EP3380589B1 - Copolymere umfassend -olefine und olefindicarbonsäureester, deren herstellung und verwendung als pour-point-depressants für rohöle, mineralöle oder mineralölprodukte - Google Patents
Copolymere umfassend -olefine und olefindicarbonsäureester, deren herstellung und verwendung als pour-point-depressants für rohöle, mineralöle oder mineralölprodukte Download PDFInfo
- Publication number
- EP3380589B1 EP3380589B1 EP16797890.7A EP16797890A EP3380589B1 EP 3380589 B1 EP3380589 B1 EP 3380589B1 EP 16797890 A EP16797890 A EP 16797890A EP 3380589 B1 EP3380589 B1 EP 3380589B1
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- European Patent Office
- Prior art keywords
- mol
- monomers
- radicals
- carbon atoms
- copolymer
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- 229920001577 copolymer Polymers 0.000 title claims description 147
- -1 dicarboxylic acid ester Chemical class 0.000 title claims description 106
- 239000010779 crude oil Substances 0.000 title claims description 46
- 239000004711 α-olefin Substances 0.000 title claims description 29
- 239000002480 mineral oil Substances 0.000 title claims description 28
- 239000000178 monomer Substances 0.000 claims description 111
- 239000000203 mixture Substances 0.000 claims description 104
- 125000004432 carbon atom Chemical group C* 0.000 claims description 85
- 150000001298 alcohols Chemical class 0.000 claims description 61
- 150000002430 hydrocarbons Chemical class 0.000 claims description 54
- 229930195733 hydrocarbon Natural products 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000009835 boiling Methods 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 32
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 28
- 235000010446 mineral oil Nutrition 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 19
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 17
- 230000032050 esterification Effects 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 230000002265 prevention Effects 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 description 40
- 239000000243 solution Substances 0.000 description 34
- 238000009472 formulation Methods 0.000 description 28
- 150000001336 alkenes Chemical class 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 20
- 239000003921 oil Substances 0.000 description 20
- 150000002148 esters Chemical class 0.000 description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 13
- 230000000994 depressogenic effect Effects 0.000 description 13
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 239000001993 wax Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000003849 aromatic solvent Substances 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 229960000735 docosanol Drugs 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 3
- VWIXGTHYBZXAPS-UHFFFAOYSA-N 15-methylhexadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCO VWIXGTHYBZXAPS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- NOOLISFMXDJSKH-OPRDCNLKSA-N Isomenthol Chemical compound CC(C)[C@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-OPRDCNLKSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000009969 flowable effect Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 description 2
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 101100490437 Mus musculus Acvrl1 gene Proteins 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- HORIEOQXBKUKGQ-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCC(C)C HORIEOQXBKUKGQ-UHFFFAOYSA-N 0.000 description 2
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- XGFDHKJUZCCPKQ-UHFFFAOYSA-N nonadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCO XGFDHKJUZCCPKQ-UHFFFAOYSA-N 0.000 description 2
- 229940078552 o-xylene Drugs 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
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- MFGALGYVFGDXIX-UHFFFAOYSA-N 2,3-Dimethylmaleic anhydride Chemical compound CC1=C(C)C(=O)OC1=O MFGALGYVFGDXIX-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
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- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
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- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- ACUZDYFTRHEKOS-UHFFFAOYSA-N decan-2-ol Chemical compound CCCCCCCCC(C)O ACUZDYFTRHEKOS-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- FDNCPIRKQFHDBX-UHFFFAOYSA-N methyl undec-2-enoate Chemical compound CCCCCCCCC=CC(=O)OC FDNCPIRKQFHDBX-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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
- 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
- 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
- C10L1/1966—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 poly-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
- C10L1/16—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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
-
- 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
- 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
- C10L10/16—Pour-point depressants
-
- 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
- C10L2200/0453—Petroleum or natural waxes, e.g. paraffin waxes, asphaltenes
-
- 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
- C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel
-
- 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
- C10L2270/00—Specifically adapted fuels
- C10L2270/02—Specifically adapted fuels for internal combustion engines
- C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
-
- 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
- C10L2270/00—Specifically adapted fuels
- C10L2270/10—Specifically adapted fuels for transport, e.g. in pipelines as a gas hydrate slurry
Definitions
- the present invention relates to copolymers comprising C 14 - to C 50 -olefins and at least two different Olefindicarbonklareestern and optionally maleic acid or maleic acid derivatives.
- the olefinic acid esters are on the one hand esters with linear C 18 - to C 50 -alkyl groups and on the other hand esters with short-chain linear, branched or cyclic alkyl groups or esters with aromatic groups.
- the invention further relates to a process for the preparation of such copolymers and their use as a pour point depressant for crude oil, mineral oil and / or mineral oil products, preferably as a pour point depressant for crude oil.
- the reservoir temperature of oil reservoirs is usually above room temperature, for example at 40 ° C to 100 ° C. From such deposits crude oil is still warm, and it cools during or after the pumping naturally more or less quickly to room temperature or at appropriate climatic conditions to temperatures below.
- Crude oils have different proportions of long-chain n-paraffins depending on their origin.
- the proportion of such paraffins may typically be from 1 to 30% by weight of the crude oil. They are often referred to as waxes.
- the paraffins can usually crystallize on cooling when falling below a certain temperature in the form of platelets. The precipitated paraffins significantly affect the fluidity of the oil.
- the platy n-paraffin crystals can form a kind of house structure that encloses the crude oil so that the crude stagnates, although the majority is still liquid. Failed paraffins can continue to clog filters, pumps, pipelines and other equipment or deposit in tanks, causing such a high level of cleaning.
- the lowest temperature at which a sample of oil just flows on cooling is called the pour point. Standardized measuring methods are used to measure the pour point. Crude oils can have pour points above room temperature. Such crude oils may solidify during or after conveying.
- suitable additives prevent the formation of said card house-like structures and thus lower the temperature at which the crude oil solidifies. Furthermore, additives can promote the formation of fine, well-crystallized, non-agglomerating paraffin crystals, so that a trouble-free oil transport is ensured. Such additives are referred to as pour-point depressants or flow improvers.
- Paraffin inhibitors or wax inhibitors are those substances which are said to prevent the deposition of paraffins or paraffin waxes on surfaces in contact with crude oils or other wax-containing oils and / or mineral oil products.
- copolymers of olefins and esters of ethylenically unsaturated dicarboxylic acids It is also known to use for this purpose copolymers of olefins and esters of ethylenically unsaturated dicarboxylic acids.
- GB 1 468 588 discloses a middle oil distillate containing an MSA-olefin copolymer esterified with C 18 to C 44 alcohols to improve low temperature properties.
- An example discloses a copolymer of MSA, C 22/28 ⁇ -monoolefins, and behenyl alcohol.
- US 2,542,542 discloses copolymers of dedecene, tetradecene, hexadecene or octadecene and maleic anhydride as an additive to lubricating oils.
- EP 214 786 A1 discloses the use of copolymers of straight chain olefins, for example, 1-octene, 1-decene, 1-dodecene, 1-tetradecene or 1-octadecene and maleic acid esters to improve the low temperature properties of fuels.
- the alcohols used for the esterification have at least 10 carbon atoms and they can be linear or branched. The document discloses that a mixture of linear and simple methyl branched alcohols can be used.
- EP 1 746 147 A1 discloses the use of copolymers of olefins and esters of ethylenically unsaturated dicarboxylic acids to lower the cloud point of fuel oils and lubricants.
- the copolymers comprise as monomers C 3 to C 50 olefins, preferably C 8 to C 88 olefins and C 1 to C 40 mono- or diesters of ethylenically unsaturated dicarboxylic acids, in particular of maleic acid.
- the C 1 - to C 40 -hydrocarbon radicals of the ester groups are preferably linear or branched C 1 - to C 40 -alkyl radicals.
- Copolymers which comprise both linear and branched alkyl radicals are not disclosed and the document contains no information on the molecular weight of the products obtained.
- the copolymers described are prepared by first reacting the olefins with maleic anhydride to give an olefin-MSA copolymer and, in a second step, in o-xylene (flash point about 30 ° C.) as solvent with alcohols. In this case, the ring of polymerized MSA units is opened. The o-xylene can be removed after completion of the reaction.
- the document further describes additive packages in which the said copolymers, optionally with further components, are formulated in suitable diluents. Diluents may be, for example, aliphatic or aromatic solvents or alkoxyalkanols.
- copolymers for use as pour-point depressants are usually carried out in chemical production facilities and the products are transported from there to the place of use, for example to an oil field or to an offshore platform. Such places of use can be in cold regions of the earth.
- concentrates of the copolymers are usually prepared in hydrocarbons. Such concentrates can be formulated by the users on site in the desired manner to ready-to-use formulations. For example, it is possible to dilute with solvent and / or add further additives.
- Particularly advantageous pour point depressants can be obtained by using C 20 - to C 24 -olefins and C 16 - to C 28 -alcohols for the preparation of said copolymers.
- Ready-to-use formulations may comprise, for example, about 20% by weight of said copolymers in high boiling organic solvents.
- High-boiling organic solvents are used because they also have a high flash point. In particular, solvents having a flash point of at least 60 ° C. are frequently used.
- Such formulations have the disadvantage that they can solidify when handled in a cold environment, for example in an Arctic environment, which is highly undesirable. The problem could be solved for example by the use of formulations with a lower concentration of polymers. As a result, however, larger amounts of solvents are needed, so that this solution must of course be more expensive. Higher costs also result in changes to the infrastructure, such as heated pipes.
- the formulations should have a lower solidification temperature, while having a substantially constant action as a pour point depressant, than known formulations.
- composition of the copolymer described (X) and organic solvents (Y), in particular hydrocarbons having a flash point ⁇ 60 ° C was found.
- copolymers (X) were found, obtainable by means of the method described.
- the novel copolymers (X) are synthesized from ethylenically unsaturated monomers. They comprise as monomers at least one ⁇ -olefin (A) and at least two different Olefindicarbonklareester (B1) and (B2).
- A ⁇ -olefin
- B1 Olefindicarbon Acidester
- B2 Olefindicarbon Acidester
- optionally maleic acid, maleic anhydride, or the corresponding methyl-substituted derivatives and / or further ethylenically unsaturated monomers, in particular monoethylenically unsaturated monomers may be copolymerized into the copolymer (X).
- R 1 is a linear, cyclic or branched, aliphatic and / or aromatic hydrocarbon radical having 14 to 50, in particular 16 to 30 carbon atoms, preferably 18 to 30 carbon atoms and particularly preferably 18 to 28 carbon atoms.
- linear or branched alkyl radicals are preferably linear or branched alkyl radicals, particularly preferably linear alkyl radicals having 14 to 50 carbon atoms, in particular linear alkyl radicals having 16 to 30 carbon atoms, preferably 18 to 30 carbon atoms, particularly preferably 18 to 28 carbon atoms and for example 18 to 24 carbon atoms.
- mixtures may be used which comprise at least two, preferably at least three, ⁇ -olefins having alkyl radicals R 1 , preferably linear alkyl radicals R 1 having 16 to 30 carbon atoms, preferably 18 to 24 carbon atoms.
- the mixtures may in particular be technical mixtures of linear aliphatic ⁇ -olefins.
- Such technical mixtures contain as main constituents aliphatic ⁇ -olefins having an even number of carbon atoms.
- the monomers (B) are monoethylenically unsaturated dicarboxylic acids or derivatives. According to the invention, the monomers (B) are at least two different monomers (B1) and (B2). In addition, optionally monomers (B3) may be present. In addition to (B1), (B2) and, if appropriate, (B3), no further monomers (B) are present.
- R 5 and R 6 are each H or methyl, preferably, in R 5 and R 6 each are H.
- R 2 is a linear n-alkyl radical having 16 to 36 carbon atoms, preferably 16 to 32 carbon atoms, in particular 16 to 26 carbon atoms.
- radicals examples include n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tetracosyl, n-hexacosyl, n- Octacosyl or n-tricontyl radicals.
- R 2 is at least one linear n-alkyl radical having 16 to 22 carbon atoms.
- R 2 is at least one linear n-alkyl radical having 22 to 26 carbon atoms.
- R 3 is at least one radical selected from the group of R 3a , R 3b , R 3c and R 3d , preferably selected from R 3b and R 3c .
- R 3a are linear 1-alkyl radicals having 1 to 10 carbon atoms, preferably 2 to 10 and particularly preferably 2 to 6 carbon atoms.
- linear 1-alkyl radicals R 3a examples include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl radicals; preference is given to n- Propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl, particularly preferred are ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl radicals and very particularly preferred are n-butyl radicals.
- R 3b are branched and / or secondary alkyl radicals having 4 to 36 carbon atoms, preferably 4 to 30, particularly preferably 4 to 17 carbon atoms.
- Branched alkyl radicals can be mono- or polysubstituted.
- branched alkyl radicals R 3b include i-butyl, t-butyl, 2,2'-dimethylpropyl, 2-ethylhexyl, 2-propylheptyl, i-nonanol, i-decyl, i-tridecyl, i Heptadecylreste, preferred are t-butyl, 2-ethylhexyl and 2-Propylheptylreste.
- secondary alkyl radicals examples include 2-butyl, 2-propyl, 2-hexyl, 2-heptyl or 2-dodecyl radicals.
- R 3c are unsubstituted or alkyl-substituted, cyclic alkyl radicals having 5 to 18 carbon atoms, preferably 6 to 10 carbon atoms. In particular, they are unsubstituted or alkyl-substituted cyclic alkyl radicals containing 5, 6 or 7 rings. It may also be bicyclic radicals. Examples of R 3c radicals include cyclopentyl, cyclohexyl, cycloheptyl, bornyl or myrthanyl radicals. Preferably, R 3c may be a cyclohexyl radical.
- R 3d is unsubstituted or alkyl-substituted aromatic hydrocarbon radicals having 6 to 36 carbon atoms.
- aromatic hydrocarbon radicals having 6 to 36 carbon atoms.
- examples of such radicals include phenyl, benzyl or toluyl radicals.
- R 4 in the formulas (B1) and (B2) are each a radical selected from the group of H, R 2 and R 3 , where R 2 and R 3 have the meaning defined above, with the proviso that that in each case 50 mol%, preferably at least 75 mol% and particularly preferably at least 95 mol% of the radicals R 4 is H. In one embodiment of the invention, all radicals R 4 are H.
- R 4 in (B1) or (B2) is H, then (B1) and (B2) are monoesters. If R 4 in (B1) or (B2) is R 2 or R 3 , it is diester.
- the monomers (B1) and (B2) comprise COOH groups.
- the COOH groups may be dissociated, and they may also be present in salt form as - COO- 1 / m X m + , where X m + is an m-valent cation.
- X m + may be alkali metal ions such as Na + , K + or ammonium ions.
- the proportion of the monomers (B1) + (B2) with respect to the sum of all monomers (B) is at least 50 mol%, preferably at least 80 mol%, Particularly preferably at least 95 mol% and very particularly preferably exclusively monomers (B1) and (B2) are present.
- the proportion of the radicals R 3 with respect to the sum of the radicals R 2 and R 3 is 1 mol% to 49 mol%, in particular 5 mol% to 45 mol%, preferably 20 mol% to 45 mol% and for example 30 mol% to 40 mol%.
- It may be only one monomer (B1), or it may be several different monomers (B1) with different radicals R 2 .
- It can be only one monomer (B2), or it can be several different monomers (B2) with different radicals R 3 .
- radicals R 3 are radicals R 3a .
- radicals R 3 are radicals R 3b and / or radicals R 3c .
- radicals R 3 are radicals R 3b .
- radicals R 3 are radicals R 3c .
- radicals R 3 are radicals R 3d .
- monomers (C) may optionally be present.
- ⁇ -olefins (A) different ⁇ -olefins such as methyl undecenoate.
- vinyl ethers, vinyl esters, N-vinyl comonomers such as vinylpyrrolidones, vinylcaprolactams, isobutene, diisobutene or polyisobutene.
- the proportion of the monomers (A) with respect to the amount of all monomers is 40 mol% to 60 mol%, preferably 45 mol% to 55 mol% and for example 48 to 52 mol%.
- the proportion of the monomers (B) with respect to the amount of all monomers is 40 mol% to 60 mol%, preferably 45 mol% to 55 mol%, and for example 48 to 52 mol%.
- the amount of additional monomers (C) is not more than 20 mol%, preferably not more than 10 mol%, more preferably not more than 5 mol%, and most preferably no further monomers (C) are present ,
- the weight-average molecular weight M w of the copolymers (X) is, according to the invention, 2000 g / mol to 25000 g / mol, preferably 4000 g / mol to 20 000 g / mol and, for example, 10 000 to 20 000 g / mol.
- this embodiment involves copolymers (X) which contain at most small amounts of maleic anhydride and / or maleic acid or the corresponding methyl derivatives, and in which the olefinic acid ester units are mainly monoesters.
- composition comprising olefin-olefinic acid ester copolymers (X) and hydrocarbons
- copolymers (X) according to the invention and preferred embodiments of the copolymers (X) have already been described above, so that reference is made at this point only to the above description.
- the organic solvents (Y) may in principle be any organic solvents, provided that the copolymers (X) are soluble therein. Preference is given to using solvents which have a flash point ⁇ 60 ° C.
- Organic solvents (Y) may be hydrocarbons.
- hydrocarbons include aliphatic, cycloaliphatic and / or aromatic solvents.
- organic solvents comprising functional groups for example alcohols or esters.
- the organic solvents are nonpolar solvents (Y1) comprising saturated aliphatic hydrocarbon groups, preferably those which have a flash point ⁇ 60 ° C.
- solvents (Y1) include saturated aliphatic alcohols or esters of saturated aliphatic ones Carboxylic acids and saturated aliphatic alcohols, with the proviso that the solvents preferably each have a flash point ⁇ 60 ° C.
- esters include esters of saturated fatty acids having at least 8 carbon atoms with saturated aliphatic alcohols, such as methyl laurate or stearic acid methyl ester. Technical mixtures of various aliphatic esters are commercially available.
- the solvents used may be esters of aliphatic or cycloaliphatic dicarboxylic acids, for example dialkyl esters of cyclohexane-1,2-dicarboxylic acid, such as cyclohexane-1,2-dicarboxylic acid diisononyl ester.
- the organic solvents (Y) are saturated aliphatic hydrocarbons (Y1) or mixtures thereof. They may be both paraffinic and naphthenic, ie saturated cyclic hydrocarbons.
- Hydrocarbons (Y1) are preferably high-boiling aliphatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C. Suitable hydrocarbons with a flash point ⁇ 60 ° C include, for example, n-undecane (flash point 60 ° C, boiling point 196 ° C) or n-dodecane (flash point 71 ° C, boiling point 216 ° C).
- hydrocarbons for example mixtures of paraffinic hydrocarbons, mixtures of paraffinic and naphthenic hydrocarbons or mixtures of isoparaffins. It is clear to the person skilled in the art that technical mixtures may still contain small residues of aromatic or unsaturated hydrocarbons.
- Technical mixtures of saturated aliphatic solvents are commercially available, for example technical mixtures of the Shellsol® D series or the Exxsol® D series.
- the organic hydrocarbons (Y) are aromatic hydrocarbons (Y3) or mixtures thereof.
- Hydrocarbons (Y3) are preferably high-boiling aromatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C.
- Suitable aromatic hydrocarbons having a flash point ⁇ 60 ° C include, for example, naphthalene.
- technical mixtures of aromatic hydrocarbons can be used.
- Technical blends of aromatic solvents are commercially available, for example, technical blends of the Shellsol® A series or the Solvesso® series.
- the organic solvents (Y) are preferably aromatic hydrocarbons (Y3).
- the concentration of the copolymers (X) in the composition according to the invention is chosen by the person skilled in the art according to the desired properties of the composition.
- the concentration of the copolymers (X) may be 15 to 75 wt .-%, preferably 15 to 45 wt .-%, particularly preferably 15 wt .-% to 30 wt .-%, for example 17 to 25 wt .-% or 18 to 22 wt .-%, each based on the sum of all components of the composition.
- the composition comprises at least one copolymer (X) and at least one aromatic hydrocarbon (Y3) having a boiling point of at least 175 ° C and a flash point ⁇ 60 ° C, wherein the Concentration, the concentration of the copolymers (X) is 15 to 30 wt .-%, preferably 17 wt .-% to 25 wt .-% and for example 18 to 22 wt .-% with respect to the sum of all components of the composition.
- the novel copolymers (X) can be prepared by free-radically polymerizing the said monomers (A), (B) and optionally (C) in the desired ratio. Radical polymerization techniques are known to those skilled in the art. In this technique, therefore, previously prepared monomers (B1) and (B2) are used for the polymerization.
- the preparation is carried out by means of an at least two-stage process, wherein in a first process step I provides a polymeric starting material from olefins and maleic anhydride or the corresponding methyl-substituted derivatives thereof and in a second process step II the maleic anhydride of the provided educt in a polymer-analogous reaction with alcohols esterified.
- a first process step I provides a polymeric starting material from olefins and maleic anhydride or the corresponding methyl-substituted derivatives thereof and in a second process step II the maleic anhydride of the provided educt in a polymer-analogous reaction with alcohols esterified.
- This procedure results in the formation of monomers (B1) and (B2) derived repeating units of the copolymer (X) thus only in the course of the polymer-analogous reaction.
- a polymeric starting material is provided. This is a copolymer of the olefins (A), a monomer (B3b) and optionally further monomers (C). Preference is given to using maleic anhydride as monomer (B3b).
- the proportion of the monomers (A) with respect to the amount of all the monomers is 40 mol% to 60 mol%, preferably 45 mol% to 55 mol%, and for example 48 to 52 mol%.
- the proportion of the monomers (B3b) with respect to the amount of all the monomers is 40 mol% to 60 mol%, preferably 45 mol% to 55 mol%, and for example 48 to 52 mol%.
- the proportion of optional monomers (C), if present at all, is not more than 20 mol%, preferably not more than 10 mol%, more preferably not more than 5 mol%, and very particularly preferably no further monomers (C ) available.
- the number-average molecular weight M n of the polymeric educt of olefin (A) and monomer (B3b) is usually from 1000 g / mol to 15000 g / mol.
- Olefin-maleic anhydride copolymers having such number average molecular weights M n are known in the art in principle and are commercially available.
- the preparation can be carried out in a manner known in principle by radical polymerization of the ⁇ -olefins (A) and the maleic anhydride or the methyl-substituted derivatives (B3b) in the desired amounts.
- A ⁇ -olefins
- B3b methyl-substituted derivatives
- the in EP 214 786 A1 in particular pages 6, lines 1 to 14 described procedure can be used. It can be polymerized both in bulk and using solvents.
- Suitable solvents are aprotic solvents such as xylene, aliphatics, alkanes, benzene or ketones.
- the solvents are at least one organic solvent (Y), in particular a hydrocarbon, preferably hydrocarbons or hydrocarbon mixtures which have a flash point ⁇ 60 ° C.
- the hydrocarbons may be, for example, saturated aliphatic hydrocarbons (Y 2) or mixtures thereof. They may be both paraffinic and naphthenic, ie saturated cyclic hydrocarbons. Hydrocarbons (Y 2) are preferably high-boiling aliphatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C. With regard to examples and preferred hydrocarbons (Y2), reference is made to the above description of the hydrocarbons (Y2).
- the hydrocarbons may also be aromatic hydrocarbons (Y3) or mixtures thereof.
- Hydrocarbons (Y3) are preferably high-boiling aromatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C. With regard to examples and preferred hydrocarbons (Y3), reference is made to the above description of the hydrocarbons (Y3).
- the radical polymerization can be carried out using conventional, thermally decomposing initiators at 80 ° C to 200 ° C, preferably at 100 ° C to 180 ° C and especially at 130 ° C to 170 ° C.
- the amount of initiator is usually from 0.1 to 10% by weight, based on the amount of the monomers, preferably from 0.2 to 5% by weight and more preferably from 0.5 to 2% by weight.
- the polymerization time is usually 1 to 12 hours.
- the person skilled in the art knows how to set the desired range of the number average molecular weight M n .
- the molecular weight can in principle known manner by the choice of polymerization temperature (the lower, the higher M n ) or by the choice of the reaction medium (aromatic solvents regulate more, ie lower M n , aliphatic regulate less, ie higher M n , without Solvent even higher M n ) are controlled.
- the resulting polymeric starting materials are obtained without solvent or as a solution.
- the copolymer (X) can of course be isolated from the solvent by methods known to those skilled in the art and used as such for process step II.
- the person skilled in the art selects a suitable concentration of the monomers in the solvent for the polymerization. For example, a concentration of the monomers in the solvent of from 20 wt.% To 80 wt.%, For example, 30 wt.% To 60 wt.% Can be selected.
- the provided polymeric educts of olefins and maleic anhydride or methylmaleic anhydride and / or dimethylmaleic anhydride are esterified in a second step with at least one alcohol R 2 OH and at least one alcohol R 3 OH polymer analogous.
- the rings of the copolymerized anhydride groups are opened and the corresponding dicarboxylic acid monoesters or dicarboxylic acid diesters are formed in a polymer-analogous reaction, depending on the amount of the alcohols and the reaction conditions.
- the alcohols R 2 OH are linear aliphatic alcohols and R 2 is a linear 1-alkyl radical having 16 to 36 carbon atoms, preferably 16 to 32 carbon atoms, particularly preferably 16 to 26 carbon atoms.
- alcohols R 2 OH examples include n-hexadecyl alcohol, n-octadecyl alcohol, n-nonadecyl alcohol, n-eicosyl alcohol, n-heneicosyl alcohol, n-docosyl alcohol, n-tetracosyl alcohol, n-hexacosyl alcohol, n-octacosyl alcohol or n-tricontyl alcohol.
- Particularly preferred are alcohols selected from the group of n-docosyl alcohol, n-tetracosyl alcohol and n-hexacosyl alcohol.
- a mixture of at least three alcohols R 2 OH which comprises at least 1-docosyl alcohol, 1-tetracosyl alcohol and 1-hexacosyl alcohol.
- the amount of said three alcohols is preferably at least 70% by weight, preferably at least 80% by weight, with respect to the amount of all the alcohols R 2 OH used.
- alcohols R 3a OH include ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol and n-decanol, preferred are n-propanol, n-butanol , n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol and n-decanol, particularly preferably ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol and very particularly preferably n butanol.
- Examples of branched and / or secondary alcohols R 3b OH include i-butanol, t-butanol, 2,2'-dimethylpropanol-1, 2-ethylhexanol-1,2-propylheptanol-1, i-nonanol, i-decanol, i Tridecanol or i-heptadecanol, 2-butanol, 2-heptanol, 2-hexanol, 2-octanol or 2-decanol, preferred are t-butanol, 2-ethylhexanol-1 and 2-propylheptanol-1 and i-heptadecanol.
- alcohols R 3c OH examples include cyclopentanol, cyclohexanol, cycloheptanol, borneol, isoborneol, menthol, neomemthol, isomenthol, neoisomenthol, or myrthanol.
- alcohols R 3d examples include phenol, toluene or benzyl alcohol.
- the alcohols R 3 OH are alcohols R 3a OH.
- the alcohols R 3 OH are alcohols R 3b OH and / or alcohols R 3c OH.
- the alcohols R 3 OH are alcohols R 3b OH.
- the alcohols R 3 OH are alcohols R 3c OH.
- the alcohols R 3 OH are alcohols R 3d OH.
- the proportion of the alcohols R 3 OH with respect to the sum of the alcohols used for the esterification R 2 OH and R 3 OH 1 mol% to 49 mol%, preferably 5 mol% to 45 mol%, 20 mol% to 45 mol% and, for example, 30 mol% to 40 mol%.
- the amount of the alcohols R 2 OH and R 3 OH used together is 0.5 to 1.5 mol / mol of anhydride units in the copolymer (X), preferably 0.8 to 1.2 mol / mol, particularly preferably 0, 9 to 1.1 mol / mol, very particularly preferably 0.95 to 1.05 mol / mol.
- the polymeranloge esterification is usually carried out at a temperature of 130 ° C to 180 ° C, preferably 140 ° C to 160 ° C.
- the esterification can be carried out in bulk or in the presence of inert solvents.
- the reaction mixture should remain liquid and homogeneous at the reaction temperature to ensure homogeneous reaction.
- the reaction can be carried out without pressure or under pressure.
- the alcohols can be completely charged or added sequentially.
- the esterification can be carried out for example in the presence of esterification catalysts such as para-toluenesulfonic acid, methanesulfonic acid or sulfuric acid.
- esterification catalysts such as para-toluenesulfonic acid, methanesulfonic acid or sulfuric acid.
- a suitable procedure is for example in the WO 2014/095408 A1 disclosed.
- the amount may be 0.05 to 0.5 mol% based on the alcohols.
- process step I is carried out in solvents, it is advantageously possible to use a solution of the polymeric starting materials obtained in process step II for process step II. Otherwise, the polymeric starting materials for process step II are dissolved in suitable inert solvents.
- the esterification is preferably carried out in hydrocarbons, preferably in hydrocarbons or hydrocarbon mixtures with a flash point ⁇ 60 ° C. In this procedure, the esterification directly gives the composition according to the invention of at least one copolymer (X) and at least one hydrocarbon.
- the hydrocarbons may be, for example, saturated aliphatic hydrocarbons (Y 2) or mixtures thereof. They may be both paraffinic and naphthenic, ie saturated cyclic hydrocarbons.
- the hydrocarbons may also be aromatic hydrocarbons (Y3) or mixtures thereof.
- Hydrocarbons (Y3) are preferably high-boiling aromatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C. With regard to examples and preferred hydrocarbons (Y3), reference is made to the above description of the hydrocarbons (Y3).
- process step II is carried out in solution and the amount of hydrocarbons used is such that a composition of at least one copolymer (X) and at least one hydrocarbon in a concentration of 15 to 85 wt .-% is formed. It can be prepared equal to a ready-to-use composition in the concentrations as described above or it can be a concentrate, for example, produced at a concentration of 50 to 70 wt .-%, which then has to be further diluted on site to the ready-to-use concentration.
- the invention further relates to copolymers (X) which are obtainable by the process just described.
- copolymers (X) which are obtainable by the process just described.
- process parameters reference is made to the method just described.
- copolymers (X) according to the invention can be used as pour-point depressants for crude oil, mineral oil and / or mineral oil products by adding at least one of the described copolymers (X) to the crude oil, the mineral oil and / or the mineral oil products.
- the copolymers (X) according to the invention are used as pour point depressants for crude oil by adding to the crude oil at least one of the copolymers (X) described above.
- pour point depressants reduce the pour point of crude oils, mineral oils and / or mineral oil products.
- the term "pour point” refers to the lowest temperature at which a sample of oil just flows when it cools down. Standardized measuring methods are used to measure the pour point.
- the copolymers (X) can be used as such.
- the copolymers (X) according to the invention are preferably used in the form of a solution.
- formulations of the copolymers (X) can be used, which may contain other components in addition to solvents.
- the copolymers (X) according to the invention should be homogeneously dispersed in the solvents used, preferably dissolved therein. In principle, all solvents which meet these requirements are suitable. Of course, mixtures of different solvents can be used.
- it is at least one organic solvent (Y), preferably an organic solvent having a flash point ⁇ 60 ° C.
- the organic solvents are nonpolar solvents (Y1) comprising saturated aliphatic hydrocarbon groups, preferably those which have a flash point ⁇ 60 ° C.
- solvents (Y1) include saturated aliphatic alcohols or esters of saturated aliphatic carboxylic acids and saturated aliphatic alcohols, with the proviso that the solvents preferably each have a flash point ⁇ 60 ° C.
- esters include esters of saturated fatty acids having at least 8 carbon atoms with saturated aliphatic alcohols, such as methyl laurate or stearic acid methyl ester. Technical mixtures of various aliphatic esters are commercially available.
- the solvents used may be esters of aliphatic or cycloaliphatic dicarboxylic acids, for example dialkyl esters of cyclohexane-1,2-dicarboxylic acid, such as cyclohexane-1,2-dicarboxylic acid diisononyl ester.
- the organic solvents are saturated aliphatic hydrocarbons (Y 2) or mixtures thereof. They may be both paraffinic and naphthenic, ie saturated cyclic hydrocarbons. Hydrocarbons (Y 2) are preferably high-boiling aliphatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C. With regard to examples and preferred hydrocarbons (Y2), reference is made to the above description of the hydrocarbons (Y2).
- the organic solvents are aromatic hydrocarbons (Y3) or mixtures thereof.
- Hydrocarbons (Y3) are preferably high-boiling aromatic hydrocarbons having a boiling point of at least 175 ° C. and preferably a flash point ⁇ 60 ° C. With regard to examples and preferred hydrocarbons (Y3), reference is made to the above description of the hydrocarbons (Y3).
- compositions of copolymers (X) and organic solvents (Y), preferably hydrocarbons may be used.
- such compositions can be obtained by using hydrocarbons, in particular hydrocarbons or hydrocarbon mixtures having a flash point ⁇ 60 ° C., for the preparation of the copolymers (X), likewise as described above.
- Ready-to-use formulations of the copolymers (X) may of course comprise further components.
- additional wax dispersants to the formulation.
- Wax dispersants stabilize formed paraffin crystals and prevent them from sedimenting.
- wax dispersants for example, alkylphenols, alkylphenol-formaldehyde resins or organic sulfonic acids such as dodecylbenzenesulfonic acid can be used.
- the concentration of the copolymers (X) in ready-to-use formulations can be from 0.5 to 45% by weight, preferably from 15 to 45% by weight, particularly preferably from 15% by weight to 30% by weight, for example from 17 to 25% by weight. -% or 18 to 22 wt .-%, each based on the sum of all components of the composition.
- the preparation of copolymers (X) and optionally of a concentrate of the copolymers (X) in solvents naturally takes place in a chemical plant
- the preparation of the ready-to-use formulation can be made as close as possible to the point at which the formulation is to be injected.
- the crude oil, mineral oil and / or mineral oil products preferably the crude added amount of copolymers of the invention (X) is measured by the expert so that the desired reduction of the pour point is achieved, where it is natural for the skilled person that the necessary amount depends on the type of crude oil. On the other hand, it is desirable for economic reasons to use as little as possible pour-point depressant.
- the copolymers (X) in an amount of from 50 to 1500 ppm with respect to the crude oil, mineral oil and / or mineral oil products.
- the amount is 100 to 1000 ppm, more preferably 250 to 600 ppm and for example 300 to 600 ppm.
- the amounts indicated relate to the copolymer (X) itself.
- the oil is crude oil.
- copolymers (X) or their solutions or formulations are added to the crude oil before the precipitation of waxes has begun, ie. at a temperature above the pour point.
- the addition may be made at a temperature not lower than 10 ° C above the pour point.
- the location of the addition of the copolymers (X) to the crude oil is suitably selected by the person skilled in the art.
- the addition can be made, for example, in the formation, downhole, wellhead, or pipeline.
- copolymers (X) or their solutions or formulations are injected into a crude oil pipeline.
- the injection may be on the oil field, i. at the beginning of the crude oil pipeline, but the injection can of course also take place at another location.
- it may be a pipeline that leads from an offshore platform to the mainland.
- the copolymers (X) can prevent pipelines from clogging if the crude cools during transportation in the pipeline. This danger is inherently particularly pronounced when it is a pipeline in a cold environment, e.g. in arctic environment.
- the copolymers (X) or their solutions or formulations are injected into a production well.
- a production well may be an offshore production well.
- the injection can be made approximately at the point where oil from the formation flows into the production well. In this way, the solidification of the crude oil in the production well and in downstream transport pipelines can prevent excessive increase of its viscosity as well as the cross-sectional constriction of pipes by paraffin deposits.
- the injection may be umbilical.
- a flexible rod comprising at least one pipe and optionally electrical lines or control lines in a protective sheath is introduced axially into a borehole or a pipeline.
- the formulation of the copolymers (X) can be injected exactly at the desired location.
- copolymers (X) according to the invention can also be used for other purposes.
- the above-described copolymers (X) or their solutions or formulations are used to prevent wax deposits on surfaces which are in contact with crude oil, mineral oil and / or mineral oil products. They are preferably surfaces which are in contact with crude oil.
- the use takes place by adding at least one of the copolymers (X) or their solutions or formulations to the crude oil, mineral oil and / or the mineral oil products.
- Preferred solutions and formulations have already been mentioned and also the nature of the use is analogous to the use as a pour point depressant.
- copolymers (X) By the partial replacement of long-chain, linear alkyl groups by short linear alkyl groups, branched alkyl groups, cyclic alkyl groups or hydrocarbon groups, copolymers (X) are obtained which can be processed into formulations, in particular about 20% formulations which have lower solidification points than those corresponding formulations of unmodified copolymers, ie exclusively copolymers comprising linear alkyl groups. As a result, the handling of such formulations is facilitated, especially in colder environment, such as Arctic environment.
- C 20/24 olefins Commercially available mixture of ⁇ -olefins, main components C 20 , C 22 and C 24 olefins C 18 ⁇ 3% by weight C 20 35 to 55% by weight C 22 25 to 45% by weight C 24 10 to 26% by weight C 26 ⁇ 2% by weight > C 26 ⁇ 0.1% by weight
- the solids content was determined by drying the products at 120 ° C, 2 h in a vacuum oven.
- the mass-average molecular weights and polydispersities are measured with a GPC system at 35 ° C.
- the system includes two columns as well as refractive index detector and UV detector.
- the eluant used is THF with 0.1% trifluoroacetic acid.
- the pour point determination was performed according to ASTM D 5853 Test Method for Pour Point of Crude Oils.
- the pour point is the minimum temperature at which a sample of a tested oil is just flowable.
- ASTM D 5853 a sample of the oil is cooled in 3 ° C increments and the flowability is tested after each step.
- a crude oil from the "Landau" oil field in southwestern Germany (Wintershall Holding GmbH) with an API grade of 37 and a pour point of 27 ° C was used.
- the polymers to be tested were used for the oil in a concentration of 300 ppm of polymer based on the crude oil.
- the pour point of a 20% strength solution of the polymer according to the invention itself was measured.
- the resulting solutions were diluted to a concentration of 20% by weight using Solvesso® 150.
- the pour point is the minimum temperature at which the 20% solution is just still flowable.
- the 20% pour point was determined according to ASTM D5985-02 (approved Jan. 1, 2014).
- the no-flow point of a 20% strength solution of the polymer according to the invention itself was measured.
- the resulting solutions were diluted to a concentration of 20% by weight using Solvesso® 150.
- the no-flow point is the temperature at which the 20% solution is just no longer flowable.
- the 20% pour point was determined according to ASTM D 7346-15 (approved July 1, 2015).
- copolymer I and 11.71 g of isoheptadecanol are melted at an external temperature of 85 ° C and after melting 20.54 g of Solvesso® 150 and 10 mg of para-toluenesulfonic acid are added. Heat to 150 ° C outside temperature and stir for 2 hours. Then 25.45 g of alcohol mixture I (C 16/22 -alcohols) are added and the mixture is stirred for a further 4 h.
- Comparative Experiment 1 (Table 1) a product according to the prior art was used, namely a product based on the MSA-olefin copolymer I, in which the MSA units are opened only with a linear C 16/22 alcohol.
- the copolymer lowers the pour point of the crude oil tested from 27 ° C to 9-12 ° C; the 20% solution solidifies at about 6.5 ° C and the pour point of the 20% solution is 9 ° C.
- Examples 3, 4 and V2 show the effect of partially replacing the linear alcohol with cyclohexanol (30, 40 and 50 mol%).
- the temperature at which the 20% solution solidifies becomes lower and lower.
- the solidification temperature of the 20% solution is -5 ° C / -5.8 ° C for the product with 50 mol% cyclohexanol (Comparative Experiment 2)
- the effect as a pour point depressant for crude oil decreases markedly (only one more) Reduction from 27 ° C to 18 ° C, instead of 27 ° C to 9 to 12 ° C as in the unmodified product).
- the amount of cyclohexanol should accordingly be less than 50 mol%.
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP15196769 | 2015-11-27 | ||
PCT/EP2016/077935 WO2017089212A1 (de) | 2015-11-27 | 2016-11-17 | COPOLYMERE UMFASSEND α-OLEFINE UND OLEFINDICARBONSÄUREESTER, DEREN HERSTELLUNG UND VERWENDUNG ALS POUR-POINT-DEPRESSANTS FÜR ROHÖLE, MINERALÖLE ODER MINERALÖLPRODUKTE |
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EP3380589A1 EP3380589A1 (de) | 2018-10-03 |
EP3380589B1 true EP3380589B1 (de) | 2019-10-30 |
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US (2) | US10781385B2 (zh) |
EP (1) | EP3380589B1 (zh) |
CN (1) | CN108291163B (zh) |
CA (1) | CA3003953C (zh) |
EA (1) | EA035184B1 (zh) |
ES (1) | ES2769078T3 (zh) |
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SG11201804366RA (en) | 2015-11-27 | 2018-06-28 | Basf Se | Copolymers comprising a-olefins and olefin dicarboxylic acid esters, production thereof, and use thereof as pour point depressants for crude oils, mineral oils, or mineral oil products |
ES2896694T3 (es) | 2016-07-05 | 2022-02-25 | Basf Se | Uso de inhibidores de la corrosión para combustibles y lubricantes |
WO2018104071A1 (de) | 2016-12-07 | 2018-06-14 | Basf Se | Wässrige zusammensetzungen von paraffininhibitoren |
CA3066844C (en) | 2017-06-27 | 2023-11-07 | Nouryon Chemicals International B.V. | Winterized pour point depressants |
WO2019002167A1 (en) * | 2017-06-27 | 2019-01-03 | Akzo Nobel Chemicals International B.V. | SPRAY DRAWERS SUITABLE FOR WINTER |
CN107469151B (zh) * | 2017-08-09 | 2020-05-22 | 青岛慧生惠众生物科技有限公司 | 一种牙槽骨修复材料及其制备方法和应用 |
SG11202002161XA (en) | 2017-09-11 | 2020-04-29 | Basf Corp | Aqueous polymer dispersions, a method for their preparation and the use thereof as pour-point depressants for crude oil, petroleum, and petroleum products |
EA038357B1 (ru) * | 2020-05-20 | 2021-08-13 | Научно-Исследовательский И Проектный Институт Нефти И Газа (Нипинг) | Депрессорная присадка |
WO2022223153A1 (en) | 2021-04-21 | 2022-10-27 | Clariant International Ltd | Polymeric pour point depressants for waxy crude oils |
US11692053B2 (en) | 2021-04-21 | 2023-07-04 | Clariant International Ltd | Polymeric pour point depressants for waxy crude oils |
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US2542542A (en) | 1948-08-02 | 1951-02-20 | Standard Oil Dev Co | Lubricating oil additives |
DE2102469C2 (de) | 1971-01-20 | 1989-06-29 | Basf Ag, 6700 Ludwigshafen | Verwendung von Äthylencopolymerisaten als Zusatz zu Erdöl und Erdölfraktionen |
US3966428A (en) | 1973-10-31 | 1976-06-29 | Exxon Research And Engineering Company | Ethylene backbone polymers in combination with ester polymers having long alkyl side chains are low viscosity distillate fuel cold flow improvers |
DE3223694A1 (de) * | 1981-09-17 | 1983-03-24 | Akzo Gmbh, 5600 Wuppertal | Copolymere aus (alpha)-(beta)-ungesaettigten dicarbonsaeureestern verfahren zu deren herstellung sowie deren verwendung |
DE3201541A1 (de) | 1982-01-20 | 1983-07-28 | Basf Ag, 6700 Ludwigshafen | Erdoelmitteldestillate mit verbesserten fliesseigenschaften |
GB8521393D0 (en) | 1985-08-28 | 1985-10-02 | Exxon Chemical Patents Inc | Middle distillate compositions |
US20050138859A1 (en) * | 2003-12-16 | 2005-06-30 | Graham Jackson | Cold flow improver compositions for fuels |
EP1746147B1 (de) * | 2005-07-22 | 2016-02-24 | Basf Se | Copolymere auf Basis von Olefinen und Estern von ethylenisch ungesättigten Carbonsäuren zur Erniedrigung des CP-Werts von Brennstoffölen und Schmierstoffen |
JP5539983B2 (ja) | 2008-07-31 | 2014-07-02 | ザ ルブリゾル コーポレイション | 新規なコポリマーおよびその潤滑組成物 |
RU2015129303A (ru) | 2012-12-18 | 2017-01-26 | Басф Се | Полимерные композиции в растворителях с высокой температурой воспламенения, способ их получения и их применение в качестве депрессантных присадок, понижающих температуру застывания сырых нефтей, нефтяных топлив или нефтепродуктов |
AR100387A1 (es) | 2014-02-18 | 2016-10-05 | Basf Se | Copolímeros que comprenden etileno, ésteres de vinilo y ésteres de ácido (met)acrílico, sus formulaciones y usos como depresor del punto de fluidez, inhibidor de cera y potenciador de flujo para petróleos crudos |
EP3164002B1 (en) * | 2014-06-03 | 2020-04-22 | Basf Se | Agrochemical suspoemulsion comprising polymer particles made of methyl (meth)acrylate and c2-c8 alkyl (meth)acrylate |
SG11201804366RA (en) | 2015-11-27 | 2018-06-28 | Basf Se | Copolymers comprising a-olefins and olefin dicarboxylic acid esters, production thereof, and use thereof as pour point depressants for crude oils, mineral oils, or mineral oil products |
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EA201891271A1 (ru) | 2018-12-28 |
US11236282B2 (en) | 2022-02-01 |
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CA3003953A1 (en) | 2017-06-01 |
US20200369972A1 (en) | 2020-11-26 |
CA3003953C (en) | 2023-10-17 |
EA035184B1 (ru) | 2020-05-12 |
US20180355266A1 (en) | 2018-12-13 |
SG11201804366RA (en) | 2018-06-28 |
EP3380589A1 (de) | 2018-10-03 |
WO2017089212A1 (de) | 2017-06-01 |
US10781385B2 (en) | 2020-09-22 |
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