DE69231820T2 - Biologisch abbaubare Schmieröle und funktionelle Flüssigkeiten - Google Patents
Biologisch abbaubare Schmieröle und funktionelle FlüssigkeitenInfo
- Publication number
- DE69231820T2 DE69231820T2 DE69231820T DE69231820T DE69231820T2 DE 69231820 T2 DE69231820 T2 DE 69231820T2 DE 69231820 T DE69231820 T DE 69231820T DE 69231820 T DE69231820 T DE 69231820T DE 69231820 T2 DE69231820 T2 DE 69231820T2
- Authority
- DE
- Germany
- Prior art keywords
- oil
- oils
- biodegradable
- substantially biodegradable
- millimicrons
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000007788 liquid Substances 0.000 title claims description 17
- 239000010687 lubricating oil Substances 0.000 title claims description 15
- 239000000203 mixture Substances 0.000 claims description 49
- 239000012530 fluid Substances 0.000 claims description 39
- 239000003921 oil Substances 0.000 claims description 23
- 229930195733 hydrocarbon Natural products 0.000 claims description 22
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000539 dimer Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000002480 mineral oil Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 235000010446 mineral oil Nutrition 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000001050 lubricating effect Effects 0.000 claims description 5
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 4
- 239000010685 fatty oil Substances 0.000 claims description 4
- 230000003606 oligomerizing effect Effects 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 description 23
- 235000019198 oils Nutrition 0.000 description 21
- 239000002199 base oil Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- -1 alkylbenzene sulfonic acids Chemical class 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
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- 230000002906 microbiologic effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 3
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- 230000003301 hydrolyzing effect Effects 0.000 description 3
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- 239000000178 monomer Substances 0.000 description 3
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- 229920013639 polyalphaolefin Polymers 0.000 description 3
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- 239000002689 soil Substances 0.000 description 3
- 239000010689 synthetic lubricating oil Substances 0.000 description 3
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical class CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229950011260 betanaphthol Drugs 0.000 description 2
- 231100000209 biodegradability test Toxicity 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- WPUKZOKYKHYASK-UHFFFAOYSA-N bis(11-methyldodecyl) hexanedioate Chemical compound CC(C)CCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCCC(C)C WPUKZOKYKHYASK-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000010725 compressor oil Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- 239000002816 fuel additive Substances 0.000 description 2
- 239000012208 gear oil Substances 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000005648 plant growth regulator Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- KAZJNODVSWJRRM-UHFFFAOYSA-N (2,3-dimethylnaphthalen-1-yl) dihydrogen phosphite Chemical compound C1=CC=C2C(OP(O)O)=C(C)C(C)=CC2=C1 KAZJNODVSWJRRM-UHFFFAOYSA-N 0.000 description 1
- YISRDGYZLHFSJW-UHFFFAOYSA-N (2-pentylphenyl) dihydrogen phosphite Chemical compound CCCCCC1=CC=CC=C1OP(O)O YISRDGYZLHFSJW-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BLFZMXOCPASACY-UHFFFAOYSA-N 1,4-bis(propan-2-ylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NC(C)C)=CC=C2NC(C)C BLFZMXOCPASACY-UHFFFAOYSA-N 0.000 description 1
- PTYXPKUPXPWHSH-UHFFFAOYSA-N 1-(butyltetrasulfanyl)butane Chemical compound CCCCSSSSCCCC PTYXPKUPXPWHSH-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical class CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- NSOAQRMLVFRWIT-UHFFFAOYSA-N 1-ethenoxydecane Chemical compound CCCCCCCCCCOC=C NSOAQRMLVFRWIT-UHFFFAOYSA-N 0.000 description 1
- BTGGRPUPMPLZNT-PGEUSFDPSA-N 2,2-bis[[(z)-octadec-9-enoyl]oxymethyl]butyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(CC)(COC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC BTGGRPUPMPLZNT-PGEUSFDPSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical class [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- KYXHKHDZJSDWEF-LHLOQNFPSA-N CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 Chemical class CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 KYXHKHDZJSDWEF-LHLOQNFPSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 229920000089 Cyclic olefin copolymer Chemical class 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- SJJISKLXUJVZOA-UHFFFAOYSA-N Solvent yellow 56 Chemical compound C1=CC(N(CC)CC)=CC=C1N=NC1=CC=CC=C1 SJJISKLXUJVZOA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- NCGQPNAQUYGWMI-UHFFFAOYSA-N [3-heptanoyloxy-2,2-bis(heptanoyloxymethyl)propyl] heptanoate Chemical compound CCCCCCC(=O)OCC(COC(=O)CCCCCC)(COC(=O)CCCCCC)COC(=O)CCCCCC NCGQPNAQUYGWMI-UHFFFAOYSA-N 0.000 description 1
- CIBXCRZMRTUUFI-UHFFFAOYSA-N [chloro-[[chloro(phenyl)methyl]disulfanyl]methyl]benzene Chemical compound C=1C=CC=CC=1C(Cl)SSC(Cl)C1=CC=CC=C1 CIBXCRZMRTUUFI-UHFFFAOYSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
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- SQDDUDMBFNWPOM-UHFFFAOYSA-L barium(2+);n-heptyl-n-phenylcarbamodithioate Chemical compound [Ba+2].CCCCCCCN(C([S-])=S)C1=CC=CC=C1.CCCCCCCN(C([S-])=S)C1=CC=CC=C1 SQDDUDMBFNWPOM-UHFFFAOYSA-L 0.000 description 1
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- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
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- 239000002530 phenolic antioxidant Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
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- 150000008117 polysulfides Polymers 0.000 description 1
- PDEDQSAFHNADLV-UHFFFAOYSA-M potassium;disodium;dinitrate;nitrite Chemical compound [Na+].[Na+].[K+].[O-]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDEDQSAFHNADLV-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000246 remedial effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical class C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- USEBTXRETYRZKO-UHFFFAOYSA-L zinc;n,n-dioctylcarbamodithioate Chemical compound [Zn+2].CCCCCCCCN(C([S-])=S)CCCCCCCC.CCCCCCCCN(C([S-])=S)CCCCCCCC USEBTXRETYRZKO-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C10M171/007—Coloured or dyes-containing lubricant compositions
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- C10M101/02—Petroleum fractions
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- C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
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- C10M133/28—Azo compounds
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Description
- Wie durchaus bekannt ist, gibt es viele Situationen, in denen ölartige Flüssigkeiten in die Umwelt freigesetzt werden. Zum Beispiel kommen im Außeneinsatz verwendete Schmieröle fast unvermeidlich in Kontakt mit den Land- und Wasserflächen der Erde. Das gleiche gilt für als Träger oder Verdünnungsmittel in landwirtschaftlichen Sprühnebeln verwendete ölige Flüssigkeiten, wie Herbizide und Pflanzenwachstums-Regulatoren. Auch bei Maschinenölen, Getriebeölen, Getriebekastenölen etc. ist ein Austritt auf Straßenpflaster- oder Erdboden- Oberflächen gewöhnlich, und somit befinden sich diese schließlich in der natürlichen Umwelt. Eine andere Quelle von derartigen Freisetzungen in die Umwelt beinhaltet das Brechen oder die Leckage von hydraulischen Hochdrucksystemen, wie Fahrzeug- Bremsleitungen, bei Bauarbeiten und Erdbewegungsgeräten oder militärischen Fahrzeugen oder Ausrüstungen verwendeten hydraulischen Systemen, und dergleichen. Gleichermaßen finden Papierfabrik-Öle und Kompressoröle ihren Weg in die natürliche Umwelt.
- Unglücklicherweise können formulierte Mineralöl-Schmiermittel und funktionelle Fluide für die Umwelt schädlich sein, da sie in den meisten Fällen nicht in akzeptabler Weise biologisch abbaubar sind. Außerdem wurde in vielen Fällen nur von Kohlenwasserstoff-artigen Fluiden angenommen, die notwendige Kombination von Eigenschaften für die gegebenen Zwecke zu besitzen und die bei der Herstellung und Anwendung solcher Produkte beteiligten wirtschaftlichen Parameter zu erfüllen. Zum Beispiel besitzen synthetische Esteröle und natürliche Öle, wie Rapsöl, Einschränkungen hinsichtlich solcher Eigenschaften, wie oxidativer Stabilität (speziell bei erhöhten Anwendungstemperaturen), hydrolytischer Stabilität, Filtrierbarkeit und Demulgierbarkeit.
- Es besteht deshalb ein Bedarf nach einem effektiven Weg zum Reduzieren des Ausmaßes und der Schwere solcher Umwelt-Mißstände, während gleichzeitig Schmiermittel und funktionelle Fluide vorgesehen werden, die wünschenswerte physikalische Eigenschaften innerhalb der Grenzen wirtschaftlicher Zwänge besitzen. Es wird davon ausgegangen, daß die Erfindung dieses Anforderung erfüllt.
- Die Erfindung beinhaltet unter anderem den wahrhaftig überraschenden Befund, daß gewisse unhydrierte Oligomere von 1-Alken-Kohlenwasserstoffen bei Exposition an mikrobiologische Agenzien von in der Umwelt in breitem Maße verfügbaren Typen im wesentlichen bioabbaubar sind. Somit kann bei Betriebsvorgängen, worin Schmieröle und funktionelle Fluide zufällig oder anderweitig in die Umwelt freigesetzt werden, die Bereitstellung und Verwendung von Schmiermitteln und funktionellen Fluiden, enthaltend solche unhydrierten 1-Olefin-Kohlenwasserstoffoligomere, in materieller Weise zum Schutz der Umwelt beitragen. Und darüber hinaus kann eine solche Bereitstellung und solche Verwendung insoweit, als erforderliche Leistungseigenschaften und wirtschaftliche Erwägungen betrachtet werden, ohne verheerende Folgen erreicht werden.
- Gemäß einer Ausführungsform dieser Erfindung wird daher bei einer Betriebsweise, bei der Schmieröl oder ein funktionelles Fluid in die Umwelt freigesetzt wird oder eine Wahrscheinlichkeit der Freisetzung in die Umwelt besteht, eine Verbesserung vorgesehen, welche das Vorsehen zur Verwendung als das Schmieröl oder funktionelle Fluid eines im wesentlichen bioabbaubaren Schmieröls oder funktionellen Fluids umfaßt, bei dem mindestens 10 Vol.-% aus mindestens einem im wesentlichen bioabbaubaren unhydrierten flüssigen Kohlenwasserstoff von schmierfähiger Viskosität bestehen, enthaltend mindestens 90% Dimer und/oder Co-Dimer, gebildet durch Oligomerisieren, unter Verwenden eines Wasser- oder Alkoholbeschleunigten Friedel-Crafts-Katalysators, eines linearen 1-Alken-Kohlenwasserstoffs mit 6 bis 20 Kohlenstoffatomen im Molekül, zusammen mit mindestens einem öligen bioabbaubaren Material. In einer anderem Ausführungsform dieser Erfindung umfaßt die Verbesserung bei einer solchen Betriebsweise das Verwenden oder Benutzen als das Schmieröl oder funktionelle Fluid in einer solchen Betriebsweise eines im wesentlichen bioabbaubaren Schmieröls oder funktionellen Fluids, von dem mindestens 10 Vol.-% bestehen aus mindestens einem im wesentlichen bioabbaubaren unhydrierten flüssigen Kohlenwasserstoff von schmierfähiger Viskosität, enthaltend mindestens 90% Dimer und/oder Co-Dimer, gebildet durch Oligomerisieren, unter Verwendung eines Wasser- oder Alkoholbeschleunigten Friedel-Crafts-Katalysators, eines linearen 1-Alken-Kohlenwasserstoffs mit 6 bis 20 Kohlenstoffatomen im Molekül.
- Mit "im wesentlichen bioabbaubar" ist in dieser Beschreibung und den beiliegenden Patentansprüchen gemeint, daß die in Rede stehende ölige Flüssigkeit bei Testen und Aufzeichnung nach dem Testverfahren CEC L-33-T-82 eine Bioabbaubarkeit von über 20%, vorzugsweise mindestens 30% und weiter bevorzugt mindestens 40% und am stärksten bevorzugt mindestens 50% aufweist. Es ist auch anzumerken, daß für die Absichten dieser Erfindung der Begriff "funktionelles Fluid", wie verwendet in der Beschreibung und den Patentansprüchen, Lösungsmittel und/oder Trägerfluide (z. B. für landwirtschaftliche Sprühnebel oder Formulierungen) als auch hydraulische Fluide, Abschrecköle, Schneidöle, Bearbeitungs- bzw. Maschinieröle, Transformatorenöle und dergleichen einschließt.
- Weitere Ausführungsformen dieser Erfindung schließen eine im wesentlichen bioabbaubare Schmieröl- oder funktionelle Fluid-Zusammensetzung ein, welche mindestens 10 Vol.-% mindestens eines im wesentlichen bioabbaubaren unhydrierten flüssigen Kohlenwasserstoffs des obenstehend beschriebenen Typs, zusammen mit dem öligen Material, umfaßt. Die im wesentlichen bioabbaubare Schmieröl- oder funktionelle Fluid-Zusammensetzung des obenstehend beschriebenen Typs kann in Kontakt mit mindestens einem mikrobiologischen Agenz kommen, das in der Lage ist, den biologischen Abbau mindestens eines wesentlichen Teiles des im wesentlichen bioabbaubaren unhydrierten flüssigen Kohlenwasserstoffs, aus dem eine derartige Schmieröl- oder funktionelle Fluid-Zusammensetzung aufgebaut ist, zu verursachen. In dieser Form der Erfindung kann ein solches mikrobiologisches Agenz in der Erde oder in einem Gewässer bzw. einer Wasseransammlung vorliegen.
- Unter den Vorteilen dieser Erfindung finden sich die überraschende wesentliche Bioabbaubarkeit der gemäß dieser Erfindung angewandten unhydrierten 1-Olefin-Oligomer-Schmiermittel und funktionellen Fluids, gemeinsam mit der Kombination an wünschenswerten Eigenschaften, welche sie besitzen. Zum Beispiel besitzen die im wesentlichen bioabbaubaren unhydrierten Poly-α-Olefin-Schmiermittel und funktionellen Fluids dieser Erfindung im allgemeinen bessere Niedertemperatur-Eigenschaften als vergleichbare Mineralöle. Und im Vergleich zu synthetischen Esterölen und natürlichen Ölen, wie Rapsöl, besitzen die im wesentlichen bioabbaubaren Schmiermittel und funktionellen Fluide dieser Erfindung im allgemeinen bessere hydrolytische Stabilität (z. B. im ASTM-Test D 2619 auf hydrolytische Stabilität), überlegene Filtrierbarkeit (z. B. in einem Naß-Filtrationstest) und bessere Demulgierbarkeit (z. B. im ASTM-Demulgierbarkeitstest D 1401).
- Nicht alle unhydrierten 1-Alken-Kohlenwasserstoff-Flüssigoligomere erfüllen die Anforderungen der Erfindung hinsichtlich wesentlicher Bioabbaubarkeit, wie sie obenstehend dargelegt wurden. So sollte in jeder gegebenen Situation das einfache Hiliamittel zu Rat gezogen werden, das prospektive unhydrierte 1-Alken-Flüssigoligomer dem CEC L-33-T-82- Testverfahren in der darin angegebenen Weise zu unterziehen, um die prozentuale Bioabbaubarkeit des betrachteten Oligomeren zu bestimmen. Allgemein gesagt, zeigen unhydrierte Flüssigoligomere von linearen 1-Alkenen, welche mindestens 50% Dimer, Trimer und/oder Tetramer enthalten, gebildet unter Verwendung eines Wasser- oder Alkoholgeförderten Friedel-Crafts-Katalysators, die Neigung, die erforderliche Bioabbaubarkeit zu besitzen, wodurch man sie als im wesentlichen bioabbaubar klassifizieren kann. Die zur Bildung solcher Oligomeren verwendeten 1-Alkene sollten 6 bis 20 Kohlenstoffatome, und vorzugsweise 8 bis 16 Kohlenstoffatome, im Molekül enthalten. Darüber hinaus sollten derartige 1-Alkene linear (d. h. im wesentlichen frei von Verzweigung und Zyklisierung) sein.
- Verfahren zur Herstellung von solchen flüssigen oligomeren 1-Alken-Kohlenwasserstoffen sind bekannt und in der Literatur berichtet; siehe zum Beispiel die U. S.-Patente Nr. 3 763 244; 3 780 128; 4 172 855 und 4 218 330, wobei selbstverständlich die Lehren darin, welche das Hydrieren der Oligomere betreffen, weggelassen werden. Wie gut bekannt ist, enthalten unhydrierte Oligomere dieses Typs restliche ethylenische Ungesättigtheit. Bevorzugte Oligomere werden durch Verwenden eines Friedel-Crafla-Katalysators (insbesondere Bortrifluorid, gefördert mit Wasser oder einem C&sub1;&submin;&sub2;&sub0;-Alkanol) unter Anwendung von Oligomerisierungsverfahren, wie sie in den vorstehenden U. S.-Patenten beschrieben sind, gebildet.
- Andere Katalysatorsysteme, welche auch eingesetzt werden können, um Oligomere von 1-Alken-Kohlenwasserstoffen zu bilden, die Schmiermittel und funktionelle Fluids vorsehen, die im wesentlichen bioabbaubar sein können, schließen Ziegler-Katalysatoren, wie Ethyl- Aluminiumsesquichlorid mit Titaniumtetrachlorid, Aluminiumalkyl-Katalysatoren, Chromoxid-Katalysatoren auf Silica- oder Alumina-Trägern und ein System, in welchem einer Bortrifluorid-Katalysator-Oligomerisierung durch eine Behandlung mit einem organischen Peroxid gefolgt wird, ein.
- Mischungen oder Gemische solcher 1-Alken-Oligomeren können bei der Ausübung dieser Erfindung ebenfalls verwendet werden, vorausgesetzt daß die Gesamtmischung die erforderliche Bioabbaubarkeit, wie obenstehend angegeben, besitzt.
- Gemäß dieser Erfindung werden Gemische von einem oder mehreren ausreichend bioabbaubaren flüssigen unhydrierten 1-Alken-Oligomeren in Kombination mit anderen öligen Materialien verwendet, welche selbst ausreichend bioabbaubar sind, so daß das resultierende Gemisch die Bioabbaubarkeits-Anforderung der Erfindung erfüllt, mit der ferneren Maßgabe, daß das resultierende Gemisch die erforderlichen Kompatibilitäts-, Stabilitäts- und Leistungskriterien für die Anwendung besitzt, für welche das Gemisch entworfen, formuliert und vorgesehen wird.
- Veranschaulichende nicht-oligomere Öle und Fluide von Schmier-Viskosität, die bei der Formulierung von im wesentlichen bioabbaubaren Schmieröl- und/oder funktionellen Fluid- Gemischen unter Befolgung dieser Erfindung verwendet werden können, schließen synthetische Ester, wie gemischte C&sub9;&submin; und C&sub1;&sub1;-Dialkylphthalate (z. B. ICI Emkarate 911P-Esteröl), Trimethylolpropantrioleat, Di(isotridecyl)adipat (z. B. BASF Glissofluid A13), Pentaerythritol-tetraheptanoat und dergleichen; im wesentlichen bioabbaubare flüssige hydrierte 1- Alken-Oligomere, wie ETHYLFLO 162-, 164- und 166-Poly-alpha-Olefinöle und Mischungen hiervon (Ethyl Corporation; Ethyl S. A.; Ethyl Canada Limited); und flüssige natürliche Fettöle und -ester, wie Castoröl, Olivenöl, Erdnußöl, Rapsöl, Maisöl, Sesamöl, Baumwollsamenöl, Sojabohnenöl, Sonnenblumenöl, Saffloröl, Hanföl, Leinöl, Tung-Öl, Oiticica-Öl, Jojoba-Öl und dergleichen ein. Solche natürlichen Fettöle können teilweise oder vollständig hydriert sein, falls gewünscht. Die einzigen Anforderungen sind hier wiederum, daß das resultierende Gemisch im wesentlichen bioabbaubar innerhalb der obenstehend angegebenen Bedeutung ist, und daß das Gemisch die erforderlichen Eigenschaften für die dafür beabsichtigte(n) Anwendung oder Anwendungen aufweist.
- Es ist auch möglich, kleine Mengen an Mineralöl in Gemische mit einem oder mehreren im wesentlichen bioabbaubaren linearen 1-Alken-Kohlenwasserstoff-Oligomeren einzuschließen, und solche Gemische können ihrerseits ein oder mehrere Basisöle (synthetische Ester, Polyalkylenglycol, hydriertes Poly-alpha-Olefin-Öl, natürliches Fettöl oder -ester, etc.) enthalten, vorausgesetzt daß die Gesamtmischung selbst im wesentlichen bioabbaubar ist. Die Menge an Mineralöl, welche in den vorstehenden Gemischen vorhanden sein kann, wird in großem Maße von den strukturellen und molekularen Merkmalen des Mineralöls abhängen, wie der Menge von vorhandenen methyl-verzweigten und zyklischen Spezies, Konfigurationen, welche einem biologischen Abbau widerstehen. Folglich sollte in jeder gegebenen Situation Hilfe bei dem CEC L-33-T-72-Testverfahren gesucht werden, um zu gewährleisten, daß die vorgeschlagene Menge des vorgeschlagenen Mineralöls in der vorgeschlagenen Gesamtmischung nicht verhindert, daß die Gesamtmischung im wesentlichen bioabbaubar ist.
- Herkömmliche Mengen von herkömmlichen Zusatzstoffen, die typischerweise in Schmierölen und/oder in funktionellen Fluiden verwendet werden, können in den flüssiges unhydriertes 1-Alken-Kohlenwasserstoff-Oligomer enthaltenden Zusammensetzungen dieser Erfindung verwendet werden, selbstverständlich vorausgesetzt daß die Zusatzstoffe, wie verwendet, miteinander kompatibel und ausreichend löslich in dem Basisöl bei den gewünschten Konzentrationen sind, damit eine homogene Lösung bei Umgebungstemperaturen vorgesehen wird. Beispiele solcher Zusatzstoffe, obwohl dem Fachmann gut bekannt, werden hier nachstehend angegeben. Es ist bemerkenswert, daß solche Zusatzstoffe an und für sich nicht selbst bioabbaubar sein müssen. Die einzige Anforderung ist, daß die verwendeten Konzentrationen - die normal relativ gering sind - in dem Basisöl das fertiggestellte Schmiermittel oder funktionelle Fluid nicht hindern sollten, im wesentlichen bioabbaubar zu bleiben.
- Um die Umwelt noch weiter zu schützen, sieht diese Erfindung gemäß ihrer bevorzugten Ausführungsformen neue Zusammensetzungen vor, welche den Nachweis von Leckage und anderen übermäßigen Freisetzungen von Schmiermittel und/oder funktionellem Fluid in die Umwelt erleichtern. Zu dem Ausmaß, falls vorhanden, daß das Schmiermittel oder funktionelle Fluid nicht bioabbaubar ist, ermöglicht somit ein früher Nachweis von solcher Leckage oder übermäßiger Freisetzung davon in die Umwelt das Ergreifen umgehender Abhilfemaßnahmen zur Einstellung weiteren Austretens oder übermäßiger Freisetzung in die Umwelt.
- Gemäß derartiger bevorzugter Ausführungsformen werden im wesentlichen bioabbaubare Schmieröl- oder funktionelle Fluid-Zusammensetzungen vorgesehen, welche einen Hauptanteil aus einem ölartigen Fluid, enthaltend eine kleine visuell wahrnehmbare chromophore Menge einer in Öl löslichen chromophoren Substanz, umfassen. Ein derartiges öliges Fluid umfaßt, bezogen auf das Volumen, mindestens 10 Prozent, vorzugsweise mindestens 25 Prozent, weiter bevorzugt mindestens 50 Prozent, noch weiter bevorzugt mindestens 75 Prozent, und am stärksten bevorzugt 90 Prozent oder mehr von mindestens einem im wesentlichen bioabbaubaren unhydrierten flüssigen Kohlenwasserstoff von schmierfähiger Viskosität, gebildet durch Oligomerisieren von 1-Alken-Kohlenwasserstoff mit 6 bis 20 Kohlenstoffatomen im Molekül und Hydrieren des so gebildeten Oligomeren. Vorzugsweise besitzt die verwendete chromophore Substanz eine Maximum-Absorptionswellenlänge innerhalb des Bereichs von 300 bis 650 Millimikron (0,30 bis 0,65 um). Typische, jedoch bevorzugte, chromophore Substanzen besitzen jeweilige Maximum- Absorptionswellenlängen von 400, 420, 515, 518 und 640 Millimikron (0,40, 0,42, 0,515, 0,518 und 0,64 um). Eine besonders bevorzugte chromophore Substanz besteht aus einer Mischung von zwei chromophoren Verbindungen, eine mit einer Maximum-Absorptionswellenlänge von etwa 420 Millimikron (0,42 um) und die andere mit einer Maximum- Absorptionswellenlänge von etwa 640 Millimikron (0,64 um), wodurch das Produkt eine grüne Färbung aufweist.
- Die folgenden Beispiele, in denen Teile und Prozentsätze der Komponente auf das Gewicht bezogen sind, veranschaulichen die Verwendung von schmierfähigem Kohlenwasserstoff, geeignet für Zusammensetzungen dieser Erfindung. Die Bioabbaubarkeits-Ergebnisse unter Anwendung des CEC L-33-T-82-Testverfahrens sind unter Bezugnahme auf einen Standard von 90% Bioabbaubarkeit für Di(isotridecyl)adipat und 20% Bioabbaubarkeit für weißes Mineralöl ausgedrückt. Im Falle des OECD-301B Modifizierten Stürm-Testverfahrens ist die Standardreferenz 90% Bioabbaubarkeit für Natriumbenzoat.
- Von einem unhydrierten 1-Dodecen-Dimer wurde gefunden, eine Bioabbaubarkeit von ungefähr 41% aufzuweisen, als es dem CEC L-33-T-82-Bioabbaubarkeit-Testverfahren unterzogen wurde.
- Eine unhydrierte Mischung von Dimeren, gebildet aus einer Mischung von 1-Tetradecen und 1-Hexadecen, zeigte eine Bioabbaubarkeit von etwa 57% in dem CEC L-33-T-82-Bioabbaubarkeit-Testverfahren.
- Chromophore Schmiermittel- und funktionelle Pluid-Basisöl-Zusammensetzungen werden gebildet durch Vermischen von 0,01% eines Methylderivats von Azobenzol-4-azo-2- naphthol mit einer Maximum-Absorptionswellenlänge von S 18 Millimikron (0,518 um) und einem ungefähren Pourpoint von -26ºC (C. I. "Solvent Red" 164) mit den synthetischen Schmierölen, wie beschrieben in den Beispielen 1 und 2. Ein Austritt oder ein Verschütten dieser im wesentlichen bioabbaubaren Schmiermittel-Zusammensetzungen wird mit bloßem Auge leicht erkannt.
- Chromophore Schmiermittel- und funktionelle Fluid-Basisöl-Zusammensetzungen werden gebildet durch Vermischen von 0,02% einer Mischung von p-Diethylaminoazobenzol mit einer Maximum-Absorptionswellenlänge von 420 Millimikron (0,42 um) und 1,4-Diisopropylaminoanthrachinon mit einer Maximum-Absorptionswellenlänge von 640 Millimikron (0,64 um) und einem ungefähren Pourpoint von -46ºC mit den synthetischen Schmierölen, wie beschrieben in den Beispielen 1 und 2. Ein Austritt oder Verschütten dieser im wesentlichen bioabbaubaren Schmiermittel-Zusammensetzungen wird visuell leicht wahrgenommen.
- Chromophore Schmiermittel- und funktionelle Fluid-Basisöl-Zusammensetzungen werden gebildet durch Vermischen von 0,025% Benzol-azo-2-naphthol mit einer Maximum-Absorptionswellenlänge von 400 Millimikron (0,40 um) und einem ungefähren Pourpoint von -23ºC mit den synthetischen Schmierölen, wie beschrieben in den Beispielen 1 und 2. Ein Austritt oder Verschütten dieser im wesentlichen bioabbaubaren Schmiermittel-Zusammensetzungen wird visuell leicht erkannt.
- Chromophore, im wesentlichen bioabbaubare Basisöl-Zusammensetzungen werden gebildet durch Auflösen der Kombination von Hoechst Fat Blue B bei einer Konzentration äquivalent zu 0,04 g/400 ml und Hoechst Fat Yellow 3 G bei einer Konzentration äquivalent zu 0,10 g/400 ml in den in den Beispielen 1 und 2 beschriebenen Fluid-Zusammensetzungen. Wenn in Kontakt mit mikrobiologischen Agenzien in der natürlichen Umwelt (Erdboden oder Wasser) stehend, werden solche Basisöle im wesentlichen zu harmlosen Materialien biologisch abgebaut.
- Die im wesentlichen bioabbaubaren Schmiermittel und funktionellen Fluide dieser Erfindung können in einer breiten Vielfalt von Anwendungen eingesetzt werden. Zum Beispiel können sie als Basisöle für Kurbelgehäuse-Schmieriittel, Automobil-Schaltungsschmiermittel, Getriebeöle, hydaulische Öle, Papierfabriköle, Kompressoröle, Außenbordrnotor-Schmiermittel (2-Takt-Öle), Kettensägen-Schmiermittel, Träger für Herbizide und Pflanzenwachstums-Regulatoren, und für andere ähnliche Anwendungen eingesetzt werden. Wenn im Laufe einer solchen Anwendung die im wesentlichen bioabbaubaren Basisöle dieser Erfindung in die Umwelt freigesetzt werden, zufällig oder anderweitig, und in Kontakt mit mikobiologischen Agenzien in der natürlichen Umwelt kommen, werden die Öle im wesentlichen bioabgebaut, und somit sind solche Öle viel weniger offensiv gegenüber der Umwelt als im wesentlichen nicht-bioabbaubare Basisöle.
- Gut bekannte Zusatzstoffe, welche in den Zusammensetzungen dieser Erfindung eingeschlossen werden können, schließen die Zinkdialkyl(C&sub3;-C&sub1;&sub0;)-, -dicycloalkyl(C&sub5;-C&sub2;&sub0;)- und/oder -diaryl(C&sub6;-C&sub2;&sub0;)-Dithiophosphat-Verschleißinhibitoren ein, im allgemeinen vorhanden in Mengen von etwa 0,5 bis 5 Gew.-%. Nützliche Detergenzien schließen die öllöslichen normalen basischen oder überalkalisierten Metall-, z. B. Calcium-, Magnesium-, Barium- etc. Salze von Petroleum-Naphthensäuren, Petroleum-Sulfonsäuren, Alkylbenzolsulfonsäuren, öllöslichen Fettsäuren, Alkylsalicylsäuren, geschwefelten oder ungeschwefelten Alkylphenaten und hydrolysierten oder unhydrolysierten phospho-geschwefelten Polyolefinen ein. Benzinmotor-Kurbelgehäuse-Schmiermittel enthalten typischerweise zum Beispiel 0,5 bis 5 Gew.-% von einem oder mehreren Detergenz-Zusatzstoffen. Dieselmotor-Kurbelgehäuse-Öle können wesentlich höhere Spiegel von Detergenz-Zusatzstoffen enthalten. Bevorzugte Detergenzien sind die normalen oder überalkalisierten Phenate, geschwefelten Phenate oder Sulfonate von Calcium und Magnesium.
- Pourpoint-Erniedriger, welche in Mengen von 0,01 bis 2 Gew.-% vorhanden sein können, schließen Wachs-alkylierte aromatische Kohlenwasserstoffe, Olefin-Polymere und -Copolymere und Acrylat- und Methacrylat-Polymere und -Copolymere ein.
- Viskositätsindex-Verbesserer, deren Konzentrationen in den Schmiermitteln von 0,2 bis 15 Gew.-% (vorzugsweise von etwa 0,5 bis etwa 5 Gew.-%) abhängig vom erforderlichen Viskositätsgrad schwanken können, schließen Kohlenwasserstoff-Polymere, gepfropft mit zum Beispiel stickstoffhaltigen Monomeren, Olefin-Polymere, wie Polybuten, Ethylen- Propylen-Copolymere, unhydrierte Polymere und Copolymere und Terpolymere von Styrol mit Isopren und/oder Butadien, Polymere von Alkylacrylaten oder Alkylmethacrylaten, Copolymere von Alkylmethacrylaten mit N-Vinylpyrrolidon oder Dimethylaminoalkylmethacrylat, post-gepfopfte Polymere von Ethylen-Propylen mit einem aktiven Monomer, wie Maleinsäureanhydrid, welche ferner mit einem Alkohol oder einem Alkylenpolyamin umgesetzt sein können, Styrol/Maleinsäureanhydrid-Polymere, nachbehandelt mit Alkoholen und Aminen, etc., ein.
- Anti-Verschleiß-Aktivität kann durch etwa 0,01 bis 2 Gew.-% in dem Öl an den zuvor erwähnten Metalldihydrocarbyl-Dithiophosphaten und den entsprechenden Vorläuferestern, phospho-geschwefelten Pinenen, geschwefelten Olefinen und Kohlenwasserstoffen, geschwefelten Fettestem und Alkylpolysulfiden vorgesehen werden. Bevorzugt sind die Zinkdihydrocarbyldithiophosphate, welche Salze von Dihydrocarbylestern von Dithiophosphorsäuren sind.
- Andere Zusatzstoffe schließen effektive Mengen von Reibungsmodifizierern oder wirtschaftlichen Treibstoffzusätzen, wie die Alkylphosphonate wie offenbart in U. S. 4 356 097; aliphatische Kohlenwasserstoff-substituierte Succinimide wie offenbart in EPO 0020037, dimere Säureester, wie offenbart in U. S. 4 105 571, Oleamid etc. ein, welche in dem Öl in Mengen von 0,1 bis 5 Gew.-% vorhanden sind. Glycerinoleate sind ein anderes Beispiel von wirtschaftlichen Treibstoffzusätzen und diese sind gewöhnlich in sehr kleinen Mengen vorhanden, wie 0,05 bis 0,2 Gew.-%, bezogen auf das Gewicht des formulierten Öls. Antioxidationsmittel oder Wärmestabilisatoren, welche verwendet werden können, schließen gehinderte Phenole, Methylen-verbrückte Polyphenole, aromatische Amin-Antioxidationsmittel, geschwefelte Phenole, Alkylphenothiazine, substituierte Triazine und Harnstoffe und Kupferverbindungen, wie Kupfernaphthenat und Kupferoleat, neben anderen, ein. Phenolische Antioxidationsmittel werden bevorzugt.
- Detergenzien und Dispergiermittel können ebenfalls in den Zusammensetzungen dieser Erfindung verwendet werden, wiederum unter der Maßgabe, daß das verwendete Material die substantielle Bioabbaubarkeit der Gesamtzusammensetzung nicht stört. Typische Dispergiermittel schließen die Reaktionsprodukte von Kohlenwasserstoff-substituierten acylierenden Mitteln, wie Alkenyl- oder Alkyl-substituierter Bernsteinsäure oder ihrem Anhydrid, mit Aminen, Phenolen, Alkoholen, Aminoalkoholen oder basischen anorganischen Materialien ein. Polyisobutenylsuccinimide von Alkylenpolyaminen sind bevorzugte Dispergiermittel dieses Typs.
- Zahlreiche Referenzen beschreiben solche Materialien und ihre Verwendung; siehe zum Beispiel die U. S.-Patente Nr. 3 163 603; 3 184 474; 3 215 707; 3 219 666; 3 271 310; 3 272 746; 3 281 357; 3 306 908; 3 311 558; 3 316 177; 3 340 281; 3 341 542; 3 346 493; 3 351 552; 3 381 022; 3 399 141; 3 415750; 3 433 744; 3 444 170; 3 448 048; 3 448 049; 3 451 933; 3 454 607; 3 467 668; 3 501 405; 3 522 179; 3 541 012; 3 542 680; 3 543 678; 3 567 637; 3 574 101; 3 576 743; 3 630 904; 3 632 510; 3 632 51 l; 3 697 428; 3 725 441; 4 234 435; Re 26 433.
- Ebenfalls nützlich sind Produkte, gebildet durch Umsetzen aliphatischer oder alicyclischer Halogenide mit Aminen, wie beschrieben zum Beispiel in U. S. 3 275 554; 3 438 757; 3 454 555 und 3 565 804.
- Mannich-Reaktionsprodukte sind ein anderer Typ von nützlichem aschelosen Dispergiermittel. Dispergiermittel dieses Typs werden zum Beispiel beschrieben in den U. S.-Patenten Nr. 2 459 112; 2 962 442; 2 984 550; 3 036 003; 3 166 516; 3 236 770; 3 355 270; 3 368 972; 3 413 347; 3 442 808; 3 448 047; 3 454 497; 3 459 661; 3 461 172; 3 493 520; 3 539 633; 3 558 743; 3 586 629; 3 591 598; 3 600 372; 3 634 515; 3 649 229; 3 697 5'74; 3 725 277; 3725 480; 3 726 882; und 3 980 569.
- Durch Nachbehandlung der verschiedenen obenstehend angegebenen Typen von Dispergiermitteln mit geeigneten Reaktanten gebildete Produkte sind ebenfalls nützlich. Produkte dieses Typs sind zum Beispiel beschrieben in den U. S.-Patenten Nr. 3 036 003; 3 087 936; 3 200 107; 3 216 936; 3 254 025; 3 256 185; 3 278 550; 3 280 234; 3 281 428; 3 282 955; 3 312 619; 3 366 569; 3 367 943; 3 373 111; 3 403 102; 3 442 808; 3 455831; 3 455 832; 3 493 520; 3 502 677; 3 513 093; 3 533 945; 3 539 633; 3 573 010; 3 579 450; 3 591 598; 3 600 372; 3 639 242; 3 649 229; 3 649 659; 3 658 836; 3 697 574; 3 702 757; 3 703 536; 3 704 308; 3 708 422; und 4 857 214.
- Polymere Dispergiermittel sind z. B. Interpolymere von Decylmethacrylat, Vinyldecylether und Olefine hohen Molekulargewichts mit Monomeren, die polare Substituenten enthalten, z. B. Aminoalkylacrylate oder -acrylamide und Poly(oxyethylen)acryiate. Typische Materialien von diesem allgemeinen Typ werden zum Beispiel in den U. S.-Patenten Nr. 3 329 658; 3 449 250; 3 S 19 565; 3 666 730; 3 687 849; und 3 702 300 beschrieben. Hochdruckwirkstoffe, welche auch korrosionsinhibierende und oxidationsinhibierende Eigenschaften aufweisen, können ebenfalls verwendet werden. Diese schließen chlorierte aliphatische Kohlenwasserstoffe, wie chloriertes Wachs; organische Sulfide und Polysulfide, wie Benzyldisulfid, Bis(chlorbenzyl)disulfid, Dibutyltetrasulfid, geschwefelten Methylester von Ölsäure, geschwefeltes Alkylphenol, geschwefeltes Dipenten und geschwefeltes Terpen; phospho-geschwefelte Kohlenwasserstoffe, wie das Reaktionsprodukt eines Phosphorsulfids mit Terpentin oder Methyloleat, Phosphorester, einschließlich hauptsächlich Dihydrocarbyl- und Trihydrocarbylphosphiten, wie Dibutylphosphit, Diheptylphosphit, Dicyclohexylphosphit, Pentylphenylphosphit, Dipentylphenylphosphit, Tridecylphosphit, Distearylphosphit, Dimethylnaphthylphosphit, Oleyl-4-pentylphenylphosphit, Polypropylen (Molekulargewicht 500)-substituiertem Phenylphosphit, Diisobutyl-substituiertem Phenylphosphit; Metall-Thiocarbamate, wie Zinkdioctyldithiocarbamat und Bariumheptylphenyldithiocarbamat; Phosphordithioate von Metallen der Gruppe II, wie Zinkdicyclohexylphosphordithioate, Zinkdioctylphosphordithioat, Barium-di-(heptylphenyl)phosphordithioate, Cadmiumdinonylphosphordithioate und das Zinksalz einer Phosphordithiosäure, hergestellt durch die Reaktion von Phosphorpentasulfid mit einem äquimolaren Gemisch von Isopropylalkohol und n-Hexylalkohol, ein.
- Viele der obenstehend erwähnten Hilfs-Hochdruckwirkstoffe und Korrosions-Oxidationsinhibitoren dienen auch als Anti-Verschleißmittel. Zinkdialkylphosphordithioate sind ein gut bekanntes Beispiel.
- Klebrigkeits-Zusätze wie HITEC®151-Additiv (Ethyl Corporation; Ethyl S. A.; Ethyl Canada Limited) sind ebenfalls nützlich.
- Andere gut bekannte Komponenten, wie Rostinhibitoren, Wachs-Modifizierer, Schauminhibitoren, Kupfer-Passivatoren, Schwefel-Abfangmittel, Dichtungs-Quellmittel, Farbstabilisatoren und ähnliche Materialien können in den Zusammensetzungen dieser Erfindung eingeschloßen sein, vorrausgesetzt natürlich, daß sie mit dem Basis-Schmiermittel und der oder den anderen verwendeten Komponente(n) kompatibel sind.
Claims (7)
1. Im wesentlichen bioabbaubare Schmieröl- oder funktionelle Fluid-Zusammensetzung,
welche mindestens 10 Vol.-% von mindestens einem im wesentlichen bioabbaubaren
unhydrierten flüssigen Kohlenwasserstoff von schmierfähiger Viskosität, enthaltend
mindestens 90% Dimer oder Co-Dimer und gebildet durch Oligomerisieren, unter
Verwendung eines Wasser- oder Alkohol-beschleunigten Friedel-Crafts-Katalysators,
eines linearen 1-Alken-Kohlenwasserstoffs mit 6 bis 20 Kohlenstoffatomen im Molekül,
zusammen mit mindestens einem bioabbaubaren ölartigen Material umfaßt.
2. Zusammensetzung gemäß Anspruch 1, wobei der mindestens eine im wesentlichen
bioabbaubare flüssige Kohlenwasserstoff eine kleine visuell wahrnehmbare chromophore
Menge mindestens einer in Öl löslichen chromophoren Substanz enthält.
3. Zusammensetzung gemäß Anspruch 2, wobei die mindestens eine in Öl lösliche
chromophore Substanz eine Maximum-Absorptionswellenlänge innerhalb des Bereichs
von 300 bis 700 Millimikron (0,3 bis 0,7 um) aufweist.
4. Zusammensetzung gemäß Anspruch 3, wobei die mindestens eine in Öl lösliche
chromophore Substanz eine Kombination von zwei derartigen Substanzen umfaßt, von
denen die eine eine Maximum-Absorptionswellenlänge von etwa 420 Millimikron (0,42
um) und die andere eine Maximum-Absorptionswellenlänge von etwa 640 Millimikron
(0,64 um) besitzt, wodurch das Produkt eine grüne Färbung aufweist.
5. Zusammensetzung gemäß mindestens einem der Ansprüche 1 bis 4, wobei das ölartige
Material ein nicht-oligomeres Öl oder Fluid ist.
6. Zusammensetzung gemäß Anspruch 5, wobei das nicht-oligomere Öl oder Fluid ein
synthetischer Ester oder ein natürliches Fettöl oder -ester ist.
7. Zusammensetzung nach mindestens einem der Ansprüche 1 bis 4, wobei das ölartige
Material ein Mineralöl ist.
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EP92300777A EP0558835B1 (de) | 1992-01-30 | 1992-01-30 | Biologisch abbaubare Schmieröle und funktionelle Flüssigkeiten |
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BR8305094A (pt) * | 1982-09-20 | 1984-05-08 | Stauffer Chemical Co | Composicao de lubrificante 10 w para transmissoes e processo de lubrificacao de maquinaria |
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US5171918A (en) * | 1990-07-19 | 1992-12-15 | Ethyl Corporation | Apparatus and oil compositions containing olefin dimer products |
DE69013905T3 (de) * | 1990-07-24 | 2005-06-02 | Ethyl Petroleum Additives Ltd., Bracknell | Biologisch abbaubare Schmieröle und funktionelle Flüssigkeiten. |
-
1992
- 1992-01-30 EP EP92300777A patent/EP0558835B1/de not_active Expired - Lifetime
- 1992-01-30 ES ES92300777T patent/ES2158843T3/es not_active Expired - Lifetime
- 1992-01-30 DE DE69231820T patent/DE69231820T2/de not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
ES2158843T3 (es) | 2001-09-16 |
EP0558835A1 (de) | 1993-09-08 |
DE69231820D1 (de) | 2001-06-13 |
EP0558835B1 (de) | 2001-05-09 |
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