AU2014339169A1 - Use of a polyalkylene glycol as an additive in a fuel - Google Patents
Use of a polyalkylene glycol as an additive in a fuelInfo
- Publication number
- AU2014339169A1 AU2014339169A1 AU2014339169A AU2014339169A AU2014339169A1 AU 2014339169 A1 AU2014339169 A1 AU 2014339169A1 AU 2014339169 A AU2014339169 A AU 2014339169A AU 2014339169 A AU2014339169 A AU 2014339169A AU 2014339169 A1 AU2014339169 A1 AU 2014339169A1
- Authority
- AU
- Australia
- Prior art keywords
- fuel
- groups
- additive
- polyalkylene glycol
- alkylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000446 fuel Substances 0.000 title claims description 77
- 239000000654 additive Substances 0.000 title claims description 55
- 229920001515 polyalkylene glycol Polymers 0.000 title claims description 53
- 230000000996 additive effect Effects 0.000 title claims description 30
- -1 alkaline earth metal salts Chemical class 0.000 claims description 93
- 239000000203 mixture Substances 0.000 claims description 41
- 239000002816 fuel additive Substances 0.000 claims description 32
- 239000003502 gasoline Substances 0.000 claims description 32
- 239000003599 detergent Substances 0.000 claims description 28
- 238000002485 combustion reaction Methods 0.000 claims description 27
- 239000002199 base oil Substances 0.000 claims description 24
- 229920002367 Polyisobutene Polymers 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 17
- 229920000768 polyamine Polymers 0.000 claims description 17
- 239000012141 concentrate Substances 0.000 claims description 16
- 230000009471 action Effects 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 8
- 150000002989 phenols Chemical class 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006268 reductive amination reaction Methods 0.000 claims description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 5
- 150000001733 carboxylic acid esters Chemical group 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 229940014800 succinic anhydride Drugs 0.000 claims description 5
- 238000007037 hydroformylation reaction Methods 0.000 claims description 4
- 238000006683 Mannich reaction Methods 0.000 claims description 3
- 230000001133 acceleration Effects 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 230000001050 lubricating effect Effects 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 description 17
- 125000001183 hydrocarbyl group Chemical group 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 235000008504 concentrate Nutrition 0.000 description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 10
- 229920000570 polyether Polymers 0.000 description 10
- 229920005862 polyol Polymers 0.000 description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 238000005191 phase separation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000003749 cleanliness Effects 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- GVVPGTZRZFNKDS-JXMROGBWSA-N geranyl diphosphate Chemical compound CC(C)=CCC\C(C)=C\CO[P@](O)(=O)OP(O)(O)=O GVVPGTZRZFNKDS-JXMROGBWSA-N 0.000 description 5
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 229940117927 ethylene oxide Drugs 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229920001083 polybutene Polymers 0.000 description 4
- 108010001861 pregnancy-associated glycoprotein 1 Proteins 0.000 description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 4
- 150000003628 tricarboxylic acids Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 3
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 3
- MPGABYXKKCLIRW-UHFFFAOYSA-N 2-decyloxirane Chemical compound CCCCCCCCCCC1CO1 MPGABYXKKCLIRW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical class CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 229920002266 Pluriol® Polymers 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- UZVAZDQMPUOHKP-UHFFFAOYSA-N 2-(7-methyloctyl)phenol Chemical compound CC(C)CCCCCCC1=CC=CC=C1O UZVAZDQMPUOHKP-UHFFFAOYSA-N 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 159000000032 aromatic acids Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical class OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000003443 succinic acid derivatives Chemical class 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 125000005591 trimellitate group Chemical group 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FIPDAJFVEZEOBT-YPKPFQOOSA-N (Z)-N-butyl-N-methyloctadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN(C)CCCC FIPDAJFVEZEOBT-YPKPFQOOSA-N 0.000 description 1
- OFKZFQNLSSEIMA-ZCXUNETKSA-N (Z)-N-dodecyl-N-methyloctadec-9-en-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCC\C=C/CCCCCCCC OFKZFQNLSSEIMA-ZCXUNETKSA-N 0.000 description 1
- NVGYSDJWLBKKLT-SEYXRHQNSA-N (Z)-N-methyl-N-propyloctadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN(C)CCC NVGYSDJWLBKKLT-SEYXRHQNSA-N 0.000 description 1
- IZOXWVSWRVVLFC-NXVVXOECSA-N (z)-n,n-dibutyloctadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN(CCCC)CCCC IZOXWVSWRVVLFC-NXVVXOECSA-N 0.000 description 1
- CWEGOSBBFLRMKN-YPKPFQOOSA-N (z)-n,n-diethyloctadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN(CC)CC CWEGOSBBFLRMKN-YPKPFQOOSA-N 0.000 description 1
- DCNHQNGFLVPROM-QXMHVHEDSA-N (z)-n,n-dimethyloctadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN(C)C DCNHQNGFLVPROM-QXMHVHEDSA-N 0.000 description 1
- ITCFPLNJTPUVKK-YPKPFQOOSA-N (z)-n,n-dipropyloctadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN(CCC)CCC ITCFPLNJTPUVKK-YPKPFQOOSA-N 0.000 description 1
- UILDOQZLAKRTDC-MSUUIHNZSA-N (z)-n-decyl-n-methyloctadec-9-en-1-amine Chemical compound CCCCCCCCCCN(C)CCCCCCCC\C=C/CCCCCCCC UILDOQZLAKRTDC-MSUUIHNZSA-N 0.000 description 1
- WSQUGKAEOVKILL-SEYXRHQNSA-N (z)-n-ethyl-n-methyloctadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN(C)CC WSQUGKAEOVKILL-SEYXRHQNSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- DSZTYVZOIUIIGA-UHFFFAOYSA-N 1,2-Epoxyhexadecane Chemical compound CCCCCCCCCCCCCCC1CO1 DSZTYVZOIUIIGA-UHFFFAOYSA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 1
- IAXXZRBTTNZGKT-UHFFFAOYSA-N 11-methyl-n,n-dipropyldodecan-1-amine Chemical compound CCCN(CCC)CCCCCCCCCCC(C)C IAXXZRBTTNZGKT-UHFFFAOYSA-N 0.000 description 1
- 125000003562 2,2-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- 125000003660 2,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003764 2,4-dimethylpentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- UHZLTTPUIQXNPO-UHFFFAOYSA-N 2,6-ditert-butyl-3-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1C(C)(C)C UHZLTTPUIQXNPO-UHFFFAOYSA-N 0.000 description 1
- BGRKGHSKCFAPCL-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=CC=C1O BGRKGHSKCFAPCL-UHFFFAOYSA-N 0.000 description 1
- VPCAZZICACQNKZ-UHFFFAOYSA-N 2-Ethyl-N-(2-ethylhexyl)-N-methyl-1-hexanamine Chemical compound CCCCC(CC)CN(C)CC(CC)CCCC VPCAZZICACQNKZ-UHFFFAOYSA-N 0.000 description 1
- RURPJGZXBHYNEM-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound C=1C=CC=C(O)C=1C=NC(C)CN=CC1=CC=CC=C1O RURPJGZXBHYNEM-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- IOHJQSFEAYDZGF-UHFFFAOYSA-N 2-dodecyloxirane Chemical compound CCCCCCCCCCCCC1CO1 IOHJQSFEAYDZGF-UHFFFAOYSA-N 0.000 description 1
- LNNNGGJEZYBFRA-UHFFFAOYSA-N 2-ethyl-N-methyl-N-propylhexan-1-amine Chemical compound CCCCC(CC)CN(C)CCC LNNNGGJEZYBFRA-UHFFFAOYSA-N 0.000 description 1
- OQADVBLQZQTGLL-UHFFFAOYSA-N 2-ethyl-n,n-dimethylhexan-1-amine Chemical compound CCCCC(CC)CN(C)C OQADVBLQZQTGLL-UHFFFAOYSA-N 0.000 description 1
- AIJVWZSWXBRBID-UHFFFAOYSA-N 2-ethyl-n,n-dipropylhexan-1-amine Chemical compound CCCCC(CC)CN(CCC)CCC AIJVWZSWXBRBID-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- GXOYTMXAKFMIRK-UHFFFAOYSA-N 2-heptyloxirane Chemical compound CCCCCCCC1CO1 GXOYTMXAKFMIRK-UHFFFAOYSA-N 0.000 description 1
- QBJWYMFTMJFGOL-UHFFFAOYSA-N 2-hexadecyloxirane Chemical compound CCCCCCCCCCCCCCCCC1CO1 QBJWYMFTMJFGOL-UHFFFAOYSA-N 0.000 description 1
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- LXVAZSIZYQIZCR-UHFFFAOYSA-N 2-nonyloxirane Chemical compound CCCCCCCCCC1CO1 LXVAZSIZYQIZCR-UHFFFAOYSA-N 0.000 description 1
- BHZBVWCLMYQFQX-UHFFFAOYSA-N 2-octadecyloxirane Chemical compound CCCCCCCCCCCCCCCCCCC1CO1 BHZBVWCLMYQFQX-UHFFFAOYSA-N 0.000 description 1
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
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- QISQZMBDDZCOTR-UHFFFAOYSA-N n,n-dipropyloctan-1-amine Chemical compound CCCCCCCCN(CCC)CCC QISQZMBDDZCOTR-UHFFFAOYSA-N 0.000 description 1
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- AKMUODCQFIEZKV-UHFFFAOYSA-N n-(2-ethylhexyl)-n-methyloctan-1-amine Chemical compound CCCCCCCCN(C)CC(CC)CCCC AKMUODCQFIEZKV-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- YHONYMIJFCYSSY-UHFFFAOYSA-N n-butyl-n-methylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)CCCC YHONYMIJFCYSSY-UHFFFAOYSA-N 0.000 description 1
- YVFQMDHXVAHBAQ-UHFFFAOYSA-N n-butyl-n-methylicosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN(C)CCCC YVFQMDHXVAHBAQ-UHFFFAOYSA-N 0.000 description 1
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- QYJWITCDDUWGBT-UHFFFAOYSA-N n-butyl-n-methylundecan-1-amine Chemical compound CCCCCCCCCCCN(C)CCCC QYJWITCDDUWGBT-UHFFFAOYSA-N 0.000 description 1
- UOCZLFWCAXSYAD-UHFFFAOYSA-N n-butyl-n-nonylnonan-1-amine Chemical compound CCCCCCCCCN(CCCC)CCCCCCCCC UOCZLFWCAXSYAD-UHFFFAOYSA-N 0.000 description 1
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- YZTRBUFACFAALH-UHFFFAOYSA-N n-dodecyl-n-methyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)CCCCCCCCCCCC YZTRBUFACFAALH-UHFFFAOYSA-N 0.000 description 1
- PZAHTXZMBSBSFM-UHFFFAOYSA-N n-ethyl-n-heptylheptan-1-amine Chemical compound CCCCCCCN(CC)CCCCCCC PZAHTXZMBSBSFM-UHFFFAOYSA-N 0.000 description 1
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- YWMZGHAFYBXDIQ-UHFFFAOYSA-N n-ethyl-n-methyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CC YWMZGHAFYBXDIQ-UHFFFAOYSA-N 0.000 description 1
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- UAZLVXVDAOJZEH-UHFFFAOYSA-N n-ethyl-n-methylundecan-1-amine Chemical compound CCCCCCCCCCCN(C)CC UAZLVXVDAOJZEH-UHFFFAOYSA-N 0.000 description 1
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- KYSDFVPIAZIJAW-UHFFFAOYSA-N n-ethyl-n-octyloctan-1-amine Chemical compound CCCCCCCCN(CC)CCCCCCCC KYSDFVPIAZIJAW-UHFFFAOYSA-N 0.000 description 1
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- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BXYHQXUPLKMYDE-UHFFFAOYSA-N n-heptyl-n-methylheptan-1-amine Chemical compound CCCCCCCN(C)CCCCCCC BXYHQXUPLKMYDE-UHFFFAOYSA-N 0.000 description 1
- LZQCOOQIFWGHOH-UHFFFAOYSA-N n-heptyl-n-methyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCCCCCC LZQCOOQIFWGHOH-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
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- IITLRKXIQJEWFI-UHFFFAOYSA-N n-methyl-n-nonylnonan-1-amine Chemical compound CCCCCCCCCN(C)CCCCCCCCC IITLRKXIQJEWFI-UHFFFAOYSA-N 0.000 description 1
- ZBYKVOSVXQAAPR-UHFFFAOYSA-N n-methyl-n-propyldecan-1-amine Chemical compound CCCCCCCCCCN(C)CCC ZBYKVOSVXQAAPR-UHFFFAOYSA-N 0.000 description 1
- DVPXFAOFNRBDOZ-UHFFFAOYSA-N n-methyl-n-propyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCC DVPXFAOFNRBDOZ-UHFFFAOYSA-N 0.000 description 1
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- NSFWZCBLACBJLN-UHFFFAOYSA-N n-methyl-n-propyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCC NSFWZCBLACBJLN-UHFFFAOYSA-N 0.000 description 1
- SXOCIAOEAPILLL-UHFFFAOYSA-N n-methyl-n-propyloctan-1-amine Chemical compound CCCCCCCCN(C)CCC SXOCIAOEAPILLL-UHFFFAOYSA-N 0.000 description 1
- FILZIXBTUOHUIC-UHFFFAOYSA-N n-methyl-n-tridecyltridecan-1-amine Chemical compound CCCCCCCCCCCCCN(C)CCCCCCCCCCCCC FILZIXBTUOHUIC-UHFFFAOYSA-N 0.000 description 1
- ISZWDCITQRHAEG-UHFFFAOYSA-N n-methyl-n-undecylundecan-1-amine Chemical compound CCCCCCCCCCCN(C)CCCCCCCCCCC ISZWDCITQRHAEG-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002552 poly(isobornyl acrylate) polymer Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 108010001843 pregnancy-associated glycoprotein 2 Proteins 0.000 description 1
- 239000000770 propane-1,2-diol alginate Substances 0.000 description 1
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229940058287 salicylic acid derivative anticestodals Drugs 0.000 description 1
- 150000003872 salicylic acid derivatives Chemical class 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Description
Use of a polyalkylene glycol to reduce fuel consumption
Description
The present invention relates to the use of a polyalkylene glycol of general formula I
HO-(A-0)P-(CH2CH2-0)m-(A-0)q-H (I) wherein A is a C3- to C2o-alkylene group or a mixture of such alkylene groups, m is a number of from 2 to 100 and p and q are each numbers of from 1 to 100, as an additive in a fuel for different purposes.
The present invention further relates to a fuel composition which comprises a gasoline fuel, the polyalkylene glycol mentioned and at least one fuel additive with detergent action.
The present invention further relates to an additive concentrate which comprises the
polyalkylene glycol mentioned and at least one fuel additive with detergent action. It is known that particular substances in the fuel reduce internal friction in the internal combustion engines, especially in gasoline engines, and thus help to save fuel. Such
substances are also referred to as lubricity improvers, friction reducers or friction modifiers. Lubricity improvers customary on the market for gasoline fuels are usually condensation products of naturally occurring carboxylic acids such as fatty acids with polyols such as glycerol or with alkanolamines, for example glyceryl monooleate.
A disadvantage of the prior art lubricity improvers mentioned is poor miscibility with other typically used fuel additives, especially with detergent additives such as polyisobuteneamines and/or carrier oils such as polyalkylene oxides. An important requirement in practice is that the component mixtures or additive concentrates provided are readily pumpable even at relatively low temperatures, especially at outside winter temperatures of, for example, down to -20°C, and remain homogene-ously stable over a prolonged period, i.e. no phase separation and/or precipitates may occur. Typically, the miscibility problems outlined are avoided by adding relatively large amounts of mixtures of paraffinic or aromatic hydrocarbons with alcohols such as tert-butanol or 2- ethylhexanol as solubilizers to the component mixtures or additive concentrates. In some cases, however, considerable amounts of these expensive solubilizers are necessary in order to achieve the desired homogeneity, and so this solution to the problem becomes uneconomic.
In addition, the prior art lubricity improvers mentioned often have the tendency to form emulsions with water in the component mixtures or additive concentrates or in the fuel itself, such that water which has penetrated can be removed again via a phase separa-tion only with difficulty or at least only very slowly.
WO 99/16849 discloses a complex ester resulting from an esterification reaction between polyfunctional alcohols and polyfunctional carboxylic acids using a chain stopping agent to form ester bonds with the remaining hydroxyl or carboxyl groups, containing as a polyfunctional carboxylic acid component dimerised and/or trimerised fatty acids. This complex ester is recommended for as an additive, a base fluid or a thickener in transmission oils, hydraulic fluids, four-stroke oils, fuel additives, com-pressor oils, greases, chain oils and for metal working rolling applications.
WO 98/1 1 178 discloses a polyol ester distillate fuel additive synthesized from a polyol an a mono- or polycarboxylic acid in such a manner that the resulting ester has uncon-erted hydroxyl groups, such polyol ester being useful as a lubricity additive for diesel fuel, jet fuel and kerosene.
WO 03/012015 discloses an additive for improving the lubricity capacity of low-sulphur fuel oils, such additive containing an ester of a bivalent or polyvalent alcohol and a mixture of
unsaturated or saturated mono- or dicarboxylic acids whose carbon length are between 8 and 30 carbon atoms.
It was an object of the present invention to provide fuel additives which firstly bring about effective fuel saving in the operation of a spark-ignited internal combustion engine, and secondly no longer have the outlined shortcomings of the prior art, i.e. more particularly not remaining homogeneously stable over a prolonged period without any phase separation and/or precipitates, poor miscibility with other fuel additives and the tendency to form emulsions with water. In addition, they should not worsen the high level of intake valve cleanliness achieved by the modern fuel additives.
Accordingly, the use of a polyalkylene glycol of general formual I as described above as an additive in a fuel for reducing fuel consumption in the operation of an internal combustion engine with this fuel has been found. Preferably, the said use as an additive in a gasoline fuel for reducing fuel consumption in the operation of a spark-ignited internal combustion engine with this fuel or as an additive in a gasoline fuel for reduction of fuel consumption in the operation of a self-ignition internal combustion engine with this fuel has been found.
It can be assumed that the cause of the fuel saving by virtue of the polyalkylene glycol mentioned is based substantially on the effect thereof as an additive which reduces internal friction in the internal combustion engines, especially in gasoline engines. The reaction product mentioned thus functions in the context of the present invention essentially as a lubricity improver. Furthermore, the use of a polyalkylene glycol as described above as an additive in a fuel for minimization of power loss in internal combustion engines and for improving acceleration of internal combustion engines has been found.
Furthermore, the use of a polylalkylene glycol as described above as an additive in a fuel for improving the lubricity of lubricant oils contained in an internal combustion engine for lubricating purposes by operating the internal combustion engine with a fuel containing an effective amount of at least one of the said polyalkylene glycol has been found.
It can be assumed that a part of the polyalkylene glycol mentioned contained in the fuel is transported via the combustion chamber where the additive containing fuel is burnt into the lubricant oils and acting there as a further lubricating agent. The advantage of this mechanism is that the said further lubricating agent is continuously refreshed by the fuel feeding.
Spark-ignition internal combustion engines are preferably understood to mean gasoline engines, which are typically ignited with spark plugs. In addition to the customary four- and two- stroke gasoline engines, spark-ignition internal combustion engines also in-clude other engine types, for example the Wankel engine. These are generally engines which are operated with conventional gasoline types, especially gasoline types accor-ding to EN 228, gasoline-alcohol mixtures such as Flex fuel with 75 to 85% by volume of ethanol, liquid pressure gas ("LPG") or compressed natural gas ("CNG") as fuel.
However, the inventive use of the polyalkylene glycol mentioned also relates to newly developed internal combustion engines such as the "HCCI" engine, which is self-igniting and is operated with gasoline fuel.
The instant invention works preferably with direct injection gasoline driven combustion engines. Variable A in general formula I comprises C3- to C2o-alkylene groups, which are normally derived from the corresponding hydrocarbyl epoxids, i.e. the corresponding alkylene oxides which are usually vicinal alkylene oxides such as 1 ,2-alkylene oxides. Examples for such alkylene oxides are 1 ,2-pro-pylene oxide, 1 ,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1 ,2- propylene oxide, 1 ,2-pentylene oxide, 1 ,2-hexylene oxide, 1 ,2-octylene oxide, 1 ,2-nonylene oxide, 1 ,2-decylene oxide, 1 ,2-undecylene oxide, 1 ,2-dodecylene oxide, 1 ,2-tetradecylene oxide, 1 ,2-hexadecylene oxide, 1 ,2-octadecylene oxide and 1 ,2-eicosylene oxide. Variable A may alternatively be definded for the above examples by formula -CHR4-CHR5- wherein R4 and R5 may independently be hydrogen or a Ci- to C18 alkyl radical with at least one of R4 and R5 being a Ci- to C18 alkyl radical and the sum of carbon atoms in R4 and R5 not exceeding the number of 20.
Variable A in general formula I may be one single species of alkylene groups or a mixture of different species of alkylene groups. Such mixture may comprise three, four or preferably two different species of alkylene groups. In case of one single species of alkylene groups, the polyalkylene glycol mentioned is a block copolymer of two or, if the two variables A at the two different sides of the -(CH2CH2-0)m-block are different, of three blocks. In case of one single species of alkylene groups, variable A normally comprises of from 8 to 20 carbon atoms. In
case of a mixture of two or of more different species of alkylene groups, the said outward- positioned moieties HO-(A-0)p- and/or -(A-0)q-H may be arranged randomly or blockwise.
In a preferred embodiment, variable A in general formula I is a mixture of two different typs of alkylene groups A1 and A2 with A1 designating one or more C3- to Cz-alkylene groups and A2 designating one or more Cs- to C2o-alkylene groups, A1 and A2 being arranged randomly or blockwise. A1 designates preferably one or more C3- to C6-alkylene groups, more preferably one or more C3- to Cs-alkylene groups, most preferably C3- and/or C4-alkylene groups. A2 designates preferably one or more Cs- to Ci6-alkylene groups, more preferably one or more Cs- to Ci4-alkylene groups, most preferably one or more Cs- to Ci2-alkylene groups.
In another preferred embodiment, variable A in general formula I is a Cs- to C2o-alky-lene group (A2) or a mixture of Cs- to C2o-alkylene groups (A2) arranged randomly. The number m of -(CH2CH2-O)- units in the middle of the polyalkylene glycol molecule is preferably from 2 to 50 or preferably from 3 to 75 or preferably from 4 to 100, more preferably from 3 to 30, and most preferably from 4 to 15.
The numbers p and q, respectively, of outward-positioned moieties -(A-O)-units are preferably each from 2 to 50, more preferably each from 3 to 35, and most preferably each from 4 to 20.
The numbers m, p and q are mean values as a statistical number, due to a distribution of alkox- ylation homologues in the product. The polyalkylene glycols mentioned are preferably obtainable by alkoxylation of polyethylene glycols of general formula II
HO-(CH2CH2-0)m-H (II) wherein m is a number of from 2 to 100, with 2 to 200 moles of a C3- to C2o-alkylene oxide or a mixture of such alkylene oxides per mole of polyethylene glycol II, the alkoxylation product being arranged randomly or blockwise. Conditions for such alkylation reactions are well known and, therefore, do not need to be described here. Polyethylene glycols of general formula II of different chain lengths are available from BASF SE (among others) under the trade name of Pluriol® E.
Typical examples of polyalkylene glycols mentioned are polyethylene glycols of general formula II with m = 4 to 15 which are alkoxylated with one or simultaneously more Cs- to Ci2-alkylene oxides (A2) resulting in random structures, or which are first alkoxylated with one or more Cs- to Ci2-alkylene oxides (A2) and subsequently alkoxylated with one or more C3- and/or C4-alkylene oxides (A1) resulting in block structures regarding A1 and A2.
The polyalkylene glycol mentioned is oil soluble, which means that, when mixed with mineral oils and/or fuels in a weight ratio of 10:90, 50:50 and 90:10, the polyalkylene glycol does not show phase separation after standing for 24 hours at room temperature for at least two weight rations out of the three weight ratios 10:90, 50:50 and 90:10.
The present invention also provides a fuel composition which comprises, in a major amount, a gasoline fuel and, in a minor amount, at least one polyalkylene glycol mentioned, and at least one fuel additive which is different from the said polyalkylene glycols and has detergent action. Typically, the amount of this at least one polyalkylene glycol in the gasoline fuel is 10 to 5000 ppm by weight, more preferably 20 to 2000 ppm by weight, even more preferably 30 to 1000 ppm by weight and especially 40 to 500 ppm by weight, for example 50 to 300 ppm by weight.
Useful gasoline fuels include all conventional gasoline fuel compositions. A typical
representative which shall be mentioned here is the Eurosuper base fuel to EN 228, which is customary on the market. In addition, gasoline fuel compositions of the specification according to WO 00/47698 are also possible fields of use for the present invention. In addition, in the context of the present invention, gasoline fuels shall also be understood to mean alcohol- containing gasoline fuels, especially ethanol-containing gasoline fuels, as described, for example, in WO 2004/090079, for example Flex fuel with an ethanol content of 75 to 85% by volume, or gasoline fuel comprising 85% by volume of ethanol ("E85"), but also the Έ100" fuel type, which is typically azeotropi-cally distilled ethanol and thus consists of approx. 96% by volume of C2H5OH and approx. 4% by volume of H2O. The polyalkylene glycol mentioned may be added to the particular base fuel either alone or in the form of fuel additive packages (for gasoline fuels also called "gasoline performance packages). Such packages are fuel additive concentrates and generally also comprise, as well as solvents, and as well as the at least one fuel additive which is different from the said polyalkylene glycols and has detergent action, a series of further components as coadditives, which are especially carrier oils, corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistats, metallocenes, metal deactivators, solubilizers, markers and/or dyes.
Detergents or detergent additives as the at least one fuel additive which is different from the said polyalkylene glycols and has detergent action, referred to hereinafter as component (D), typically refer to deposition inhibitors for fuels. The detergent additives are preferably amphiphilic substances which possess at least one hydrophobic hydrocarbyl radical having a number-average molecular weight (Mn) of 85 to 20 000, especially of 300 to 5000, in particular of 500 to 2500, and at least one polar moiety.
In a preferred embodiment, the inventive fuel composition comprises, as the at least one fuel additive (D) which is different from the said polyalkylene glycols and has detergent action, at least one representative which is selected from: (Da) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties;
(Db) nitro groups, optionally in combination with hydroxyl groups; (Dc) hydroxyl groups in combination with mono- or polyamino groups, at least one nitrogen atom having basic properties;
(Dd) carboxyl groups or their alkali metal or alkaline earth metal salts; (De) sulfo groups or their alkali metal or alkaline earth metal salts;
(Df) polyoxy-C2-C4-alkylene moieties terminated by hydroxyl groups, mono- or polyamino groups, at least one nitrogen atom having basic properties, or by carbamate groups; (Dg) carboxylic ester groups;
(Dh) moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups; and/or (Di) moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines.
The hydrophobic hydrocarbon radical in the above detergent additives, which ensures the adequate solubility in the fuel composition, has a number-average molecular weight (Mn) of 85 to 20 000, especially of 300 to 5000, in particular of 500 to 2500. Useful typical hydrophobic hydro- carbyl radicals, especially in conjunction with the polar moieties (Da), (Dc), (Dh) and (Di), are relatively long-chain alkyl or alkenyl groups, especially the polypropenyl, polybutenyl and poly- isobutenyl radicals each having Mn = 300 to 5000, especially 500 to 2500, in particular 700 to 2300.
Examples of the above groups of detergent additives include the following:
Additives comprising mono- or polyamino groups (Da) are preferably polyalkenemono- or poly- alkenepolyamines based on polypropene or on highly-reactive (i.e. having predominantly termi- nal double bonds in the a- and/or β-position such as vinylidene double bonds) or conventional (i.e. having predominantly internal double bonds) polybutene or polyisobutene having Mn = 300 to 5000. Such detergent additives based on highly-reactive polybutene or polyisobutene, which
are normally prepared by hydroformylation of the poly(iso)butene and subsequent reductive amination with ammonia, monoamines or polyamines, are known from EP-A 244 616. When the preparation of the additives proceeds from polybutene or polyisobutene having predominantly internal double bonds (usually in the β- and/or γ- positions), one possible preparative route is by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to give the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogen- ating) conditions. The amines used here for the amination may be, for example, ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetri- amine, triethylenetetramine or tetraethylenepentamine. Corresponding additives based on poly- propene are described in particular in WO-A-94/24231.
Further preferred additives comprising monoamino groups (Da) are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-97/03946.
Further preferred additives comprising monoamino groups (Da) are the compounds
obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A-196 20 262.
Additives comprising nitro groups (Db), optionally in combination with hydroxyl groups, are preferably reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-96/03367 and in WO-A 96/03479. These reaction products are generally mixtures of pure nitropolyisobutenes (e.g. α,β-dinitropolyisobutene) and mixed hydroxynitropoly- isobutenes (e.g. a-nitro-3-hydroxypolyisobutene).
Additives comprising hydroxyl groups in combination with mono- or polyamino groups (Dc) are in particular reaction products of polyisobutene epoxides obtainable from polyisobutene having preferably predominantly terminal double bonds and Mn = 300 to 5000, with ammonia or mono- or polyamines, as described in particular in EP-A-476 485.
Additives comprising carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) are preferably copolymers of C2-C4o-olefins with maleic anhydride which have a total molar mass of 500 to 20 000 and some or all of whose carboxyl groups have been converted to the alkali metal or alkaline earth metal salts and any remainder of the carboxyl groups has been reacted with alcohols or amines. Such additives are disclosed in particular by EP-A-307 815. Such additives serve mainly to prevent valve seat wear and can, as described in WO-A-87/01 126, advantageously be used in combination with customary fuel detergents such as poly(iso)buteneamines or polyetheramines.
Additives comprising sulfo groups or their alkali metal or alkaline earth metal salts (De) are preferably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinate, as described in particular in EP-A-639 632. Such additives serve mainly to prevent valve seat wear and can be used advantageously in combination with customary fuel detergents such as
poly(iso)buteneamines or polyetheramines.
Additives comprising polyoxy-C2-C4-alkylene moieties (Df) are preferably polyethers or polyetheramines which are obtainable by reaction of C2-C6o-alkanols, C6-C3o-alkane-diols, mono- or di- C2-C3o-alkylamines, Ci-C3o-alkylcyclohexanols or Ci-C3o-alkylphenols with 1 to 30 mol of eth- ylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described in particular in EP-A-310 875, EP-A- 356 725, EP-A-700 985 and US-A-4 877 416. In the case of polyethers, such products also have carrier oil properties. Typical examples of these are tridecanol butoxylates, isotridecanol butoxylates, isononyl-phenol butoxylates and polyisobutenol butoxylates and propoxylates and also the corresponding reaction products with ammonia.
Additives comprising carboxylic ester groups (Dg) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those having a minimum viscosity of 2 mm2/s at 100°C, as described in particular in DE-A-38 38 918. The mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids, and particularly suitable ester alcohols or ester polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimelli- tates of isooctanol, of isononanol, of isodecanol and of isotridecanol. Such products also have carrier oil properties.
Additives comprising moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups (Dh) are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and especially the corresponding derivatives of polyiso- butenylsuccinic anhydride which are obtainable by reacting conventional or high-reactivity polyisobutene having Mn = 300 to 5000 with maleic anhydride by a thermal route or via the chlorinated polyisobutene. Of particular interest in this context are derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. The moieties having hydroxyl and/or amino and/or amido and/or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines which, in addition to the amide function, also have free amine groups, succinic acid derivatives having an acid and an amide function, carboximides with monoamines, carboximides with di- or polyamines which, in addition to the imide function, also have free amine groups, or diimides which are formed by the reaction of di- or polyamines with two succinic acid derivatives. Such fuel addi- tives are described especially in US-A-4 849 572.
The detergent additives from group (Dh) are preferably the reaction products of alkyl- or alkenyl- substituted succinic anhydrides, especially of polyisobutenylsuccinic anhydrides ("PIBSAs"), with amines and/or alcohols. These are thus derivatives which are derived from alkyl-, alkenyl- or polyisobutenylsuccinic anhydride and have amino and/or amido and/or imido and/or hydroxyl groups. It is self-evident that these reaction products are obtainable not only when substituted succinic anhydride is used, but also when substituted succinic acid or suitable acid derivatives, such as succinyl halides or succinic esters, are used.
The additized fuel may comprise at least one detergent based on a polyisobutenyl-substituted succinimide. Especially of interest are the imides with aliphatic polyamines. Particularly preferred polyamines are ethylenediamine, diethylenetriamine, triethylenetetramine, pen- taethylenehexamine and in particular tetraethylenepentamine. The polyisobutenyl radical has a number-average molecular weight Mn of preferably from 500 to 5000, more preferably from 500 to 2000 and in particular of about 1000.
Additives comprising moieties (Di) obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene- substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl-substituted phenols may originate from conventional or high-reactivity poly- isobutene having Mn = 300 to 5000. Such "polyisobutene Mannich bases" are described especially in EP-A-831 141 .
The inventive fuel composition comprises the at least one fuel additive which is different from the polyalkylene glycols mentioned and has detergent action, and is normally selected from the above groups (Da) to (Di), in an amount of typically 10 to 5000 ppm by weight, more preferably of 20 to 2000 ppm by weight, even more preferably of 30 to 1000 ppm by weight and especially of 40 to 500 ppm by weight, for example of 50 to 250 ppm by weight. The detergent additives (D) mentioned are preferably used in combination with at least one carrier oil. In a preferred embodiment, the inventive fuel composition comprises, in addition to the at least one polyalkylene glycol mentioned and the at least one fuel additive which is different than the polyalkylene glycol mentioned and has detergent action, as a further fuel additive in a minor amount, at least one carrier oil.
Suitable mineral carrier oils are the fractions obtained in crude oil processing, such as brightstock or base oils having viscosities, for example, from the SN 500 - 2000 class; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Likewise useful is a fraction which is obtained in the refining of mineral oil and is known as "hydrocrack oil" (vacuum distillate cut having a boiling range of from about 360 to 500°C, obtainable from natural mineral oil which has been catalytically hydrogenated under high pressure and isomerized and also de- paraffinized). Likewise suitable are mixtures of abovementioned mineral carrier oils.
Examples of suitable synthetic carrier oils are selected from: polyolefins (poly-alpha-olefins or poly(internal olefin)s), (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic esters of long-chain alkanols. For the avoidance of doubt, the said (poly)alkoxylates and polyethers which are suitable as synthetic carrier oils for the instant invention, are different from the polyalkylene glycols mentioned.
Examples of suitable polyolefins are olefin polymers having Mn = from 400 to 1800, in particular based on polybutene or polyisobutene (hydrogenated or unhydrogenated).
Examples of suitable polyethers or polyetheramines are preferably compounds comprising polyoxy-C2-C4-alkylene moieties which are obtainable by reacting C2-C6o-alkanols, C6-C30- alkanediols, mono- or di-C2-C3o-alkylamines, Ci-C3o-alkylcyclohexanols or Ci-C3o-alkylphenols with from 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group, and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described in particular in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4,877,416. For example, the polyether-amines used may be poly-C2-C6-alkylene oxide amines or functional derivatives thereof. Typical examples thereof are tridecanol butoxylates or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates, and also the corresponding reaction products with ammonia.
Examples of carboxylic esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A-38 38 918. The mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids; suitable ester alcohols or polyols are in particular long-chain representatives having, for example, from 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, for example di(n- or isotridecyl) phthalate.
Further suitable carrier oil systems are described, for example, in DE-A-38 26 608, DE-A-41 42 241 , DE-A-43 09 074, EP-A-0 452 328 and EP-A-0 548 617.
Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having from about 5 to 35, for example from about 5 to 30, C3-C6-alkylene oxide units, for example selected from propylene oxide, n-butylene oxide and isobutylene oxide units, or mixtures thereof. Nonlim- iting examples of suitable starter alcohols are long-chain alkanols or phenols substituted by long-chain alkyl in which the long-chain alkyl radical is in particular a straight-chain or branched C6-Ci8-alkyl radical. Preferred examples include tridecanol and nonylphenol.
Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A-101 02 913.
Preferred carrier oils are synthetic carrier oils, particular preference being given to poly-ethers.
When a carrier oil is used in addition, it is added to the inventive additized fuel in an amount of preferably from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight and in particular from 20 to 100 ppm by weight.
In a preferred embodiment, the inventive fuel composition comprises, in addition to the at least one polyalkylene glycol mentioned, the at least one fuel additive which is different from the pol- ylalkylene glycol mentioned and has detergent action, and optionally the at least one carrier oil, as a further fuel additive in a minor amount at least one tertiary hydrocarbyl amine of formula NR1R2R3 wherein R1, R2 and R3 are the same or different Ci- to C2o-hydrocarbyl residues with the proviso that the overall number of carbon atoms in formula NR1R2R3 does not exceed 30.
Tertiary hydrocarbyl amines have proven to be advantageous with regard to use as perfor- mance additives in fuels controlling deposits. Besides their superior performance behavior, they are also good to handle as their melting points are normally low enough to be usually liquid at ambient temperature.
"Hydrocarbyl residue" for R1 to R3 shall mean a residue which is essentially composed of carbon and hydrogen, however, it can contain in small amounts heteroatomes, especially oxygen and/or nitrogen, and/or functional groups, e.g. hydroxyl groups and/or carboxylic groups, to an extent which does not distort the predominantly hydrocarbon character of the residue. Hydrocarbyl residues are preferably alkyl, alkenyl, alkinyl, cycloalkyl, aryl, alkylaryl or arylalkyl groups. Especially preferred hydrocarbyl residues for R1 to R3 are linear or branched alkyl or alkenyl groups.
The overall number of carbon atoms in the tertiary hydrocarbyl amine mentioned is at most 30, preferably at most 27, more preferably at most 24, most preferably at most 20. Preferably, the minimum overall number of carbon atoms in formula NR1R2R3 is 6, more preferably 8, most preferably 10. Such size of the tertiary hydrocarbyl amine mentioned corresponds to molecular weight of about 100 to about 450 for the largest range and of about 150 to about 300 for the smallest range; most usually, tertiary hydrocarbyl amines mentioned within a molecular range of from 100 to 300 are used. The three Ci- to C2o-hydrocarbyl residues may be identical or different. Preferably, they are different, thus creating an amine molecular which exhibits an oleophobic moiety (i.e. the more polar amino group) and an oleophilic moiety (i.e. a hydrocarbyl residue with a longer chain length or a larger volume). Such amine molecules with oleophobic/oleophilic balance have proved to show the best deposit control performance according the present invention.
Preferably, a tertiary hydrocarbyl amine of formula NR1R2R3 is used wherein at least two of hydrocarbyl residues R1, R2 and R3 are different with the proviso that the hydrocarbyl residue with
the most carbon atoms differ in carbon atom number from the hydrocarbyl residue with the second most carbon atoms in at least 3, preferably in at least 4, more preferably in at least 6, most preferably in at least 8. Thus, the tertiary amines mentioned exhibit hydrocarbyl residues of two or three different chain length or different volume, respectively.
Still more preferably, a tertiary hydrocarbyl amine of formula N R1 R2R3 is used wherein one or two of R1 to R3 are C7- to C2o-hydrocarbyl residues and the remaining two or one of R1 to R3 are Ci- to C4-hydrocarbyl residues. The one or the two longer hydrocarbyl residues, which may be in case of two residues identical or different, exhibit from 7 to 20, preferably from 8 to 18, more preferably from 9 to 16, most preferably from 10 to 14 carbon atoms. The one or the two remaining shorter hydrocarbyl residues, which may be in case of two residues identical or different, exhibit from 1 to 4, preferably from 1 to 3, more preferably 1 or 2, most preferably 1 carbon atom(s). Besides the desired de- posit controlling performance, the oleophilic long-chain hydrocarbyl residues provide further advantageous properties to the tertiary amines, i.e. high solubility for gasoline fuels and low volatility.
More preferably, tertiary hydrocarbyl amines of formula N R1 R2R3 are used, wherein R1 is a Cs- to Ci8-hydrocarbyl residue and R2 and R3 are independently of each other Ci- to C4-alkyl radicals. Still more preferably, tertiary hydrocarbyl amines of formula N R1 R2R3 are used, wherein R1 is a C9- to Ci6-hydrocarbyl residue and R2 and R3 are both methyl radicals.
Examples for suitable linear or branched Ci- to C2o-alkyl residues for R1 to R3 are: methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec. -butyl, tert-butyl, n-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl,1 ,1 -dimethylpropyl,1 ,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4- methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1 - methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1 ,1 -dimethylpentyl, 1 ,2-dimethylpentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dime-thylpentyl, 2,5- dimethylpentyl, 2-diethylpentyl, 3-diethyl-pentyl, n-octyl, 1 -methylheptyl, 2-methylheptyl, 3- methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1 ,1 -dimethylhexyl, 1 ,2- dimethylhexyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethyl-hexyl, 2,5-dimethylhexyl, 2,6- dimethylhexyl, 2-ethyl-hexyl, 3-ethylhexyl, 4-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, 1 - propylheptyl, 2-propyl-heptyl, 3-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, iso-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl.
Examples for suitable linear or branched C2- to C2o-alkenyl and -alkinyl residues for R1 to R3 are: vinyl, allyl, oleyl and propin-2-yl. Tertiary hydrocarbyl amines of formula N R1 R2R3 with long-chain alkyl and alkenyl residues can also preferably be obtained or derived from natural sources, i.e. from plant or animal oils and lards. The fatty amines derived from such sources which are suitable as such tertiary hydro-
carbyl amines normally form mixtures of differents similar species such as homologues, e.g. tallow amines containing as main components tetradecyl amine, hexadecyl amine, octadecyl amine and octadecenyl amine (oleyl amine). Further examples of suitable fatty amines are: coco amines and palm amines. Unsaturated fatty amines which contain alkenyl residues can be hydrogenated und used in this saturated form.
Examples for suitable C3- to C2o-cycloalkyl residues for R1 to R3 are: cyclopropyl, cyclobutyl, 2- methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethyl-cyclohexyl, 2,4- dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5- dimethylcyclohexyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, cyclooctyl and cy- clodecyl.
Examples for suitable C7- to C2o-aryl, -alkylaryl or -arylalkyl residues for R1 to R3 are: naphthyl, tolyl, xylyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, benzyl, 1 -phenyl-ethyl, 2-phenylethyl, 3- phenylpropyl and 4-butylphenyl.
Typical examples for suitable tertiary hydrocarbyl amines of formula NR1R2R3 are the following:
N,N-dimethyl-n-butylamine, N,N-dimethyl-n-pentylamine, N,N-dimethyl-n-hexylamine, N,N- dimethyl-n-heptylamine, N,N-dimethyl-n-octylamine, N,N-dimethyl-2-ethylhexyl-amine, N,N-di- methyl-n-nonylamine, Ν,Ν-dimethyl-iso-nonylamine, N,N-dimethyl-n-decylamine, N,N-dimethyl- 2-propylheptylamine, N,N-dimethyl-n-undecylamine, N,N-dimethyl-n-dodecylamine, N,N- dimethyl-n-tridecylamine, Ν,Ν-dimethyl-iso-tridecyl-amine, N,N-dimethyl-n-tetradecylamine, N,N-dimethyl-n-hexadecylamine, N,N-di-methyl-n-octadecylamine, N,N-dimethyl-eicosylamine, N,N-dimethyl-oleylamine;
N,N-diethyl-n-heptylamine, N,N-diethyl-n-octylamine, N,N-diethyl-2-ethylhexylamine, N,N- diethyl-n-nonylamine, Ν,Ν-diethyl-iso-nonylamine, N,N-diethyl-n-decylamine, N,N-diethyl-2- propylheptylamine, N,N-diethyl-n-undecylamine, N,N-diethyl-n-dodecylamine, N,N-diethyl-n- tridecylamine, Ν,Ν-diethyl-iso-tridecylamine, N,N-diethyl-n-tetradecyl-amine, N,N-diethyl-n- hexadecylamine, N,N-di-ethyl-n-octadecylamine, Ν,Ν-diethyl-eicosylamine, N,N-diethyl- oleylamine;
N,N-di-(n-propyl)-n-heptylamine, N,N-di-(n-propyl)-n-octylamine, N,N-di-(n-propyl)-2- ethylhexylamine, N,N-di-(n-propyl)-n-nonylamine, N,N-di-(n-propyl)-iso-nonylamine, N,N-di-(n- propyl)-n-decylamine, N,N-di-(n-propyl)-2-propylheptylamine, N,N-di-(n-propyl)-n-undecylamine, N,N-di-(n-propyl)-n-dodecylamine, N,N-di-(n-propyl)-n-tri-decylamine, N,N-di-(n-propyl)-iso- tridecylamine, N,N-di-(n-propyl)-n-tetradecylamine, N,N-di-(n-propyl)-n-hexadecylamine, N,N-di- (n-propyl)-n-octadecylamine, N,N-di-(n-propyl)-eicosylamine, N,N-di-(n-propyl)-oleylamine;
N , N-di-(n-butyl)-n-heptylamine, N , N-di-(n-butyl)-n-octylamine, N , N-di-(n-butyl)-2-ethyl- hexylamine, N,N-di-(n-butyl)-n-nonylamine, N,N-di-(n-butyl)-iso-nonylamine, N,N-di-(n-butyl)-n-
decylamine, N,N-di-(n-butyl)-2-propylheptylamine, N,N-di-(n-butyl)-n-undecyl-amine, N,N-di-(n- butyl)-n-dodecylamine, N,N-di-(n-butyl)-n-tridecylamine, N,N-di-(n-butyl)-iso-tridecylamine, N,N- di-(n-butyl)-n-tetradecylamine, N,N-di-(n-butyl)-n-hexa-decylamine, N,N-di-(n-butyl)-n- octadecylamine, N,N-di-(n-butyl)-eicosylamine, N,N-di-(n-butyl)-oleyl-amine;
N-methyl-N-ethyl-n-heptylamine, N-methyl-N-ethyl-n-octylamine, N-methyl-N-ethyl-2- ethylhexylamine, N-methyl-N-ethyl-n-nonylamine, N-methyl-N-ethyl-iso-nonylamine, N-methyl- N-ethyl-n-decylamine, N-methyl-N-ethyl-2-propylheptylamine, N-methyl-N-ethyl-n- undecylamine, N-methyl-N-ethyl-n-dodecylamine, N-methyl-N-ethyl-n-tridecylamine, N-methyl- N-ethyl-iso-tridecylamine, N-methyl-N-ethyl-n-tetradecylamine, N-methyl-N-ethyl-n- hexadecylamine, N-methyl-N-ethyl-n-octadecylamine, N-methyl-N-ethyl-eicosyl-amine, N- methyl-N-ethyl-oleylamine;
N-methyl-N-(n-propyl)-n-heptylamine, N-methyl-N-(n-propyl)-n-octylamine, N-methyl-N-(n- propyl)-2-ethylhexylamine, N-methyl-N-(n-propyl)-n-nonylamine, N-methyl-N-(n-propyl)-iso- nonylamine, N-methyl-N-(n-propyl)-n-decylamine, N-methyl-N-(n-propyl)-2-propylheptylamine, N-methyl-N-(n-propyl)-n-undecylamine, N-methyl-N-(n-propyl)-n-dodecylamine, N-methyl-N-(n- propyl)-n-tridecylamine, N-methyl-N-(n-propyl)-iso-tri-decylamine, N-methyl-N-(n-propyl)-n- tetradecylamine, N-methyl-N-(n-propyl)-n-hexa-decylamine, N-methyl-N-(n-propyl)-n- octadecylamine, N-methyl-N-(n-propyl)-eicosyl-amine, N-methyl-N-(n-propyl)-oleylamine;
N-methyl-N-(n-butyl)-n-heptylamine, N-methyl-N-(n-butyl)-n-octylamine, N-methyl-N-(n-butyl)-2- ethylhexylamine, N-methyl-N-(n-butyl)-n-nonylamine, N-methyl-N-(n-butyl)-iso-nonylamine, N- methyl-N-(n-butyl)-n-decylamine, N-methyl-N-(n-butyl)-2-propylheptyl-amine, N-methyl-N-(n- butyl)-n-undecylamine, N-methyl-N-(n-butyl)-n-dodecylamine, N-methyl-N-(n-butyl)-n- tridecylamine, N-methyl-N-(n-butyl)-iso-tridecylamine, N-methyl-N-(n-butyl)-n-tetradecylamine, N-methyl-N-(n-butyl)-n-hexadecylamine, N-methyl-N-(n-butyl)-n-octadecylamine, N-methyl-N-(n- butyl)-eicosylamine, N-methyl-N-(n-butyl)-oleylamine; N-methyl-N,N-di-(n-heptyl)-amine, N-methyl-N,N-di-(n-octyl)-amine, N-methyl-N,N-di-(2- ethylhexyl)-amine, N-methyl-N,N-di-(n-nonyl)-amine, N-methyl-N,N-di-(iso-nonyl)-amine, N- methyl-N,N-di-(n-decyl)-amine, N-methyl-N,N-di-(2-propylheptyl)-amine, N-methyl-N,N-di-(n- undecyl)-amine, N-methyl-N,N-di-(n-dodecyl)-amine, N-methyl-N,N-di-(n-tridecyl)-amine, N- methyl-N,N-di-(iso-tridecyl)-amine, N-methyl-N,N-di-(n-tetra-decyl)-amine;
N-ethyl-N , N-di-(n-heptyl)-amine, N-ethyl-N , N-di-(n-octyl)-amine, N-ethyl-N , N-di-(2-ethylhexyl)- amine, N-ethyl-N, N-di-(n-nonyl)-amine, N-ethyl-N, N-di-(iso-nonyl)-amine, N-ethyl-N, N-di-(n- decyl)-amine, N-ethyl-N, N-di-(2-propylheptyl)-amine, N-ethyl-N, N-di-(n-undecyl)-amine, N-ethyl- N,N-di-(n-dodecyl)-amine, N-ethyl-N, N-di-(n-tridecyl)-amine, N-ethyl-N, N-di-(iso-tridecyl)-amine, N-ethyl-N, N-di-(n-tetradecyl)-amine;
N-(n-butyl)-N,N-di-(n-heptyl)-amine, N-(n-butyl)-N,N-di-(n-octyl)-amine, N-(n-butyl)-N,N-di-(2- ethylhexyl)-amine, N-(n-butyl)-N,N-di-(n-nonyl)-amine, N-(n-butyl)-N,N-di-(iso-nonyl)-amine, N- (n-butyl)-N,N-di-(n-decyl)-amine, N-(n-butyl)-N,N-di-(2-propylheptyl)-amine, N-(n-butyl)-N,N-di- (n-undecyl)-amine, N-(n-butyl)-N,N-di-(n-dodecyl)-amine, N-(n-butyl)-N,N-di-(n-tridecyl)-amine, N-(n-butyl)-N,N-di-(iso-tridecyl)-amine;
N-methyl-N-(n-heptyl)-N-(n-dodecyl)-amine, N-methyl-N-(n-heptyl)-N-(n-octadecyl)-amine, N- methyl-N-(n-octyl)-N-(2-ethylhexyl)-amine, N-methyl-N-(2-ethylhexyl)-N-(n-dodecyl)-amine, N- methyl-N-(2-propylheptyl)-N-(n-undecyl)-amine, N-methyl-N-(n-decyl)-N-(n-dodecyl)-amine, N- methyl-N-(n-decyl)-N-(-tetradecyl)-amine, N-methyl-N-(n-decyl)-N-(n-hexadecyl)-amine, N- methyl-N-(n-decyl)-N-(n-octadecyl)-amine, N-methyl-N-(n-decyl)-N-oleylamine, N-methyl-N-(n- dodecyl)-N-(iso-tridecyl)-amine, N-methyl-N-(n-dodecyl)-N-(n-tetradecyl)-amine, N-methyl-N-(n- dodecyl)-N-(n-hexa-decyl)-amine, N-methyl-N-(n-dodecyl)-oleylamine; Also suitable tertiary hydrocarbyl amines of formula NR1R2R3 are monocyclic structures, wherein one of the short-chain hydrocarbyl residue forms with the nitrogen atom and with the other short-chain hydrocarbyl residue a five- or six-membered ring. Oxygen atoms and/or further nitrogen atoms may additionally be present in such five- or six-membered ring. In each case, such cyclic tertiary amines carry at the nitrogen atom or at one of the nitrogen atoms, respec- tively, the long-chain C7- to C2o-hydrocarbyl residue. Examples for such monocyclic tertiary amines are N-(C7- to C2o-hydrocarbyl)-piperidines, N-(C7- to C2o-hydrocarbyl)-piperazines and N-(C7- to C2o-hydrocarbyl)-morpholines.
The inventive fuel composition may comprise further customary coadditives, as described be- low:
Corrosion inhibitors suitable as such coadditives are, for example, succinic esters, in particular with polyols, fatty acid derivatives, for example oleic esters, oligomerized fatty acids and substituted ethanolamines.
Demulsifiers suitable as further coadditives are, for example, the alkali metal and alkaline earth metal salts of alkyl-substituted phenol- and naphthalenesulfonates and the alkali metal and alkaline earth metal salts of fatty acid, and also alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylates or tert-pentylphenol ethoxylates, fatty acid, alkylphenols, condensation products of ethylene oxide and propylene oxide, e.g. ethylene ox- ide-propylene oxide block copolymers, polyethyleneimines and polysiloxanes. For the avoidance of doubt, the said condensation products of ethylene oxide and propylene oxide which are suitable as demusifiers for the instant invention, are different from the polyalkylene glycols mentioned.
Dehazers suitable as further coadditives are, for example, alkoxylated phenol-formal-dehyde condensates.
Antifoams suitable as further coadditives are, for example, polyether-modified poly-siloxanes.
Antioxidants suitable as further coadditives are, for example, substituted phenols, e.g. 2,6-di- tert-butylphenol and 2,6-di-tert-butyl-3-methylphenol, and also phenylenedi-amines, e.g. N,N'-di- sec-butyl-p-phenylenediamine.
Metal deactivators suitable as further coadditives are, for example, salicylic acid derivatives, e.g. N,N'-disalicylidene-1 ,2-propanediamine. Suitable solvents, especially also for fuel additive packages, are, for example, nonpolar organic solvents, especially aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit" and the technical solvent mixtures of the designations Shellsol® (manufacturer: Royal Dutch / Shell Group), Exxol® (manufacturer: ExxonMobil) and Solvent Naphtha. Also useful here, especially in a blend with the nonpolar organic solvents mentioned, are polar organic sol- vents, in particular alcohols such as tert-butanol, isoamyl alcohol, 2-ethylhexanol and 2- propylheptanol.
When the coadditives and/or solvents mentioned are used in addition in gasoline fuel, they are used in the amounts customary therefor.
In an especially preferred embodiment, as the at least one fuel additive (D) to be used together with the polyalkylene glycol mentioned which is different from the said polyalkylenen glycol and has detergent action is selected from (Da) polyisobutene monoamines or polyisobutene polyam- ines having Mn = 300 to 5000, having predominantly vinylidene double bonds (normally at least 50 mol-% of vinylidene double bonds, especially at least 70 mol-% of vinylidene double bonds) and having been prepared by hydroformylation of the respective polyisobutene and subsequent reductive amination with ammonia, monoamines or polyamines. Such polyisobutene monoamines and polyisobutene polyamines are preferably applied in combination with at least one mineral or synthetic carrier oil, more preferably in combination with at least one polyether-based or polyetheramine-based carrier oil, most preferably in combination with at least one C6-C18- alcohol-started polyether having from about 5 to 35 C3-C6-alkylene oxide units, especially selected from propylene oxide, n-butylene oxide and isobutylene oxide units, as described above.
The present invention also provides an additive concentrate which comprises at least one poly- alkylene glycol mentionend, and at least one fuel additive which is different from the said polyalkylene glycols and has detergent action. Otherwise, the inventive additive concentrate may comprise the further coadditives mentioned above. In case of additive concentrates for gasoline fuels, such additive concentrates are also called gasoline performance packages. The at least one polyalkylene glycol mentioned is present in the inventive additive concen-trate preferably in an amount of 1 to 99% by weight, more preferably of 15 to 95% by weight and especially of 30 to 90% by weight, based in each case on the total weight of the concentrate.
The at least one fuel additive which is different from the polyalkylene glycols mentioned and has detergent action is present in the inventive additive concentrate preferably in an amount of 1 to 99% by weight, more preferably of 5 to 85% by weight and especially of 10 to 70% by weight, based in each case on the total weight of the concentrate.
The polyalkylene glycol mentioned mentioned provides for quite a series of advantages and unexpected performance and handling improvements in view of the respective solutions proposed in the art. Effective fuel saving in the operation of a spark-ignited internal combustion engine is achieved. The respective fuel additive concentrates remain homogeneously stable over a prolonged period without any phase separation and/or precipitates. Miscibility with other fuel additives is improved and the tendency to form emulsions with water is suppressed. The high level of intake valve and combus-tion chamber cleanliness achieved by the modern fuel additives is not being worsened by the presence of the polyalkylene glycol mentioned in the fuel, the level of intake valve and combustion chamber cleanliness is even in most cases increased. Power loss in internal combustion engines is minimized and acceleration of internal combus-tion engines is improved. The presence of the polyalkylene glycol mentioned in the fuel also provides for an improved lubricating performance of the lubricating oils in the internal combustion engine. The examples which follow are intended to further illustrate the present invention without restricting it.
Examples Example 1 : Preparation of a polyalkylene glycol "PAG 1 "
Polyethylene glycol (m = about 4) available from BASF SE under the trade name of Pluriol® E 200 was dried and simultaneously reacted with 12 moles of 1 ,2-dodecylene oxide per mole of polyethylene glycol and 20 moles of 1 ,2-butylene oxide per mole of polyethylene oxide in the presence of sodium methoxide as an alkoxylation catalyst at 130°C, resulting in randomly arranged outward-positioned -(A-O)-units. The polyalky-lene glycol obtained after purification proceedings by ion exchange resin, exhibited a kinematic viscosity of 27 mm2/s at 100°C.
Example 2: Preparation of a polyalkylene glycol "PAG 2"
Polyethylene glycol (m = about 9) available from BASF SE under the trade name of Pluriol® E 405 was dried and simultaneously reacted with 12 moles of 1 ,2-dodecylene oxide per mole of polyethylene glycol and 20 moles of 1 ,2-butylene oxide per mole of polyethylene oxide in the presence of sodium methoxide as an alkoxylation catalyst at 130°C, resulting in randomly arranged outward-positioned -(A-O)-units. The polyalkylene glycol obtained after purification proceedings by ion exchange resin, exhibited a kinematic viscosity of 27 mm2/s at 100°C.
Example 3: Storage stability
48.0% by weight of a customary gasoline performance package ("GPP 1 ") containing as detergent additive component Kerocom® PIBA (a polyisobutene monoamine made by BASF SE, based on a polyisobutene with Mn = 1000) and usual polyether-based carrier oils, aliphatic hydrocarbons as a diluent, demulsifiers and corrosion inhibitors in customary amounts, 37.7% by weight of xylene and 14.3% by weight of polyalkylene glycol of Example 1 ("PAG 1 ") above, were mixed at 20°C and stored thereafter in a sealed glass bottle at -20°C for 42 days. At the beginning of this storage period and then after each 7 days, the mixture was evaluated visually and checked for possible phase separation and precipitation. It is the aim that the mixture remains clear ("c"), homogeneous ("h") and liquid ("I") after storage and does not exhibit any phase separation ("ps") or precipitation ("pr"). The following table shows the results of the evaluations: after 7 days c, h,
after 14 days c, h,
after 21 days c, h,
after 28 days c, h,
after 35 days c, h,
after 42 days c, h,
Result: pass
Example 4: Engine cleanliness tests In order to demonstrate that the polyalkylene glycols mentioned do not decrease engine cleanliness and that engine cleanliness is in most cases even increased by the polyalkylene glycols mentioned, the average IVD values and the TCD values were determined with 250 mg/kg of the same gasoline performance package ("GPP 1 ") as used in Example 3 above containing additionally 150 mg/kg of polyalkylene glycol "PAG 1 ", and, for comparison, with 250 mg/kg of the same gasoline performance package without "PAG 1 " (referred to as "GPP 2"), according to CEC F-20-98 with a Mercedes Benz M1 1 1 E engine using a customary RON 95 E10 gasoline fuel and a customary RL-223/5 engine oil. The following table shows the results of the deter-minations: Additive average IVD [mg/valve] TCD [mg]
GPP 1 3.25 4639
GPP 2 13.25 5109
Claims (1)
- ClaimsThe use of a polyalkylene glycol of general formula IHO-(A-0)P-(CH2CH2-0)m-(A-0)q-H (I) wherein A is a C3- to C2o-alkylene group or a mixture of such alkylene groups, m is a number of from 2 to 100 and p and q are each numbers of from 1 to 100, as an additive in a fuel for reducing fuel consumption in the operation of an internal combustion engine with this fuel.The use of a polyalkylene glycol as described in claim 1 as an additive in a fuel for minimization of power loss in internal combustion engines and for improving acceleration of internal combustion engines.The use of a polyalkylene glycol as described in claim 1 as an additive in a fuel for improving the lubricity of lubricant oils contained in an internal combustion engine for lubricating purposes by operating the internal combustion engine with a fuel containing an effective amount of at least one of the said polyalkylene glycols.The use according to one or more of claims 1 to 3, wherein A in general formula I is a mixture of two different typs of alkylene groups A1 and A2 with A1 designating one or more C3- to C7-alkylene groups and A2 designating one or more Cs- to C2o-alky-lene groups, A1 and A2 being arranged randomly or blockwise.The use according to one or more of claims 1 to 3, wherein A in general formula I is a Cs- to C2o-alkylene group (A2) or a mixture of Cs- to C2o-alkylene groups (A2) ar-ranged randomly.The use according to one or more of claims 1 to 3 of a polyalkylene glycol obtain-able by alkoxylation of polyethylene glycols of general formula IIHO-(CH2CH2-0)m-H (II) wherein m is a number of from 2 to 100, with 2 to 200 moles of a C3- to C2o-alkylene oxide or a mixture of such alkylene oxides per mole of polyethylene glycol II, the alkoxylation product being arranged randomly or blockwise.7. A fuel composition comprising, in a major amount, a gasoline fuel and, in a minor amount, at least one polyalkylene glycol as described in claims 1 and 4 to 6, and at least one fuel additive which is different from the said polyalkylene glycol and has detergent action.8. The fuel composition according to claim 7 comprising as the fuel additive which is different from the said polyalkylene glycol and has detergent action, at least one representative (D) selected from:(Da) mono- or polyamino groups having up to 6 nitrogen atoms, at least onenitrogen atom having basic properties; (Db) nitro groups, optionally in combination with hydroxyl groups;(Dc) hydroxyl groups in combination with mono- or polyamino groups, at leastone nitrogen atom having basic properties; (Dd) carboxyl groups or their alkali metal or alkaline earth metal salts;(De) sulfonic acid groups or their alkali metal or alkaline earth metal salts;(Df) polyoxy-C2-C4-alkylene moieties terminated by hydroxyl groups, mono- orpolyamino groups, at least one nitrogen atom having basic properties, or by carbamate groups;(Dg) carboxylic ester groups; (Dh) moieties derived from succinic anhydride and having hydroxyl and/or aminoand/or amido and/or imido groups; and/or(Di) moieties obtained by Mannich reaction of substituted phenols withaldehydes and mono- or polyamines.9. The fuel composition according to claim 7 or 8, additionally comprising, as a further fuel additive in a minor amount, at least one carrier oil.10. The fuel composition according to claims 7 to 9, additionally comprising, as a further fuel additive in a minor amount, at least one tertiary hydrocarbyl amine of formula NR1R2R3 wherein R1, R2 and R3 are the same or different Ci- to C2o-hydro-carbyl residues with the proviso that the overall number of carbon atoms in formula NR1R2R3 does not exceed 30.1 1 . The fuel composition according to claims 7 to 10, comprising at least one repre-sentative (D) selected from (Da) polyisobutene monoamines or polyisobutene poly-amines having Mn =300 to 5000, having at least 50 mol-% of vinylidene double bonds and having been prepared by hydroformylation of the respective polyiso-butene and subsequent reductive amination with ammonia, monoamines or poly-amines, in combination with at least one mineral or synthetic carrier oil.12. An additive concentrate comprising at least one polyalkylene glycol as described in claims 1 and 4 to 6, and at least one fuel additive which is different from the poly-alkylene glycol and has detergent action.13. An additive concentrate according to claim 12, comprising at least one represent-tative (D) selected from (Da) polyisobutene monoamines or polyisobutene poly-amines having Mn = 300 to 5000, having at least 50 mol-% of vinylidene double bonds and having been prepared by hydroformylation of the respective polyiso-butene and subsequent reductive amination with ammonia, monoamines or poly-amines, and further comprising at least one mineral or synthetic carrier oil.
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| US14/062,347 US20150113859A1 (en) | 2013-10-24 | 2013-10-24 | Use of polyalkylene glycol to reduce fuel consumption |
| PCT/EP2014/071933 WO2015058993A2 (en) | 2013-10-24 | 2014-10-14 | Use of a polyalkylene glycol to reduce fuel consumption |
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-
2013
- 2013-10-24 US US14/062,347 patent/US20150113859A1/en not_active Abandoned
-
2014
- 2014-10-14 EP EP14786833.5A patent/EP3060637B1/en not_active Not-in-force
- 2014-10-14 MY MYPI2016000674A patent/MY183894A/en unknown
- 2014-10-14 CN CN201480065730.8A patent/CN105992810B/en not_active Expired - Fee Related
- 2014-10-14 SG SG11201603065YA patent/SG11201603065YA/en unknown
- 2014-10-14 US US15/031,474 patent/US9957455B2/en not_active Expired - Fee Related
- 2014-10-14 CN CN201810427793.3A patent/CN108611134A/en active Pending
- 2014-10-14 AU AU2014339169A patent/AU2014339169B2/en not_active Ceased
- 2014-10-14 CA CA2928509A patent/CA2928509A1/en not_active Abandoned
- 2014-10-14 WO PCT/EP2014/071933 patent/WO2015058993A2/en not_active Ceased
- 2014-10-14 KR KR1020167013636A patent/KR20160075674A/en not_active Withdrawn
- 2014-10-14 PL PL14786833T patent/PL3060637T3/en unknown
- 2014-10-14 RU RU2016119772A patent/RU2016119772A/en unknown
- 2014-10-23 AR ARP140103996A patent/AR099734A1/en active IP Right Grant
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