of 1900 and an ethylene oxide content of 50% by weight was used as the polyethylene / polypropylene-glycol block copolymer.
Als Lösungsmittel wurden Heptan, Mihagol, ein Gemisch von C10-C12-Paraffinen der Firma Wintershall, sowie Solvesso® 150, ein Gemisch aromatischer Kohlenwasserstoffe, der ExxonMobil Chemical eingesetzt.Heptane, Mihagol, a mixture of C 10 -C 12 paraffins from Wintershall, and Solvesso® 150, a mixture of aromatic hydrocarbons from ExxonMobil Chemical, were used as solvents.
Als Ionenaustauscher wurde der unter dem Namen Ambossol® kommerziell erhältliche der Firma Clariant eingesetzt.Clariant, commercially available under the name Ambossol®, was used as the ion exchanger.
Die Maleinierung der Polyisobutylene zu den entsprechenden Bemsteinsäureanhydriden erfolgte nach an sich bekannten Methoden und ist zum Beispiel in der DE-A 195 19 042, der DE:A 43 19 671 und der DE-A 43 19 672 beschrieben.The maleination of the polyisobutylenes to the corresponding succinic anhydrides was carried out according to methods known per se and is described, for example, in DE-A 195 19 042, DE : A 43 19 671 and DE-A 43 19 672.
Die erhaltenen Verbindungen wurden über die Säurezahl, die OH-Zahl, die Viskosität und/oder die IR-Spektren charakterisiert. Die OH-Zahl wurde bei Verwendung hochsiedender Lösungsmittel lösungsmittelbereinigt bestimmt, d. h. daß die OH-Zahl der Verbindungen im jeweiligen Lösungsmittel gemessen und dann auf die Reinsubstanz extrapoliert wurde. Bei niedrigsiedenden Lösungsmitteln wie Heptan wurde das Lösungsmittel durch Destillation entfernt, und die OH-Zahl von der Reinsubstanz bestimmt.The compounds obtained were characterized via the acid number, the OH number, the viscosity and / or the IR spectra. The OH number was determined using solvent when using high-boiling solvents, i. H. that the OH number of the compounds in the respective solvent was measured and then extrapolated to the pure substance. In the case of low-boiling solvents such as heptane, the solvent was removed by distillation and the OH number was determined from the pure substance.
Die Bestimmung der Viskositäten erfolgte stets gemäß DLN 51562.The viscosities were always determined in accordance with DLN 51562.
Tabelle 1 : Zusammensetzung der Verbindungen der allgemeinen Formel (Ia) bzw. (Ib)Table 1: Composition of the compounds of the general formula (Ia) or (Ib)
Herstellung der Verbindung A:Preparation of compound A:
Ein 11- Vierhalskolben mit Rührer, Tropftrichter und Thermoelement wird mit 250 g PIBSA 550 befullt und auf 90°C erwärmt. 67 g Diethanolamin werden via Tropftrichter binnen 5 Minuten dosiert. Das Gemisch wird stufenweise auf 130°C bzw. 170°C erwärmt. Nach 2 Stunden bei 170°C wird das braune Reaktionsprodukt bei 100°C filtriert.An 11 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 250 g PIBSA 550 and heated to 90 ° C. 67 g of diethanolamine are metered in via a dropping funnel within 5 minutes. The mixture is gradually heated to 130 ° C or 170 ° C. After 2 hours at 170 ° C, the brown reaction product is filtered at 100 ° C.
Herstellung der Verbindung B:Preparation of compound B:
Ein 21- Vierhalskolben mit Rührer, Destillationsbrücke und Thermoelement wird mit 525 g PIBSA 550, 650 g Solvesso® 150 und 175 g Trihydroxymethylaminomethan (TRIS) befullt. Das Gemisch wird stufenweise auf 130°C bzw. 170°C erwärmt. Freigesetztes Wasser wird per Stickstoffstrom entfernt; die Reaktionsdauer beträgt 3 Stunden. Die OH- Zahl wurde lösungsmittelbereinigt zu 250 bestimmt.
Herstellung der Verbindung C:A 21 four-necked flask with stirrer, distillation bridge and thermocouple is filled with 525 g PIBSA 550, 650 g Solvesso® 150 and 175 g trihydroxymethylaminomethane (TRIS). The mixture is gradually heated to 130 ° C or 170 ° C. Released water is removed using a stream of nitrogen; the reaction time is 3 hours. The OH number was determined to be 250 when adjusted for solvent. Preparation of compound C:
Ein 11- Vierhalskolben mit Rührer, Destillationsbrücke und Thermoelement wird mit 310 g PIBSA 750 und 60 g D-Sorbit befüllt. Das Gemisch wird stufenweise auf 160°C bzw. 220°C erwärmt. Freigesetztes Wasser wird per Stickstoffstrom entfernt; nach 3 Stunden bei 220°C wird mit 200 g Mihagol verdünnt und heiß filtriert. Man erhält eine gelbe, zähviskose Produktlösung (65%).An 11 four-necked flask with stirrer, distillation bridge and thermocouple is filled with 310 g PIBSA 750 and 60 g D-sorbitol. The mixture is gradually heated to 160 ° C or 220 ° C. Released water is removed using a stream of nitrogen; after 3 hours at 220 ° C, diluted with 200 g of Mihagol and filtered hot. A yellow, viscous product solution (65%) is obtained.
Herstellung der Verbindung D:Preparation of compound D:
Ein 21- Vierhalskolben mit Rührer, Tropftrichter und Thermoelement wird mit 350 g Pluriol® E 300 befüllt und bei 90°C 30 Minuten im Vakuum entgast. Über einen Tropftrichter werden bei 80°C binnen 5 Minuten eine Lösung von 650 g PIBSA 380 in 350 g Heptan dosiert. Das Gemisch wird stufenweise auf 110°C bzw. 140°C erwärmt. Heptan wird dabei bei reduziertem Druck (350 mbar) abdestilliert. Nach 3 Stunden bei 140°C erhält man ein gelbes Produkt mit einer Viskosität von 105 mm2/s (100°C); OH-Zahl: 70, Säure-Zahl: 73; IR: intensive Bande bei 1735 cm"1 (Ester).A 21 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 350 g Pluriol® E 300 and degassed at 90 ° C for 30 minutes in a vacuum. A solution of 650 g of PIBSA 380 in 350 g of heptane is metered into a dropping funnel at 80 ° C. in the course of 5 minutes. The mixture is gradually heated to 110 ° C or 140 ° C. Heptane is distilled off under reduced pressure (350 mbar). After 3 hours at 140 ° C., a yellow product with a viscosity of 105 mm 2 / s (100 ° C.) is obtained; OH number: 70, acid number: 73; IR: intense band at 1735 cm "1 (ester).
Herstellung der Verbindung E:Establishing connection E:
Ein 21- Vierhalskolben mit Rührer, Tropftrichter und Thermoelement wird mit 300 g Pluriol® E 300 befüllt und bei 90°C 30 Minuten im Vakuum entgast. Über einen Tropftrichter werden bei 80°C binnen 5 Minuten eine Lösung von 750 g PIBSA 550 in 450 g Heptan dosiert. Das Gemisch wird stufenweise auf 110°C bzw. 140°C erwärmt. Heptan wird dabei bei reduziertem Druck (350 mbar) abdestilliert. Nach 3 Stunden bei 140°C werden bei 95°C portionsweise 105 g Diethanolamin zugegeben. Nach weiteren 20 Minuten bei 95°C wird das orangebraune Produkt heiß filtriert. OH-Zahl: 55; IR: intensive Bande bei 1736 cm"1 (Ester).A 21 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 300 g Pluriol® E 300 and degassed at 90 ° C for 30 minutes in a vacuum. A solution of 750 g of PIBSA 550 in 450 g of heptane is metered into a dropping funnel at 80 ° C. within 5 minutes. The mixture is gradually heated to 110 ° C or 140 ° C. Heptane is distilled off under reduced pressure (350 mbar). After 3 hours at 140 ° C, 105 g of diethanolamine are added in portions at 95 ° C. After a further 20 minutes at 95 ° C, the orange-brown product is filtered hot. OH number: 55; IR: intense band at 1736 cm "1 (ester).
Herstellung der Verbindung F:Establishing connection F:
Ein 21- Vierhalskolben mit Rührer, Tropftrichter und Thermoelement wird mit 400 g Pluriol® E 600 befüllt und bei 90°C 30 Minuten im Vakuum entgast. Über einen
Tropftrichter wird bei 80°C binnen 5 Minuten eine Lösung von 790 g PIBSA 1000 in 450 g Heptan dosiert. Das Gemisch wird stufenweise auf 110°C bzw. 140°C erwärmt. Heptan wird dabei unter reduziertem Druck (350 mbar) abdestilliert. Nach 3 Stunden bei 140°C erhält man ein gelbes Produkt mit einer Viskosität von 1650 mm2/s (100°C). OH-Zahl: 43; SZ: 40; IR: intensive Bande bei 1734 cm"1 (Ester).A 21 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 400 g Pluriol® E 600 and degassed in a vacuum at 90 ° C for 30 minutes. About one In the dropping funnel, a solution of 790 g of PIBSA 1000 in 450 g of heptane is metered in at 80 ° C. in the course of 5 minutes. The mixture is gradually heated to 110 ° C or 140 ° C. Heptane is distilled off under reduced pressure (350 mbar). After 3 hours at 140 ° C., a yellow product with a viscosity of 1650 mm 2 / s (100 ° C.) is obtained. OH number: 43; SZ: 40; IR: intense band at 1734 cm "1 (ester).
Herstellung der Verbindung G:Establishing connection G:
Ein 11- Vierhalskolben mit Rührer, Tropftrichter und Thermoelement wird mit 150 g Pluriol® E 1500 befullt und bei 90°C 30 Minuten im Vakuum entgast. Über einen Tropftrichter wird bei 80°C binnen 5 Minuten eine Lösung von 280 g PIBSA 2300 in 300 g Mihagol dosiert. Das Gemisch wird stufenweise auf 110°C bzw. 140°C erwärmt. Nach 3 Stunden bei 140°C erhält man eine gelbe, hochviskose Produktlösung. Viskosität 1750 mm2/s, 100°C; OH-Zahl: 9; SZ: 8,1 ; IR: Bande bei 1736 cm"1.An 11 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 150 g Pluriol® E 1500 and degassed in a vacuum at 90 ° C for 30 minutes. A solution of 280 g PIBSA 2300 in 300 g Mihagol is dosed within 5 minutes at 80 ° C using a dropping funnel. The mixture is gradually heated to 110 ° C or 140 ° C. After 3 hours at 140 ° C, a yellow, highly viscous product solution is obtained. Viscosity 1750 mm 2 / s, 100 ° C; OH number: 9; SZ: 8.1; IR: band at 1736 cm "1 .
Herstellung der Verbindung H:Preparation of compound H:
Ein 11- Vierhalskolben mit Rührer, Tropftrichter und Thermoelement wird mit 150 g Pluriol® E 4000 befüllt und bei 90°C 30 Minuten im Vakuum entgast. Über einen Tropftrichter wird bei 80 °C binnen 5 Minuten eine Lösung von 250 g PIBSA 5200 in 300 g Mihagol dosiert. Das Gemisch wird stufenweise auf 110°C bzw. 140°C erwärmt. Nach 3 Stunden bei 140°C erhält man eine beigefarbenes Wachs. OH-Zahl: 4,3; SZ: 3,5; IR: Bande bei 1736 cm"1 (Ester).An 11 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 150 g Pluriol® E 4000 and degassed in a vacuum at 90 ° C for 30 minutes. A solution of 250 g PIBSA 5200 in 300 g Mihagol is dosed within 5 minutes at 80 ° C using a dropping funnel. The mixture is gradually heated to 110 ° C or 140 ° C. After 3 hours at 140 ° C, a beige wax is obtained. OH number: 4.3; SZ: 3.5; IR: band at 1736 cm "1 (ester).
Herstellung der Verbindung I:Preparation of compound I:
Die Synthese erfolgt analog der Synthese der Verbindung H aus PIBSA (Basis: reaktives PIB 8400; Mw/Mn = 1,45) und Pluriol® E 5000. Das Produkt wird als cremefarbenes Wachs (60%ig in Mihagol) isoliert; IR: 1737 cm"1.The synthesis is carried out analogously to the synthesis of the compound H from PIBSA (basis: reactive PIB 8400; M w / M n = 1.45) and Pluriol® E 5000. The product is isolated as a cream-colored wax (60% in Mihagol); IR: 1737 cm "1 .
Herstellung der Verbindung J für Vergleichsbeispiel 1 :
Die Synthese erfolgt analog der Synthese der Verbindung A aus PIBSA 1000 (Basis: reaktives PIB 1000; Mw/Mn = 1,31) und Diethanolamin (siehe auch US 4,708,753). Das Produkt wird als braune, hochviskose Flüssigkeit isoliert, und hat einen geringeren hydrophilen Anteil A-R als Verbindung A.Preparation of compound J for comparative example 1: The synthesis is carried out analogously to the synthesis of compound A from PIBSA 1000 (basis: reactive PIB 1000; M w / M n = 1.31) and diethanolamine (see also US Pat. No. 4,708,753). The product is isolated as a brown, highly viscous liquid and has a lower hydrophilic content of AR than compound A.
Herstellung der Verbindung K:Establishing connection K:
Die Synthese erfolgt analog der Synthese der Verbindung F aus PIBSA 1000 (Basis: reaktives PIB 1000; Mw/Mn = 1,31) und Pluronic® PE 3500. Das Produkt wird als orangegelbe, hochviskose Flüssigkeit isoliert. Viskosität: 2100 mm /s ; 100°C.The synthesis is carried out analogously to the synthesis of compound F from PIBSA 1000 (basis: reactive PIB 1000; M w / M n = 1.31) and Pluronic® PE 3500. The product is isolated as an orange-yellow, highly viscous liquid. Viscosity: 2100 mm / s; 100 ° C.
Herstellung der Verbindung L:Preparation of compound L:
Ein 11- Vierhalskolben mit Rührer, Tropftrichter und Thermoelement wird mit 75 g einer 45%-igen methanolischen Lösung von Cholin der Firma Fluka und 150 g Mihagol befullt. Methanol wird anschließend bei 50 °C und reduziertem Druck (50 mbar) entfernt (45 Minuten). Zu dieser Suspension dosiert man 200 g PIBSA 550 und erwärmt innerhalb von 15 Minuten auf 90°C. Nach 60 Minuten wird auf 170°C erhöht und weitere zwei Stunden gerührt. Das braune Reaktionsprodukt wird bei 100°C filtriert.An 11 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 75 g of a 45% methanolic solution of choline from Fluka and 150 g of Mihagol. Methanol is then removed at 50 ° C and reduced pressure (50 mbar) (45 minutes). 200 g of PIBSA 550 are added to this suspension and the mixture is heated to 90 ° C. in the course of 15 minutes. After 60 minutes, the temperature is raised to 170 ° C. and the mixture is stirred for a further two hours. The brown reaction product is filtered at 100 ° C.
Herstellung der Verbindung M für Vergleichsbeispiel 2:Preparation of compound M for comparative example 2:
Ein 11- Vierhalskolben mit Rührer, Tropftrichter und Thermoelement wird mit 300 g PIBSA 2300, 200 g PIBSA 1000 sowie 200 g Mihagol befüllt und auf 95°C erwärmt. Bei 95°C werden 17,2 g Ethylenglykol dosiert. Das Gemisch wird auf 130°C erwärmt und bei dieser Temperatur drei Stunden gerührt. Das braune Reaktionsprodukt wird bei 100°C filtriert.An 11 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 300 g PIBSA 2300, 200 g PIBSA 1000 and 200 g Mihagol and heated to 95 ° C. 17.2 g of ethylene glycol are metered in at 95.degree. The mixture is heated to 130 ° C. and stirred at this temperature for three hours. The brown reaction product is filtered at 100 ° C.
Der Emulgator des Vergleichsbeispiels 2 wurde dem Prinzip der WO 00/15740 nach, Beispiel C-l, S. 34, hergestellt.The emulsifier of comparative example 2 was produced according to the principle of WO 00/15740 according to example C-1, p. 34.
Herstellung der Verbindung N für Vergleichsbeispiel 3:
(Die Herstellung erfolgt analog zu Verbindung F. Verbindung F enthält jedoch einen Anteil A-R von 35,3%, während in Verbindung N der hydrophile Anteil A-R 15,4% beträgt.)Preparation of compound N for comparative example 3: (The preparation is carried out analogously to compound F. However, compound F contains an AR of 35.3%, while in compound N the hydrophilic fraction AR is 15.4%.)
Ein 21- Vierhalskolben mit Rührer, Tropftrichter und Thermoelement wird mit 100 g Pluriol® E 200 befüllt und bei 90°C 30 Minuten im Vakuum entgast. Über einen Tropftrichter wird bei 80°C binnen 5 Minuten eine Lösung von 590 g PIBSA 1000 in 450 g Heptan dosiert. Das Gemisch wird stufenweise auf 110°C bzw. 140°C erwärmt. Heptan wird dabei unter reduziertem Druck (350 mbar) abdestilliert. Nach 3 Stunden bei 140°C erhält man ein bernsteinfarbenes Produkt mit einer Viskosität von 1450 mm2/s (100°C).A 21 four-necked flask with stirrer, dropping funnel and thermocouple is filled with 100 g Pluriol® E 200 and degassed in a vacuum at 90 ° C for 30 minutes. A solution of 590 g of PIBSA 1000 in 450 g of heptane is metered into a dropping funnel at 80 ° C. within 5 minutes. The mixture is gradually heated to 110 ° C or 140 ° C. Heptane is distilled off under reduced pressure (350 mbar). After 3 hours at 140 ° C., an amber-colored product with a viscosity of 1450 mm 2 / s (100 ° C.) is obtained.
Beispiel 2: Herstellung der Wasser-in-Kraftstoff-EmulsionenExample 2: Preparation of the water-in-fuel emulsions
Die Herstellung bzw. die Zusammensetzung der Kraftstoffgemische ist in Tabelle 2 zusammengestellt.The production or the composition of the fuel mixtures is summarized in Table 2.
Die hydrophilen bzw. wasserlöslichen Bestandteile wurden vorab in der wässrigen Phase gelöst, lipophile Komponenten im Dieselöl. Mit einem Ultra-Turrax® (Jahnke und Kunkel Laborgerät T25) wurden 500 g dieser Mischung mit 100 ml Wasser 15 min lang mit einer Umdrehungszahl von 24000/min homogenisiert. Die Herstellung der Emulsion im technischen Maßstab bzw. die motorischen Tests erfolgte analog der DE-A 198 56 604 der Anmelderin (angemeldet am 8.12.1998), mit einer dort beschriebenen Mischdüse. Der Druck im Mischapparat betrug bei einem Umsatz von (gesamt) 12 kg/h 50 bis 200 bar (vor der Blende), bevorzugt 120 bar.The hydrophilic or water-soluble components were previously dissolved in the aqueous phase, lipophilic components in the diesel oil. With an Ultra-Turrax® (Jahnke and Kunkel laboratory device T25) 500 g of this mixture were homogenized with 100 ml water for 15 minutes at a speed of 24000 / min. The emulsion was produced on an industrial scale and the motor tests were carried out analogously to DE-A 198 56 604 by the applicant (registered on December 8, 1998), with a mixing nozzle described there. The pressure in the mixing apparatus was 50 to 200 bar (in front of the orifice), preferably 120 bar, with a conversion of (total) 12 kg / h.
Tabelle 2 (siehe nächste Seite): Zusammensetzung der EmulsionenTable 2 (see next page): Composition of the emulsions
* Als Biozid wurde entweder Glyoxal oder Glutaraldehyd verwendet.* Either glyoxal or glutaraldehyde was used as the biocide.
In den Beispielen 1, 2, 6 und 7 wurden erfindungsgemäße niedermolekulare Verbindungen, in den Beispielen 3, 4 und 5 wurden erfindungsgemäße Mischungen aus nieder- und hochmolekularen Verbindungen eingesetzt.
In Examples 1, 2, 6 and 7, low molecular weight compounds according to the invention were used; in Examples 3, 4 and 5, mixtures of low and high molecular weight compounds according to the invention were used.
Beispiel 3: Untersuchungen zur Stabilität der Wasser-in-Kraftstof -EmulsionenExample 3: Studies on the stability of the water-in-fuel emulsions
Die Größe der Wassertropfen wurde physikalisch per Laserbeugung (X3, 2- Werte) mit einem Malvem Mastersizer 2000 der Firma Malvem Instruments GmbH bestimmt. Die Meßmethode ist beispielsweise beschrieben in Terence Allen, Particle Size Measurement,
Volume 1, 5ft Edition, Kluwer Academic Publishers, Dordrecht, Netherlands 1999. In Abhängigkeit von der tatsächlich vorliegenden Größenverteilung kommen neben der Laserlichtbeugung noch weitere Methoden wie z. B. die dynamische Lichtstreuung, Einzelpartikelzähler und Ultraschallextinktion in Frage.The size of the water drops was physically determined by laser diffraction (X3, 2 values) using a Malvem Mastersizer 2000 from Malvem Instruments GmbH. The measurement method is described, for example, in Terence Allen, Particle Size Measurement, Volume 1, 5 ft Edition, Kluwer Academic Publishers, Dordrecht, Netherlands 1999. Depending on the actual size distribution, there are other methods besides laser light diffraction such as: B. the dynamic light scattering, single particle counter and ultrasonic extinction in question.
Die Größe der Wassertropfen ist ein Maß für die Güte der Emulsion. Je kleiner die Tropfengröße, desto besser bzw. stabiler ist die Emulsion. Die entsprechenden Werte für die Tropfengröße (die X3, 2- Werte) sind in Tabelle 3 zusammengestellt. Wie Tabelle 3 zu entnehmen ist, weisen die Emulsionen unter Verwendung der erfindungsgemäßen Verbindungen als auch der erfindungsgemäßen Mischungen zum Teil deutlich kleinere Tropfengrößen auf als die Vergleichsemulsionen. Daß die Tropfengröße wirklich ein Maß für die Stabilität der Emulsion bei Raumtemperatur ist, zeigt sich an den durch Lagerversuche ermittelten Werten für die Stabilität. Die Emulsionen mit größeren Tropfengrößen weisen auch eine schlechtere Lagerstabilität auf.The size of the water drops is a measure of the quality of the emulsion. The smaller the drop size, the better or more stable the emulsion. The corresponding values for the drop size (the X3, 2 values) are summarized in Table 3. As can be seen in Table 3, the emulsions using the compounds according to the invention and also the mixtures according to the invention sometimes have significantly smaller drop sizes than the comparison emulsions. The fact that the drop size is really a measure of the stability of the emulsion at room temperature is shown by the stability values determined by storage tests. The emulsions with larger droplet sizes also have poorer storage stability.
Tabelle 3: Tropfengröße und Stabilität der Wasser-in-Kraftstoff-EmulsionenTable 3: Drop size and stability of the water-in-fuel emulsions
12 Wochen; ** 1 Woche12 weeks; ** 1 week
Die Stabilität der Emulsionen wurde in einem statischen Lagertest bei 20°C (12 Wochen lang) und zusätzlich unter wechselnden Temperaturen (-20°C und 70°C, jeweils 1 Woche lang) überprüft. Hierzu wurde die Emulsion in einen skalierten 100 ml-Standzylinder gefüllt und nach den angegebenen Bedingungen auf ihre Güte hin optisch begutachtet.
Verglichen mit der Verwendung von Emulgatoren aus dem Stand der Technik (Vergleichsbeispiele) ist unter Verwendung der erfindungsgemäßen Emulgatoren und deren Gemische eine zum Teil signifikante Verbesserung der Lagerstabilität zu beobachten. Die Beurteilung der Lagerversuche bei -20°C erfolgte anschließend bei Raumtemperatur. Die Emulsion gemäß Beispiel 2 ist nach dem Auftauen auch ohne Frostschutzzusatz (z. B. Monoethylenglykol) vergleichsweise homogen. Ansonsten erfolgte nach bzw. auch schon bei Erwärmung eine Phasenseparation, ein sogenanntes "Brechen" der Emulsion.The stability of the emulsions was checked in a static storage test at 20 ° C (for 12 weeks) and additionally under changing temperatures (-20 ° C and 70 ° C, each for 1 week). For this purpose, the emulsion was filled into a scaled 100 ml standing cylinder and its quality was assessed visually in accordance with the specified conditions. Compared to the use of emulsifiers from the prior art (comparative examples), a partially significant improvement in the storage stability can be observed using the emulsifiers according to the invention and their mixtures. The storage tests at -20 ° C were then assessed at room temperature. After thawing, the emulsion according to Example 2 is comparatively homogeneous even without the addition of anti-freeze (e.g. monoethylene glycol). Otherwise, phase separation, a so-called "breaking" of the emulsion, took place after or even when heated.
Ein Vergleich der Qualität der erfindungsgemäßen Emulsionen mit einer Emulsion nach der WO 00/15740 (Beispiel C-1, S. 34, Vergleichsbeispiel 2) beweist, daß eine Kombination einer niedermolekularen Komponente und einer höhermolekularen Komponente zu einer entsprechend verbrückten Verbindung zu einem signifikant schlechteren Emulgator führt als eine erfindungsgemäße Mischung der isolierten Verbindungen.A comparison of the quality of the emulsions according to the invention with an emulsion according to WO 00/15740 (Example C-1, p. 34, Comparative Example 2) proves that a combination of a low molecular weight component and a higher molecular weight component to form a correspondingly bridged compound results in a significantly worse one Emulsifier performs as a mixture according to the invention of the isolated compounds.
Beispiel 4: Verwendung der erfindungsgemäßen Verbindungen der allgemeinen Formel (I) als Rostschutz- und VerschleißschutzadditiveExample 4: Use of the compounds of the general formula (I) according to the invention as rust protection and wear protection additives
Ein 20 x 40 mm großes Eisenblech wird mit 40 μm Glasperlen gestrahlt und anschließend - in Anlehnung an ASTM D-665 - in die unter Beispiel 2 hergestellten Emulsionen getaucht und bei 40 ± 1°C für 24 Stunden gelagert. Nach 24 Stunden wird das Eisenblech auf Rostbildung hin untersucht. Hierbei bedeuten:A 20 x 40 mm sheet of iron is blasted with 40 μm glass beads and then - based on ASTM D-665 - immersed in the emulsions prepared in Example 2 and stored at 40 ± 1 ° C for 24 hours. After 24 hours, the iron sheet is examined for rust formation. Here mean:
++ keine Rostbildung; +0, geringfügiger Rostansatz;++ no rust formation; +0, slight rust;
-0, Rostbildung auf mehr als 25% der Fläche des Testblechs; Rostbildung auf mehr als 50% des Testblechs.-0, rust formation on more than 25% of the area of the test sheet; Rust formation on more than 50% of the test sheet.
Wie den Ergebnissen der Tabelle 4 zu entnehmen ist, konnte bei Verwendung der erfindungsgemäßen Verbindungen als korrosionsinhibierende Zusätze teilweise nur geringfügiger Rostansatz beobachtet werden. Im Gegensatz dazu trat bei Verwendung von Cι3-Oxoalkohol-Ethoxylat auf mehr als 50% der Fläche des Testblechs Rostbildung auf.As can be seen from the results in Table 4, when using the compounds according to the invention as corrosion-inhibiting additives, in some cases only slight rust formation was observed. In contrast to this, rust formation occurred on more than 50% of the surface of the test sheet when using C 3 -oxoalcohol ethoxylate.
Beispiel 5: Verwendung der erfindungsgemäßen Verbindungen der allgemeinen Formel (I) in Kraftstoffen und deren Verschleißschutz- Verhalten
In einem unadditivierten Diesel-Kraftstoff (Miro, Karlsruhe) wurden jeweils die tabellarisch aufgeführten Verbindungen gelöst. Die Konzentration an Additiv im Dieselkraftstoff betrug 75 ppm. Die Beurteilung des Verschleißschutzverhaltens erfolgte per HFRR-Test (High Frequency Roller Rig Test), der gemäß ISO 12156-1 durchgeführt wurde. Die Länge der entstehenden Riefen wurde vermessen und als Maß für den Verschleiß herangezogen. Je kürzer die Riefen waren, desto besser war der Verschleißschutz des zugeführten Additivs. Zum Vergleich wurde unaddivierter Diesel- Kraftstoff verwendet. Wie Tabelle 4 zu entnehmen ist, schützten die erfindungsgemäßen Verbindungen vor Verschleiß.Example 5: Use of the compounds of the general formula (I) according to the invention in fuels and their wear protection behavior The connections listed in the table were solved in an unadditized diesel fuel (Miro, Karlsruhe). The concentration of additive in the diesel fuel was 75 ppm. The wear protection behavior was assessed using the HFRR test (High Frequency Roller Rig Test), which was carried out in accordance with ISO 12156-1. The length of the resulting grooves was measured and used as a measure of wear. The shorter the scoring, the better the wear protection of the additive added. Unaddivated diesel fuel was used for comparison. As can be seen from Table 4, the compounds according to the invention protected against wear.
Tabelle 4:Table 4:
Claims
Verbindung der allgemeinen Formel (Ia) und (Ib)Compound of the general formula (Ia) and (Ib)
(Ia) (Ib)(Ia) (Ib)
wobei La für eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 300 bis 1000 steht,where L a stands for a polyisobutylenyl group with a number average molecular weight M n of 300 to 1000,
Lb für eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 2000 bis 20000 steht,L b represents a polyisobutylenyl group with a number average molecular weight M n of 2,000 to 20,000,
-A- für -O-, -N(H)- oder -N(RJ)- steht,-A- stands for -O-, -N (H) - or -N (R J ) -,
M* für H+, ein AlkalimetalHon, 0,5 Erdalkalimetallionen oder NH steht, wobei in NE + ein oder mehrere H durch Alkylreste ersetzt sein können, undM * stands for H + , an alkali metal honey, 0.5 alkaline earth metal ions or NH, where one or more H in NE + can be replaced by alkyl radicals, and
R für einen linearen oder verzweigten gesättigten Kohlenwasserstoffrest steht, der mindestens einen Substituenten ausgewählt aus der Gruppe OH, NH2 oder NH3 + und gegebenenfalls ein oder mehrere C(O)H-Gruppen trägt und gegebenenfalls ein oder mehrere nicht-benachbarte -O- und/oder sekundäre Amine und/oder tertiäre Amine enthält, und wobei in den NH2- oder NH3 +-Gruppen ein oder mehrere H durch Alkylreste ersetzt sein können, undR represents a linear or branched saturated hydrocarbon radical which bears at least one substituent selected from the group OH, NH 2 or NH 3 + and optionally one or more C (O) H groups and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, and wherein one or more H in the NH 2 - or NH 3 + groups can be replaced by alkyl radicals, and
R1 für einen linearen oder verzweigten gesättigten Kohlenwasserstoffrest steht, der gegebenenfalls einen oder mehrere Substituenten ausgewählt aus der Gruppe OH, NH2, NH + oder C(O)H trägt und gegebenenfalls ein oder mehrere nichtbenachbarte -O- und/oder sekundäre Amine und/oder tertiäre Amine enthält, und wobei in den NH2- oder NH3 -Gruppen ein oder mehrere H durch Alkylreste ersetzt sein können, und der Anteil von A-R an der Verbindung der allgemeinen Formel (Ia) bzw. (Ib) mindestens 20 Gew.-% beträgt.R 1 stands for a linear or branched saturated hydrocarbon radical which optionally carries one or more substituents selected from the group OH, NH 2 , NH + or C (O) H and optionally one or more non-adjacent -O- and / or secondary amines and / or contains tertiary amines, and wherein one or more H in the NH 2 or NH 3 groups can be replaced by alkyl radicals, and the proportion of AR in the compound of the general formula (Ia) or (Ib) is at least 20% by weight.
2. Verbindung nach Anspruch 1, dadurch gekennzeichnet, daß La für eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht M„ von 350 bis 950, insbesondere von 350 bis 650, und Lb für eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht von 2000 bis 12000, insbesondere von2. Compound according to claim 1, characterized in that L a for a polyisobutylenyl group with a number average molecular weight M "from 350 to 950, in particular from 350 to 650, and L b for a polyisobutylenyl group with a number average molecular weight from 2000 to 12000, in particular from
2300 bis 5000, steht.2300 to 5000.
3. Verbindung nach Ansprach 1 oder 2, dadurch gekennzeichnet, daß La und Lb für eine Polyisobutylenylgruppe stehen, die eine Polydispersität ≤ 3,0, bevorzugt von 1,1 bis 2,5, besonders bevorzugt von 1,1 bis 2,0, aufweist.3. Compound according to spoke 1 or 2, characterized in that L a and L b represent a polyisobutylenyl group having a polydispersity ≤ 3.0, preferably from 1.1 to 2.5, particularly preferably from 1.1 to 2, 0.
4. Verbindung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß La und Lb für eine Polyisobutylenylgruppe stehen, die zu mindestens 80 Gew.-% aus4. A compound according to any one of claims 1 to 3, characterized in that L a and L b represent a polyisobutylenyl group, which consists of at least 80 wt .-%
Isobutyleneinheiten aufgebaut ist.Isobutylene units is built up.
5. Verbindung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Anteil von A-R an der Verbindung der allgemeinen Formel (Ia) und (Ib) mindestens 25 Gew.-%, insbesondere 35 bis 60 Gew.-% beträgt.5. A compound according to any one of claims 1 to 4, characterized in that the proportion of A-R in the compound of general formula (Ia) and (Ib) is at least 25% by weight, in particular 35 to 60% by weight.
6. Verbindung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß A = - O- und R ein monovalenter Rest eines Oligomeren oder Polymeren von Ethylenoxid und/oder Propylenoxid oder ein monovalenter Rest eines Blockcopoly- meren von Ethylen- und Propylenoxid ist.6. A compound according to any one of claims 1 to 5, characterized in that A = - O- and R is a monovalent radical of an oligomer or polymer of ethylene oxide and / or propylene oxide or a monovalent radical of a block copolymer of ethylene and propylene oxide.
7. Mischung enthaltend7. Containing mixture
(a) höchstens 99 Gew.-%, bevorzugt von 98 bis 80 Gew.-%, besonders bevorzugt von 97 bis 85 Gew.-%, mindestens einer Verbindung der allgemeinen Formel (Ia),(a) at most 99% by weight, preferably from 98 to 80% by weight, particularly preferably from 97 to 85% by weight, of at least one compound of the general formula (Ia),
(Ia) (Ib) (Ia) (Ib)
(b) mindestens 1 Gew.-%, bevorzugt 2 bis 20 Gew.-%, besonders bevorzugt 3 bis 15 Gew.-%, mindestens einer Verbindung der allgemeinen Formel (Ib),(b) at least 1% by weight, preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight, of at least one compound of the general formula (Ib),
wobei La eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 300 bis 1000 und Lb eine Polyisobutylenylgruppe mit einem zahlenmittleren Molekulargewicht Mn von 2000 bis 20000 ist,where L a is a polyisobutylenyl group with a number average molecular weight M n of 300 to 1000 and L b is a polyisobutylenyl group with a number average molecular weight M n of 2000 to 20,000,
-A- für -O-, -N(H)- oder -N(R')- steht,-A- stands for -O-, -N (H) - or -N (R ') -,
M1" für ϊt, ein Alkalimetallion, 0,5 Erdalkalimetallionen oder NH4 1" steht, wobei in t " ein oder mehrere H durch Alkylreste ersetzt sein können,M 1 "stands for ϊt, an alkali metal ion, 0.5 alkaline earth metal ions or NH 4 1" , where in t " one or more H can be replaced by alkyl radicals,
R für einen linearen oder verzweigten gesättigten Kohlenwasserstoffrest steht, der mindestens einen Substituenten ausgewählt aus der Gruppe OH, NH2 oder NH3 + und gegebenenfalls ein oder mehrere C(O)H-Gruppen trägt und gegebenenfalls ein oder mehrere nicht-benachbarte -O- und/oder sekundäre Amine und/oder tertiäre Amine enthält, und wobei in den NH2- oder NH3 +-Gruppen ein oder mehrere H durch Alkylreste ersetzt sein können, undR represents a linear or branched saturated hydrocarbon radical which bears at least one substituent selected from the group OH, NH 2 or NH 3 + and optionally one or more C (O) H groups and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, and wherein one or more H in the NH 2 - or NH 3 + groups can be replaced by alkyl radicals, and
R1 für einen linearen oder verzweigten gesättigten Kohlenwasserstoffrest steht, der gegebenenfalls einen oder mehrere Substituenten ausgewählt aus der Gruppe OH, NH2, NH3 + oder C(O)H trägt und gegebenenfalls ein oder mehrere nicht- benachbarte -O- und/oder sekundäre Amine und/oder tertiäre Amine enthält, und wobei in den NH2- oder NH3 +-Grappen ein oder mehrere H durch Alkylreste ersetzt sein können, undR 1 stands for a linear or branched saturated hydrocarbon radical which optionally carries one or more substituents selected from the group OH, NH 2 , NH 3 + or C (O) H and optionally one or more non-adjacent -O- and / or contains secondary amines and / or tertiary amines, and wherein in the NH 2 - or NH 3 + groups one or more H may be replaced by alkyl radicals, and
der Anteil von A-R an der Verbindung der allgemeinen Formel (Ia) mindestens 10 Gew.-% beträgt und an der Verbindung der allgemeinen Formel (Ib) mindestens 20the proportion of A-R in the compound of the general formula (Ia) is at least 10% by weight and in the compound of the general formula (Ib) at least 20
Gew.-% beträgt.% By weight.
8. Mischung nach Anspruch 7, dadurch gekennzeichnet, daß der Anteil von A-R an der Verbindung der allgemeinen Formel (Ia) mindestens 15 Gew.-%, bevorzugt mindestens 20 Gew.-%, besonders bevorzugt mindestens 25 Gew.-%, ganz besonders bevorzugt 35 bis 60 Gew.-%, und/oder an der Verbindung der allgemeinen Formel (Ib) mindestens 25 Gew.-%, insbesondere 35 bis 60 Gew.-%, beträgt.8. Mixture according to claim 7, characterized in that the proportion of AR in the compound of the general formula (Ia) is at least 15% by weight, preferably at least 20% by weight, particularly preferably at least 25% by weight, very particularly preferably 35 to 60 wt .-%, and / or on the compound of general formula (Ib) is at least 25% by weight, in particular 35 to 60% by weight.
9. Mischung nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß La und oder Lb für eine Polyisobutylenylgruppe stehen, die zu mindestens 80 Gew.-% aus Isobutyleneinheiten aufgebaut ist.9. Mixture according to claim 7 or 8, characterized in that L a and or L b represent a polyisobutylenyl group which is composed of at least 80% by weight of isobutylene units.
10. Verfahren zur Herstellung von Verbindungen der allgemeinen Formel (Ia) und (Ib) gemäß einem der Ansprüche 1 bis 6, bei dem Polyisobutylen mit Fumarsäure- dichlorid, Fumarsäure, Maleinsäuredichlorid, Maleinsäure oder10. A process for the preparation of compounds of general formula (Ia) and (Ib) according to any one of claims 1 to 6, in which polyisobutylene with fumaric acid dichloride, fumaric acid, maleic acid dichloride, maleic acid or
Maleinsäureanhydrid umgesetzt, das erhaltene Reaktionsprodukt mit Ethylenoxid, Propylenoxid, Alkanolaminen, Polyaminen, Oligoalkoholen, Polyolen, Oligoalkylenglykolen, Polyalkylenglykolen, Kohlenhydraten oder Zuckern zur Reaktion gebracht und die vorhandene freie Carboxylgruppe gegebenenfalls mit NH3, einem Amin oder einem (Erd)Alkalimetallsalz in das entsprechende Salz überführt wird.Maleic anhydride reacted, the reaction product obtained is reacted with ethylene oxide, propylene oxide, alkanolamines, polyamines, oligoalcohols, polyols, oligoalkylene glycols, polyalkylene glycols, carbohydrates or sugars and the free carboxyl group present, if appropriate, with NH 3 , an amine or an (earth) alkali metal salt in the corresponding Salt is transferred.
11. Verwendung einer Verbindung der allgemeinen Formel (Ia) und/oder (Ib) gemäß einem der Ansprüche 1 bis 6 und/oder einer Mischung gemäß einem der Ansprüche 7 bis 9 als oberflächenaktive Substanz, als Emulgator, als Verschleißschutzadditiv, als schmierfahigkeitsverbessemder oder korrosionsinhibierender Zusatz in Kraftstoffen, Schmierstoffen, Kraftstoffadditiv- und Schmierstoffadditiv- Konzentraten oder als korrosionsinhibierender Zusatz in wasserhaltigen Flüssigkeiten.11. Use of a compound of general formula (Ia) and / or (Ib) according to one of claims 1 to 6 and / or a mixture according to one of claims 7 to 9 as a surface-active substance, as an emulsifier, as a wear protection additive, as a lubricity-improving or corrosion-inhibiting Additive in fuels, lubricants, fuel additive and lubricant additive concentrates or as a corrosion-inhibiting additive in water-containing liquids.
12. Verwendung nach Anspruch 11, wobei die Verbindung und/oder die Mischung als Emulgator bei der Herstellung von Wasser-in-Öl-Emulsionen, insbesondere von Wasser-in-Kraftstoff-Emulsionen, oder als Tensid für industrielle und kosmetische Wasch- und Reinigungsformulierungen verwendet wird.12. Use according to claim 11, wherein the compound and / or the mixture as an emulsifier in the production of water-in-oil emulsions, in particular water-in-fuel emulsions, or as a surfactant for industrial and cosmetic washing and cleaning formulations is used.
13. Kraftstoff, Schmierstoff, Kraftstoffadditivkonzentrat, Schmierstoffadditivkonzentrat und wasserhaltige Flüssigkeit enthaltend eine oder mehrere Verbindungen der allgemeinen Formel (Ia) und/oder (Ib) gemäß einem der Ansprüche 1 bis 6 und/oder eine Mischung gemäß einem der Ansprüche 7 bis 9, vorzugsweise Wasser-in-Kraftstoff-Emulsion enthaltend 60 bis 95 Gew.-%13. Fuel, lubricant, fuel additive concentrate, lubricant additive concentrate and water-containing liquid containing one or more compounds of the general formula (Ia) and / or (Ib) according to one of claims 1 to 6 and / or a mixture according to one of claims 7 to 9, preferably Water-in-fuel emulsion containing 60 to 95% by weight
Kraftstoff, vorzugsweise Dieselkraftstoff, 3 bis 35 Gew.-% Wasser und 0,2 bis 10 Gew.-%», vorzugsweise 0,5 bis 5 Gew.-%, einer oder mehrerer Verbindungen der allgemeinen Formel (Ia) und/oder (Ib) gemäß einem der Ansprüche 1 bis 6 und/oder einer Mischung gemäß einem der Ansprüche 7 bis 9 als Emulgator.Fuel, preferably diesel fuel, 3 to 35% by weight of water and 0.2 to 10 % By weight, preferably 0.5 to 5% by weight, of one or more compounds of the general formula (Ia) and / or (Ib) according to one of Claims 1 to 6 and / or a mixture according to one of Claims 7 to 9 as an emulsifier.
14. Wasch- und Reinigungsformulierung enthaltend eine oder mehrere Verbindungen der allgemeinen Formel (Ia) und/oder (Ib) gemäß einem der Ansprüche 1 bis 6 und/oder eine Mischung gemäß einem der Ansprüche 7 bis 9.14. washing and cleaning formulation containing one or more compounds of the general formula (Ia) and / or (Ib) according to one of claims 1 to 6 and / or a mixture according to one of claims 7 to 9.
15. Emulsion nach Ansprach 13, dadurch gekennzeichnet, daß neben einer oder mehreren Verbindungen der allgemeinen Formel (Ia) und/oder (Ib) ein oder mehrere weitere Emulgatoren, vorzugsweise Sorbitanmonooleat, C13- Oxoalkoholethoxylate oder Alkylphenolethoxylate, und/oder ein oder mehrere Biozide, bevorzugt NFLfNO3 und/oder Glyoxal, besonders bevorzugt Glyoxal, vorhanden sind.15. Emulsion according spoke 13, characterized in that in addition to one or more compounds of the general formula (Ia) and / or (Ib) one or more further emulsifiers, preferably sorbitan monooleate, C 13 - oxo alcohol ethoxylates or alkylphenol ethoxylates, and / or one or more Biocides, preferably NFL f NO 3 and / or glyoxal, particularly preferably glyoxal, are present.
16. Verfahren zur Herstellung einer Emulsion nach Ansprach 13 oder 15, dadurch gekennzeichnet, daß die jeweiligen Komponenten miteinander vermischt und in an sich bekannter Weise emulgiert werden, vorzugsweise in einer Mischdüse. 16. A method for producing an emulsion according to spoke 13 or 15, characterized in that the respective components are mixed together and emulsified in a manner known per se, preferably in a mixing nozzle.
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PCT/EP2002/005516 WO2002094889A2 (en) | 2001-05-22 | 2002-05-17 | Low-molecular and high-molecular emulsifiers, particularly based on polyisobutylene, and mixtures thereof |
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US5712348A (en) * | 1996-03-13 | 1998-01-27 | E. I. Du Pont De Nemours And Company | Maleic acid copolymers with fluorinated thioether end-cap |
DK0939855T3 (en) * | 1996-11-22 | 2001-09-17 | Clariant Gmbh | Additives to inhibit gas hydrate formation |
US5858029A (en) * | 1997-01-13 | 1999-01-12 | Mobil Oil Corporation | Friction reducing additives for fuels and lubricants |
US6372855B1 (en) * | 1998-08-31 | 2002-04-16 | The Yokohama Rubber Co., Ltd. | Polymer containing isobutylene as repeating unit and rubber composition containing the same |
-
2001
- 2001-05-22 DE DE10125158A patent/DE10125158A1/en not_active Withdrawn
-
2002
- 2002-05-17 CN CNA02810580XA patent/CN1511167A/en active Pending
- 2002-05-17 EP EP02750949A patent/EP1404726A2/en not_active Withdrawn
- 2002-05-17 JP JP2002592363A patent/JP2004531614A/en not_active Withdrawn
- 2002-05-17 WO PCT/EP2002/005516 patent/WO2002094889A2/en not_active Application Discontinuation
- 2002-05-17 CA CA002448033A patent/CA2448033A1/en not_active Abandoned
- 2002-05-17 US US10/478,476 patent/US20040154216A1/en not_active Abandoned
- 2002-05-17 AU AU2002338977A patent/AU2002338977A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
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See references of WO02094889A2 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023051747A1 (en) | 2021-09-30 | 2023-04-06 | 中国石油化工股份有限公司 | Lubricity improver and application thereof in oil product |
Also Published As
Publication number | Publication date |
---|---|
JP2004531614A (en) | 2004-10-14 |
CA2448033A1 (en) | 2002-11-28 |
WO2002094889A3 (en) | 2003-11-27 |
WO2002094889A2 (en) | 2002-11-28 |
CN1511167A (en) | 2004-07-07 |
AU2002338977A1 (en) | 2002-12-03 |
US20040154216A1 (en) | 2004-08-12 |
DE10125158A1 (en) | 2002-12-05 |
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