US3803034A - Pour point depression - Google Patents
Pour point depression Download PDFInfo
- Publication number
- US3803034A US3803034A US00286651A US28665172A US3803034A US 3803034 A US3803034 A US 3803034A US 00286651 A US00286651 A US 00286651A US 28665172 A US28665172 A US 28665172A US 3803034 A US3803034 A US 3803034A
- Authority
- US
- United States
- Prior art keywords
- terpolymer
- oil
- pour point
- ethylene
- oils
- 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.)
- Expired - Lifetime
Links
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 239000003921 oil Substances 0.000 claims description 53
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 239000005977 Ethylene Substances 0.000 claims description 22
- 238000009835 boiling Methods 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- 239000010779 crude oil Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 7
- 239000010687 lubricating oil Substances 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 abstract description 46
- 150000002148 esters Chemical class 0.000 abstract description 13
- 230000000994 depressogenic effect Effects 0.000 abstract description 12
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 10
- 229940102838 methylmethacrylate Drugs 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000003999 initiator Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- -1 propylene, butylene Chemical group 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 235000008504 concentrate Nutrition 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical group CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- HQEBIIQRJHCZNH-UHFFFAOYSA-N 2-ethenyl-1-methylnaphthalene Chemical compound C1=CC=C2C(C)=C(C=C)C=CC2=C1 HQEBIIQRJHCZNH-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011436 cob Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000010735 electrical insulating oil Substances 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- YSWBCVAMKPSAPW-UHFFFAOYSA-N ethenyl heptanoate Chemical compound CCCCCCC(=O)OC=C YSWBCVAMKPSAPW-UHFFFAOYSA-N 0.000 description 1
- UJRIYYLGNDXVTA-UHFFFAOYSA-N ethenyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC=C UJRIYYLGNDXVTA-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- NWJTZFZQVYJIHU-UHFFFAOYSA-N ethenyl nonanoate Chemical compound CCCCCCCCC(=O)OC=C NWJTZFZQVYJIHU-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 description 1
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- ZQZUENMXBZVXIZ-UHFFFAOYSA-N ethenyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC=C ZQZUENMXBZVXIZ-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- YJSSCAJSFIGKSN-UHFFFAOYSA-N hex-1-en-2-ylbenzene Chemical compound CCCCC(=C)C1=CC=CC=C1 YJSSCAJSFIGKSN-UHFFFAOYSA-N 0.000 description 1
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010743 number 2 fuel oil Substances 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- FMCKIFRVQWUXOM-UHFFFAOYSA-N pent-1-en-2-yl acetate Chemical compound CCCC(=C)OC(C)=O FMCKIFRVQWUXOM-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 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
- 125000002348 vinylic group Chemical group 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of a saturated carboxylic or carbonic acid
- C10M145/08—Vinyl esters of a saturated carboxylic or carbonic acid
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
- C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
- C10M145/14—Acrylate; Methacrylate
-
- 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
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
- C10M2209/062—Vinyl esters of saturated carboxylic or carbonic acids, e.g. vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
Definitions
- Such hydrocarbon oils are sometimes referred to as heavier oils and contain components which, upon encountering low temperatures, crystallize to form solid precipitates. These crystals become active centers for further crystallization, with the result that the oil congeals and loses its free flowing properties.
- the oils are of diversified chemical composition and many of the heavier oils contain waxy components in varying concentrations. These waxy components crystallize readily at low temperatures. Because of the variations in chemical compositions, different oils respond differently to pour point depressant additives. Accordingly, there is a need for novel pour point depressants which will low temperatures.
- the present invention is directed to novel terpolymers for use as pour point depressants in such oils.
- the oils may be classified as those having pour points of above about 20 F.
- the oil may have an initial boiling point as low as 175 F. and end boiling point of above l,000 F. under vacuum or practically not distillable but, as hereinbefore set forth, contains components which are responsible for the loss of fluidity.
- Illustrative examples of such oils include middle distillates, specialty oils, lubricating oils, residual oils, crude oils, etc. These oils may be untreated or resulting from conventional fractionation, solvent extraction, caustic treating, acid treating, dewaxing, desulfurizing, thermal cracking, catalytic cracking, reforming or other processing operations, etc.
- the middle distillates include oils within the boiling range of from about 250 to 750 F. and include kerosene, jet fuel, diesel oil, burner oil, gas oil, fuel oil, light cycle oil, specialty oils such as solvent oils, cleaning oils for use in cleaning metallic equipment, electrical insulating oil which is used in transformers or circuit breakers, hydraulic oils,'etc.
- the lubricating oils may be conventional lubricating oils having boiling points, for example, within the range of 650 to l,050 F. or more or selected fractions thereof for special uses.
- the residual oils may result from fractionation to remove lower boiling components or heavier oils resulting from processing operations and may have initial boiling points of 600 F. or more.
- problems are encountered in the transportation and storage of crude oils and reduced crude oils at low temperatures and especially in cold climates.
- the present invention relates to a hydrocarbon oil containing components which cause the oil to lose fluidity at low temperature, said oil containing, in a pour point depressant concentration, a ter- 7 polymer of C -C -olefin, aryl-c -C -alkylene and unsaturated ester of the formula:
- R is hydrogen or C -C -alkyl and R is C C alkyl.
- the terpolymer embraced in the above definition is believed to comprise a new composition of matter.
- the composition may also contain all or a portion of a free radical initiator and particularly organic peroxide used in the preparation of the terpolymer, as well as some of the solvent, when employed which is not subsequently removed from the composition.
- the initiator if present, will be in a minor concentration and the solvent probably is present in a chemically uncombined state.
- Such retained solvent will increase solubility of the terpolymer and, as will be hereinafter set forth, the terpolymer may be commingled with additional solvent to form a fluid concentrate for use as a pour point depressant.
- one component of the terpolymer is a C -C -olefin and preferably a C -C olefin.
- ethylene is a particularly preferred olefin.
- Other preferred olefins include propylene, butylene, amylene and hexylene.
- olefins comprise heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecyle'ne, octadecylene, nonadecylene, eicosylene, heneicosylene, docosylene. It is understood that the olefin may be of straight or branched chain, with the double bond preferably in a terminal position. With two double bonds, they may be conjugated or randomly located in such a manner that one double bond is in a terminal position.
- Another component of the terpolymer is an aryl-C C -alkylene and preferably a phenyl-C -C -alkylene which also may be named as an alkenyl aromatic.
- the double bond of the alkylene moiety is positioned between the alpha and beta carbon atoms and thus is in close proximity to the aromatic ring.
- styrene is an es-v pecially preferred alkenyl aromatic.
- alkenyl aromatics contain up to 6 carbon atoms in the alkenyl moiety and include alpha-methylstyrene, alphaethylstyrene, 'alpha-propylstyrene, and alphabutylstyrene.
- the alkylene moiety may contain from 7 to 22 carbon atoms and may contain two or more double bonds therein, with a double bond in a terminal position and a terminal carbon atom attached to two hydrogen atoms.
- Such higher boiling olefinic moieties may be separated as specific fractions from particular processing steps or may be prepared by polymerization of olefinic and/or diolefinic C -C olefins.
- the phenyl alkylene may be prepared by conventional alkylation of benzene with the olefin or in any other suitable manner.
- other vinyl aromatics may be used as vinyl naphthalene, alpha-methyl-vinyl naphthalene, etc., but not necessarily with equivalent results.
- the aryl alkylene may contain one or more substituents attached to the aryl ring.
- substituents may be selected from alkyl of l to 12 carbon atoms, alkoxy containing from I to 12 carbon atoms in the alkyl moiety, phenoxy, hydroxy, halogen and preferably chlorine or bromine, etc. in a preferred embodiment, only one such substituent is attached to the phenyl ring and preferably in a position para to the alkylene moiety. When two substituents are attached to the phenyl ring, they preferably are in the 3,4- or 3,5- positions. 1
- esters which may be generically termed alkylcarboxyethylenes or vinylic alkanoates.
- esters which may be generically termed alkylcarboxyethylenes or vinylic alkanoates.
- illustrative examples include vinyl acetate, vinyl propionate, vinyl butyrate, preferably vinyl isobu tyrate, vinyl valerate, vinyl hexanoate, vinyl heptanoate, vinyl caprylate, vinyl nonanoate, vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, etc.
- illustrative compounds comprise isopropenyl acetate, l-ethylvinyl acetate, 1- propylvinyl acetate, l-butylvinyl acetate, etc., and corresponding higher molecular weight alkanoates.
- formula II illustrates alkylcarboxyethylenes, carbalkoxyethylenes or derivatives of acrylic acid.
- lllustrative examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, capryl acrylate, lauryl acrylate, myristyl acrylate, palmityl acrylate, stearyl acrylate, etc.
- R ismethyl
- the corresponding methacrylates will comprise a component of the terpolymer.
- Methylmethacrylate, ethylmethacrylate, propylmethacrylate and butylmethacrylate are particularly preferred in this embodiment.
- the various olefins, phenyl alkylenes and unsaturated esters are not necessarily equivalent for use in preparation of the terpolymers.
- These components will be selected with reference to the particular terpolymer to be prepared which, in turn, will depend upon the particular oil in which it is to be used.
- an unsaturated ester of formula l and an unsaturated ester of formula II are both used in preparing a tetrapolymer.
- different oils respond differently to additives.
- the particular components will be selectedwith regard to availability, cost and reactivity in forming the desired terpolymer.
- the terpolymer is prepared in any suitable manner.
- the terpolymer is produced by polymerization using conventional initiators of the free radical type such as benzoyl peroxide, tert-butyl peroxide, di-tert-butyl peroxide, cumene peroxide, 2,2- azobisbutyronitrile, etc.
- the peroxide generally is used in a concentration of from about 0.1% to and preferably 1-2% by weight of the liquid monomers.
- a typical hydrocarbon polymerization solvent is used, as for example, benzene, toluene, xylene, aromatic commercial solvents such as Espesol, alcohols, ketones, esters, halogenated hydrocarbons, etc.
- the temperature of polymerization is generally within the range of from about 150 to about 350 F. and preferably from about 275 to about 325 F.
- the pressure may be within the range of from about 500 to 2,000 or more and preferably 800 to 1,500 lbs. per sq. in.
- the time of reaction will be sufficient to accomplish the desired polymerization and may range from 1 to 12 hours or more and preferably 2 to 6 hours.
- the autoclave is first purged-with nitrogen and then charged with a solution of methylmethacrylate in benzene, a solution of styrene in benzene and a solution of tertiary butyl peroxide in benzene.
- the autoclave then is closed tightly, purged with'ethylene, vented and pressurized with ethylene to the desired pressure, heated to the desired temperature and maintained therein for the desired time.
- purging of the autoclave may be omitted and the polymerization effected in the presence of a small amount of air.
- the autoclave is allowed to cool and the products withdrawn, filtered and evaporated, preferably under vacuum, to remove solvent and to recover the terpolymer. It is understood that this is a preferred method of preparing the terpolymer batchwise when using the peroxide type initiator and that other suitable methods may be employed. in another embodiment, preparation of the terpolymer is effected in a continuous manner. in this embodiment, the reaction chamber is maintained at the desired temperature and contains some form of packing, such as glass beads, berl saddles, raschig rings, etc.
- a solution of the phenyl alkylene, unsaturated ester and peroxide initiator is prepared and charged to the reaction chamber, with ethylene under high pressure being separately charged to thereaction chamber.
- the solution and ethylene may be passed concurrently but preferably are passed counter currently into the reaction chamber.
- the solution may be introduced into an upper portion of the reaction chamber and the ethylene is introduced into a lower portion thereof.
- the phenyl alkylene, unsaturated ester and/or peroxide catalyst may be introduced separately into the reaction chamber. Regardless of the specific method employed, excess ethylene is withdrawn, preferably from an upper portion of the reaction chamber, and reused in the process.
- the liquid effluent from the reaction chamber is withdrawn, preferably from a lower portion thereof, and is processed in any suitable manner to recover the terpolymer, preferably by filtering and then vacuum distillation. to remove the solvent.
- metal oxides or other initiators of free radicals for promoting polymerization may be used.
- the reactants are used in any suitable proportions. in general the olefin, and particularly ethylene, will be used in a large overall proportion. Overall means the amount of ethylene totally present in gaseous and liquid phase within the system. Since the critical temperature of ethylene is only 50 F., the ethylene will be in gaseous state under the conditions of copolymerization. Only a small part of the ethylene will be dissolved in the liquid phase. it was found that, with an overall excess of to 300:1, only 4 to 20:1 mole ratio of ethylene to other monomers was actually present in the liquid reaction mixture, i.e. in the monomers and initiator in the solvent. The amount of ethylene dissolved in the liquid phase depends on the nature and amount of the solvent, temperature and pressure of ethylene.
- the mole ratios in the terpolymer may comprise from 5 to 30 and preferably 10 to 25 mole proportions of ethylene, from about 0.5 to 5 and preferably 1 to 3 mole proportions of styrene and from about 0.5 to 5 and preferably 1 to 3 mole proportions of unsaturated ester.
- the molecular weight of the terpoly mer may range from about 500 to 5,000 or more and preferably from about 1,000 to about 3,000 and more particularly from about 1,500 to about 2,500.
- all or a major portion of the solvent is removed from the product and the terpolymer is recovered as a solid material.
- at least a substantial portion of the solvent is allowed to remain and the terpolymer is recovered as a concentrated solution for use as a concentrate to be incorporated as a pour point depressant in the oil.
- other solvents may be used to comprise a more homogeneous solution for use as a pour point depressant.
- the novel terpolymer of the present invention is a very effective pour point depressant. It is believed that the phenyl moiety being attached to the main polymeric chain forms an improved pour point depressant of increased solubility as compared, for example, to copolymers of olefin and unsaturated ester.
- the chemical structure of the copolymer can vary, depending upon the specific character of the reactants, and mode of preparation. It may form a polyethylenic straight chain to which phenyl and polar alkyls are attached and some incidental alkyls resulting from some branching and chain termination mode. Also, as hereinbefore set forth, a small amount of the peroxide catalyst may enter into the reaction, as well as the final composition containing some unremoved solvent. Regardless of the specific chemical structure, the terpolymer, prepared as described herein, is a very effective pour point depressant.
- the terpolymer is useful in many different oils and thus extends the range of its applicabilwhich will vary with the particular hydrocarbon oil and I may comprise one or more of anti-oxidant, corrosion or rust inhibitor, viscosity index improver, cetane improver, metal deactivator, dye, etc.
- EXAMPLE I This example describes the preparation of a terpolymer of ethylene, styrene and methylmethacrylate. The preparation was'made in a 3 liter rotating autoclave which first was purged with nitrogen and then charged with 5 g. (0.05 mole) methylmethacrylate in 100 g. of
- the styrene to methylmethacrylate ratio in the terpolymer is 1:1 and the ratio of ethylene to the total of other reactants is 10.4:1.
- the average molecular weight of the terpolymer is 2,800.
- EXAMPLE II Another terpolymer preparation was made in substantially the same manner as described in Example I except that the solvent used in this preparation was toluene. Specifically, the rotating autoclave was charged with 5 g. (0.05 mole) of methylmethacrylate in 100 g. of toluene, 5.02 g. (0.05 mole) of styrene in l00 g. of toluene and l g. (0.007 mole) of tert-butyl peroxide in 100 g. of toluene. Following purging and pressurizing to atmospheres with ethylene, the autoclave was heated and maintained at 284 F. for 4 hours. After cooling, 308 g. of liquid was withdrawn from the autoclave, filtered and evaporated to remove solvent, to yield 14 g. of soft and tacky dry solid product. The average molecular weight of the terpolymer is l 180.
- a terpolymer is prepared in substantially the same manner as described in Example I except that the unsaturated ester is vinyl acetate.
- the reactants are charged to the rotating autoclave in mole ratios of ethylenezstyrenewinyl acetate of 1511.5:1. Following completion of the reaction and-removal of the benzene solvent, the product is recovered as a solid terpolymer.
- EXAMPLE IV Another terpolymer is prepared in substantially the same manner as described in Example II except that alpha-methylstyrene is used-as the phenyl alkylene.
- the reactants are used in a mole ratio of ethyleneztransbetamethylstyrene:methylmethacrylate of 12:l:l.5. After cooling of the autoclave, filtering and vacuum distillation to remove the solvent, the solid terpolymer product is recovered.
- EXAMPLE V Another preparation is made in the same manner as described in Example II except that vacuum distillation to remove the toluene solvent is omitted and the resultant solution is utilized as a liquid concentrate for adding as a pour point depressant to a hydrocarbon oil.
- EXAMPLE VI The terpolymer prepared as described in Example I was utilized as a pour point depressant in a commercial light cycle oil having a pour point of 2 F. and a boiling range of 358709 F. The terpolymer was evaluated at different concentrations, based on active ingredient, ranging from a high of 500 ppm (parts per million) down to a low of 10 ppm. The data was reported in the following table.
- EXAMPLE VII The terpolymer prepared as described in Example II is used in a concentration of 250 ppm in a commercial No. 2 fuel oil having a boiling range of 428677 F. and a pour point of 10 F. The addition of the terpolymer serves to decrease the pour point to -20 F.
- Hydrocarbon oil containing components which cause the oil to lose fluidity at low temperature, said oil containing, in a pour point depressant concentration, a terpolymer of from about 5 to 30 mole proportions of ethylene, from about 0.5 to 5 mole proportions of styrene and from about 0.5 to 5 mole proportions of methylmethacrylate, said interpolymer having a molecular weight of from about 500 to about 5,000.
- hydrocarbon oil of claim I being middle distillate within the boiling range of from about 250 to about 750 F.
- the hydrocarbon oil of claim 1 being lubricating oil.
- hydrocarbon oil of claim 1 being residual oil having an initial boiling point of at least 600 F.
- hydrocarbon oil of claim 1 being reduced crude oil.
- the hydrocarbon oil of claim 1 being crude oil.
- composition of claim 1 further characterized in that the styrene and methylmethacryl-ate are in equimolar proportion and the ratio of the ethylene to the total styrene and methylmethacrylate reactants is about 10:1, the average molecular weight of the interpolyrner being about 2,800.
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Abstract
Hydrocarbon oil which loses fluidity at low temperature containing, in a pour point depressant concentration, a terpolymer of C2-C22-olefin, aryl-C2-C22-alkylene and unsaturated ester. Specific pour point depressants are terpolymer of ethylene-styrene-methylmethacrylate or terpolymer of ethylenestyrene-vinyl acetate.
Description
United States Patent 1 Dasch 1 Apr. 9, 1974 POUR POINT DEPRESSION I [75] Inventor: Alexander Gay Dasch, Chicago, Ill.
[73] Assignee: Universal Oil Products Company, Des Plaines, I11.
22 Filed: Sept. 5, 1972 211 Appl. No.: 286,651
[52] US. Cl 252/57, 252/56 R, 44/62 [51] Int. Cl. C10m l/28, ClOm H26 [58] Field of Search 252/56 R, 57; 44/62;
[56] References Cited UNITED STATES PATENTS 3.462.249 8/1969 Tunkel.....; 44/62 FOREIGN PATENTS OR APPLICATIONS 1,244,205 8/1971 Great Britain Primary E.\'uminer-w. Cannon Assismnt Eruniinew-W. Cannon Attorney, Agent, or Firm-James R. Hoatson, .lr.; Bernard L. Kramer; William H. Page, II
[ ABSTRACT 7 Claims, No Drawings POUR POINT DEPRESSION BACKGROUND OF THE INVENTION The problems associated with the loss of fluidity of hydrocarbon oils at low temperatures are of considerable concern. Such loss of fluidity interferes with the satisfactory storing and transporting of the oil, as well as in mixing or blending of different oil fractions and in filtering operations. This problem is of increasing concern with the discovery of oil in subarctic areas, with the use of jet fuels at altitudes where temperatures of 50 F. or lower may be encountered, etc.
Such hydrocarbon oils are sometimes referred to as heavier oils and contain components which, upon encountering low temperatures, crystallize to form solid precipitates. These crystals become active centers for further crystallization, with the result that the oil congeals and loses its free flowing properties. The oils are of diversified chemical composition and many of the heavier oils contain waxy components in varying concentrations. These waxy components crystallize readily at low temperatures. Because of the variations in chemical compositions, different oils respond differently to pour point depressant additives. Accordingly, there is a need for novel pour point depressants which will low temperatures.
DESCRIPTION OF THE INVENTION The present invention is directed to novel terpolymers for use as pour point depressants in such oils. The oils may be classified as those having pour points of above about 20 F. The oil may have an initial boiling point as low as 175 F. and end boiling point of above l,000 F. under vacuum or practically not distillable but, as hereinbefore set forth, contains components which are responsible for the loss of fluidity. Illustrative examples of such oils include middle distillates, specialty oils, lubricating oils, residual oils, crude oils, etc. These oils may be untreated or resulting from conventional fractionation, solvent extraction, caustic treating, acid treating, dewaxing, desulfurizing, thermal cracking, catalytic cracking, reforming or other processing operations, etc. The middle distillates include oils within the boiling range of from about 250 to 750 F. and include kerosene, jet fuel, diesel oil, burner oil, gas oil, fuel oil, light cycle oil, specialty oils such as solvent oils, cleaning oils for use in cleaning metallic equipment, electrical insulating oil which is used in transformers or circuit breakers, hydraulic oils,'etc. The lubricating oils may be conventional lubricating oils having boiling points, for example, within the range of 650 to l,050 F. or more or selected fractions thereof for special uses. The residual oils may result from fractionation to remove lower boiling components or heavier oils resulting from processing operations and may have initial boiling points of 600 F. or more. As mentioned earlier, problems are encountered in the transportation and storage of crude oils and reduced crude oils at low temperatures and especially in cold climates.
In one embodiment, the present invention relates to a hydrocarbon oil containing components which cause the oil to lose fluidity at low temperature, said oil containing, in a pour point depressant concentration, a ter- 7 polymer of C -C -olefin, aryl-c -C -alkylene and unsaturated ester of the formula:
' H n o H R 0 1I-o=c-o'-ii-n' or IIt J=&-0R'
I II
in which R is hydrogen or C -C -alkyl and R is C C alkyl.
The terpolymer embraced in the above definition is believed to comprise a new composition of matter. The composition may also contain all or a portion of a free radical initiator and particularly organic peroxide used in the preparation of the terpolymer, as well as some of the solvent, when employed which is not subsequently removed from the composition. However, the initiator, if present, will be in a minor concentration and the solvent probably is present in a chemically uncombined state. Such retained solvent will increase solubility of the terpolymer and, as will be hereinafter set forth, the terpolymer may be commingled with additional solvent to form a fluid concentrate for use as a pour point depressant.
As hereinbefore set forth, one component of the terpolymer is a C -C -olefin and preferably a C -C olefin. In one embodiment, ethylene is a particularly preferred olefin. Other preferred olefins include propylene, butylene, amylene and hexylene. Other olefins comprise heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecyle'ne, octadecylene, nonadecylene, eicosylene, heneicosylene, docosylene. It is understood that the olefin may be of straight or branched chain, with the double bond preferably in a terminal position. With two double bonds, they may be conjugated or randomly located in such a manner that one double bond is in a terminal position.
Another component of the terpolymer is an aryl-C C -alkylene and preferably a phenyl-C -C -alkylene which also may be named as an alkenyl aromatic. In a particularly preferred embodiment, the double bond of the alkylene moiety is positioned between the alpha and beta carbon atoms and thus is in close proximity to the aromatic ring. In this embodiment, styrene is an es-v pecially preferred alkenyl aromatic. Other preferred alkenyl aromatics contain up to 6 carbon atoms in the alkenyl moiety and include alpha-methylstyrene, alphaethylstyrene, 'alpha-propylstyrene, and alphabutylstyrene. In another embodiment, but not necessarily with equivalent results, the alkylene moiety may contain from 7 to 22 carbon atoms and may contain two or more double bonds therein, with a double bond in a terminal position and a terminal carbon atom attached to two hydrogen atoms. Such higher boiling olefinic moieties may be separated as specific fractions from particular processing steps or may be prepared by polymerization of olefinic and/or diolefinic C -C olefins. The phenyl alkylene may be prepared by conventional alkylation of benzene with the olefin or in any other suitable manner. In still another embodiment instead of the phenyl alkylene, other vinyl aromatics may be used as vinyl naphthalene, alpha-methyl-vinyl naphthalene, etc., but not necessarily with equivalent results.
In another embodiment, the aryl alkylene may contain one or more substituents attached to the aryl ring. These substituents may be selected from alkyl of l to 12 carbon atoms, alkoxy containing from I to 12 carbon atoms in the alkyl moiety, phenoxy, hydroxy, halogen and preferably chlorine or bromine, etc. in a preferred embodiment, only one such substituent is attached to the phenyl ring and preferably in a position para to the alkylene moiety. When two substituents are attached to the phenyl ring, they preferably are in the 3,4- or 3,5- positions. 1
Another component of the terpolymer is an unsaturated ester of the formulas hereinbefore set forth. The formula 1, to the left, illustrates esters which may be generically termed alkylcarboxyethylenes or vinylic alkanoates. illustrative examples include vinyl acetate, vinyl propionate, vinyl butyrate, preferably vinyl isobu tyrate, vinyl valerate, vinyl hexanoate, vinyl heptanoate, vinyl caprylate, vinyl nonanoate, vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, etc. When R is alkyl, illustrative compounds comprise isopropenyl acetate, l-ethylvinyl acetate, 1- propylvinyl acetate, l-butylvinyl acetate, etc., and corresponding higher molecular weight alkanoates.
Referring to the formulas hereinbefore set forth, formula II, to the right, illustrates alkylcarboxyethylenes, carbalkoxyethylenes or derivatives of acrylic acid. lllustrative examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, capryl acrylate, lauryl acrylate, myristyl acrylate, palmityl acrylate, stearyl acrylate, etc. When R ismethyl, the corresponding methacrylates will comprise a component of the terpolymer. Methylmethacrylate, ethylmethacrylate, propylmethacrylate and butylmethacrylate are particularly preferred in this embodiment.
it is understood that the various olefins, phenyl alkylenes and unsaturated esters are not necessarily equivalent for use in preparation of the terpolymers. These components will be selected with reference to the particular terpolymer to be prepared which, in turn, will depend upon the particular oil in which it is to be used. In another embodiment, an unsaturated ester of formula l and an unsaturated ester of formula II are both used in preparing a tetrapolymer. As hereinbefore set forth, different oils respond differently to additives. Also, the particular components will be selectedwith regard to availability, cost and reactivity in forming the desired terpolymer.
The terpolymer is prepared in any suitable manner. in one embodiment, the terpolymer is produced by polymerization using conventional initiators of the free radical type such as benzoyl peroxide, tert-butyl peroxide, di-tert-butyl peroxide, cumene peroxide, 2,2- azobisbutyronitrile, etc. The peroxide generally is used in a concentration of from about 0.1% to and preferably 1-2% by weight of the liquid monomers. Conveniently, a typical hydrocarbon polymerization solvent is used, as for example, benzene, toluene, xylene, aromatic commercial solvents such as Espesol, alcohols, ketones, esters, halogenated hydrocarbons, etc. The temperature of polymerization is generally within the range of from about 150 to about 350 F. and preferably from about 275 to about 325 F. The pressure may be within the range of from about 500 to 2,000 or more and preferably 800 to 1,500 lbs. per sq. in. The time of reaction will be sufficient to accomplish the desired polymerization and may range from 1 to 12 hours or more and preferably 2 to 6 hours.
In one specific method of preparation of the terpolymer, utilizing a rotating autoclave as the reaction zone, the autoclave is first purged-with nitrogen and then charged with a solution of methylmethacrylate in benzene, a solution of styrene in benzene and a solution of tertiary butyl peroxide in benzene. The autoclave then is closed tightly, purged with'ethylene, vented and pressurized with ethylene to the desired pressure, heated to the desired temperature and maintained therein for the desired time. In some cases, purging of the autoclave may be omitted and the polymerization effected in the presence of a small amount of air.
Following completion of the reaction, the autoclave is allowed to cool and the products withdrawn, filtered and evaporated, preferably under vacuum, to remove solvent and to recover the terpolymer. It is understood that this is a preferred method of preparing the terpolymer batchwise when using the peroxide type initiator and that other suitable methods may be employed. in another embodiment, preparation of the terpolymer is effected in a continuous manner. in this embodiment, the reaction chamber is maintained at the desired temperature and contains some form of packing, such as glass beads, berl saddles, raschig rings, etc. in one method, a solution of the phenyl alkylene, unsaturated ester and peroxide initiator is prepared and charged to the reaction chamber, with ethylene under high pressure being separately charged to thereaction chamber. In one method, the solution and ethylene may be passed concurrently but preferably are passed counter currently into the reaction chamber. For example, the solution may be introduced into an upper portion of the reaction chamber and the ethylene is introduced into a lower portion thereof. In still anothermethod, the phenyl alkylene, unsaturated ester and/or peroxide catalyst may be introduced separately into the reaction chamber. Regardless of the specific method employed, excess ethylene is withdrawn, preferably from an upper portion of the reaction chamber, and reused in the process. The liquid effluent from the reaction chamber is withdrawn, preferably from a lower portion thereof, and is processed in any suitable manner to recover the terpolymer, preferably by filtering and then vacuum distillation. to remove the solvent. In another embodiment, metal oxides or other initiators of free radicals for promoting polymerization may be used.
The reactants are used in any suitable proportions. in general the olefin, and particularly ethylene, will be used in a large overall proportion. Overall means the amount of ethylene totally present in gaseous and liquid phase within the system. Since the critical temperature of ethylene is only 50 F., the ethylene will be in gaseous state under the conditions of copolymerization. Only a small part of the ethylene will be dissolved in the liquid phase. it was found that, with an overall excess of to 300:1, only 4 to 20:1 mole ratio of ethylene to other monomers was actually present in the liquid reaction mixture, i.e. in the monomers and initiator in the solvent. The amount of ethylene dissolved in the liquid phase depends on the nature and amount of the solvent, temperature and pressure of ethylene. The mole ratios in the terpolymer may comprise from 5 to 30 and preferably 10 to 25 mole proportions of ethylene, from about 0.5 to 5 and preferably 1 to 3 mole proportions of styrene and from about 0.5 to 5 and preferably 1 to 3 mole proportions of unsaturated ester.-The molecular weight of the terpoly mer may range from about 500 to 5,000 or more and preferably from about 1,000 to about 3,000 and more particularly from about 1,500 to about 2,500.
In one embodiment, all or a major portion of the solvent is removed from the product and the terpolymer is recovered as a solid material. In another embodiment, at least a substantial portion of the solvent is allowed to remain and the terpolymer is recovered as a concentrated solution for use as a concentrate to be incorporated as a pour point depressant in the oil. In still another embodiment, other solvents may be used to comprise a more homogeneous solution for use as a pour point depressant.
As hereinbefore set forth, the novel terpolymer of the present invention is a very effective pour point depressant. It is believed that the phenyl moiety being attached to the main polymeric chain forms an improved pour point depressant of increased solubility as compared, for example, to copolymers of olefin and unsaturated ester.
The chemical structure of the copolymer can vary, depending upon the specific character of the reactants, and mode of preparation. It may form a polyethylenic straight chain to which phenyl and polar alkyls are attached and some incidental alkyls resulting from some branching and chain termination mode. Also, as hereinbefore set forth, a small amount of the peroxide catalyst may enter into the reaction, as well as the final composition containing some unremoved solvent. Regardless of the specific chemical structure, the terpolymer, prepared as described herein, is a very effective pour point depressant. As another advantage to the present invention, the terpolymer is useful in many different oils and thus extends the range of its applicabilwhich will vary with the particular hydrocarbon oil and I may comprise one or more of anti-oxidant, corrosion or rust inhibitor, viscosity index improver, cetane improver, metal deactivator, dye, etc.
The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.
EXAMPLE I This example describes the preparation of a terpolymer of ethylene, styrene and methylmethacrylate. The preparation was'made in a 3 liter rotating autoclave which first was purged with nitrogen and then charged with 5 g. (0.05 mole) methylmethacrylate in 100 g. of
benzene, 5.02 g. (0.05 mole) of styrene in 100 g. of I evaporated (20 torr.) to yield 25 g. of tacky solid. The styrene to methylmethacrylate ratio in the terpolymer is 1:1 and the ratio of ethylene to the total of other reactants is 10.4:1. The average molecular weight of the terpolymer is 2,800.
EXAMPLE II Another terpolymer preparation was made in substantially the same manner as described in Example I except that the solvent used in this preparation was toluene. Specifically, the rotating autoclave was charged with 5 g. (0.05 mole) of methylmethacrylate in 100 g. of toluene, 5.02 g. (0.05 mole) of styrene in l00 g. of toluene and l g. (0.007 mole) of tert-butyl peroxide in 100 g. of toluene. Following purging and pressurizing to atmospheres with ethylene, the autoclave was heated and maintained at 284 F. for 4 hours. After cooling, 308 g. of liquid was withdrawn from the autoclave, filtered and evaporated to remove solvent, to yield 14 g. of soft and tacky dry solid product. The average molecular weight of the terpolymer is l 180.
' EXAMPLE III A terpolymer is prepared in substantially the same manner as described in Example I except that the unsaturated ester is vinyl acetate. The reactants are charged to the rotating autoclave in mole ratios of ethylenezstyrenewinyl acetate of 1511.5:1. Following completion of the reaction and-removal of the benzene solvent, the product is recovered as a solid terpolymer.
EXAMPLE IV Another terpolymer is prepared in substantially the same manner as described in Example II except that alpha-methylstyrene is used-as the phenyl alkylene. The reactants are used in a mole ratio of ethyleneztransbetamethylstyrene:methylmethacrylate of 12:l:l.5. After cooling of the autoclave, filtering and vacuum distillation to remove the solvent, the solid terpolymer product is recovered.
EXAMPLE V Another preparation is made in the same manner as described in Example II except that vacuum distillation to remove the toluene solvent is omitted and the resultant solution is utilized as a liquid concentrate for adding as a pour point depressant to a hydrocarbon oil.
EXAMPLE VI The terpolymer prepared as described in Example I was utilized as a pour point depressant in a commercial light cycle oil having a pour point of 2 F. and a boiling range of 358709 F. The terpolymer was evaluated at different concentrations, based on active ingredient, ranging from a high of 500 ppm (parts per million) down to a low of 10 ppm. The data was reported in the following table.
TABLE I Additive Pour Point Concentration Pour Point Depression ppm "F F.
None 2 From the data in the above table, it will be seen that the terpolymer was very effective in lowering the pour point of the oil. Even in a concentration as low as ppm, the pour point was lowered from -2 to F.
EXAMPLE VII The terpolymer prepared as described in Example II is used in a concentration of 250 ppm in a commercial No. 2 fuel oil having a boiling range of 428677 F. and a pour point of 10 F. The addition of the terpolymer serves to decrease the pour point to -20 F.
EXAMPLE VIII The flowing properties of crude oil in subarctic areas is improved by incorporating therein 250 ppm of the terpolymer prepared as described in Example I.
EXAMPLE IX The pour point properties of lubricating oil are improved by incorporating therein 1,000 ppm of the terpolymer prepared as described in Example II.
I claim as my invention:
1. Hydrocarbon oil containing components which cause the oil to lose fluidity at low temperature, said oil containing, in a pour point depressant concentration, a terpolymer of from about 5 to 30 mole proportions of ethylene, from about 0.5 to 5 mole proportions of styrene and from about 0.5 to 5 mole proportions of methylmethacrylate, said interpolymer having a molecular weight of from about 500 to about 5,000.
2. The hydrocarbon oil of claim I being middle distillate within the boiling range of from about 250 to about 750 F. I
3. The hydrocarbon oil of claim 1 being lubricating oil.
4. The hydrocarbon oil of claim 1 being residual oil having an initial boiling point of at least 600 F.
5. The hydrocarbon oil of claim 1 being reduced crude oil.
6. The hydrocarbon oil of claim 1 being crude oil.
7. The composition of claim 1 further characterized in that the styrene and methylmethacryl-ate are in equimolar proportion and the ratio of the ethylene to the total styrene and methylmethacrylate reactants is about 10:1, the average molecular weight of the interpolyrner being about 2,800.
Claims (6)
- 2. The hydrocarbon oil of claim 1 being middle distillate within the boiling range of from about 250* to about 750* F.
- 3. The hydrocarbon oil of claim 1 being lubricating oil.
- 4. The hydrocarbon oil of claim 1 being residual oil having an initial boiling point of at least 600* F.
- 5. The hydrocarbon oil of claim 1 being reduced crude oil.
- 6. The hydrocarbon oil of claim 1 being crude oil.
- 7. The composition of claim 1 further characterized in that the styrene and methylmethacrylate are in equimolar proportion and the ratio of the ethylene to the total styrene and methylmethacrylate reactants is about 10:1, the average molecular weight of the interpolymer being about 2,800.
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US00286651A US3803034A (en) | 1972-09-05 | 1972-09-05 | Pour point depression |
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US00286651A US3803034A (en) | 1972-09-05 | 1972-09-05 | Pour point depression |
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US3803034A true US3803034A (en) | 1974-04-09 |
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Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4080304A (en) * | 1975-06-16 | 1978-03-21 | The Dow Chemical Company | Hydrocarbon oil compositions containing polymers to control viscosity temperature relationship |
US4139480A (en) * | 1975-08-11 | 1979-02-13 | Exxon Research & Engineering Co. | Multifunctional alternating interpolymer lubricating oil additive |
US4292045A (en) * | 1979-05-10 | 1981-09-29 | Imperial Chemical Industries Limited | Modification of liquid hydrocarbons |
US4356003A (en) * | 1979-03-19 | 1982-10-26 | Imperial Chemical Industries Limited | Copolymers |
US4362533A (en) * | 1976-12-13 | 1982-12-07 | The Dow Chemical Company | Terpolymers of ethylene, vinyl acetate, and styrene as pour point depressants for distillate fuels |
US4396398A (en) * | 1980-10-01 | 1983-08-02 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Antimisting additives for aviation fuels |
US4452610A (en) * | 1981-08-07 | 1984-06-05 | Imperial Chemical Industries Plc | Modified liquid hydrocarbons |
EP0136698A2 (en) * | 1983-10-03 | 1985-04-10 | Ethyl Corporation | Cold flow improver |
US4985048A (en) * | 1987-12-16 | 1991-01-15 | Hoechst Aktiengesellschaft | Polymer mixtures for improving the low-temperature flow properties of mineral oil distillates |
US5028239A (en) * | 1989-05-12 | 1991-07-02 | Nalco Chemical Company | Fuel dewatering additives |
JP2003286495A (en) * | 2002-01-23 | 2003-10-10 | Sanyo Chem Ind Ltd | Flow-improving agent and fuel oil composition |
US6686037B2 (en) * | 1998-12-17 | 2004-02-03 | Bush Industries, Inc. | Wood veneer comprising ethylene styrene interpolymer layer and process for producing the same |
WO2006097289A1 (en) * | 2005-03-16 | 2006-09-21 | Basf Aktiengesellschaft | Terpolymers based on olefins, unsaturated carboxylic acid esters and vinyl aromatics in the form of additives to fuel oils and lubricants |
EP1705196A1 (en) * | 2005-03-21 | 2006-09-27 | Basf Aktiengesellschaft | Olefins, unsaturated carboxylic esters and vinyl aromatics based terpolymers as additives for fuel oils and lubricants. |
US10087310B2 (en) | 2013-03-15 | 2018-10-02 | California Institute Of Technology | Associative polymers and related compositions, methods and systems |
US10119084B2 (en) | 2015-09-18 | 2018-11-06 | California Institute Of Technology | Associative polymers to control formation of particulate matter from ignitable compositions and related compositions, methods and systems |
US10400186B2 (en) | 2009-04-17 | 2019-09-03 | California Institute Of Technology | Associative polymers for mist-control |
-
1972
- 1972-09-05 US US00286651A patent/US3803034A/en not_active Expired - Lifetime
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4080304A (en) * | 1975-06-16 | 1978-03-21 | The Dow Chemical Company | Hydrocarbon oil compositions containing polymers to control viscosity temperature relationship |
US4139480A (en) * | 1975-08-11 | 1979-02-13 | Exxon Research & Engineering Co. | Multifunctional alternating interpolymer lubricating oil additive |
US4362533A (en) * | 1976-12-13 | 1982-12-07 | The Dow Chemical Company | Terpolymers of ethylene, vinyl acetate, and styrene as pour point depressants for distillate fuels |
US4356003A (en) * | 1979-03-19 | 1982-10-26 | Imperial Chemical Industries Limited | Copolymers |
US4292045A (en) * | 1979-05-10 | 1981-09-29 | Imperial Chemical Industries Limited | Modification of liquid hydrocarbons |
US4334891A (en) * | 1979-05-10 | 1982-06-15 | Imperial Chemical Industries Limited | Modification of liquid hydrocarbons |
US4396398A (en) * | 1980-10-01 | 1983-08-02 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Antimisting additives for aviation fuels |
US4452610A (en) * | 1981-08-07 | 1984-06-05 | Imperial Chemical Industries Plc | Modified liquid hydrocarbons |
EP0136698A2 (en) * | 1983-10-03 | 1985-04-10 | Ethyl Corporation | Cold flow improver |
EP0136698A3 (en) * | 1983-10-03 | 1985-07-10 | Ethyl Corporation | Cold flow improver |
US4985048A (en) * | 1987-12-16 | 1991-01-15 | Hoechst Aktiengesellschaft | Polymer mixtures for improving the low-temperature flow properties of mineral oil distillates |
US5028239A (en) * | 1989-05-12 | 1991-07-02 | Nalco Chemical Company | Fuel dewatering additives |
US6686037B2 (en) * | 1998-12-17 | 2004-02-03 | Bush Industries, Inc. | Wood veneer comprising ethylene styrene interpolymer layer and process for producing the same |
JP2003286495A (en) * | 2002-01-23 | 2003-10-10 | Sanyo Chem Ind Ltd | Flow-improving agent and fuel oil composition |
WO2006097289A1 (en) * | 2005-03-16 | 2006-09-21 | Basf Aktiengesellschaft | Terpolymers based on olefins, unsaturated carboxylic acid esters and vinyl aromatics in the form of additives to fuel oils and lubricants |
EP1705196A1 (en) * | 2005-03-21 | 2006-09-27 | Basf Aktiengesellschaft | Olefins, unsaturated carboxylic esters and vinyl aromatics based terpolymers as additives for fuel oils and lubricants. |
US10400186B2 (en) | 2009-04-17 | 2019-09-03 | California Institute Of Technology | Associative polymers for mist-control |
US10087310B2 (en) | 2013-03-15 | 2018-10-02 | California Institute Of Technology | Associative polymers and related compositions, methods and systems |
US10494509B2 (en) | 2013-03-15 | 2019-12-03 | California Institute Of Technology | Associative polymers and related compositions, methods and systems |
US10119084B2 (en) | 2015-09-18 | 2018-11-06 | California Institute Of Technology | Associative polymers to control formation of particulate matter from ignitable compositions and related compositions, methods and systems |
US10428286B2 (en) | 2015-09-18 | 2019-10-01 | California Institute Of Technology | Associative polymers for use in a flow and related compositions, methods and systems |
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