CN104837872B - 乙烯‑乙烯基酯共聚物和(甲基)丙烯酸烷基酯构成的聚合物组合物,其制备方法及其作为原油、矿物油或矿物油产品的倾点下降剂的用途 - Google Patents
乙烯‑乙烯基酯共聚物和(甲基)丙烯酸烷基酯构成的聚合物组合物,其制备方法及其作为原油、矿物油或矿物油产品的倾点下降剂的用途 Download PDFInfo
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- CN104837872B CN104837872B CN201380064066.0A CN201380064066A CN104837872B CN 104837872 B CN104837872 B CN 104837872B CN 201380064066 A CN201380064066 A CN 201380064066A CN 104837872 B CN104837872 B CN 104837872B
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- 239000000203 mixture Substances 0.000 title claims abstract description 98
- 229920000642 polymer Polymers 0.000 title claims abstract description 81
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 52
- 239000010779 crude oil Substances 0.000 title claims abstract description 43
- 229920001567 vinyl ester resin Polymers 0.000 title claims abstract description 43
- 125000005250 alkyl acrylate group Chemical group 0.000 title claims abstract description 41
- 239000002480 mineral oil Substances 0.000 title claims abstract description 34
- 235000010446 mineral oil Nutrition 0.000 title claims abstract description 34
- 230000000994 depressogenic effect Effects 0.000 title claims abstract description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000005977 Ethylene Substances 0.000 title abstract description 3
- 238000002360 preparation method Methods 0.000 title description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims description 71
- 239000002904 solvent Substances 0.000 claims description 37
- 229910052799 carbon Inorganic materials 0.000 claims description 34
- 229930195733 hydrocarbon Natural products 0.000 claims description 29
- 150000002430 hydrocarbons Chemical class 0.000 claims description 29
- 239000003921 oil Substances 0.000 claims description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims description 26
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000003129 oil well Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- -1 alkyl vinyl ethers Chemical class 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 24
- 229920001577 copolymer Polymers 0.000 description 22
- 150000002148 esters Chemical class 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 150000001721 carbon Chemical group 0.000 description 14
- 239000012141 concentrate Substances 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 9
- 239000001993 wax Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229920000578 graft copolymer Polymers 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 7
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229960000735 docosanol Drugs 0.000 description 5
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosanyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical class C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 125000002619 bicyclic group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- KQNPFQTWMSNSAP-UHFFFAOYSA-N alpha-isobutyric acid Natural products CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 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 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 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 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 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
- HOWGUJZVBDQJKV-UHFFFAOYSA-N n-propyl-nonadecane Natural products CCCCCCCCCCCCCCCCCCCCCC HOWGUJZVBDQJKV-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Natural products CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- 235000005956 Cosmos caudatus Nutrition 0.000 description 1
- 244000293323 Cosmos caudatus Species 0.000 description 1
- 239000004439 Isononyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241000545760 Unio Species 0.000 description 1
- 239000007877 V-601 Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- ZZUXGPFNNBRUEG-UHFFFAOYSA-N dodecane prop-2-enoic acid Chemical compound CCCCCCCCCCCC.C(C=C)(=O)O ZZUXGPFNNBRUEG-UHFFFAOYSA-N 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N n-decyl alcohol Natural products CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DNPFOADIPJWGQH-UHFFFAOYSA-N octan-3-yl prop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C=C DNPFOADIPJWGQH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical class CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
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Abstract
本发明涉及可通过在至少一种乙烯‑乙烯基酯共聚物存在下自由基聚合至少两种不同的(甲基)丙烯酸烷基酯而获得的聚合物组合物,其中使用包含具有直链C12‑C60烷基的(甲基)丙烯酸烷基酯和与其不同的具有直链C1‑C11烷基和/或支化C4‑C60烷基的(甲基)丙烯酸烷基酯的混合物作为所述(甲基)丙烯酸烷基酯。本发明进一步涉及该聚合物组合物作为原油、矿物油或矿物油产品的倾点下降剂的用途。
Description
本发明涉及可通过在至少一种乙烯-乙烯基酯共聚物存在下自由基聚合至少两种不同的(甲基)丙烯酸烷基酯而获得的聚合物组合物,其中所用的(甲基)丙烯酸烷基酯为包含具有直链C12-C60烷基的(甲基)丙烯酸烷基酯和不同的具有直链C1-C11烷基和/或支化C4-C60烷基和/或环状C5-C20烷基的(甲基)丙烯酸烷基酯的混合物。本发明进一步涉及该聚合物组合物作为原油、矿物油或矿物油产品的倾点下降剂的用途。
地下矿物油地层通常具有较高的温度。在将原油开采至地表之后,采出的原油根据开采温度和储存或运输条件而因此以或高或低的程度冷却。
根据其来源,原油具有不同比例的蜡,所述蜡基本上由长链正构链烷烃构成。根据原油类型,该链烷烃的比例通常可占原油重量的1-30%。当温度在冷却期间降至低于特定水平时,所述链烷烃可结晶,通常呈片状。沉淀的链烷烃显著破坏了油的流动性。片状正构链烷烃晶体可形成一种包封原油的纸牌屋(houses-of-cards)结构,从而使得尽管主要部分仍为液体,原油也停止流动。在冷却期间油试样仍正好流动时的最低温度称为倾点(“流动点”)。为了测量倾点,使用标准化测试方法。沉淀的链烷烃可堵塞过滤器、泵、管道和其他设备或者沉积于罐中,因此必需高水平清洁。
油藏的油藏温度通常高于室温,例如为40-100℃。原油在仍温热时从该油藏中采出,且在开采期间或之后或快或慢地自然冷却至室温,或者在相应的气候条件下冷却至更低的温度。原油可能具有高于室温的倾点,从而使得该类原油可在开采期间或之后固化。
已知可借助合适的添加剂降低原油的倾点。这可防止链烷烃在采出原油的冷却期间沉淀。合适的添加剂首先防止形成所述的纸牌屋结构,由此降低原油的固化温度。此外,添加剂可促进形成细碎、良好结晶的非附聚 链烷烃晶体,从而确保油的运输不受干扰。该添加剂也称为倾点下降剂或流动改进剂。
链烷烃抑制剂或蜡抑制剂是指旨在防止链烷烃或石蜡在与原油或其他含蜡油和/或矿物油产品接触的表面上沉积的那些物质。
已知乙烯共聚物作为流动改进剂的用途,尤其是乙烯和不饱和酯的共聚物的用途。其实例描述于DE-A-21 02 469或EP 84 148 A2中。
DE-A-16 45 785公开了具有降低的倾点的燃料油混合物。所述混合物包含至少3重量%具有含至少18个碳原子的未支化饱和侧链的聚合物,例如不饱和单羧酸和二羧酸的烷基酯的均聚物或共聚物以及各种烷基乙烯基醚的均聚物或共聚物。
DE-A-20 47 448公开了用于降低链烷烃基原油的粘度的添加剂。所述添加剂为聚乙烯醚和乙烯-乙酸乙烯酯共聚物的混合物。
EP 486 836A1公开了矿物油中间馏分油,例如汽油、柴油或燃料油,其包含聚合物添加剂以改进寒冷条件下的流动性能。所述聚合物添加剂为常规乙烯基流动改进剂如乙烯和乙酸乙烯酯、丙酸乙烯酯或丙烯酸乙基己酯的共聚物与(甲基)丙烯酸直链或支化C8-C18烷基酯和/或直链或支化C18-C28烷基乙烯基醚的共聚物以40:60-95:5重量比的组合,且所述(甲基)丙烯酸烷基酯和/或烷基乙烯基醚的共聚物和所述常规流动改进剂可呈混合物的形式或者所述(甲基)丙烯酸烷基酯和/或烷基乙烯基醚的共聚物可全部或部分接枝在所述常规流动改进剂上。所述烷基优选为未支化的,但可存在至多20重量%的环状和/或支化结构部分。在制备接枝共聚物的唯一实施例中,丙烯酸正十二烷基酯和正十八烷基乙烯基醚接枝至具有约2500g/mol平均摩尔质量Mn的乙烯和丙酸乙烯酯的共聚物上。用于该制备的溶剂为异十一烷,且在随后的稀释阶段使用芳族溶剂。
US 4,608,411公开了用于防止蜡从原油中沉积的接枝共聚物。主链由乙烯和选自C2-C18单羧酸的乙烯酯、不饱和单羧酸的C1-C12酯或不饱和α,β-二羧酸或其酯或酐的单体的共聚物构成。在其上接枝丙烯酸烷基酯的均聚物或共聚物,其中其烷基具有至少12个碳原子且至少20%的烷基具有至少22个碳原子。所提出的溶剂为各种烃。
该类用作倾点下降剂的接枝共聚物通常在化学生产场所制备,并将产物由此运输至应用场所如油田或海上平台。该应用场所可为地球的寒冷区域。为了节约运输成本,通常制备所述接枝共聚物于烃中的浓缩物,例如具有50-80重量%聚合物的聚合物含量的浓缩物。该浓缩物可直接使用或者可由用户以所需方式现场配制以获得即用型配制剂。例如,可用溶剂稀释和/或添加其他添加剂。
特别有利的倾点下降剂可通过使用具有C18-C22碳基团的(甲基)丙烯酸烷基酯制备所述基于乙烯-乙烯基酯共聚物的接枝共聚物而获得。然而,该产品的缺点在于其在烃中的溶液,尤其是所述浓缩物可在冷却至室温期间固化。因此,必须首先将它们熔融以使用,这意味着用户的额外工作。
因此,本发明的目的是提供改进的用于原油的倾点下降剂,且这些应可以类似于已知产品通过在乙烯-乙烯基酯共聚物存在下自由基聚合(甲基)丙烯酸烷基酯而获得。所述改进的产品应对倾点具有与已知产品相同的影响。然而,它们还应在于烃中的浓缩溶液中为液体,且因此应可以以简单方式将其添加至原油中。
因此,已发现了可通过在至少一种乙烯-乙烯基酯共聚物(B)存在下自由基聚合单烯属不饱和单体(A)而获得的聚合物组合物:
■单体(A)包含基于所有单体(A)的量为至少70重量%的(甲基)丙烯酸烷基酯(A1),
■乙烯-乙烯基酯共聚物(B)包含55-85重量%的乙烯和15-45重量%通式H2C=CH-O-(O)C-R1(III)的乙烯基酯,其中R1为H或C1-C4烃基,且
■单体(A)的量为70-90重量%,乙烯-乙烯基酯共聚物(B)的量为10-30重量%,基于单体(A)和乙烯-乙烯基酯共聚物(B)一起的总和,且其中(甲基)丙烯酸烷基酯(A1)为如下物质的混合物:
(A1a)50-99摩尔%的至少一种通式H2C=C(R2)-COOR3的(甲基)丙烯酸烷基酯(A1a),其中R2为H或甲基且R3为具有12-60个碳原子的直链烷基,和
(A1b)1-49摩尔%的至少一种通式H2C=C(R2)-COOR4的(甲基)丙烯酸烷基酯(A1b),其中R2如已定义的那样且R4为选自基团R4a,R4b和R4c的
饱和脂族烃基,且所述基团各自定义如下:
R4a:具有1-11个碳原子的直链烷基,
R4b:具有4-60个碳原子的支化烷基,且
R4c:具有5-20个碳原子的环状烃基,
条件是(A1a)和(A1b)的量的总和相加为100摩尔%。
在本发明优选的实施方案中,所述聚合物组合物进一步包含烃,更优选具有≥60℃闪点的烃作为溶剂。
在本发明的另一方面中,发现了所述聚合物组合物(优选溶于烃中)作为原油、矿物油和/或矿物油产品的倾点下降剂的用途,其中将至少一种所述类型的聚合物组合物添加至原油、矿物油和/或矿物油产品中。
本发明的具体细节如下:
所用的起始物质
单体(A)
所用的单体(A)为单烯属不饱和单体,条件是至少70重量%的单体(A)为(甲基)丙烯酸烷基酯(A1)。根据本发明,(甲基)丙烯酸烷基酯(A1)为至少一种(甲基)丙烯酸烷基酯(A1a)和至少一种(甲基)丙烯酸烷基酯(A1b)的混合物。
(甲基)丙烯酸烷基酯(A1)
(甲基)丙烯酸烷基酯(A1a)
(甲基)丙烯酸烷基酯(A1a)具有通式H2C=C(R2)-COOR3,其中R2为H或甲基且R3为具有12-60个碳原子,优选16-30个碳原子,更优选18-24个碳原子,例如18-22个碳原子的直链烷基。R3可为1-十六烷基、1-十八烷基、1-十九烷基、1-二十烷基、1-二十一烷基、1-二十二烷基、1-二十四烷基、1-二十六烷基、1-二十八烷基或1-三十烷基。应理解的是还可使用各种(甲基)丙烯酸烷基酯(A1a)的混合物。例如,可使用其中R3表示C16和C18基团或C18、C20和C22基团的混合物。
在优选实施方案中,所用的至少一种(甲基)丙烯酸烷基酯(A1a)为(甲基)丙烯酸1-二十二烷基酯((丙烯酸)山萮基酯),即R3为具有22个碳原子的直链烷基。在本发明特别优选的实施方案中,所用(甲基)丙烯酸烷基酯(A1a)的至少40重量%为(甲基)丙烯酸1-二十二烷基酯。有利地,可使用包含(甲基)丙烯酸1-十八烷基酯、(甲基)丙烯酸1-二十烷基酯和(甲基)丙烯酸1-二十二烷基酯的混合物。各种(甲基)丙烯酸酯的该类混合物也可商购获得。除所提及的(甲基)丙烯酸C18/C20/C22酯之外,它们还可包含少量作为副产物的具有更高或更低碳数量的(甲基)丙烯酸酯。例如,混合物可包含40-55重量%(甲基)丙烯酸1-十八烷基酯、10-15重量%(甲基)丙烯酸1-二十烷基酯和35-45重量%(甲基)丙烯酸1-二十二烷基酯。
(甲基)丙烯酸烷基酯(A1b)
(甲基)丙烯酸烷基酯(A1b)具有通式H2C=C(R2)-COOR4,其中R2如已定义的那样且R4为选自基团R4a,R4b和R4c的饱和脂族烃基,且所述基团各自定义如下:
R4a:具有1-11个,优选2-10个,更优选2-6个碳原子的直链烷基,
R4b:具有4-60个,优选4-30个,更优选4-17个碳原子的支化烷基,且
R4c:具有5-20个,优选6-12个,更优选6-10个,例如10个碳原子的环状烷基。
直链烷基R4a的实例包括乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基和正十一烷基,优选正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基和正癸基,特别优选乙基、正丙基、正丁基、正戊基和正己基,非常特别优选正丁基。
支化烷基R4b可为单支化的或多重支化的。支化烷基R4b的实例包括异丁基、叔丁基、2,2’-二甲基丙基、2-乙基己基、2-丙基庚基、异壬醇、异癸基、异十三烷基、异十七烷基,优选叔丁基、2-乙基己基和2-丙基庚基。
环状烷基R4c可为单环或多环的,尤其是双环的。其可额外被直链和/或支化烷基取代。环状烷基R4c的实例包括环戊基、环己基、4-甲基环己基、环庚基、双环[2.2.1]庚基、双环[2.2.2]辛基或2-(1,7,7-三甲基双环[2.2.1]庚基。
在本发明的一个实施方案中,基团R4为基团R4a和R4b。
在优选实施方案中,基团R4为基团R4b,优选具有4-30个碳原子的基团R4b,更优选具有4-17个碳原子的基团R4b。
在另一优选实施方案中,基团R4为基团R4c,优选具有6-10个碳原子的 基团R4c。
应理解的是也可使用各种(甲基)丙烯酸烷基酯(A1b)的混合物。
其他单体(A)
除单体(A1)之外,还可任选使用不同于单体(A1),即单体(A1a)和(A1b)的其他单烯属不饱和单体(A2)。借助其他单体(A)以及(甲基)丙烯酸烷基酯(A1),可改变本发明聚合物组合物的性能并使其与所需性能匹配。本领域技术人员可进行适当的选择。
其他单体(A2)尤其可为包含烃基且不对应于上述单体(A1a)和(A1b)定义的(甲基)丙烯酸酯。
这些尤其包括通式H2C=CHR2-COOR5的(甲基)丙烯酸酯(A2a),其中R2如上所定义,且R5为具有6-30个,优选6-18个碳原子的未取代或烷基取代的芳族烃基。芳族烃基R5的实例包括苯基、4-甲基苯基、苄基或2-苯基乙基。
其他单体(A2)还可为通式H2C=C(R2)-COOR6的(甲基)丙烯酸酯(A2b),其中R2为H或甲基,且R6为具有1-60个,优选2-30个碳原子且可被OH基团取代和/或其中不相邻的碳原子可被氧原子替代的直链或支化脂族和/或芳族烃基。换言之,R3基团可因此包含OH基团和/或醚基-O-。(甲基)丙烯酸酯(A2b)的实例包括(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、丙烯酸苯氧基乙酯或聚丙二醇单(甲基)丙烯酸酯。
其他单体(A2)还可为通式H2C=C(R2)-COOR7的(甲基)丙烯酸酯(A2c),其中R2为H或甲基且R7为具有5-30个,优选6-17个碳原子的未取代或烷基取代的饱和环状脂族烃基。基团R7的实例为环己基。
其他单体(A2)还可为通式H2C=CH-O-(O)C-R7的乙烯基酯(A2d),其中R7为具有1-60个碳原子,优选2-30个碳原子的直链或支化烷基。基团R7的实例包括甲基、乙基、正丙基或正丁基。
单体(A)的量
根据本发明,50-99摩尔%的单体(A1)为单体(A1a)且1-50摩尔%的单体(A1)为单体(A1b),条件是(A1a)和(A1b)的总和相加为100摩尔%。换言之,单体(A1)因此仅为单体(A1a)和(A1b)的混合物。优选使用50-90摩尔%单体 (A1a)和10-50摩尔%单体(A1b),特别优选使用70-90摩尔%单体(A1a)和10-30摩尔%单体(A1b)。
当使用环状烷基R4c时,发现特别有用的是使用50-80摩尔%单体(A1a)和20-50摩尔%单体(A1b),优选55-75摩尔%单体(A1a)和25-45摩尔%单体(A1b)。
根据本发明,(甲基)丙烯酸烷基酯(A1)的量基于所有单体(A)的总量为至少70重量%,优选至少80重量%,更优选至少95重量%。最优选单体(A)仅为(甲基)丙烯酸烷基酯(A1)。
乙烯-乙烯基酯共聚物(B)
所用的乙烯-乙烯基酯共聚物(B)包含乙烯和通式H2C=CH-O-(O)C-R1的乙烯基酯。在该式中,R1为H或C1-C4烃基,例如甲基、乙基、正丙基或正丁基。R1优选为H、甲基或乙基,更优选为甲基。
除乙烯和乙烯基酯之外,还可任选存在其他单体。然而,该类其他单体的量基于所有单体的量应不超过20重量%,优选10重量%,特别优选不存在除乙烯和乙烯基酯之外的其他单体。
乙烯-乙烯基酯共聚物(B)中的乙烯的量基于所有单体的量为55-85重量%,且乙烯基酯的量为15-45重量%。
优选地,乙烯的量为55-75重量%,且乙烯基酯的量为25-45重量%,更优选为30-40重量%;最优选乙烯的量为60-70重量%,且乙烯基酯的量为30-40重量%。
所用的乙烯-乙烯基酯共聚物(B)的重均分子量Mw优选为至少30000g/mol,例如30000-200000g/mol,优选为50000-150000g/mol。
聚合物组合物及其制备
本发明的聚合物组合物可通过在乙烯-乙烯基酯共聚物(B)存在下自由基聚合单体(A)而获得。
单体(A)与乙烯-乙烯基酯共聚物(B)的混合比根据待合成的聚合物组合物所需的性能选择,且单体(A)的量基于单体(A)和乙烯-乙烯基酯共聚物(B)的总和应为至少50重量%。一般而言,单体(A)的量为70-90重量%,且乙烯-乙烯基酯共聚物(B)的量为10-30重量%。优选地,单体(A)的量为75-85 重量%,且乙烯-乙烯基酯共聚物(B)的量为15-25重量%。
溶剂
在本发明的优选实施方案中,所述聚合物组合物进一步包含合适的溶剂。所述聚合物组合物应均匀分散于其中,优选溶于其中。原则上,所有满足这些要求的溶剂都是合适的。当然也可使用不同溶剂的混合物。
所述聚合物组合物在溶剂中的浓度由本领域技术人员根据待制备的配制剂所需的性能选择。在本发明的优选实施方案中,所述浓度为20-80重量%,优选30-70重量%,例如40-55重量%聚合物组合物,基于包括所用溶剂在内的所有组合物组分的总和。使用该浓缩物的优点在于可保持由生产场所至应用场所如采油设备的低运输成本。
所述溶剂可为例如包含饱和脂族烃基的非极性溶剂,优选具有≥60℃闪点的那些。该类溶剂的实例包括饱和脂族烃、饱和脂族醇或饱和脂族羧酸与饱和脂族醇的酯,条件是所述溶剂各自具有≥60℃的闪点。醇的实例包括具有至少8个碳原子的脂族醇,例如1-辛醇、1-癸醇或1-十二烷醇。酯的实例包括具有至少8个碳原子的饱和脂肪酸与饱和脂族醇的酯,例如月桂酸甲酯或硬脂酸甲酯。各种脂族酯的工业混合物可商购获得。在本发明的另一实施方案中,可使用脂族或脂环族二羧酸的酯,例如环己烷-1,2-二甲酸的二烷基酯如环己烷-1,2-二甲酸二异壬基酯。
在本发明的优选实施方案中,所用的溶剂为烃。这些可为脂族烃、脂环族烃和/或芳族烃。优选具有≥60℃闪点的烃或烃混合物。
所述烃可例如为饱和脂族溶剂或溶剂混合物。这些可为链烷属的或环烷属的,即饱和环状烃。优选具有至少175℃的沸点且优选具有≥60℃闪点的高沸点脂族烃。具有≥60℃闪点的合适烃包括例如正十一烷(闪点为60℃,沸点为196℃)或正十二烷(闪点为71℃,沸点为216℃)。可优选使用烃的工业混合物,例如链烷烃的混合物、链烷烃和环烷烃的混合物或异构链烷烃的混合物。对本领域技术人员显而易见的是所述工业混合物仍可包含少量芳烃或不饱和烃的残留物。然而,芳烃和/或不饱和烃的含量应通常<1重量%,优选<0.5重量%,更优选<0.1重量%。饱和脂族溶剂的工业混合物可商购获得,例如D系列或D系列的工业混合物。
所述烃也可为芳族溶剂或溶剂混合物。在本发明的一个实施方案中,所述烃为甲苯或包含甲苯的溶剂混合物。在另一实施方案中,所述烃为具有至少175℃沸点且优选具有≥60℃闪点的高沸点芳烃。具有≥60℃闪点的合适芳烃包括例如萘。可优选使用芳烃的工业混合物。芳族溶剂的工业混合物可商购获得,例如A系列或系列的工业混合物。
可特别有利地使用具有≥60℃闪点的脂族烃与具有≥60℃闪点的芳烃的混合物。
自由基聚合
该自由基聚合的实施原则上是本领域技术人员所已知的。自由基聚合原则上可借助本体聚合,通过在乙烯-乙烯基酯共聚物(B)和用于自由基聚合的引发剂存在下且在不存在溶剂下聚合单体(A)而进行。该细节描述于EP486836A1第4页第38-46行中。
在本发明的优选实施方案中,所述制备借助溶液聚合进行。适于该目的的溶剂原则上为单体(A)、乙烯-乙酸乙烯酯共聚物(B)和所形成的聚合物组合物在具有充分的溶解性(即使在所需的高浓度下)或者至少均匀分散且在聚合期间不参与任何不希望的反应的那些。更特别地,它们自身应不可聚合且没有任何过度的调节作用。
所述溶剂优选为烃,优选上文所述的脂族烃和/或芳烃,尤其是具有≥60℃闪点的那些。有利地,在该程序的情况下获得了包含溶剂的可用作倾点下降剂的即用型聚合物组合物,而在聚合后无需任何其他后处理步骤。
对在溶液中的聚合而言,首先提供处于所选溶剂,优选烃中的(甲基)丙烯酸烷基酯(A1a)、(甲基)丙烯酸烷基酯(A1b)、任选的其他单体(A)和共聚物(B)的溶液。所述溶剂可例如为甲苯。
溶解通过剧烈混合各组分,例如通过搅拌而进行。例如,可首先溶解单体(A),然后向所述溶液中添加固体乙烯-乙烯基酯共聚物(B),或者首先溶解乙烯-乙烯基酯共聚物(B)并添加单体(A)。溶解可通过升高温度,例如升至约50-80℃而促进。
在本发明的一个变型中,处于烃,优选具有≥60℃闪点的脂族烃中的(甲基)丙烯酸烷基酯(A1a)的溶液可通过如下方式提供:在烃中用醇R3OH酯化 (甲基)丙烯酸,并在与用于聚合的其他组分混合之后将所得溶液用于聚合。酯化可通过原则上为本领域技术人员所已知的方法,例如通过EP 486 836A1所述的方法进行。
自由基聚合使用用于自由基聚合的热引发剂进行。当然,对所用的引发剂加以选择以使得其可溶于聚合介质中。优选的聚合引发剂包括油溶性偶氮化合物,尤其是具有50-70℃的10小时半衰期的那些。合适引发剂的实例包括2,2’-偶氮双(2-甲基丙酸二甲酯)(10小时半衰期,约66℃)、2,2’-偶氮双(2-甲基丁腈)(10小时半衰期,约67℃)或2,2’-偶氮双(2,4-二甲基戊腈)(10小时半衰期,约51℃)。该类引发剂可商购获得(购自Wako)。单体(A)与引发剂的重量比通常为约100:1-150:1,优选125:1-140:1。在聚合开始时,可存在全部量的引发剂,但优选逐步添加引发剂。添加可分批或连续,优选连续进行。
此外,可以以原则上已知的方式添加分子量调节剂。调节剂的实例包括醇如异丙醇、烯丙醇或丁烯-2-醇,硫醇如乙硫醇,或醛如巴豆醛。分子量调节剂的量基于单体(A)通常为1-4重量%,优选基于单体(A)为2-3重量%。
自由基聚合以原则上已知的方式通过加热反应混合物而引发。聚合温度应高于引发剂的10小时半衰期且通常为至少50℃。已发现有用的聚合温度为50-90℃。一般而言,聚合以原则上已知的方式在保护气体如氮气或氩气下进行。
溶液中的聚合可通过首先将起始物质的溶液装入合适的典型的搅拌式反应釜中而进行,合适的话事先实施在所述装置中的溶解。单体(A)在溶剂中的浓度由本领域技术人员根据待制备的混合物所需的性能选择。在本发明的优选实施方案中,所述浓度为40-80重量%,例如45-55重量%。需要的话,向所述溶液中添加一种或多种分子量调节剂。在达到所需的聚合温度之后,将聚合引发剂的溶液逐步添加至待聚合的混合物中。添加持续时间可为0.5-10小时,并非旨在将本发明限制至该范围。在引发剂的添加结束后,通常应为另一聚合时间。这可例如为0.5-5小时。这获得了本发明聚合物混合物的溶液。
借助所述制备方法,可获得聚合物组合物,优选处于溶剂,优选烃中的聚合物组合物。单体(A)在乙烯-乙烯基共聚物(B)存在下的聚合防止了聚合物组分在溶液中彼此分离。当单体(A)—在其他条件相同下—与乙烯-乙烯基酯共聚物(B)分开聚合且在聚合后将由单体(A)形成的聚合物的溶液与乙烯-乙烯基酯共聚物(B)的溶液组合时,聚合反应的结果不同。该类混合物可再次分离。
尽管不希望受限于特定理论,然而该效果可由在聚合期间单体(A)至少部分接枝至乙烯-乙烯基酯共聚物(B)上解释。所述单体的其他部分可在不接枝的情况下聚合。这获得了具有包含单体(A)的侧基的乙烯-乙烯基酯接枝共聚物和包含单体(A)的均聚物或共聚物。以原则上已知的方式,该部分接枝防止了所述两种聚合物组分的分离。还可发生非显著的接枝,且由乙烯-乙烯基酯共聚物(B)和单体(A)的均聚物或共聚物形成“居间配位物”(interjacent complex)。在该配位物中,所述聚合物主要为物理键接的,却是稳定的,例如如US 7,001,903B2所述。
所述配制剂作为倾点下降剂的用途
根据本发明,所得聚合物组合物,尤其是处于烃,优选具有≥60℃闪点的那些中的聚合物组合物可通过将所详述的至少一种聚合物配制剂添加至原油、矿物油和/或矿物油产品中而用作原油、矿物油和/或矿物油产品的倾点下降剂。此外,当然也可使用起倾点下降剂作用的其他配制剂。
倾点下降剂降低了原油、矿物油和/或矿物油产品的倾点。倾点(“流动点”)是指油试样在冷却期间仍正好流动时的最低温度。对倾点的测量使用标准化测试方法。
就本发明的用途而言,可直接使用所述聚合物组合物。
然而,优选使用处于合适溶剂中且除所述溶剂之外还可包含其他组分的聚合物组合物的配制剂。
可使用浓缩物,例如在溶剂中具有50-80重量%聚合物总含量的浓缩物。该浓缩物可借助上述方法制备。然而,也可用其他溶剂稀释,优选用脂族烃和/或芳烃和/或用其他组分将其配制。
例如,可向所述配制剂中添加额外的蜡分散剂。蜡分散剂稳定所形成 的链烷烃晶体并防止其沉降。所用的蜡分散剂可例如为烷基酚、烷基酚-甲醛树脂或十二烷基苯磺酸。可用配制剂的浓度可例如为20-50重量%,优选25-40重量%的根据本发明制得的聚合物和除溶剂之外的任选其他组分,该数字基于包括溶剂在内的所有组分的总量。尽管所述配制剂当然在化工厂中生产,然而可有利地现场生产即用型配制剂,即例如直接在采油场所生产。
本发明的用途通过将本发明聚合物组合物或包含聚合物组合物的配制剂添加至原油、矿物油和/或矿物油产品中,优选添加至原油中而实现。
使用至少一种(甲基)丙烯酸烷基酯(A1a)和至少一种(甲基)丙烯酸烷基酯(A1b)的组合制备的本发明聚合物组合物的优点在于即使在室温和约45-70重量%浓度下,其在烃中的溶液仍为液态。该浓缩物可无需在使用前熔融该浓缩物而使用。这使得显著更容易地使用该产品操作。
所述配制剂通常以使得聚合物组合物的添加量基于油为50-1500ppm的量使用。该量优选为100-1000ppm,更优选为250-600ppm,例如为300-600ppm。该量基于所述聚合物组合物自身,不包括所存在的任何溶剂以及所述配制剂的任选其他组分。
在本发明的优选实施方案中,所述油为原油且将所述配制剂注入原油管线中。注入可优选在油田,即原油管线起始处进行,但注入当然还可在其他地点进行。更特别地,所述管线可为海上平台的上岸导管(Festland führt)。对海上平台和炼油厂而言,防爆特别重要,因此基于具有≥60℃闪点的溶剂的本发明配制剂非常显著地简化了操作。此外,原油在海上平台的水下上岸导管中的冷却自然特别快,尤其是当所述管线处于冷水(例如具有低于10℃水温)中。
在本发明的另一实施方案中,所述油为原油且将所述配制剂注入采油井中。此时,所述采油井也可尤其为导向海上平台的采油井。注入优选大致在油从地层流入采油井中的地点进行。以此方式可防止原油在采油井中固化或者其粘度过度增大。
所述配制剂的其他用途
本发明的聚合物组合物当然还可用于其他目的。
在本发明的另一实施方案中,上文详述的聚合物组合物,尤其是处于溶剂,尤其烃中的配制剂用于防止与原油、矿物油和/或矿物油产品接触的表面上的蜡沉积物。该用途通过将至少一种上文详述的聚合物配制剂添加至原油、矿物油和/或矿物油产品中而实施。已提及了优选的配制剂,且使用方式也类似于作为倾点下降剂的用途。除本发明配制剂之外,当然也可使用起蜡抑制剂作用的其他配制剂。
下文实施例旨在详细阐述本发明:
A制备聚合物混合物
所用的起始物质:
表1中实施例3的实验方法
80:20(重量/重量)丙烯酸山萮醇酯/丙烯酸2-丙基庚酯的共聚物
在具有Teflon搅拌器、夹套式盘管冷凝器和Dosimat的四颈烧瓶中,在75℃下将216.8g丙烯酸山萮醇酯和54.2g丙烯酸丙基庚酯溶于217g甲苯中,然后在搅拌下添加66.4g上述乙烯-乙酸乙烯酯共聚物并溶解。在78-80℃下,经4小时计量加入8.2g溶于3.2g甲苯中的烯丙醇,然后计量加入1.15g溶于31.4g甲苯中的2,2’-偶氮异丁酸二甲酯引发剂(WakoV-601)。在82℃下进一步聚合2.5小时之后,将所述混合物用106.3g甲苯稀释并冷却至40℃,然后添加0.42g三乙醇胺。在又搅拌30分钟之后,将所述混合物经280μm快筛(Schnellsieb)过滤。
所得溶液具有48重量%聚合物组合物的浓度。
其他实施例和对比实施例通过相同的方法实施,不同之处在于改变第二丙烯酸酯的类型以及丙烯酸山萮醇酯与第二丙烯酸酯之比。所选的单体和比例各自汇总于表1中。在所有实验中,所得聚合物组合物的浓度均为48重量%。
B所得聚合物组合物的性能测试
使用所得的共聚物溶液实施如下各测试:
测定共聚物的K值
所得共聚物的K值(根据H.Fikentscher,Cellulosechemie,第13卷,第58-64以及71-74页(1932)测量)在2%(重量/体积)甲苯溶液中测定。所述值汇 总于表1中。
测定分子量
所得各共聚物的数均分子量Mn和重均分子量Mw通过凝胶渗透色谱法在作为溶剂的四氢呋喃中测定。所述值汇总于表1中。
测定粘度
在上述试验中获得的各接枝共聚物溶液的运动粘度在50℃下用乌贝洛德粘度计测定。所述值汇总于表1中。
评价稳定性
测定各聚合物溶液的稳定性,尤其就是否保持具有长时稳定性且不具有相分离倾向的溶液而言。为此,将合成后制得的配制剂储存于室温下。如果在储存开始后24小时内发生明显的相分离,则评估为负(-),否则为(+)。所述值汇总于表1中。
测定倾点
倾点的测定根据ASTM D 5853“原油倾点的测试方法”进行。倾点是所测试的油试样仍正好自由流动时的最低温度。为此,根据ASTM D 5853,将油试样以各自为3℃的步长冷却,并在每步之后测试流动性。对所述测试而言,使用获自德国西南部“Landau”油田的具有37API度和27℃倾点的原油(Wintershall Holding GmbH)。为了测定倾点的降低,将待测试的接枝共聚物以在每种情况下基于原油为100ppm、300ppm或1500ppm聚合物的浓度用于所述油中。所述值汇总于表1中。在一些试样上测量两次或三次。在这些情况下,所有测量值均报告在表中。
表1:实施例和对比实施例的结果
表1(续表):实施例和对比实施例的结果
表1(续表):实施例和对比实施例的结果
所述实施例和对比实施例显示,在除丙烯酸山萮醇酯之外还使用其他(甲基)丙烯酸烷基酯(A1b)下,可获得即使作为浓缩物(48重量%聚合物组合物)在甲苯溶液中仍为液态的聚合物组合物。仅包含丙烯酸山萮醇酯的聚合物混合物在相同的条件下在甲苯溶液中为固态。
然而,并非所有(甲基)丙烯酸烷基酯都同等有效。具有支化烷基的(甲基)丙烯酸烷基酯或者具有较短直链烷基的那些是有效的。使用包含OH基或醚基的丙烯酸酯不能获得液态产物,而是固态产物。同样地,在单体(A1b)的比例超过50摩尔%的情况下,聚合物混合物作为倾点下降剂的性能非常显著地变劣。包含73摩尔%丙烯酸叔丁酯的聚合物组合物为液态,然而作为倾点下降剂完全无效。
在实验19中获得作为倾点下降剂的非常优异的效果。所述聚合物使用75重量%丙烯酸山萮醇酯和25重量%甲基丙烯酸环己酯的单体混合物制备。
Claims (26)
1.一种可通过在至少一种乙烯-乙烯基酯共聚物(B)存在下自由基聚合单烯属不饱和单体(A)而获得的聚合物组合物:
■单体(A)包含基于所有单体(A)的量为至少70重量%的(甲基)丙烯酸烷基酯(A1),
■乙烯-乙烯基酯共聚物(B)包含55-85重量%的乙烯和15-45重量%通式H2C=CH-O-(O)C-R1的乙烯基酯,其中R1为H或C1-C4烃基,且
■单体(A)的量为70-90重量%,乙烯-乙烯基酯共聚物(B)的量为10-30重量%,基于单体(A)和乙烯-乙烯基酯共聚物(B)一起的总和,
其中(甲基)丙烯酸烷基酯(A1)为如下物质的混合物:
(A1a)50-99摩尔%的至少一种通式H2C=C(R2)-COOR3的(甲基)丙烯酸烷基酯(A1a),其中R2为H或甲基且R3为具有18-30个碳原子的直链烷基,和
(A1b)1-49摩尔%的至少一种通式H2C=C(R2)-COOR4的(甲基)丙烯酸烷基酯(A1b),其中R2为H或甲基且R4为选自基团R4a,R4b和R4c的烃基,且所述基团各自定义如下:
R4a:具有1-11个碳原子的直链烷基,
R4b:具有4-60个碳原子的支化烷基,且
R4c:具有5-20个碳原子的环状烃基,
条件是(A1a)和(A1b)的量的总和相加为100摩尔%。
2.根据权利要求1的聚合物组合物,其中R3为具有18-24个碳原子的直链烷基。
3.根据权利要求1的聚合物组合物,其中R4a为具有2-6个碳原子的直链烷基。
4.根据权利要求2的聚合物组合物,其中R4a为具有2-6个碳原子的直链烷基。
5.根据权利要求1-4中任一项的聚合物组合物,其中R4b为具有4-30个碳原子的支化烷基。
6.根据权利要求1-4中任一项的聚合物组合物,其中R4b为具有4-17个碳原子的支化烷基。
7.根据权利要求1-4中任一项的聚合物组合物,其中R4c为具有6-10个碳原子的环状烷基。
8.根据权利要求5的聚合物组合物,其中R4c为具有6-10个碳原子的环状烷基。
9.根据权利要求1-4中任一项的聚合物组合物,其中所用的乙烯-乙烯基酯共聚物(B)的平均分子量Mw为至少30000g/mol。
10.根据权利要求1-4中任一项的聚合物组合物,其中乙烯-乙烯基酯共聚物(B)包含55-75重量%乙烯和25-40重量%乙烯基酯。
11.根据权利要求1-4中任一项的聚合物组合物,其中乙烯-乙烯基酯共聚物(B)包含60-75重量%乙烯和25-40重量%乙烯基酯。
12.根据权利要求1-4中任一项的聚合物组合物,其中单体(A)的量为75-85重量%且乙烯-乙烯基酯共聚物(B)的量为15-25重量%,基于单体(A)和乙烯-乙烯基酯共聚物(B)的总和。
13.根据权利要求1-4中任一项的聚合物组合物,其进一步包含烃作为溶剂。
14.根据权利要求13的聚合物组合物,其中所述烃具有≥60℃的闪点。
15.根据权利要求13的聚合物组合物,其中所述聚合物组合物在溶剂中的浓度基于混合物所有组分的总和为20-80重量%。
16.根据权利要求14的聚合物组合物,其中所述聚合物组合物在溶剂中的浓度基于混合物所有组分的总和为20-80重量%。
17.根据权利要求1-16中任一项的聚合物组合物作为原油、矿物油和/或矿物油产品的倾点下降剂的用途,包括将至少一种根据权利要求1-16中任一项的聚合物组合物添加至原油、矿物油和/或矿物油产品中。
18.根据权利要求17的用途,其中所用的聚合物组合物进一步包含烃作为溶剂。
19.根据权利要求18的用途,其中所述烃具有≥60℃的闪点。
20.根据权利要求17-19中任一项的用途,其中所用的聚合物组合物额外包含至少一种蜡分散剂。
21.根据权利要求17-19中任一项的用途,其中添加量基于油为50-1500ppm的聚合物组合物。
22.根据权利要求17-19中任一项的用途,其中油为原油并将所述聚合物组合物注入原油管线中。
23.根据权利要求17-19中任一项的用途,其中油为原油并将所述聚合物组合物注入采油井中。
24.根据权利要求22的用途,其中注入在海上平台上进行。
25.根据权利要求23的用途,其中注入在海上平台上进行。
26.根据权利要求1-16中任一项的聚合物组合物在防止与原油、矿物油和/或矿物油产品接触的表面上的蜡沉积物中的用途,包括将至少一种根据权利要求1-16中任一项的聚合物组合物添加至原油、矿物油和/或矿物油产品中。
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EP12197726.8 | 2012-12-18 | ||
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PCT/EP2013/075746 WO2014095412A1 (de) | 2012-12-18 | 2013-12-06 | Polymere zusammensetzungen aus ethylen-vinylester-copolymeren alkyl(meth)acrylaten, verfahren zu deren herstellung und deren verwendung als pour-point-depressants für rohöle, mineralöle oder mineralölprodukte |
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CA (1) | CA2889070C (zh) |
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US11066615B2 (en) | 2015-05-22 | 2021-07-20 | Nouryon Chemicals International B.V. | Copolymers of bicyclic (meth)acrylate and alkyl (meth)acrylate and their use as rheology modifiers in fuels |
CN107624126A (zh) * | 2015-05-22 | 2018-01-23 | 国际壳牌研究有限公司 | 燃料组合物 |
MY196080A (en) * | 2015-05-22 | 2023-03-14 | Shell Int Research | Fuel Composition and use Thereof |
EP3298052B1 (en) * | 2015-05-22 | 2019-03-27 | Akzo Nobel Chemicals International B.V. | Copolymers of bicyclic (meth)acrylates and alkyl (meth)acrylates and their use as rheology modifiers in fuels. |
DE102015226635A1 (de) | 2015-12-23 | 2017-06-29 | Clariant International Ltd | Polymerzusammensetzungen mit verbesserter Handhabbarkeit |
BR112018015586A2 (pt) | 2016-02-05 | 2018-12-26 | Akzo Nobel Chemicals Int Bv | copolímero, conjunto de aditivos para combustíveis, método de preparação de copolímero, método de preparação de conjunto de aditivos para combustível, e uso de polímero ou conjunto de aditivos |
CA3015143C (en) | 2016-03-10 | 2023-10-03 | Basf Se | Aqueous polymer dispersions, a method for their preparation and the use thereof as pour-point depressants for crude oil, petroleum, and petroleum products |
WO2018054892A1 (de) | 2016-09-21 | 2018-03-29 | Basf Se | TERPOLYMERE AUS MALEINSÄUREANHYDRID, ACRYLATEN UND ALPHA-OLEFINEN, INSBESONDERE ZUR VERWENDUNG ALS FLIEßVERBESSERER FÜR ERDÖL |
CA3041834A1 (en) | 2016-12-07 | 2018-06-14 | Basf Se | Aqueous compositions of paraffin inhibitors |
MX2020002740A (es) | 2017-09-11 | 2020-07-21 | Basf Corp | Dispersiones polimericas acuosas, un metodo para su preparacion y uso como depresores del punto de vertido para petroleo crudo, petroleo y productos de petroleo. |
EP3774997A1 (en) | 2018-03-26 | 2021-02-17 | Basf Se | Hyperbranched polyethers and their use, especially as pour point depressant and wax inhibitors |
EP3798261A1 (de) | 2019-09-26 | 2021-03-31 | Clariant International Ltd | Polymerzusammensetzungen und ihre verwendung als pour point depressant in paraffinhaltigen kohlenwasserstoffölen |
CN112877108B (zh) * | 2021-01-21 | 2023-04-28 | 上海应用技术大学 | 一种生物柴油降凝剂组合物及其制备方法与应用 |
CN112898476A (zh) * | 2021-01-21 | 2021-06-04 | 上海应用技术大学 | 一种二元聚合物生物柴油降凝剂及其制备方法与应用 |
WO2023025636A1 (en) | 2021-08-27 | 2023-03-02 | Basf Se | Aqueous dispersions of paraffin inhibitors |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL148099B (nl) | 1966-03-17 | 1975-12-15 | Shell Int Research | Werkwijze voor het verlagen van het vloeipunt van een brandstofmengsel. |
DE2047448A1 (de) | 1970-09-26 | 1972-03-30 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | Additiv zur Viskositatserniedrigung in paraffinbasischen Rohölen |
DE2102469C2 (de) | 1971-01-20 | 1989-06-29 | Basf Ag, 6700 Ludwigshafen | Verwendung von Äthylencopolymerisaten als Zusatz zu Erdöl und Erdölfraktionen |
DE3201541A1 (de) | 1982-01-20 | 1983-07-28 | Basf Ag, 6700 Ludwigshafen | Erdoelmitteldestillate mit verbesserten fliesseigenschaften |
FR2572410B1 (fr) | 1984-10-25 | 1987-09-04 | Elf Aquitaine | Copolymeres d'ethylene greffes utilisables notamment comme additifs pour l'inhibition du depot de paraffines dans les huiles brutes et compositions renfermant les huiles et lesdits additifs |
DE3725059A1 (de) * | 1987-07-29 | 1989-02-09 | Roehm Gmbh | Polymere fliessverbesserer fuer mitteldestillate |
DE3905681A1 (de) * | 1989-02-24 | 1990-08-30 | Basf Ag | Konzentrierte mischungen von pfropfcopolymerisaten aus estern von ungesaettigten saeuren und ethylen-vinylester-copolymerisaten |
DE4036227A1 (de) | 1990-11-14 | 1992-05-21 | Basf Ag | Erdoelmitteldestillate mit verbesserten fliesseigenschaften in der kaelte |
DE19823396A1 (de) | 1998-05-26 | 1999-12-02 | Bayer Ag | Synergistische insektizide Mischungen |
US7541315B2 (en) * | 2003-09-11 | 2009-06-02 | Baker Hughes Incorporated | Paraffin inhibitor compositions and their use in oil and gas production |
EP1674554A1 (de) * | 2004-12-24 | 2006-06-28 | Clariant Produkte (Deutschland) GmbH | Additive für schwefelarme Mineralöldestillate, umfassend Pfropfcopolymer auf Basis von Ethylen-Vinylacetat-Copolymeren |
DE102006001380A1 (de) * | 2006-01-11 | 2007-07-26 | Clariant International Limited | Additive für schwefelarme Mineralöldestillate, umfassend Pfropfcopolymere auf Basis von Ethylen-Vinylacetat-Copolymeren |
FR2943678B1 (fr) * | 2009-03-25 | 2011-06-03 | Total Raffinage Marketing | Polymeres (meth)acryliques de bas poids moleculaire, exempts de composes soufres,metalliques et halogenes et de taux de monomeres residuels faible,leur procede de preparation et leurs utilisations |
ATE547472T1 (de) * | 2009-09-25 | 2012-03-15 | Evonik Rohmax Additives Gmbh | Zusammensetzung zur verbesserung der kaltflusseigenschaften von brennstoffölen |
DE102009060389A1 (de) * | 2009-12-24 | 2011-06-30 | Clariant International Ltd. | Kälteadditive mit verbesserter Fließfähigkeit |
CN102559302B (zh) * | 2011-12-28 | 2014-03-12 | 临沂实能德环保燃料化工有限责任公司 | 一种柴油降凝剂及制备方法 |
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CN104837872A (zh) | 2015-08-12 |
AU2013361819A1 (en) | 2015-05-21 |
WO2014095412A1 (de) | 2014-06-26 |
CA2889070C (en) | 2017-11-28 |
MY178549A (en) | 2020-10-15 |
AR094081A1 (es) | 2015-07-08 |
BR112015013238B1 (pt) | 2021-05-25 |
BR112015013238A2 (pt) | 2017-07-11 |
ES2634864T3 (es) | 2017-09-29 |
AU2013361819B2 (en) | 2017-02-02 |
RU2654059C9 (ru) | 2018-12-03 |
RU2654059C2 (ru) | 2018-05-16 |
RU2015129305A (ru) | 2017-02-02 |
CA2889070A1 (en) | 2014-06-26 |
EP2935346A1 (de) | 2015-10-28 |
EP2935346B1 (de) | 2017-04-26 |
MX2015007941A (es) | 2015-10-09 |
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