EP3256506A1 - Block copolymers and the use thereof for improving the cold properties of fuels or combustibles - Google Patents
Block copolymers and the use thereof for improving the cold properties of fuels or combustiblesInfo
- Publication number
- EP3256506A1 EP3256506A1 EP16703775.3A EP16703775A EP3256506A1 EP 3256506 A1 EP3256506 A1 EP 3256506A1 EP 16703775 A EP16703775 A EP 16703775A EP 3256506 A1 EP3256506 A1 EP 3256506A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fuel
- block copolymer
- alkyl
- additive
- chosen
- 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- Withdrawn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
- 239000000446 fuel Substances 0.000 title claims abstract description 211
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 102
- 239000000654 additive Substances 0.000 claims abstract description 133
- 230000000996 additive effect Effects 0.000 claims abstract description 87
- 229920001577 copolymer Polymers 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 125000002015 acyclic group Chemical group 0.000 claims abstract description 32
- 238000004062 sedimentation Methods 0.000 claims abstract description 27
- 239000012141 concentrate Substances 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 65
- 125000000217 alkyl group Chemical group 0.000 claims description 31
- 238000003860 storage Methods 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims description 24
- -1 vinylbenzyl Chemical group 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 23
- 239000005977 Ethylene Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 12
- 239000000295 fuel oil Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 235000013311 vegetables Nutrition 0.000 claims description 10
- 239000003225 biodiesel Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 229920001897 terpolymer Polymers 0.000 claims description 9
- 125000005208 trialkylammonium group Chemical group 0.000 claims description 9
- 229920001567 vinyl ester resin Polymers 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 125000005907 alkyl ester group Chemical group 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 239000003505 polymerization initiator Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 238000012661 block copolymerization Methods 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 150000002891 organic anions Chemical class 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229920000359 diblock copolymer Polymers 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 16
- 235000019198 oils Nutrition 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 8
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- KXADPELPQCWDHL-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1.COC1=CC=CC=C1 KXADPELPQCWDHL-UHFFFAOYSA-N 0.000 description 5
- 230000005587 bubbling Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 238000001542 size-exclusion chromatography Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 4
- 239000002816 fuel additive Substances 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N methyl phenyl ether Natural products COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- KPORSMDXMDNWRZ-UHFFFAOYSA-N octadecyl 2-bromopropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)Br KPORSMDXMDNWRZ-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229920006301 statistical copolymer Polymers 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000010775 animal oil Substances 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000003412 degenerative effect Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- VGUWFGWZSVLROP-UHFFFAOYSA-N 1-pyridin-2-yl-n,n-bis(pyridin-2-ylmethyl)methanamine Chemical compound C=1C=CC=NC=1CN(CC=1N=CC=CC=1)CC1=CC=CC=N1 VGUWFGWZSVLROP-UHFFFAOYSA-N 0.000 description 2
- MONMFXREYOKQTI-UHFFFAOYSA-M 2-bromopropanoate Chemical compound CC(Br)C([O-])=O MONMFXREYOKQTI-UHFFFAOYSA-M 0.000 description 2
- ILLHORFDXDLILE-UHFFFAOYSA-N 2-bromopropanoyl bromide Chemical compound CC(Br)C(Br)=O ILLHORFDXDLILE-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 2
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 238000009666 routine test Methods 0.000 description 2
- 229930195734 saturated hydrocarbon Chemical group 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Chemical group 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- GVTLFGJNTIRUEG-ZHACJKMWSA-N (e)-n-(3-methoxyphenyl)-3-phenylprop-2-enamide Chemical class COC1=CC=CC(NC(=O)\C=C\C=2C=CC=CC=2)=C1 GVTLFGJNTIRUEG-ZHACJKMWSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- XXSPGBOGLXKMDU-UHFFFAOYSA-M 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C([O-])=O XXSPGBOGLXKMDU-UHFFFAOYSA-M 0.000 description 1
- MNNZINNZIQVULG-UHFFFAOYSA-N 2-chloroethylbenzene Chemical compound ClCCC1=CC=CC=C1 MNNZINNZIQVULG-UHFFFAOYSA-N 0.000 description 1
- NKRVGWFEFKCZAP-UHFFFAOYSA-N 2-ethylhexyl nitrate Chemical compound CCCCC(CC)CO[N+]([O-])=O NKRVGWFEFKCZAP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- KQNZLOUWXSAZGD-UHFFFAOYSA-N benzylperoxymethylbenzene Chemical compound C=1C=CC=CC=1COOCC1=CC=CC=C1 KQNZLOUWXSAZGD-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- BKTKLDMYHTUESO-UHFFFAOYSA-N ethyl 2-bromo-2-phenylacetate Chemical compound CCOC(=O)C(Br)C1=CC=CC=C1 BKTKLDMYHTUESO-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- POPMFUHEDYAERX-UHFFFAOYSA-N octadecan-2-yl 2-bromopropanoate Chemical compound BrC(C(=O)OC(C)CCCCCCCCCCCCCCCC)C POPMFUHEDYAERX-UHFFFAOYSA-N 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000003381 solubilizing effect Effects 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
- 238000005482 strain hardening Methods 0.000 description 1
- SFXOHDOEOSCUCT-UHFFFAOYSA-N styrene;hydrochloride Chemical compound Cl.C=CC1=CC=CC=C1 SFXOHDOEOSCUCT-UHFFFAOYSA-N 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1625—Hydrocarbons macromolecular compounds
- C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
- C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1625—Hydrocarbons macromolecular compounds
- C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
- C10L1/165—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
- C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/234—Macromolecular compounds
- C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
- C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
- C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
- C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
- C10L2200/0446—Diesel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/08—Inhibitors
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
- C10L2250/04—Additive or component is a polymer
Definitions
- the present invention relates to block copolymers and additive concentrates containing such copolymers.
- the invention relates to their use as an additive for fuels, in particular the use of such additives to improve the cold-holding properties of fuels during storage and / or their use at low temperatures.
- the present invention also relates to fuel and fuel compositions additive with a cold-flow additive (CFI) comprising such copolymers.
- CFI cold-flow additive
- Fuels containing n-alkyl, iso-alkyl or n-alkenyl substituted compounds such as paraffin waxes are known to exhibit deteriorated flow properties at low temperatures, typically below 0 ° C.
- the average distillates obtained from crude oils of petroleum origin by distillation such as diesel or heating oil contain different amounts of n-alkanes or n-paraffins according to their origin.
- These n-alkyl, iso-alkyl or n-alkenyl substituted compounds tend to crystallize by lowering the temperature, clogging pipes, lines, pumps and filters, for example in motor vehicle fuel systems.
- paraffins In winter or under conditions of use of fuels or fuels below 0 ° C, the phenomenon of crystallization can lead to the decrease of the flow properties of fuels and, consequently, difficulties during their transport, storage and / or their use.
- the cold operability of fuels is important, especially for starting cold engines. If the paraffins are crystallized at the bottom of the tank, they can be driven to start in the fuel system and particularly clog filters and prefilters arranged upstream of the injection systems (pump and injectors). Similarly, for the storage of domestic fuel oils, paraffins precipitate at the bottom of the tank and can be driven and obstruct the pipes upstream of the pump and the boiler supply system (nozzle and filter).
- CFIs cold flow improvers
- CFI Cold Flow Additives
- TLF Filtration Limit Temperature
- PE pour point
- TLF additives Temporal Limit of Filtration
- TLF Temperature Limit of Filtration
- the document FR2903418 describes in particular the use of a combination of a polyacrylate or polymethacrylate with a cold-cooling additive (CFI) of the EVA or EVP type, to reveal the effectiveness of the CFI additives by amplifying their effect on the TLF.
- CFI cold-cooling additive
- another purpose of the flow enhancement additives is to ensure the dispersion of the paraffin crystals, so as to retard or prevent the sedimentation of the crystals of the crystals.
- paraffins and thus the formation of a paraffin-rich layer in the bottom of containers, tanks or storage tanks; these paraffin-dispersing additives are referred to as anti-settling additives or WASA (acronym for Wax Anti-Settling Additive).
- Modified alkylphenol aldehyde resins have been described in FR2969620 as an anti-sedimentation additive in combination with a TLF additive.
- This requirement is particularly important for fuels comprising one or more n-alkyl, iso-alkyl or n-alkenyl substituted compounds having a tendency to crystallize in said fuels when stored and / or used at low temperatures. .
- the object of the present invention is to propose novel additives and concentrates containing them which can advantageously be used as additives to improve the cold-holding properties of these fuels, when they are stored and / or when they are used low temperature, typically below 0 ° C, in particular as anti-settling additives.
- the object of the present invention is furthermore to propose new additives and concentrates containing them acting both on the TLF and retarding and / or preventing the sedimentation of the crystals of n-alkyl, isoalkyl or n-substituted-substituted compounds. alkenyl, in particular paraffins.
- Another object of the invention is to provide a fuel or fuel composition having improved cold-holding properties, particularly at temperatures below 0 ° C, preferably below -5 ° C.
- the invention therefore relates to a block copolymer as defined in claim 1 and an additive concentrate comprising such a block copolymer as defined in claim 15.
- the Applicant has furthermore discovered that the block copolymer and the additive concentrate make it possible to improve the cold-holding properties of fuels comprising one or more n-alkyl, iso-alkyl or n-alkenyl-substituted compounds having a tendency to crystallize in said fuels during storage and / or use at low temperatures.
- the block copolymer and the additive concentrate according to the invention can be used to retard or prevent the sedimentation of the crystals of the n-alkyl, isoalkyl or n-alkenyl substituted compounds of the fuel or fuel when storage and / or use at low temperatures.
- the applicant has furthermore formulated fuel or fuel compositions as defined in claim 19.
- the subject of the present invention relates, in particular, to a block copolymer comprising:
- a block A consisting of a chain of structural units derived from one or more ⁇ , ⁇ -unsaturated alkyl acrylate or methacrylate monomers
- a block B consisting of a chain of structural units derived from one or more ⁇ , ⁇ -unsaturated monomers chosen from styrene derivatives whose aromatic nucleus is substituted with at least one group R chosen from the groups:
- the block copolymer also comprises (iii) a terminal chain I consisting of a linear or branched, cyclic or acyclic, saturated or unsaturated, C 1 to C 32, preferably C 4 to C, hydrocarbonaceous chain; 24 plus preferably C10 to C2 4, said chain being located in the terminal position of said block copolymer
- the ⁇ , ⁇ -unsaturated monomer of the block A is chosen from linear or branched C 1 to C 34, preferably C 6 to C 24 , and more preferably C 8 to C 24 alkyl acrylates or methacrylates .
- the ⁇ , ⁇ -unsaturated monomer of block B is chosen from styrene derivatives whose aromatic ring is substituted by at least one C 1 to C 24, preferably C 1 to C 12, alkyl ester group. , preferably the acetoxy group, said ester group being in the meta, ortho or para position on the aromatic ring, preferably in the para position.
- the ⁇ , ⁇ -unsaturated monomer of block B is chosen from styrene derivatives whose aromatic ring is substituted by at least one linear or branched, preferably acyclic, C 1 -C 12 hydrocarbon-based chain, preferably C 1 -C 8 , preferably an alkyl group, said chain being optionally substituted by one or more groups containing a quaternary ammonium salt, preferably a trialkylammonium salt.
- the ⁇ , ⁇ -unsaturated monomer of the B block is chosen from the isomers of the (vinylbenzyl) trialkylammonium salts in the ortho, meta or para position, preferably in the para position, pure or mixture.
- the alkyl substituents of the ammonium are identical or different and independently selected from alkyl Cl to C10, preferably C, to C 4, linear or branched, acyclic Preferably, more preferentially methyl or ethyl.
- the block copolymer is obtained by block copolymerization and controlled, preferably, using a polymerization initiator comprising the terminal chain I.
- the block copolymer is a diblock copolymer. According to a particular preferred embodiment, the block copolymer is represented by the following formula I) or (II):
- n is an integer between 2 and 20, preferably between 3 and 16,
- p is an integer of 2 to 20, preferably 3 to 16,
- R 0 is chosen from hydrogen or the methyl group
- R 1 is chosen from linear or branched, C 1 to C 32, preferably C 4 to C 24, more preferably C 1 to C 24 hydrocarbon-based, cyclic or acyclic, saturated or unsaturated hydrocarbon chains, preferably the alkyl groups,
- R 2 is selected from hydrocarbon chains, straight or branched acyclic preferably Ci-C32, preferably C 4 -C 24, more preferably C 1 0 -C 24, more preferably alkyl groups,
- R 3 is a substituent in the ortho, meta or para position on the aromatic ring, preferably in the para position, selected from the group consisting of:
- R 7 is chosen from C 1 to C 24 , preferably C 1 to C 2, more preferably C 1 to C 6 alkyl groups, which are linear or branched, preferably acyclic, and
- X " is chosen from hydroxide ions, halides and organic anions, preferably chlorine and,
- R 8 Rg and R-io are the same or different and independently selected from alkyl groups C1 to Ci 0, preferably to C 4, linear or branched, of preferably acyclic, more preferably the methyl or ethyl group, R 4 is chosen from the group consisting of:
- halogens preferably bromine
- R 5 and R 6 are identical or different and independently selected from the group consisting of hydrogen and C 1 to C 10 alkyl groups, preferably C 1 to C 6 alkyl groups; C 4 , linear or branched, more preferably acyclic, even more preferably the methyl group.
- the object of the present invention also relates to the use of a block copolymer according to the invention as an anti-sedimentation additive.
- the block copolymer according to the invention is used as an additive improving the cold-holding properties of a fuel or fuel from one or more sources selected from the group consisting of mineral sources, preferably oil, animal, vegetable and synthetic.
- the fuel or fuel comprises one or more n-alkyl, iso-alkyl or n-alkenyl substituted compounds having a tendency to crystallize in said fuel or a fuel during storage and / or use at a low temperature.
- the block copolymer is used in combination with at least one cold-cooling additive (CFI) improving the low-temperature flow properties of said fuel or fuel during storage and / or low-temperature use thereof.
- CFI cold-cooling additive
- the block copolymer also makes it possible to amplify the fluidifying effect of the cold-flow-making additive (CFI) by improving the Filtration Limit Temperature (TLF) according to the NF EN 1 16 standard of said fuel or combustible.
- CFI cold-flow-making additive
- TEZ Filtration Limit Temperature
- the object of the present invention also relates to an additive concentrate comprising a block copolymer according to the invention, mixed with an organic liquid.
- the organic liquid is inert with respect to the block copolymer and miscible with fuels or fuels from one or more sources selected from the group consisting of mineral sources, preferably petroleum, animal, plant and synthetic.
- the fuel or fuel comprises one or more n-alkyl, iso-substituted compounds alkyl or n-alkenyl having a tendency to crystallize in said fuel or a fuel during storage and / or use at low temperature.
- the additive concentrate comprises at least one cold-cooling additive (CFI) improving the cold behavior, preferably improving the low-temperature flow properties of the fuel or fuel during its storage and / or its use at low temperatures.
- CFI cold-cooling additive
- said cold-cooling additive being preferably chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s) (EVA and / or EVP), alone or as a mixture.
- the object of the present invention is also to provide the use of such a concentrate for retarding or preventing the sedimentation of the crystals of the n-alkyl, isoalkyl or n-alkenyl substituted compounds of the fuel or fuel during its storage. and / or use at low temperatures.
- the fuel or fuel is preferably selected from gas oils, bio-gas oils, gas oil and bio-diesel fuel mixtures type B x and fuel oils, preferably domestic fuel oils (FOD).
- the object of the present invention is also to provide a fuel or fuel composition comprising:
- a fuel or fuel from one or more sources selected from the group consisting of mineral sources, preferably petroleum, animal, vegetable and synthetic, advantageously selected from gas oils, bio-gas oils, mixtures of diesel fuel and bio-diesel type B x and fuel oils, preferably the domestic fuel oils (FOD), said fuel or fuel cell comprising one or more compounds with substituents n-alkyl, iso-alkyl or n-alkenyl having a tendency to crystallisation in said fuel or fuel during storage and / or use at low temperature,
- sources selected from the group consisting of mineral sources, preferably petroleum, animal, vegetable and synthetic, advantageously selected from gas oils, bio-gas oils, mixtures of diesel fuel and bio-diesel type B x and fuel oils, preferably the domestic fuel oils (FOD), said fuel or fuel cell comprising one or more compounds with substituents n-alkyl, iso-alkyl or n-alkenyl having a tendency to crystallisation in said fuel or fuel during storage and / or use at low temperature
- CFI cold-improving cold-forming additive
- EVA and or EVP cold-improving cold-forming additive
- the composition contains at least 10 ppm, preferably at least 50 ppm, advantageously between 10 and 5000 ppm, more preferably between 10 and 1000 ppm of the block copolymer (2) and at least 10 ppm, preferably at least 10 ppm. at least 50 ppm, advantageously between 10 and 5 000 ppm, more preferably between 10 and 1 000 ppm of the cold-flow additive (3).
- a block copolymer comprising at least one block A and at least one block B is prepared according to any known method of block copolymerization and controlled from at least two types of ⁇ , ⁇ -unsaturated monomers.
- the sequenced and controlled polymerization is preferably chosen from controlled radical polymerization, for example by atom transfer radical polymerization (ATRP), the radical polymerization by nitroxide (NMP).
- ATRP atom transfer radical polymerization
- NMP nitroxide
- degenerative transfer processes such as degenerative transfer polymerization ("ITRP-iodine transfer radical polymerization") or radical transfer polymerization reversible addition-fragmentation chain reaction (RAFT)
- ATRP-derived polymerizations such as polymerizations using initiators for continuous regeneration of the activator (ICAR - Initiators for continuous activator regeneration ) or using regenerative activators by electron transfer (ARGET in English "activators regenerated by electron transfer”).
- the polymerization may advantageously be carried out starting from at least two types of ⁇ , ⁇ -unsaturated monomers and from a polymerization initiator comprising a terminal chain I.
- the polymerization is typically carried out in a solvent, under an inert atmosphere, at a reaction temperature generally ranging from 0 to 200 ° C, preferably from 50 ° C to 130 ° C.
- the solvent may be chosen from polar solvents, in particular ethers such as anisole (methoxybenzene) or tetrahydrofuran or apolar solvents, in particular paraffins, cycloparaffins, aromatics and alkylaromatics having from 1 to 19 carbon atoms. carbon, for example, benzene, toluene, cyclohexane, methylcyclohexane, n-butene, n-hexane, n-heptane and the like.
- the reaction is generally carried out under vacuum in the presence of an initiator, a ligand and a catalyst.
- an initiator such as N, N, N ', N ", N" -Pentamethyldiethylenetriamine (PMDETA), 1,1,4,7,10,10-hexamethyltriethylene tetramine (HMTETA), 2,2'-Bipyridine (BPY) and Tris (2-pyridylmethyl) amine (TPMA).
- PMDETA 1,1,4,7,10,10-hexamethyltriethylene tetramine
- BPY 2,2'-Bipyridine
- TPMA Tris (2-pyridylmethyl) amine
- the ATRP polymerization is preferably carried out in a solvent chosen from polar solvents.
- Block A consists of a chain of structural units derived from one or more ⁇ , ⁇ -unsaturated acrylate or alkyl methacrylate monomers.
- the ⁇ , ⁇ -unsaturated monomer of block A is, preferably, chosen from linear or branched, C 1 to C 34, preferably C 6 to C 24 , more preferably C 8 to C 24 alkyl acrylates or methacrylates. .
- Block B consists of a chain of structural units derived from one or more ⁇ , ⁇ -unsaturated monomers chosen from styrenic derivatives whose aromatic nucleus is substituted by at least one group R chosen from the groups:
- the ⁇ , ⁇ -unsaturated monomer of block B is chosen from styrenic derivatives whose aromatic ring is substituted by at least one C 1 -C 2 4, preferably C 1 -C 4, alkyl ester group.
- Ci 2 preferably the acetoxy group.
- the alkyl ester group can be in the ortho, meta or para position on the aromatic ring, preferably in the para position.
- the ⁇ , ⁇ -unsaturated monomer of block B is chosen from styrenic derivatives whose aromatic ring is substituted by at least one hydrocarbon chain, linear or branched, preferably acyclic, C 1 -C 12, preferably C 1 -C 8 , preferably an alkyl group, said chain being optionally substituted by one or more groups containing a quaternary ammonium salt, preferably a trialkylammonium salt.
- the aromatic nucleus of the ⁇ , ⁇ -unsaturated monomer of block B comprises one or more groups containing a quaternary ammonium salt, preferably a trialkylammonium salt.
- the ⁇ , ⁇ -unsaturated monomer of block B is chosen from the isomers of (vinylbenzyl) trialkylammonium salts, pure or mixture.
- the substituent of the styrenic ring may be in the ortho, meta or para position, preferably in the para position.
- the (vinylbenzyl) trialkylammonium salts are preferred.
- the alkyl substituents of ammonium are identical or different and, chosen independently from C1 to C, preferably C1 to C4 alkyl , linear or branched, preferably acyclic, more preferably the methyl or ethyl group.
- the counter ion of the quaternary ammonium salt may be chosen from hydroxide ions, halides and organic anions such as carboxylates or alcoholates. We will preferably choose the hydroxide or halide ions, preferably chloride.
- the block copolymer comprises a terminal chain I consisting of a linear or branched, cyclic or acyclic, saturated or unsaturated, C 1 to C 32, preferably C 4 to C 24, hydrocarbon-based chain , more preferably in C10 to C24 .
- cyclic hydrocarbon chain means a hydrocarbon chain at least a part of which is cyclic, in particular aromatic. This definition does not exclude hydrocarbon chains comprising both an acyclic and a cyclic moiety.
- the terminal chain I may comprise an aromatic hydrocarbon chain, for example a benzene chain and / or a linear or branched, saturated and acyclic hydrocarbon-based chain, in particular an alkyl chain.
- the terminal chain I is, preferably, selected from alkyl chains, preferably linear, more preferably alkyl chains of at least 4 carbon atoms, even more preferably of at least 12 carbon atoms.
- the terminal chain I is located in the terminal position of the block copolymer. It can be introduced into the block copolymer by means of the polymerization initiator.
- the terminal chain I may, advantageously, constitute at least a part of the polymerization initiator and is positioned within the polymerization initiator in order to introduce, during the first polymerization initiation step. , the terminal chain I in the terminal position of the block copolymer.
- the polymerization initiator is, for example, chosen from free radical initiators used in the ATRP polymerization process. These free radical initiators well known to those skilled in the art are described in particular in the article "Atom Transfer Radical Polymerization: current status and future prospects, Macromolecules, 45, 4015-4039, 2012".
- the polymerization initiator is, for example, chosen from alkyl esters of a carboxylic acid substituted with a halidegide, preferably a bromine in the alpha position, for example ethyl 2-bromopropionate or ⁇ -bromoisobutyrate.
- a halidegide preferably a bromine in the alpha position
- ethyl 2-bromopropionate or ⁇ -bromoisobutyrate ethyl chloride, benzyl choride or bromide, ethyl ⁇ -bromophenylacetate and chloroethylbenzene.
- ethyl 2-bromopropionate may make it possible to introduce into the copolymer the terminal chain I in the form of a C 2 alkyl chain and benzyl bromide in the form of a benzyl group.
- the block copolymer is a diblock copolymer.
- the structure of the block copolymer may be of the IAB or IBA type, advantageously IAB.
- the terminal chain I may be directly linked to block A or B according to the structure IAB or IBA respectively, or to be linked via a linking group, for example an ester, amide, amine or ether function.
- the linking group then forms a bridge between the terminal chain I and the block A or B.
- the block copolymer can also be functionalized at the end of the chain according to any known method, in particular by hydrolysis or nucleophilic substitution, in particular for an ATRP polymerization which produces a copolymer having a halide in the terminal position. It is thus possible to introduce a terminal chain ⁇ by post-functionalization of the block copolymer.
- the terminal chain ⁇ advantageously comprises a hydrocarbon chain, linear or branched, cyclic or acyclic, C 1 to C 32, preferably C 1 to C 24, more preferably C 1 to C 0 , even more preferably an alkyl group, optionally substituted by a or more groups containing at least one heteroatom selected from N and O.
- this functionalization may, for example, be carried out by treating the copolymer IAB or IBA obtained by ATRP with a primary alkylamine to C 32 or an alcohol to C 32 under conditions soft so as not to modify the functions present on blocks A, B and I.
- the block copolymer is represented by the following formula (I) or (II):
- n is an integer between 2 and 20, preferably between 3 and 16,
- p is an integer of 2 to 20, preferably 3 to 16,
- R 0 is chosen from hydrogen or the methyl group
- R 1 is chosen from linear or branched, C 1 to C 32, preferably C 4 to C 24, more preferably C 1 to C 24 hydrocarbon-based, cyclic or acyclic, saturated or unsaturated hydrocarbon chains, even more preferentially alkyl groups
- R 2 is chosen from linear or branched, preferably acyclic, C 1 to C 32, preferably C 4 to C 24, more preferably C 1 to C 24 hydrocarbon-based chains, even more preferentially alkyl groups,
- R 3 is a substituent in the ortho, meta or para position on the aromatic ring, preferably in the para position, selected from the group consisting of:
- R 7 is chosen from C 1 to C 24 , preferably C 1 to C 2, more preferably C 1 to C 6 alkyl groups, which are linear or branched, preferably acyclic, and
- X " is chosen from hydroxide ions, halides and organic anions, preferably chlorine and,
- R 8 , R 8 and R 10 are identical or different and chosen independently from C 1 to C 10 , preferably C 1 to C 4 , alkyl groups which are linear or branched, preferably acyclic, more preferably the methyl or ethyl group,
- R 4 is selected from the group consisting of:
- halogens preferably bromine
- R 5 and R 6 are identical or different and independently selected from the group consisting of hydrogen and C 1 to C 10 , preferably C 1 to C 4 , alkyl groups, linear or branched, more preferably acyclic, still more preferably methyl group.
- the group R-1 may consist of the terminal chain I as described above and / or the group F3 ⁇ 4 may consist of the terminal chain ⁇ as described above.
- the molar and / or mass ratio between block A and B in the block copolymer, and in particular the m, n and p values of formulas (I) and (II) will be chosen so that the block copolymer is soluble in the fuel or fuel and / or the organic liquid of the concentrate for which it is intended.
- this ratio and these values m, n and p will be optimized according to the fuel or fuel and / or the organic liquid so as to obtain the best properties when cold.
- the molar ratio between the blocks A and B is advantageously between 1: 10 and 10: 1, preferably between 1: 2 and 2: 1, more preferably between 1: 0.5 and 0. 5: 2.
- Other blocks may optionally be present in the block copolymer insofar as they do not fundamentally change the character of the block copolymer.
- block copolymers containing only A and B blocks will be preferred.
- the equivalents of the monomers of the block A and of the block B reacted during the polymerization reaction are identical or different and, independently, between 2 and 20, preferably between 3 and 16.
- number of equivalents is meant the ratio between the amounts of material (in moles) of the monomers of the block A and the block B during the polymerization reaction.
- the block copolymer may advantageously be used as a cold-holding additive for the fuel or fuel obtained from one or more sources selected from the group consisting of the sources mineral, preferably petroleum, animal, vegetable and synthetic.
- cold-holding additive an additive that improves the cold-holding properties of a fuel or fuel, especially the cold operability during storage and / or its use at low temperature, typically less than 0 ° C, preferably below -5 ° C.
- the block copolymer is particularly advantageous as a fuel or fuel additive comprising one or more n-alkyl, iso-alkyl or n-alkenyl substituted compounds having a tendency to crystallize in the fuel or fuel, during storage and / or of its use at low temperature.
- the fuels or fuels may be chosen from liquid hydrocarbon fuels or liquid fuels alone or as a mixture.
- the liquid hydrocarbon fuels or fuels comprise, in particular, middle distillates having a boiling point of between 100 and 500 ° C.
- These distillates may for example be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates obtained from catalytic cracking and / or hydrocracking of distillates under vacuum, distillates resulting from conversion processes such as ARDS (by atmospheric residue desulphurisation) and / or visbreaking, distillates from the recovery of Fischer Tropsch cuts, distillates resulting from the BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination, and / or biodiesels of animal and / or vegetable origin and / or oils and / or esters of vegetable and / or animal oils.
- the sulfur content of the fuels or fuels is preferably less than 5000 ppm, preferably less than 500 ppm, and more preferably less than 50 ppm, or even less than 10 ppm and advantageously without sulfur.
- the fuel or fuel is preferably selected from gas oils, biodiesel, gasolines type B x and fuel oils, preferably domestic fuel oils (FOD).
- Diesel fuel of type B x for a diesel engine means a diesel fuel which contains x% (v / v) of vegetable or animal oil esters (including used cooking oils) converted by a process chemical called transesterification reacting this oil with an alcohol to obtain fatty acid esters (EAG). With methanol and ethanol, respectively, fatty acid methyl esters are obtained (EMAG) and fatty acid ethyl esters (EEAG).
- EAG fatty acid esters
- EMAG fatty acid methyl esters
- EEAG fatty acid ethyl esters
- the letter "B” followed by a number indicates the percentage of EAG contained in the diesel fuel.
- a B99 contains 99% of EAG and 1% of middle distillates of fossil origin, the B20, 20% of EAG and 80% of middle distillates of fossil origin etc.
- type B diesel fuels 0 which do not contain oxygenated compounds
- type Bx gasolines which contain x% (v / v) of vegetable oil esters or fatty acids, most often methyl esters (EMHV or EMAG).
- EAG methyl esters
- the term fuel is designated by the term B100.
- the fuel or fuel is selected from gas oils, biodiesel and gasolines type B x .
- the block copolymer described above is used as an anti-sedimentation additive.
- the block copolymer advantageously makes it possible to retard or prevent the sedimentation of the crystals of the n-alkyl, iso-alkyl or n-alkenyl substituted compounds.
- the block copolymer may advantageously be used to retard or prevent the sedimentation of the crystals of n-alkanes, preferably the n-alkanes containing at least 12 carbon atoms, more preferably at least 20 carbon atoms, and even more preferably at least 24.
- the block copolymer is advantageously also used as a cold-holding additive in combination with at least one cold-cooling additive (CFI) improving the low temperature flow properties of the fuel or fuel during its storage and / or its use at low temperature.
- CFI cold-cooling additive
- the cold-flow-making additive is preferably chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture.
- copolymers of ethylene and of unsaturated ester such as ethylene / vinyl acetate copolymers (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / methyl methacrylate (EMMA), and ethylene / alkyl fumarate described, for example, in US3048479, US3627838, US3790359, US3961961 and EP261957.
- the cold-flow additive is advantageously chosen from copolymers of ethylene and of vinyl ester (s), alone or as a mixture, in particular ethylene / vinyl acetate (EVA) and ethylene / ethylene copolymers. vinyl propionate (EVP), more preferably ethylene / vinyl acetate copolymers (EVA).
- the block copolymer is advantageously used to amplify the fluidizing (flow) effect of the cold-flow additive (CFI) by improving the temperature limit of filterability (TLF) of the fuel or fuel, the TLF being measured according to the standard NF EN 1 16.
- TLF booster This effect is usually called the "TLF booster” effect insofar as the presence of the block copolymer improves the fluidifying nature of the CFI additive.
- This improvement is reflected, in particular, by a significant decrease in the TLF of the fuel composition or fuel additive with this combination compared to the same fuel composition or fuel additive only with the CFI additive, at the same rate of treatment.
- a significant reduction of the TLF results in a reduction of at least 3 ° C of the TLF according to the NF EN 1 16 standard.
- the block copolymer has a double effect, "TLF booster" and antisedimentation. .
- the block copolymer may be added to the fuels within the refinery, and / or be incorporated downstream of the refinery, optionally, in admixture with other additives, in the form of an additive concentrate, further called according to the use "additive package".
- the block copolymer is used as a cold-holding additive in the fuel or fuel at a content, advantageously at least 10 ppm, preferably at least 50 ppm, more preferably at a content of between 10 and 5000 ppm, more preferably more preferably between 10 and 1000ppm.
- an additive concentrate comprises the block copolymer as described above, mixed with an organic liquid.
- the organic liquid must be inert with respect to the block copolymer and miscible with fuels or fuels as described above.
- miscible means that the block copolymer and the organic liquid form a solution or a dispersion so as to facilitate the mixing of the block copolymer in the fuels according to the conventional methods of additive fuel or fuels.
- the organic liquid must be miscible with the fuels comprising one or more n-alkyl, iso-alkyl or n-alkenyl substituted compounds having a tendency to crystallize in said fuel or a fuel during storage and / or use at a low temperature.
- the fuel or fuel is preferably selected from gas oils, biodiesel, gasolines type B x and fuel oils, preferably domestic fuel oils (FOD).
- the organic liquid is advantageously chosen from aromatic hydrocarbon solvents such as the solvent marketed under the name "SOLVESSO", alcohols, ethers and other oxygenated compounds and paraffinic solvents such as hexane, pentane or isoparaffins, alone. or in mixture.
- aromatic hydrocarbon solvents such as the solvent marketed under the name "SOLVESSO”
- alcohols, ethers and other oxygenated compounds and paraffinic solvents such as hexane, pentane or isoparaffins, alone. or in mixture.
- the additive concentrate advantageously comprises at least one cold-cooling additive (CFI) improving the cold-resistance, preferably improving the low-temperature flow properties of the fuel or fuel during its storage and / or its use at low temperature. low temperature.
- CFI cold-cooling additive
- the cold-flow-making additive (CFI) is preferably chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture as described herein. -above.
- the additive concentrate may also comprise one or more other additives commonly used in fuels or fuels and different from the block copolymer described above.
- the additive concentrate may typically comprise one or more other additives selected from detergents, anti-corrosion agents, dispersants, demulsifiers, defoamers, biocides, re-deodorants, procetane additives, modifiers lubricant additives or lubricity additives, combustion assistants (catalytic combustion and soot promoters), cloud point improvers, pour point, TLF, agents anti-settling agents, anti-wear agents and / or conductivity modifiers.
- additives selected from detergents, anti-corrosion agents, dispersants, demulsifiers, defoamers, biocides, re-deodorants, procetane additives, modifiers lubricant additives or lubricity additives, combustion assistants (catalytic combustion and soot promoters), cloud point improvers, pour point, TLF, agents anti-settling agents, anti-wear agents and / or conductivity modifiers.
- procetane additives in particular (but not limited to) selected from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aryl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably ter-butyl peroxide;
- anti-foam additives in particular (but not limited to) selected from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides from vegetable or animal oils. Examples of such additives are given in EP861882, EP663000, EP736590;
- detergent and / or anti-corrosion additives in particular (but not limited to) selected from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkylamines, polyetheramines, quaternary ammonium salts and triazole derivatives; examples of such additives are given in the following documents: EP0938535, US2012 / 00101 12 and WO2012 / 004300.
- lubricity additives or anti-wear agents in particular (but not limited to) selected from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and monocarboxylic acid derivatives and polycyclic.
- lubricity additives or anti-wear agents are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784.
- cloud point additives including (but not limited to) selected from the group consisting of long-chain olefin terpolymers / (meth) acrylic ester / maleimide, and fumaric acid / maleic acid ester polymers. Examples of such additives are given in FR2528051, FR2528051, FR2528423, EP1 12195, EP172758, EP271385, EP291367;
- anti-sedimentation additives and / or paraffin dispersants in particular (but not exclusively) selected from the group consisting of polyamine-amidated (meth) acrylic acid / alkyl (meth) acrylate copolymers, alkenylsuccinimides of polyamine, phthalamic acid derivatives and double chain fatty amine; alkylphenol resins.
- examples of such additives are given in the following documents: EP261959, EP593331, EP674689, EP327423, EP512889, EP832172; US2005 / 0223631; US5998530; W093 / 14178.
- polyfunctional cold operability additives selected from the group consisting of olefin and alkenyl nitrate polymers as described in EP573490;
- additives are generally added in an amount ranging from 100 to 1000 ppm (each).
- Such an additive concentrate may be the same as that of the block copolymer described above, in particular the concentrate may be used to retard or prevent the sedimentation of the crystals of the n-alkyl substituted compounds, iso-alkyl or n-alkenyl of the fuel or fuel during storage and / or use at low temperatures.
- the additive concentrate may advantageously comprise between 5 and 99% by weight, preferably between 10 and 80%, more preferably between 25 and 70% of block copolymer as described above.
- the additive concentrate may typically comprise from 1 to 95% by weight, preferably 10 to 70%, more preferably 25 to 60% organic liquid, the remainder corresponding to the block copolymer and, optionally, other additives different from the block copolymer as described above.
- solubility of the block copolymer in the organic liquids, the fuels or the fuels described above will depend in particular on the average molecular weight and number, respectively M w and M n, of the block copolymer.
- the average molar masses M w and M n of the block copolymer will be chosen so that the block copolymer is soluble in the fuel or fuel and / or the organic liquid of the concentrate for which it is intended.
- the average molar masses M w and M n of the block copolymer may also have an influence on the effectiveness of this block copolymer as a cold-holding additive.
- the block copolymer advantageously has a weight average molecular weight (Mw) of between 1,000 and 30,000 g. mol "1 , preferably between 4000 and 10,000 g, mol " 1 , more preferably less than 4000 g. mol "1 , and / or a number-average molar mass (Mn) of between 1,000 and 15,000 g. mol- 1 , preferably between 4,000 and 10,000 g. mol "1 , more preferably less than 4000 g, mol " 1 .
- Mw weight average molecular weight
- Mw weight average molecular weight
- Mn number-average molar mass
- the number and weight average molar masses are measured by Size Exclusion Chromatography (SEC).
- SEC Size Exclusion Chromatography
- a fuel or fuel composition is prepared according to any method known for adding:
- a cold-cooling additive improving the cold resistance of the fuel or fuel, the fuel or fuel, the copolymer and the cold-flow-making additive (CFI) being as described above.
- the block copolymer is present in the fuel or fuel composition in an amount sufficient to retard or prevent the sedimentation of the crystals of said n-alkyl, iso-alkyl or n-alkenyl substituted compounds during storage and / or use. at a low temperature of said fuel or fuel (1).
- the fuel or fuel composition advantageously comprises at least 10 ppm, preferably at least 50 ppm, advantageously between 10 and 5000 ppm, more preferably between 10 and 1000 ppm of the block copolymer described above.
- the cold-flow-making additive (CFI) is preferably chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture.
- the cold-flow additive is advantageously chosen from copolymers of ethylene and of vinyl ester (s), alone or as a mixture, in particular ethylene / vinyl acetate copolymers (EVA) and ethylene / vinyl propionate (EVP), more preferably ethylene / vinyl acetate copolymers (EVA).
- the coolant additive (CFI) is present in the fuel or fuel composition in an amount sufficient to improve the low temperature flow behavior of the fuel or fuel (1) during storage and / or use at low temperature.
- the fuel or fuel composition advantageously comprises at least 10 ppm, preferably at least 50 ppm, more preferably between 10 and 5 000 ppm, more preferably between 10 and 1 ppm ppm of the cold-flow additive (CFI).
- CFI cold-flow additive
- the fuel or fuel composition (1) may also contain one or more other additives other than the additives (2) and (3) selected from detergents, anticorrosive agents, dispersants, demulsifiers, antifoam agents, biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion aids (catalytic combustion promoters and soot), cloud point improvers, pour point, TLF, anti-settling agents, anti-wear agents and / or conductivity modifiers .
- additives other additives other than the additives (2) and (3) selected from detergents, anticorrosive agents, dispersants, demulsifiers, antifoam agents, biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion aids (catalytic combustion promoters and soot), cloud point improvers, pour point, TLF, anti-settling agents, anti-wear agents and / or conductivity modifiers .
- a method for improving the cold-holding properties of a fuel or fuel composition derived from one or more sources selected from the group consisting of mineral sources, preferably oil, animal, vegetable and synthetic comprises the successive stages of:
- the additive composition is constituted by the additive concentrate according to the invention.
- step b) treatment of the fuel composition or fuel with the amount determined in step a) of block copolymer and, optionally, with the cold-flow additive (CFI).
- CFI cold-flow additive
- the process for improving the cold-holding properties is advantageously intended for a fuel or fuel composition comprising one or more n-alkyl, iso-alkyl or n-alkenyl-substituted compounds having a tendency to crystallize. in said fuel or fuel during storage and / or use at a low temperature.
- Step a) is carried out according to any known process and is common practice in the field of fuel additives. This step involves defining a representative characteristic of the cold-holding properties of the fuel or fuel, such as anti-sedimentation characteristics, setting the target value and then determining the improvement that is required to achieve the specification.
- the determination of the amount of block copolymer to be added to the fuel or fuel composition to achieve the specification will typically be made by comparison with the fuel or fuel composition containing the CFI additive but without block copolymer.
- the amount of block copolymer required to treat the fuel or fuel composition may vary depending on the nature and origin of the fuel or fuel, particularly depending on the level of n-alkyl, isoalkyl or n-substituted compounds. -alkenyl. The nature and origin of the fuel or fuel can therefore be also a factor to consider for step a).
- the method for improving the cold-holding properties may also comprise an additional step after step b) of checking the target reached and / or adjusting the treatment rate with the block copolymer as a cold-working additive and, optionally, with the cold-flow additive (CFI).
- CFI cold-flow additive
- the THF is evaporated on a rotary evaporator and the octadecyl 2-bromopropionate is dissolved in 100 ml of dichloromethane.
- the organic phase is washed twice with a 10% aqueous solution of hydrochloric acid, three times with water, twice with an aqueous solution of 1 M sodium hydroxide and then three times with water.
- the organic phase is dried with sodium sulfate.
- Example 1 Synthesis of a block copolymer IAB dodecyl acrylate / 4-acetoxystyrene -
- a solution of initiator I is prepared by dissolving 1 equivalent of 2- octadecyl bromopropionate (1 g, 405 g.mol -1 ) in 4 ml of anisole The solution is degassed by bubbling nitrogen before use.
- a monomer solution A / catalyst / ligand is obtained by dissolving in 8 ml of anisole, 7 equivalents of dodecyl acrylate (4.15 g, 240 g mol -1 ), 0.4 equivalent of copper bromide (142 mg 143 gmol -1 ) and 0.4 equivalents of 1, 1, 4,7,10,10-hexamethyltriethylene tetramine (227 mg, 230 g / mol -1 ), and then degassing the solution thus obtained by bubbling. nitrogen.
- a monomer B / catalyst / ligand solution is obtained by dissolving in 4 ml of anisole 14 equivalents of 4-acetoxystyrene (5.61 g, 162 gmol -1 ), 0.4 equivalent of copper bromide (142 mg, 143 g). gmol "1 ) and 0.4 equivalents of 1,1,7,7,10,10-hexamethyltriethylene tetramine (227 mg, 230 gmol -1 ).
- the initiator solution is added under a stream of nitrogen to the monomer solution A / catalyst / ligand.
- the mixture is placed under vacuum, with magnetic stirring, at 90 ° C., protected from light.
- the progress of the reaction is monitored by 1 H NMR spectroscopy (Bruker 400 MHz spectrometer). After 10 hours of reaction, all the dodecyl acrylate is consumed. After degassing by bubbling nitrogen, the monomer solution B / catalyst / ligand is then added to the reaction medium. After 18h, 97% of the 4-acetoxystyrene is consumed. After 18 h at 90 ° C, the reaction is stopped by immersing the flask in liquid nitrogen.
- the molar masses are measured by a Malvern Viscotek GPC Max TDA 305 equipped with two PLGel Mixed C column gel columns from Agilent and a radiation detector. ionizing.
- the solvent used is chloroform (+1% triethylamine) and the flux is set at 1 ml.min -1 Calibration is carried out with standard samples of polystyrene with low dispersities.
- the values are measured by a Varian device equipped with TOSOHAAS TSK gel columns and an ionizing radiation detector.
- the solvent used is THF and the flux is set at 1 ml.min -1 Calibration is carried out with standard samples of polystyrene with low dispersities.
- EXAMPLE 2 Synthesis of a Dodecyl Acrylate / 4-Acetoxystyrene Statistical Copolymer A solution of initiator I is prepared by dissolving 1 equivalent of 2-5 octadecyl bromopropionate (1 g, 405 g, mol- 1 ) in 4 mL.
- the solution is degassed by bubbling with nitrogen 1 1 equivalents of dodecyl acrylate (6.53 g, 240 g.mol -1 ) previously purified on a column of basic alumina, 14 equivalents of 4- acetoxystyrene (5.61 g, 162 g mol -1 ) previously purified on a basic alumina column, 0.4 equivalents of copper bromide (0.142 mg, 143 g mol -1 ) and 0.40 equivalents of 1.1 , 4,7,10,10-Hexamethyltriethylenetetramine (227 mg, 230 g, mol- 1 ) are dissolved in 8 ml of anisole, the solution is degassed by bubbling with nitrogen.
- the initiator solution I is added under a stream of nitrogen to the monomer solution, and the mixture is then subjected to magnetic stirring at 90 ° C., in the absence of light.
- the reaction is stopped by immersing the flask in liquid nitrogen. 100 ml of THF are added and the mixture is then passed through a column of basic alumina to remove the catalyst. The copolymer is precipitated in 400 ml of cold methanol and then dried under vacuum. 10 g (5060 g. Mol "1 mass rdt 79%) of s-li random copolymer A 12 8 B 10 ac 14 after precipitation into 400 mL of cold methanol and drying under vacuum.
- Example 3 Synthesis of a Dodecyl Acrylate / 4-Acetoxystyrene Statistical Copolymer
- Another random copolymer s-li 8 A 12 7 B ac 14 was synthesized according to the same protocol as Example 2 but with 7 equivalents of acrylate of dodecyl instead of 1 1. (74% mass yield)
- composition Ci to C 5 is produced by solubilizing 100 ppm by weight of copolymer (100% of active material) in a GOM gas oil composition containing 300 ppm by weight of a cold-flow additive (CFI) marketed under the name CP7936C which is a Ethylene Vinyl Acetate (EVA) having 30.5% w / w vinyl acetate and 70% w / w concentration in an aromatic solvent (Solvesso 150).
- CFI cold-flow additive
- a control composition C 0 corresponding to the GOM gas oil containing only 440 ppm by weight of the cold-flow-rate additive (CFI) EVA described above was also tested, this rate corresponding to an equivalent polymer treatment rate. to that of compositions Ci to C 5 .
- the performance of the copolymers as an anti-sedimentation additive (WASA) is evaluated by testing their ability to avoid the sedimentation of fuel compositions C x additive with conventional EVA.
- the anti-settling properties of the fuel compositions C x are evaluated by the following ARAL sedimentation test: 250mL of the fuel composition C x are cooled in 250mL test pieces in a climatic chamber at -13 ° C.
- each copolymer as a TLF booster additive is also evaluated by testing their ability to lower the Cold Filter Plugging Point (CFPP) in C x fuel compositions with conventional EVA.
- CFPP Cold Filter Plugging Point
- the anti-sedimentation effect is observed only for the fuel compositions Ci, C 2 and C 3 . No anti-sedimentation effect is observed for the compositions C 4 and C 5 containing the copolymers obtained by random polymerization.
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Application Number | Priority Date | Filing Date | Title |
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EP15305206.3A EP3056527A1 (en) | 2015-02-11 | 2015-02-11 | Block copolymers and use thereof for improving the cold properties of fuels |
PCT/EP2016/052685 WO2016128377A1 (en) | 2015-02-11 | 2016-02-09 | Block copolymers and the use thereof for improving the cold properties of fuels or combustibles |
Publications (1)
Publication Number | Publication Date |
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EP3256506A1 true EP3256506A1 (en) | 2017-12-20 |
Family
ID=52595245
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15305206.3A Withdrawn EP3056527A1 (en) | 2015-02-11 | 2015-02-11 | Block copolymers and use thereof for improving the cold properties of fuels |
EP16703775.3A Withdrawn EP3256506A1 (en) | 2015-02-11 | 2016-02-09 | Block copolymers and the use thereof for improving the cold properties of fuels or combustibles |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15305206.3A Withdrawn EP3056527A1 (en) | 2015-02-11 | 2015-02-11 | Block copolymers and use thereof for improving the cold properties of fuels |
Country Status (10)
Country | Link |
---|---|
US (1) | US20180030363A1 (en) |
EP (2) | EP3056527A1 (en) |
KR (1) | KR20170134342A (en) |
CN (1) | CN107406565A (en) |
BR (1) | BR112017017179A2 (en) |
CA (1) | CA2975028A1 (en) |
EA (1) | EA201791783A1 (en) |
MX (1) | MX2017010139A (en) |
WO (1) | WO2016128377A1 (en) |
ZA (1) | ZA201705222B (en) |
Families Citing this family (4)
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FR3041349B1 (en) | 2015-09-18 | 2020-01-24 | Total Marketing Services | COPOLYMER FOR USE AS A FUEL DETERGENT ADDITIVE |
FR3041362B1 (en) * | 2015-09-18 | 2017-10-13 | Total Marketing Services | DETERGENT ADDITIVE FOR FUEL |
WO2019183050A1 (en) * | 2018-03-21 | 2019-09-26 | The Lubrizol Corporation | Polyacrylamide antifoam components for use in diesel fuels |
US11629303B2 (en) | 2018-11-30 | 2023-04-18 | Total Marketing Services | Quaternary fatty amidoamine compound for use as an additive for fuel |
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-
2015
- 2015-02-11 EP EP15305206.3A patent/EP3056527A1/en not_active Withdrawn
-
2016
- 2016-02-09 KR KR1020177024446A patent/KR20170134342A/en unknown
- 2016-02-09 EP EP16703775.3A patent/EP3256506A1/en not_active Withdrawn
- 2016-02-09 BR BR112017017179A patent/BR112017017179A2/en not_active Application Discontinuation
- 2016-02-09 CA CA2975028A patent/CA2975028A1/en not_active Abandoned
- 2016-02-09 MX MX2017010139A patent/MX2017010139A/en unknown
- 2016-02-09 CN CN201680015212.4A patent/CN107406565A/en active Pending
- 2016-02-09 WO PCT/EP2016/052685 patent/WO2016128377A1/en active Application Filing
- 2016-02-09 EA EA201791783A patent/EA201791783A1/en unknown
- 2016-02-09 US US15/549,618 patent/US20180030363A1/en not_active Abandoned
-
2017
- 2017-08-02 ZA ZA2017/05222A patent/ZA201705222B/en unknown
Also Published As
Publication number | Publication date |
---|---|
CN107406565A (en) | 2017-11-28 |
KR20170134342A (en) | 2017-12-06 |
MX2017010139A (en) | 2017-11-01 |
ZA201705222B (en) | 2019-07-31 |
BR112017017179A2 (en) | 2018-04-03 |
CA2975028A1 (en) | 2016-08-18 |
EP3056527A1 (en) | 2016-08-17 |
EA201791783A1 (en) | 2017-12-29 |
WO2016128377A1 (en) | 2016-08-18 |
US20180030363A1 (en) | 2018-02-01 |
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