EP2531587B9 - Lubricating greases containing lignosulfonate, the production thereof, and the use thereof - Google Patents
Lubricating greases containing lignosulfonate, the production thereof, and the use thereof Download PDFInfo
- Publication number
- EP2531587B9 EP2531587B9 EP11711018.9A EP11711018A EP2531587B9 EP 2531587 B9 EP2531587 B9 EP 2531587B9 EP 11711018 A EP11711018 A EP 11711018A EP 2531587 B9 EP2531587 B9 EP 2531587B9
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- calcium
- acid
- salt
- carbon atoms
- 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.)
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- 229920001732 Lignosulfonate Polymers 0.000 title claims description 40
- 230000001050 lubricating effect Effects 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000203 mixture Substances 0.000 claims description 50
- 239000011575 calcium Substances 0.000 claims description 41
- 239000000654 additive Substances 0.000 claims description 40
- 239000004519 grease Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000002199 base oil Substances 0.000 claims description 31
- 229910052791 calcium Inorganic materials 0.000 claims description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 239000000344 soap Substances 0.000 claims description 26
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 21
- 239000000920 calcium hydroxide Substances 0.000 claims description 21
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 21
- 239000008139 complexing agent Substances 0.000 claims description 21
- 239000000314 lubricant Substances 0.000 claims description 21
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 19
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 19
- 239000000194 fatty acid Substances 0.000 claims description 19
- 229930195729 fatty acid Natural products 0.000 claims description 19
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 18
- 150000002148 esters Chemical class 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- -1 calcium hydroxide Chemical class 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 150000004665 fatty acids Chemical class 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 13
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 230000035515 penetration Effects 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 159000000007 calcium salts Chemical class 0.000 claims description 8
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 238000005461 lubrication Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000012990 dithiocarbamate Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229920000193 polymethacrylate Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 241001465754 Metazoa Species 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052961 molybdenite Inorganic materials 0.000 claims description 3
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000010775 animal oil Substances 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 150000001622 bismuth compounds Chemical class 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- WDNQRCVBPNOTNV-UHFFFAOYSA-N dinonylnaphthylsulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 WDNQRCVBPNOTNV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001002 functional polymer Polymers 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 239000006078 metal deactivator Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 150000004763 sulfides Chemical class 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 5
- 239000005864 Sulphur Substances 0.000 claims 4
- 159000000013 aluminium salts Chemical class 0.000 claims 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 3
- 150000008064 anhydrides Chemical class 0.000 claims 3
- 239000004411 aluminium Substances 0.000 claims 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical class OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims 1
- PEFNMPZKHOCMSW-UHFFFAOYSA-H [Al+3].[Al+3].[O-]O[O-].[O-]O[O-].[O-]O[O-] Chemical class [Al+3].[Al+3].[O-]O[O-].[O-]O[O-].[O-]O[O-] PEFNMPZKHOCMSW-UHFFFAOYSA-H 0.000 claims 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 1
- 239000007866 anti-wear additive Substances 0.000 claims 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims 1
- 239000000347 magnesium hydroxide Substances 0.000 claims 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims 1
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 claims 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 claims 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 claims 1
- 239000003925 fat Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 11
- 239000001639 calcium acetate Substances 0.000 description 11
- 235000011092 calcium acetate Nutrition 0.000 description 11
- 229960005147 calcium acetate Drugs 0.000 description 11
- 239000002562 thickening agent Substances 0.000 description 11
- 230000008859 change Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229920005610 lignin Polymers 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 239000012467 final product Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000003760 tallow Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- AKEUNCKRJATALU-UHFFFAOYSA-N 2,6-dihydroxybenzoic acid Chemical compound OC(=O)C1=C(O)C=CC=C1O AKEUNCKRJATALU-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 235000015278 beef Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 235000019801 trisodium phosphate Nutrition 0.000 description 4
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000003879 lubricant additive Substances 0.000 description 3
- 229940073769 methyl oleate Drugs 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 150000003626 triacylglycerols Chemical class 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 235000012216 bentonite Nutrition 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- VMDFASMUILANOL-WXXKFALUSA-N bisoprolol fumarate Chemical compound [H+].[H+].[O-]C(=O)\C=C\C([O-])=O.CC(C)NCC(O)COC1=CC=C(COCCOC(C)C)C=C1.CC(C)NCC(O)COC1=CC=C(COCCOC(C)C)C=C1 VMDFASMUILANOL-WXXKFALUSA-N 0.000 description 2
- LVGQIQHJMRUCRM-UHFFFAOYSA-L calcium bisulfite Chemical compound [Ca+2].OS([O-])=O.OS([O-])=O LVGQIQHJMRUCRM-UHFFFAOYSA-L 0.000 description 2
- 235000010260 calcium hydrogen sulphite Nutrition 0.000 description 2
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- JMFRWRFFLBVWSI-NSCUHMNNSA-N coniferol Chemical compound COC1=CC(\C=C\CO)=CC=C1O JMFRWRFFLBVWSI-NSCUHMNNSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 125000002293 monolignol group Chemical group 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
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- 239000005060 rubber Substances 0.000 description 2
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- NIIFDLGMJJFCFY-UHFFFAOYSA-N lithium;dihydrogen borate Chemical compound [Li+].OB(O)[O-] NIIFDLGMJJFCFY-UHFFFAOYSA-N 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
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/065—Sulfides; Selenides; Tellurides
- C10M2201/066—Molybdenum sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/26—Waterproofing or water resistance
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/36—Seal compatibility, e.g. with rubber
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- the invention relates to a process for the preparation of calcium lignosulfonate greases, such lubricating greases and their use
- Lignin is a complex polymer based on phenylpropane units, which are interlinked with each other with a range of different chemical bonds. Lignin occurs in plant cells together with cellulose and hemicellulose. Lignin itself is a cross-linked macromolecule with average molecular weights of e.g. greater than 10,000 g / mol (weight average).
- lignin As monomer building blocks of lignin, essentially 3 types of monolignol monomers can be identified, which differ from each other in the degree of methoxylation. These are p- cumaryl alcohol, coniferyl alcohol, and sinapyl alcohol. These lignols are incorporated into the lignin structure in the form of hydroxyphenyl (H), guaiacyl (G), and syn-ring (S) units. Muscovy plants (Gymnosperms), such as pine trees, contain overwhelmingly G units and small amounts of H units. All lignins contain small amounts of incomplete or modified monolignols. The primary function of lignins in plants is to provide mechanical stability by cross-linking the plant polysaccharides. Lignin represents about 1/3 of the dry mass of wood and roughly represents 30% of the non-fossil organic carbon mass on Earth. It is the third most common organic material after cellulose and chitin and thus also a very readily available renewable raw material for industrial products
- Lignosulfonate is a by-product of papermaking with the sulfite process.
- chopped wood is heated to chips under pressure (eg 5 to 7 bar) for about 7 to 15 hours in the presence of calcium hydrogen sulphite solution and then the lignosulphonic acid in the form of calcium lignosulphonate is removed from the lignocellulose by a washing and precipitation process.
- calcium hydrogen sulfite it is also possible to use magnesium, sodium or ammonium sulfite bases, which leads to the corresponding magnesium, sodium and ammonium salts of lignin sulfonic acid.
- lignosulfonates are widely used as a base for the plasticization and liquefaction of concrete and mortar. Another use find lignosulfonates as Pelletierangesmittel in the concentrated feed industry and in other areas as a dispersant or complexing agent.
- Tribochemically acting extreme pressure (high pressure) and anti-wear (EP / AW) additives used in today's grease formulations account for a not inconsiderable amount of the formulation costs and are thus often the price-driving factor for greases.
- Common lubricant additives and solid lubricants are usually not based on renewable resources and are often difficult to biodegrade.
- most common wear protection additives and friction-reducing lubricant additives require a complex synthetic chemistry and therefore represent a major cost factor. Therefore, especially when using solid lubricants for highly loaded friction points dominate comparatively expensive materials such as MoS 2 or PTFE.
- the object of the invention is thus to avoid the disadvantages of the prior art described above, and to provide lignosulfonates both as a cost structurant and as a wear-protective, friction-reducing and anti-aging additive in lubricating greases and at the same time to provide good water resistance of the greases.
- Low boiling components are those components which boil at up to about 100 ° C at normal pressure, such as water or C 1 to C 4 alcohols.
- the base fat Preferably, to produce the base fat to temperatures of about 120 ° C or better above 180 ° C heated.
- the conversion to the base fat takes place in a heated reactor, which can also be designed as an autoclave or vacuum reactor.
- a second step by cooling the formation of the thickener structure is completed and, if appropriate, further constituents, such as additives and / or base oil, are added to set the desired consistency or the desired property profile.
- the second step may be carried out in the reactor of the first step, but preferably the base grease from the reactor is transferred to a separate stirred tank for cooling and mixing in the optional further constituents.
- the resulting grease is homogenized, filtered and / or vented.
- Ca / Li, Li / Ca and calcium thickened normal and complex soap fats are preferably used, in which calcium lignosulfonate is added even before the reaction phase to produce the base fat and incorporated into the grease structure by way of a thermal process in such a way that is very homogeneous oil-insoluble form and leads to high dropping point temperatures.
- alkaline earth salts preferably calcium salts
- lignosulfonate ensures that no salification takes place both in the preparation of the base fat and in the application.
- the salification, in particular to the sodium salts, must be prevented in order to obtain a lignosulfonate-containing grease with good water resistance and at the same time a high dropping point. Therefore, avoid the use of sodium lignosulfonate and sodium hydroxide.
- the fat is not emulsified by water according to the test according to DIN 51807-1 (Issue: 1979-04) or the evaluation level 1-90 (test at 90 ° C) corresponds.
- Water resistance is also understood to mean that the grease according to the test according to DIN 51807-2 (1990-03 edition) corresponds to the evaluation level 1-80 (test at 80 ° C.).
- Suitable base oils are customary lubricating oils which are liquid at room temperature.
- the base oil preferably has a kinematic viscosity of 20 to 2500 mm 2 / s, in particular 40 to 500 mm 2 / s at 40 ° C.
- the base oils can be classified as mineral oils or synthetic oils.
- Mineral oils are, for example, considered to be naphthenic and paraffinic mineral oils according to API Group I classification.
- Synthetic oils which may be mentioned are polyethers, esters, polyalphaolefins, polyglycols and alkylaromatics and mixtures thereof.
- the polyether compound may have free hydroxyl groups, but may also be fully etherified or end groups esterified and / or prepared from a starting compound having one or more hydroxy and / or carboxyl groups (-COOH).
- esters of an aromatic di-, tri- or tetracarboxylic acid C2- to C22-alcohols present in or in a mixture
- esters of adipic acid, sebacic acid trimethylolpropane, neopentyl glycol, pentaerythritol or dipentaerythritol with aliphatic branched or unbranched, saturated or unsaturated C2 to C22-carboxylic acids, C18 dimer acid esters with C2 to C22 alcohols, complex esters, as individual components or in any desired mixture.
- the soaps produced are either pure calcium soaps or mixtures containing calcium soaps, in particular besides calcium soaps also lithium soaps and / or aluminum soaps, one or more saturated or unsaturated mono-carboxylic acids with 10 to 32 carbon atoms, optionally substituted, in particular with 12 to 22 carbon atoms, particularly preferred corresponding hydroxycarboxylic acids.
- Suitable carboxylic acids are, for example, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid or behenic acid, and preferably 12-hydroxystearic acid.
- the free acid group and corresponding lower alcohol esters can be used with saponification, z.
- the soap becomes a complex soap by the presence of a complexing agent.
- the lubricating grease compositions according to the invention containing complexing soaps (presence of a complexing agent) have increased dropping points, for example greater than 200 ° C. (DIN ISO 2176).
- the complexing agent to 0.5 to 20 wt.%, In particular 0.5 to 10 wt.% Used.
- the complexing agent (a) is preferably exclusively a calcium salt, in particular if it is used as calcium acetate for the preparation of the base fat.
- Particularly suitable mono-carboxylic acids are acetic acid and propionic acid.
- hydroxybenzoic acids such as parahydroxybenzoic acid, salicylic acids, 2-hydroxy-4-hexylbenzoic acid, metahydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentisic acid), 2,6-dihydroxybenzoic acid (gammaresorcylic acid) or 4-hydroxy-4-methoxybenzoic acid.
- Adipic acid (C 6 H 10 O 4 ), sebacic acid (C 10 H 18 O 4 ), azelaic acid (C 9 H 16 O 4 ) and / or 3- tert -butyl adipic acid (C 10 H 18 O 4 ).
- borate (b) for example, metaborate, diborate, tetraborate or orthoborate, e.g. Monolithium orthoborate or calcium orthoborate.
- Suitable phosphates are alkali metal (preferably lithium) and alkaline earth metal (preferably calcium) dihydrogen phosphate, hydrogen phosphate, or pyrophosphate.
- bentonites such as montmorillonite (whose sodium ions may be exchanged or partially exchanged with ammonium ions), aluminosilicates, clays, silicic acid (eg Aerosil), oil-soluble polymers (eg polyolefins, poly (meth) acrylates, polyisobutylenes, polybutenes, may additionally be added or PS) or di- and polyureas are used as co-thickener.
- the bentonites, aluminosilicates, clays, silicic acid and / or oil-soluble polymers may be added to make the base fat or added later as an additive in the second step.
- the di- and polyureas can be added as an additive.
- compositions according to the invention optionally further contain additives as additives.
- additives in the context of the invention are antioxidants, anti-wear agents, corrosion inhibitors, detergents, dyes, lubricity improvers, viscosity additives, friction reducers and high-pressure additives.
- the grease compositions of this invention contain conventional anti-corrosive, oxidative, and anti-metallope additives which act as chelates, radical scavengers, UV transducers, reaction layer formers, and the like.
- solid lubricants may, for example, polymer powder such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulfides such as molybdenum disulfide, tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth, tin and zinc, inorganic salts of alkali and alkaline earth metals, such as calcium Carbonate, sodium and calcium phosphates are used.
- polymer powder such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulfides such as molybdenum disulfide, tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth, tin and zinc
- metal sulfides such as molybdenum disulfide, tungsten disulfide or mixed sul
- Solid lubricants can be divided into the following four groups: layered structure compounds such as molybdenum disulfide and tungsten disulfide, graphite, hexagonal boron nitride, and some metal halides; oxidic and hydroxidic compounds of the transition and alkaline earth metals or their carbonates or phosphates; soft metals and / or plastics.
- the desired advantageous lubrication properties can be adjusted by the use of lignosulfonates, without having to use solid lubricants. In many cases, these can be dispensed with completely or at least can be significantly minimized. As far as solid lubricants are used graphite can be used advantageously.
- lignosulfonate calcium lignosulfonates having a molecular weight (Mw, weight average) of greater than 10,000, in particular greater than 12,000 or even greater than 15,000 g / mol are used, for example from greater than 10,000 to 66,000 g / mol or 16,000-65,000 g / mol, which in particular 2 to 12% by weight, in particular 4 to 10% by weight, of sulfur (calculated as elemental sulfur) and / or 5 to 15% by weight, in particular 8 to 15% by weight of calcium (calculated Ca).
- Mw molecular weight
- the weight average molecular weight is determined, for example, by size exclusion chromatography.
- a suitable method is the SEC-MALLS method as described in the article by GE Fredheim, SM Braaten and BE Christensen, "Comparison of molecular weight and molecular weight distribution of softwood and hardwood lignosulfonates” published in “Journal of Wood Chemistry and Technology", Vol.23, No.2, pages 197-215, 2003 and the article " Molecular weight determination of lignosulfonates by size exclusion chromatography and multi-angle laser scattering "of the same authors, published in Journal of Chromatography A, Volume 942, Issue 1-2, 4 January 2002, pages 191-199 (Mobile phase: phosphate-DMSO-SDS, stationary phase: Jordi-glucose DVB as described under 2.5).
- Suitable calcium lignosulfonates are, for example, the commercially available products Norlig 11 D and Borrement Ca 120 from Borregard Lignotech.
- the lubricating grease according to the invention is characterized by the features of claim 14 and the lubricating grease, as used in the method according to the invention, by the preferred features of claim 6.
- lignosulfonates act as structure formers for water-resistant lubricating greases with simultaneous properties as solid lubricant or wear protection additive and aging stabilizer.
- surprisingly synergistic effects of lignin sulfonate with other solid lubricants e.g. observed with graphite or calcium carbonate.
- lignosulfonates are multifunctional components for lubricants. Due to their high number of polar groups and aromatic structures, their polymeric structure and their low solubility in all types of lubricating oils, lignosulfonates are not only suitable as thickener constituents but also as solid lubricants in lubricating greases and lubricating pastes. In addition, the sulfur content promotes the EP / AW effect in the lubricating greases and the phenolic structures provide an age-inhibiting effect.
- the lignosulfonate structure has a predominantly planar structure due to its large number of polymeric and polar aromatic units.
- Thickening oils consisting of unmodified or slightly modified native fatty acid esters with metal soaps based on animal or vegetable fatty acids and lignosulfonates used as the only other thickener and simultaneous additive component, we obtain greases, except for the calcium hydroxide used for metal soaps exclusively based on renewable Raw materials were produced. These are resistant to aging and wear, as well as increasing the load stress and reducing friction by the use of lignosulfonates as thickener component.
- the greases according to the invention are particularly suitable for use in or for constant velocity universal joint, rolling bearings and gearbox.
- the lubricating greases are also suitable for loss lubrication in the environmentally sensitive field (for example in mining or agriculture).
- TPE thermoplastic polyetheresters
- CR chloroprenes
- the final product was homogenized on a toothed colloid mill.
- the fat thus obtained is e.g. suitable as constant velocity universal joint grease.
- the final product was homogenized on a toothed colloid mill.
- the fat thus obtained is e.g. suitable as rolling bearing grease.
- the batch was heated in a predetermined temperature program to 225 ° C with stirring, thereby evaporating the added water and the water of reaction.
- additives were added to the batch at certain temperatures.
- the final product was homogenized on a Zahnkolloidmühle.
- the fat thus obtained is e.g. suitable as rolling bearing grease.
- methyl oleate ester Into a reactor, 3500 g of methyl oleate ester, 975 g of calcium 12-hydroystearate, 225 g of calcium acetate and 15 g of calcium borate were charged. The batch was heated in a predetermined temperature program to 200 ° C with stirring. In the cooling phase, additives were added to the batch at certain temperatures. After adjusting the batch to the desired consistency by adding 180 g of methyl oleate ester, the final product was homogenized on a 3-roll mill. The resulting grease is based on predominantly renewable raw materials.
- Methyloleate ester 841 g calcium 12-hydroystearate, 219.5 g calcium acetate, 15 g calcium borate and 418 g calcium lignosulfonate (Norlig 11 D powder from Borregard Lignotech) were introduced into a reactor in 1965 g.
- the batch was heated in a predetermined temperature program to 200 ° C with stirring. In the cooling phase, additives were added to the batch at certain temperatures. After adjusting the batch to the desired consistency by adding 1684 g of trimethylolproprantrioleate ester, the final product was homogenized on a 3-roll mill. The resulting grease is based on predominantly renewable raw materials.
- Example Formulations I and J correspond to the preparation of Example H using different amounts of calcium 12-hydroxy stearate, calcium acetate and calcium lignin sulfonate, as well as different compositions of ester base oils.
- the greases obtained in this way are based on predominantly renewable raw materials.
- Table 1 Cardan shaft grease formulations ⁇ / b> example A B reference invention description Calcium complex Calcium complex with MoS2 with 6% lignosulfonate 1.
- Characteristics method unit 4.1 General physical data Penetration forfeited DIN ISO 2137 0.1mm 263 315 Penetration rolled 60 double acts DIN ISO 2137 0.1mm 351 340 Copper corrosion 24h / 100 ° C DIN 51811 Rank 1-100 1-100 Dropping point DIN ISO 2176 ° C 240 280 Oil separation 18h / 40 ° C DIN 51817 % 0.4 2.1 Oil separation 7d / 40 ° C DIN 51817 % 2 8.9 4.2 Water resistance static water resistance 3h / 90 ° C DIN 51807-1 Rank 1-90 1-90 Washout loss at 80 ° C DIN 51807-2 Rank 1 1 4.3 Reduction of friction SRV at 80 ° C (40Hz, 1.5mm amplitude, 500N load) ASTM D D5707-05 friction 0,107 0.097 course calm calm SRV at 150 ° C (40Hz, 1.5mm amplitude, 500N load) ASTM D D5707-05 friction 0.097 0.085 course calm calm 4.4 Wear protection effect VKA
- lignosulfonate calcium ligninsulfonate 0.0 6.0 0 5.1 1.2 fatty acids / triglycerides: 12-HSA 8.0 5.0 mixed fatty acid 6.9 5.6 Mixed triglyceride 6.8 5.4 1.3
- Alkali Hydroxide LiOH * H2O 0.6 0.4 Ca (OH) 2 1.6 1.0 2.5 2.0 1.4
- Complexing agent sebacic 2.9 1.8 Ca acetate 3.9 2.4 7.0 5.7 Ca-borate 0.4 0.3 2.
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Description
Die Erfindung betrifft ein Verfahren zur Herstellung calciumligninsulfonathaltiger Schmierfette, derartige Schmierfette und deren VerwendungThe invention relates to a process for the preparation of calcium lignosulfonate greases, such lubricating greases and their use
Lignin ist ein komplexes Polymer basierend auf Phenylpropaneinheiten, die untereinander mit einer Bandbreite unterschiedlicher chemischer Bindungen vernetzt sind. Lignin tritt auf in pflanzlichen Zellen zusammen mit Cellulose und Hemicellulose. Lignin selbst ist ein vernetztes Makromolekül mit mittleren Molmassen von z.B. größer 10000 g/mol (Gewichtsmittel).Lignin is a complex polymer based on phenylpropane units, which are interlinked with each other with a range of different chemical bonds. Lignin occurs in plant cells together with cellulose and hemicellulose. Lignin itself is a cross-linked macromolecule with average molecular weights of e.g. greater than 10,000 g / mol (weight average).
Als Monomerbausteine des Lignins können im Wesentlichen 3 Arten von Monolignol-Monomeren identifiziert werden, welche sich im Methoxyilierungsgrad voneinander unterscheiden. Dies sind p-Cumarylalkohol, Coniferylalkohol, and Sinapylalkohol. Diese Lignole sind in Form von Hydroxyphenyl (H)-, Guaiacyl (G)- und Synringal (S)-Einheiten in die Ligninstruktur eingebaut. Nacktsamige Pflanzen (Gymnospermen) wie z.B. Kiefern enthalten überwirkend G-Einheiten und geringe Anteile an H-Einheiten. Alle Lignine enthalten kleine Anteile an unvollständigen oder modifizierten Monolignolen. Die primäre Funktion von Ligninen in Pflanzen ist, diesen mechanische Stabilität zu verleihen durch Quervernetzung der pflanzlichen Polysaccharide. Lignin stellt etwa 1/3 der Trockenmasse von Holz dar und repräsentiert in grober Schätzung 30% der nichtfossilen organischen Kohlenstoffmasse auf der Erde. Es ist das dritthäufigste organische Material nach Cellulose und Chitin und somit auch ein sehr gut verfügbarer nachwachsender Rohstoff für industrielle Erzeugnisse.As monomer building blocks of lignin, essentially 3 types of monolignol monomers can be identified, which differ from each other in the degree of methoxylation. These are p- cumaryl alcohol, coniferyl alcohol, and sinapyl alcohol. These lignols are incorporated into the lignin structure in the form of hydroxyphenyl (H), guaiacyl (G), and syn-ring (S) units. Muscovy plants (Gymnosperms), such as pine trees, contain overwhelmingly G units and small amounts of H units. All lignins contain small amounts of incomplete or modified monolignols. The primary function of lignins in plants is to provide mechanical stability by cross-linking the plant polysaccharides. Lignin represents about 1/3 of the dry mass of wood and roughly represents 30% of the non-fossil organic carbon mass on Earth. It is the third most common organic material after cellulose and chitin and thus also a very readily available renewable raw material for industrial products.
Ligninsulfonat fällt als Nebenprodukt bei der Papierherstellung mit dem Sulfitverfahren an. Dabei wird zu Hackschnitzeln zerkleinertes Holz unter Druck (z.B. 5 bis 7 bar) für ca. 7 bis 15 Stunden in Gegenwart von Calciumhydrogensulfitlauge erhitzt und anschließend über einen Wasch- und Fällungsprozess die Ligninsulfonsäure in Form von Calciumligninsulfonat aus der Lignocellulose entfernt. Anstelle von Calciumhydrogensulfit lassen sich auch Magnesium-, Natrium- oder Ammoniumsulfit- Laugen verwenden, was zu den entsprechenden Magnesium-, Natrium- und Ammoniumsalzen der Ligninsulfonsäure führt.Lignosulfonate is a by-product of papermaking with the sulfite process. In this process, chopped wood is heated to chips under pressure (eg 5 to 7 bar) for about 7 to 15 hours in the presence of calcium hydrogen sulphite solution and then the lignosulphonic acid in the form of calcium lignosulphonate is removed from the lignocellulose by a washing and precipitation process. Instead of calcium hydrogen sulfite, it is also possible to use magnesium, sodium or ammonium sulfite bases, which leads to the corresponding magnesium, sodium and ammonium salts of lignin sulfonic acid.
Durch Eindampfen der Waschlauge erhält man pulverförmige Ligninsulfonate. Die jährliche weltweite Produktion an Ligninsulfonaten beträgt ca. 55 Mio. Tonnen.Evaporation of the wash liquor gives powdered lignosulfonates. The annual worldwide production of lignosulfonates amounts to approx. 55 million tons.
Natrium-, Calcium- und Magnesium-Ligninsulfonate werden häufig als Grundstoff für die Plastifizierung und Verflüssigung von Beton und Mörtel eingesetzt. Eine weitere Verwendung finden Ligninsulfonate als Pelletierhilfsmittel in der Kraftfutterindustrie sowie in anderen Bereichen als Dispergier- oder Komplexierungsmittel.Sodium, calcium and magnesium lignosulfonates are widely used as a base for the plasticization and liquefaction of concrete and mortar. Another use find lignosulfonates as Pelletierhilfsmittel in the concentrated feed industry and in other areas as a dispersant or complexing agent.
In heutigen Schmierfettformulierungen eingesetzte tribochemisch wirkende Extreme Pressure (Hochdruck) und Anti-Wear (Verschleißschutz) - Additive (EP/AW-Additive) nehmen einen nicht unerheblichen Anteil der Formulierungskosten ein und sind somit oft der preistreibende Faktor für Schmierfette.Tribochemically acting extreme pressure (high pressure) and anti-wear (EP / AW) additives used in today's grease formulations account for a not inconsiderable amount of the formulation costs and are thus often the price-driving factor for greases.
Viele dieser Additive werden in aufwendigen mehrstufigen Syntheseverfahren hergestellt und ihre Verwendung ist durch in vielen Fällen auftretende toxikologische Nebenwirkungen sowohl in der Art der Anwendung, als auch in ihrer Einsatzkonzentration in der Endformulierung begrenzt. In einigen Anwendungen, z.B. in Gleichlaufgelenkwellen oder in langsam laufenden und hochbelasteten Wälzlagern lassen sich auch durch flüssige Additive Mangelschmierungszustände bzw. eine Berührung der Reibpartner nicht vermeiden. In diesen Fällen wurden in der bisherigen Praxis Festschmierstoffe auf Basis von anorganischen Verbindungen (z.B. Ca- und Zn-Phosphatsalze), Kunststoffpulvern (z.B. PTFE) oder Metallsulfiden (z.B MoS2) eingesetzt. Auch diese Komponenten sind oft teuer und beeinflussen die Gesamtkosten einer Schmierstoffformulierung entscheidend.Many of these additives are prepared by elaborate multi-step synthesis procedures and their use is limited by toxicological side effects that occur in many cases, both in the way they are used and in their use concentration in the final formulation. In some applications, for example in constant velocity universal joint shafts or in slow-moving and heavily loaded roller bearings, insufficient lubrication conditions or contact between the friction partners can not be avoided even with liquid additives. In these cases, solid lubricants based on inorganic compounds (eg Ca and Zn phosphate salts), plastic powders (eg PTFE) or metal sulfides (eg MoS 2 ) have been used in the past practice. These components are often expensive and have a significant impact on the overall cost of a lubricant formulation.
Bisherige Praxis bei der Schmierfettherstellung ist die Zugabe dieser Additive in einem zweiten, dem eigentlichen chemischen Reaktionsprozess der Verdickerbildung nachgelagerten Prozessschritt. Bei diesem müssen Additive, insbesondere Festschmierstoffe, durch intensive Misch- und Scherprozesse mit erhöhtem mechanischem Aufwand homogen in das vergleichsweise hochviskose Schmierfett verteilt werden, um ihre optimale Wirkung zu erzielen. Aus heutiger Sicht erweist sich Folgendes häufig als nachteilig und hat Anlass zur vorliegenden Erfindung gegeben.Previous practice in the production of grease is the addition of these additives in a second, downstream of the actual chemical reaction process of thickening process step. In this additive, especially solid lubricants must be distributed by intensive mixing and shearing processes with increased mechanical effort homogeneously in the relatively high viscosity grease to achieve their optimum effect. From today's perspective, the following often proves to be disadvantageous and has given rise to the present invention.
Aus der
Gängige Schmierstoff-Additive und Festschmierstoffe basieren i.d.R. nicht auf nachwachsenden Rohstoffen und sind häufig nur schwer biologisch abbaubar. Darüber hinaus machen die meisten gängigen Verschleißschutzadditive und reibwertmindernden Schmierstoffadditive eine aufwendige Synthesechemie erforderlich und stellen daher einen großen Kostenfaktor dar. Insbesondere beim Einsatz von Festschmierstoffen für hochbelastete Reibstellen dominieren daher vergleichsweise teure Materialien wie MoS2 oder PTFE.Common lubricant additives and solid lubricants are usually not based on renewable resources and are often difficult to biodegrade. In addition, most common wear protection additives and friction-reducing lubricant additives require a complex synthetic chemistry and therefore represent a major cost factor. Therefore, especially when using solid lubricants for highly loaded friction points dominate comparatively expensive materials such as MoS 2 or PTFE.
Aufgabe der Erfindung ist es somit, die oben beschriebenen Nachteile des Standes der Technik zu vermeiden, und Ligninsulfonate sowohl als kostengünstige Strukturbildner als auch als verschleißschützendes, reibungsminderndes und alterungsschützendes Additiv in Schmierfetten zur Verfügung zu stellen und gleichzeitig eine gute Wasserbeständigkeit der Schmierfette zu bewirken.The object of the invention is thus to avoid the disadvantages of the prior art described above, and to provide lignosulfonates both as a cost structurant and as a wear-protective, friction-reducing and anti-aging additive in lubricating greases and at the same time to provide good water resistance of the greases.
Durch die Anwesenheit von Ligninsulfonat kann der Einsatz anderer gängiger Schmierstoffadditive und Festschmierstoffe, insbesondere MoS2, minimiert oder auf diese sogar verzichtet werden.Due to the presence of lignosulfonate, the use of other common lubricant additives and solid lubricants, in particular MoS 2 , can be minimized or even dispensed with.
Die Erfindung ist durch die unabhängigen Ansprüche bezeichnet. Bevorzugte Ausgestaltungen sind Gegenstand der Unteransprüche oder nachfolgend beschrieben.The invention is characterized by the independent claims. Preferred embodiments are subject of the dependent claims or described below.
Nach dem der vorliegenden Erfindung zugrunde liegenden Verfahren wird zunächst eine Vorstufe (Basisfett) erstellt durch Zusammenfügen von zumindest
- Grundöl
- Fettsäuren und/oder deren Ester oder deren Salze, wobei das Fettsäuresalz zumindest teilweise ein Calciumsalz ist, zur Herstellung von Seifen enthaltend zumindest Calciumseifen,
- ggf. organische und/oder anorganische Komplexierungsmittel
- Erdalkalihydroxide, wobei die Erdalkalihydroxide zumindest CaOH umfassen,
- ggf. Wasser (z.B. als Teil der Hydroxide) und
- Ca-Ligninsulfonat mit mittleren Molekulargewichten (Gewichtsmittel) von größer 10000 g/mol.
- base oil
- Fatty acids and / or their esters or their salts, where the fatty acid salt is at least partially a calcium salt, for the preparation of soaps containing at least calcium soaps,
- optionally organic and / or inorganic complexing agents
- Alkaline earth hydroxides, the alkaline earth hydroxides comprising at least CaOH,
- optionally water (eg as part of the hydroxides) and
- Ca lignosulfonate having weight average molecular weights of greater than 10,000 g / mol.
Niedrig siedende Komponenten sind solche Komponenten die bei bis etwa 100°C bei Normaldruck sieden wie Wasser oder C1- bis C4- Alkohole.Low boiling components are those components which boil at up to about 100 ° C at normal pressure, such as water or C 1 to C 4 alcohols.
Vorzugsweise wird zur Herstellung des Basisfetts auf Temperaturen von über 120°C oder besser größer 180°C erhitzt. Die Umsetzung zum Basisfett erfolgt in einem beheizten Reaktor, der auch als Autoklav oder Vakuumreaktor ausgeführt sein kann.Preferably, to produce the base fat to temperatures of about 120 ° C or better above 180 ° C heated. The conversion to the base fat takes place in a heated reactor, which can also be designed as an autoclave or vacuum reactor.
Nachfolgend wird in einem zweiten Schritt durch Abkühlen die Bildung der Verdickerstruktur vervollständigt und ggf. weitere Bestandteile wie Additive und/oder Grundöl zur Einstellung der gewünschten Konsistenz oder des gewünschten Eigenschaftsprofils zugegeben. Der zweite Schritt kann in dem Reaktor des ersten Schrittes ausgeführt werden, vorzugsweise wird aber das Basisfett aus dem Reaktor in einen separaten Rührkessel zum Abkühlen und Einmischen der ggf. weiteren Bestandteile überführt.Subsequently, in a second step by cooling, the formation of the thickener structure is completed and, if appropriate, further constituents, such as additives and / or base oil, are added to set the desired consistency or the desired property profile. The second step may be carried out in the reactor of the first step, but preferably the base grease from the reactor is transferred to a separate stirred tank for cooling and mixing in the optional further constituents.
Im Bedarfsfall wird das so gewonnene Schmierfett homogenisiert, filtriert und/oder entlüftet.If necessary, the resulting grease is homogenized, filtered and / or vented.
Es kommen vorzugsweise Ca/Li-, Li/Ca- und Calcium-verdickte Normal- und Komplexseifenfette zum Einsatz, bei denen Calciumligninsulfonat bereits vor der Reaktionsphase zur Herstellung des Basisfetts zugegeben und über einen thermischen Prozess so in die Schmierfettstruktur eingebaut wird, dass es in sehr homogener ölunlöslicher Form vorliegt und zu hohen Tropfpunkttemperaturen führt.Ca / Li, Li / Ca and calcium thickened normal and complex soap fats are preferably used, in which calcium lignosulfonate is added even before the reaction phase to produce the base fat and incorporated into the grease structure by way of a thermal process in such a way that is very homogeneous oil-insoluble form and leads to high dropping point temperatures.
Durch den Einsatz von Erdalkalisalzen, vorzugsweise Calciumsalzen, sowohl auf Seite der Fettsäuresalze als auch des Ligninsulfonats wird sichergestellt, dass keine Umsalzung sowohl bei der Herstellung des Basisfettes als auch in der Anwendung stattfindet.The use of alkaline earth salts, preferably calcium salts, both on the side of the fatty acid salts and the lignosulfonate ensures that no salification takes place both in the preparation of the base fat and in the application.
Die Umsalzung, insbesondere zu den Natriumsalzen, muss verhindert werden, um ein ligninsulfonathaltiges Schmierfett mit guter Wasserbeständigkeit und gleichzeitig hohem Tropfpunkt zu erhalten. Deshalb ist der Einsatz von Natriumligninsulfonat und Natriumhydroxid zu vermeiden. Unter Wasserbeständigkeit wird verstanden, dass das Fett gemäß der Prüfung nach DIN 51807-1 (Ausgabe: 1979-04) nicht durch Wasser emulgiert wird bzw. der Bewertungsstufe 1-90 (Prüfung bei 90°C) entspricht. Unter Wasserbeständigkeit wird daneben auch verstanden, dass das Fett gemäß der Prüfung nach DIN 51807-2 (Ausgabe 1990-03) der Bewertungsstufe 1-80 (Prüfung bei 80°C) entspricht.The salification, in particular to the sodium salts, must be prevented in order to obtain a lignosulfonate-containing grease with good water resistance and at the same time a high dropping point. Therefore, avoid the use of sodium lignosulfonate and sodium hydroxide. Under water resistance is understood that the fat is not emulsified by water according to the test according to DIN 51807-1 (Issue: 1979-04) or the evaluation level 1-90 (test at 90 ° C) corresponds. Water resistance is also understood to mean that the grease according to the test according to DIN 51807-2 (1990-03 edition) corresponds to the evaluation level 1-80 (test at 80 ° C.).
Durch die gleichzeitige Anwendung eines Alkaliüberschusses in Form von überschüssigem Calciumhydroxid und ggf. zusätzlich Calciumacetat oder anderer Calciumsalze als Komplexierungsmittel soll sichergestellt werden, dass auch geringe Reste an freien Sulfonsäure-Gruppen in der Ligninsulfonsäure neutralisiert und einer hygroskopischen sowie wasseremulgierenden und korrosionsfördernden Wirkung entzogen werden. Durch eine hohe Prozesstemperatur von größer 120°C, insbesondere größer 180°C wird zusätzlich sichergestellt, dass die noch im Ligninsulfonat eingetragene Restfeuchte komplett aus dem Reaktionsmedium verdampft wird und ggf. nicht neutralisierte Bestandteile des Ligninsulfonats durch Calciumhydroxid neutralisiert werden.By the simultaneous use of an excess of alkali in the form of excess calcium hydroxide and optionally additionally calcium acetate or other calcium salts as a complexing agent to ensure that even small residues of free sulfonic acid groups are neutralized in the lignosulfonic acid and removed hygroscopic and water emulsifying and corrosive effect. By a high process temperature of greater than 120 ° C, in particular greater than 180 ° C is additionally ensured that the residual moisture still registered in the lignosulfonate is completely evaporated from the reaction medium and possibly neutralized components of the lignosulfonate are neutralized by calcium hydroxide.
Als Grundöle sind übliche bei Raumtemperatur flüssige Schmieröle geeignet. Das Grundöl weist vorzugsweise eine kinematische Viskosität von 20 bis 2500 mm2/s, insbesondere von 40 bis 500 mm2/s bei 40 °C auf.Suitable base oils are customary lubricating oils which are liquid at room temperature. The base oil preferably has a kinematic viscosity of 20 to 2500 mm 2 / s, in particular 40 to 500 mm 2 / s at 40 ° C.
Die Grundöle können als Mineralöle oder Syntheseöle klassifiziert werden. Als Mineralöle werden z.B. betrachtet naphthenbasische und paraffinbasische Mineralöle gemäß Klassifizierung nach API Group I. Chemisch modifizierte aromaten- und schwefelarme Mineralöle mit geringem Anteil an gesättigten Verbindungen und gegenüber Group I - Ölen verbessertem Viskositäts-/Temperatur-Verhalten, klassifiziert nach API Group II und III, sind ebenfalls geeignet.The base oils can be classified as mineral oils or synthetic oils. Mineral oils are, for example, considered to be naphthenic and paraffinic mineral oils according to API Group I classification. Chemically modified low aromatic and low sulfur mineral oils with low content of saturated compounds and Group I oils improved viscosity / temperature behavior, classified according to API Group II and III , are also suitable.
Als Syntheseöle genannt seien Polyether, Ester, Polyalphaolefine, Polyglykole und Alkylaromaten und deren Mischungen. Die Polyether-Verbindung kann freie Hydroxylgruppen aufweisen, aber auch vollständig verethert oder Endgruppen verestert sein und/oder aus einer Startverbindung mit einer oder mehreren Hydroxy- und/oder Carboxylgruppen (-COOH) hergestellt sein. Möglich sind auch Polyphenylether, ggf. alkyliert, als alleinige Komponenten oder besser noch als Mischkomponenten. Geeignet einsetzbar sind Ester einer aromatischen Di-, Tri- oder Tetracarbonsäure, mit einem oder in Mischung vorliegenden C2- bis C22-Alkoholen, Ester von Adipinsäure, Sebacinsäure, Trimethylolopropan, Neopentylglykol, Pentaerythrit oder Dipentaerythrit mit aliphatischen verzweigten oder unverzweigten, gesättigten oder ungesättigten C2 bis C22-Carbonsäuren, C18-Dimersäureestern mit C2 bis C22-Alkoholen, Komplexester, als Einzelkomponenten oder in beliebiger Mischung.Synthetic oils which may be mentioned are polyethers, esters, polyalphaolefins, polyglycols and alkylaromatics and mixtures thereof. The polyether compound may have free hydroxyl groups, but may also be fully etherified or end groups esterified and / or prepared from a starting compound having one or more hydroxy and / or carboxyl groups (-COOH). Also possible are polyphenyl ethers, optionally alkylated, as sole components or even better as mixed components. Suitable for use are esters of an aromatic di-, tri- or tetracarboxylic acid, C2- to C22-alcohols present in or in a mixture, esters of adipic acid, sebacic acid, trimethylolpropane, neopentyl glycol, pentaerythritol or dipentaerythritol with aliphatic branched or unbranched, saturated or unsaturated C2 to C22-carboxylic acids, C18 dimer acid esters with C2 to C22 alcohols, complex esters, as individual components or in any desired mixture.
Die hergestellten Seifen sind entweder reine Calciumseifen oder Gemische enthaltend Calciumseifen, insbesondere neben Calciumseifen auch Lithiumseifen und/oder Aluminiumseifen, einer oder mehrerer gesättigter oder ungesättigter Mono-Carbonsäuren mit 10 bis 32 Kohlenstoffatomen, ggf. substituiert, insbesondere mit 12 bis 22 Kohlenstoffatomen, besonders bevorzugt entsprechende Hydroxycarbonsäuren. Geeignete Carbonsäuren sind z.B. Laurinsäure, Myristinsäure, Palmitinsäure, Ölsäure, Stearinsäure oder Behensäure sowie bevorzugt 12-Hydroxystearinsäure. Anstelle der freien Säuregruppe können auch entsprechende niedere Alkoholester unter Verseifung eingesetzt werden, z. B. entsprechende Triglyceride sowie die Methyl-, Ethyl-, Propyl-, Isopropyl- oder sec.-Butylester der Säure/Hydroxysäure, um eine bessere Dispersion zu erzielen.The soaps produced are either pure calcium soaps or mixtures containing calcium soaps, in particular besides calcium soaps also lithium soaps and / or aluminum soaps, one or more saturated or unsaturated mono-carboxylic acids with 10 to 32 carbon atoms, optionally substituted, in particular with 12 to 22 carbon atoms, particularly preferred corresponding hydroxycarboxylic acids. Suitable carboxylic acids are, for example, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid or behenic acid, and preferably 12-hydroxystearic acid. Instead of the free acid group and corresponding lower alcohol esters can be used with saponification, z. B. corresponding triglycerides and the methyl, ethyl, propyl, isopropyl or sec-butyl ester of acid / hydroxy acid to achieve a better dispersion.
Die Seife wird durch die Anwesenheit eines Komplexierungsmittels zur Komplexseife. Die erfindungsgemäßen Schmierfettzusammensetzungen enthaltend Komplexseifen (Anwesenheit eines Komplexierungsmittels) weisen erhöhte Tropfpunkte auf, von z.B. größer 200°C (DIN ISO 2176). Geeigneterweise wird das Komplexierungsmittel zu 0,5 bis 20 Gew.%, insbesondere 0,5 bis 10 Gew.% eingesetzt.The soap becomes a complex soap by the presence of a complexing agent. The lubricating grease compositions according to the invention containing complexing soaps (presence of a complexing agent) have increased dropping points, for example greater than 200 ° C. (DIN ISO 2176). Suitably, the complexing agent to 0.5 to 20 wt.%, In particular 0.5 to 10 wt.% Used.
Komplexierungsmittel im Sinne der vorliegenden Erfindung sind:
- (a) das Alkalisalz (bevorzugt Lithiumsalz) ausgenommen Natriumsalz, Erdalkalisalz (bevorzugt Calciumsalz) oder Aluminiumsalz einer gesättigten oder ungesättigten Mono - Carbonsäure oder auch Hydroxycarbonsäuren mit 2 bis 8, insbesondere 2 bis 4 Kohlenstoffatomen oder einer Di-Carbonsäure mit 2 bis 16, insbesondere 2 bis 12 Kohlenstoffatomen, jeweils ggf. substituiert, und/oder
- (b) das Alkali- und/oder Erdalkalisalz der Borsäure und/oder Phosphorsäure, insbesondere deren Umsetzungsprodukte mit LiOH und/oder Ca(OH)2.
- (a) the alkali salt (preferably lithium salt) excluding sodium salt, alkaline earth salt (preferably calcium salt) or aluminum salt of a saturated or unsaturated mono-carboxylic acid or hydroxycarboxylic acids having 2 to 8, in particular 2 to 4 carbon atoms or a di-carboxylic acid having 2 to 16, in particular 2 to 12 carbon atoms, each optionally substituted, and / or
- (b) the alkali and / or alkaline earth metal salt of boric acid and / or phosphoric acid, in particular their reaction products with LiOH and / or Ca (OH) 2 .
Bevorzugt ist das Komplexierungsmittel (a) ausschließlich ein Calciumsalz, insbesondere wenn dieses als Calciumacteat zur Herstellung des Basisfetts eingesetzt wird. Als Mono-Carbonsäuren sind insbesondere geeignet Essigsäure und Propionsäure. Ebenfalls geeignet sind auch Hydroxybenzoesäuren wie Parahydroxybenzoesäure, Salicylsäuren, 2-Hydroxy-4-hexylbenzoesäure, Metahydroxybenzoesäure, 2,5-Dihydroxybenzoesäure (Gentisinsäure), 2,6-Dihydroxybenzoesäure (Gammaresorcylsäure) oder 4-Hydroxy-4-methoxybenzoesäure. Als Dicarbonsäuren sind insbesondere geeignet Adipinsäure (C6H10O4), Sebacinsäure (C10H18O4), Azelainsäure (C9H16O4) und/oder 3-tert.-Butyl-Adipinsäure (C10H18O4).The complexing agent (a) is preferably exclusively a calcium salt, in particular if it is used as calcium acetate for the preparation of the base fat. Particularly suitable mono-carboxylic acids are acetic acid and propionic acid. Also suitable are hydroxybenzoic acids such as parahydroxybenzoic acid, salicylic acids, 2-hydroxy-4-hexylbenzoic acid, metahydroxybenzoic acid, 2,5-dihydroxybenzoic acid (gentisic acid), 2,6-dihydroxybenzoic acid (gammaresorcylic acid) or 4-hydroxy-4-methoxybenzoic acid. Adipic acid (C 6 H 10 O 4 ), sebacic acid (C 10 H 18 O 4 ), azelaic acid (C 9 H 16 O 4 ) and / or 3- tert -butyl adipic acid (C 10 H 18 O 4 ).
Als Borat (b) kann beispielsweise Metaborat, Diborat, Tetraborat oder Orthoborat, wie z.B. Monolithiumorthoborat oder Calciumorthoborat, eingesetzt werden. Als Phosphate kommen Alkali- (bevorzugt Lithium-) sowie Erdalkali-(bevorzugt Calcium-) dihydrogenphosphat, -hydrogenphosphat, oder - pyrophosphat in Frage.As the borate (b), for example, metaborate, diborate, tetraborate or orthoborate, e.g. Monolithium orthoborate or calcium orthoborate. Suitable phosphates are alkali metal (preferably lithium) and alkaline earth metal (preferably calcium) dihydrogen phosphate, hydrogen phosphate, or pyrophosphate.
Fakultativ können zusätzlich Bentonite, wie Montmorillonit (deren Natrium-Ionen ggf. durch Ammonium-Ionen ausgetauscht bzw. teilausgetauscht sind), Aluminosilikate, Tonerden, Kieselsäure (z.B. Aerosil), öllösliche Polymere (z.B. Polyolefine, Poly(meth)acrylate, Polyisiobutylene, Polybutene oder PS) oder auch Di- und Polyharnstoffe als Co-Verdicker eingesetzt werden. Die Bentonite, Aluminosilikate, Tonerden, Kieselsäure und/oder öllöslichen Polymere können zur Herstellung des Basisfetts zugegeben sein oder später als Additiv im zweiten Schritt zugegeben werden. Die Di- und Polyharnstoffe können als Additiv zugesetzt werden.In addition, bentonites, such as montmorillonite (whose sodium ions may be exchanged or partially exchanged with ammonium ions), aluminosilicates, clays, silicic acid (eg Aerosil), oil-soluble polymers (eg polyolefins, poly (meth) acrylates, polyisobutylenes, polybutenes, may additionally be added or PS) or di- and polyureas are used as co-thickener. The bentonites, aluminosilicates, clays, silicic acid and / or oil-soluble polymers may be added to make the base fat or added later as an additive in the second step. The di- and polyureas can be added as an additive.
Die erfindungsgemäßen Zusammensetzungen enthalten ggf. weiterhin Additive als Zusatzstoffe. Übliche Zusatzstoffe im Sinne der Erfindung sind Antioxidationsmittel, Verschleißschutzmittel, Korrosionsschutzmittel, Detergentien, Farbstoffe, Schmierfähigkeitsverbesserer, Viskositätsadditive, Reibungsminderer und Hochdruckadditive.The compositions according to the invention optionally further contain additives as additives. Usual additives in the context of the invention are antioxidants, anti-wear agents, corrosion inhibitors, detergents, dyes, lubricity improvers, viscosity additives, friction reducers and high-pressure additives.
Beispielhaft genannt seien:
- Antioxidationsmittel wie Amin-Verbindungen (z.B. Alkylamine oder 1-Phenyl-aminonaphthalin), aromatische Amine, wie z.B. Phenylnaphtylamine oder Diphenylamine, Phenol-Verbindungen (z.B. 2.6-Di-tert-butyl-4-methylphenol), Sulfurantioxidantien, Zinkdithiocarbamat oder Zinkdithiophosphat;
- Hochdruckadditive wie organische Chlorverbindungen, Schwefel, Phosphor oder Calciumborat, Zinkdithiophosphat, organische Bismuthverbindungen;
- die "Öligkeit" verbessernde Wirkstoffe wie C2- bis C6- Polyole, Fettsäuren, Fettsäureester oder tierische oder pflanzliche Öle;
- Antikorrosionsmittel wie z.B. Petroleumsulfonat, Dinonylnaphtalinsulfonat oder Sorbitanester;
- Metalldeaktivatoren wie z.B. Benzotriazol oder Natriumnitrit;
- Viskositätsverbesserer wie z.B. Polymethacrylat, Polyisobutylen, oligo-Dec-1-ene, und Polystyrole;
- Verschleißschutzadditive und Reibungsminderer wie Organomolybdänkomplexe (OMC), Molybdän-di-alkyl-dithiophosphate, Molybdän-di-alkyl-dithiocarbamate oder Molybdänsulfid-di-alkyl-dithiocarbamate, insbesondere Molybdän-di-n-butyldithiocarbamat und Molybdändisulfid-di-alkyldithiocarbamat (Mo2OmSn(dialkylcarbamat)2 mit m = 0 bis 3 und n = 4 bis 1),
- Reibungsminderer wie z.B. funktionelle Polymere wie z.B. Oleylamide, organische Verbindungen auf Polyether- und Amidbasis, z.B. Alkylpolyethylenglykoltetradecylenglykolether.
- Antioxidants, such as amine compounds (eg, alkylamines or 1-phenylaminonaphthalene), aromatic amines, such as phenylnaphthylamine or diphenylamine, phenolic compounds (eg, 2,6-di-tert-butyl-4-methylphenol), sulfur antioxidants, zinc dithiocarbamate, or zinc dithiophosphate;
- High pressure additives such as organic chlorine compounds, sulfur, phosphorus or calcium borate, zinc dithiophosphate, organic bismuth compounds;
- the "oiliness" improving agents such as C2 to C6 polyols, fatty acids, fatty acid esters or animal or vegetable oils;
- Anti-corrosion agents such as petroleum sulfonate, dinonylnaphthalenesulfonate or sorbitan esters;
- Metal deactivators such as benzotriazole or sodium nitrite;
- Viscosity improvers such as polymethacrylate, polyisobutylene, oligo-dec-1-ene, and polystyrenes;
- Wear protection additives and friction modifiers such as organomolybdenum complexes (OMC), molybdenum di-alkyl dithiophosphates, molybdenum di-alkyl dithiocarbamates or molybdenum sulfide di-alkyl dithiocarbamates, in particular molybdenum di-n-butyl dithiocarbamate and molybdenum disulfide di-alkyl dithiocarbamate (Mo 2 O m S n (dialkylcarbamate) 2 with m = 0 to 3 and n = 4 to 1),
- Friction reducers such as functional polymers such as oleylamides, organic compounds based on polyether and amide, for example Alkylpolyethylenglykoltetradecylenglykolether.
Darüber hinaus enthalten die erfindungsgemäßen Schmierfettzusammensetzungen übliche Additive gegen Korrosion, Oxidation und zum Schutz gegen Metalleinflüsse, die als Chelatverbindungen, Radikalfänger, UV-Umwandler, Reaktionsschichtbildner und dergleichen wirken.In addition, the grease compositions of this invention contain conventional anti-corrosive, oxidative, and anti-metallope additives which act as chelates, radical scavengers, UV transducers, reaction layer formers, and the like.
Als Festschmierstoffe können z.B. Polymerpulver wie Polyamide, Polyimide oder PTFE, Graphit, Metalloxide, Bornitrid, Metallsulfide wie z.B. Molybdändisulfid, Wolframdisulfid oder Mischsulfide auf Basis von Wolfram, Molybdän, Bismuth, Zinn und Zink, anorganische Salze der Alkali- und Erdalkalimetalle, wie z.B. Calcium-Carbonat, Natrium- und Calciumphosphate, eingesetzt werden. Festschmierstoffe können in folgende vier Gruppen unterteilt werden: Verbindungen mit Schichtgitterstruktur, wie Molybdändisulfid und Wolframdisulfid, Graphit, hexagonales Bornitrid und einige Metallhalogenide; oxidische und hydroxidische Verbindungen der Übergangs- und Erdalkalimetalle bzw. deren Carbonate oder Phosphate; weiche Metalle und/oder Kunststoffe. Die gewünschten vorteilhaften Schmierungseigenschaften lassen sich durch den Einsatz von Ligninsulfonaten einstellen, ohne dass Festschmierstoffe eingesetzt werden müssen. In vielen Fällen kann auf diese gänzlich verzichtet werden oder aber diese können zumindest deutlich minimiert werden. Soweit Festschmierstoffe eingesetzt werden ist Graphit vorteilhaft einsetzbar.As solid lubricants may, for example, polymer powder such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulfides such as molybdenum disulfide, tungsten disulfide or mixed sulfides based on tungsten, molybdenum, bismuth, tin and zinc, inorganic salts of alkali and alkaline earth metals, such as calcium Carbonate, sodium and calcium phosphates are used. Solid lubricants can be divided into the following four groups: layered structure compounds such as molybdenum disulfide and tungsten disulfide, graphite, hexagonal boron nitride, and some metal halides; oxidic and hydroxidic compounds of the transition and alkaline earth metals or their carbonates or phosphates; soft metals and / or plastics. The desired advantageous lubrication properties can be adjusted by the use of lignosulfonates, without having to use solid lubricants. In many cases, these can be dispensed with completely or at least can be significantly minimized. As far as solid lubricants are used graphite can be used advantageously.
Als Ligninsulfonat werden Calcium-Ligninsulfonate mit Molekulargewicht (Mw, Gewichtsmittel) von größer 10000, insbesondere größer 12000 oder sogar größer 15000 g/mol eingesetzt, z.B. von größer 10000 bis 66000 g/mol oder 16000 - 65000 g/mol, welche insbesondere 2 bis 12 Gew.%, insbesondere 4 bis 10 Gew.%, Schwefel (berechnet als elementarer Schwefel) und/oder 5 bis 15 Gew.%, insbesondere 8 bis 15 Gew.% Calcium (berechnet Ca) enthalten. Neben Calcium-Ligninsulfonaten können auch andere Erdalkali-Ligninsulfonate zusätzlich eingesetzt sein. Das mittlere Molekulargewicht (Gewichtsmittel) wird z.B. mit der Größenausschluss-Chromatographie bestimmt. Eine geeignete Methode ist die SEC-MALLS Methode wie beschrieben in dem Artikel
Das erfindungsgemäße Schmierfett ist gekennzeichnet durch die Merkmale des Anspruchs 14 und das Schmierfett, wie im erfindungsgemäßen Verfahren eingesetzt, durch die Vorzugsmerkmale des Anspruchs 6.The lubricating grease according to the invention is characterized by the features of claim 14 and the lubricating grease, as used in the method according to the invention, by the preferred features of claim 6.
Es wurde nun gefunden, dass Ligninsulfonate als Strukturbildner für wasserbeständige Schmierfette mit gleichzeitigen Eigenschaften als Festschmierstoff bzw. Verschleißschutzadditiv und Alterungsstabilisator wirken. Gleichzeitig wurden überraschend synergistische Wirkungen des Ligninsulfonats mit anderen Festschmierstoffen, z.B. mit Graphit oder Calciumcarbonat beobachtet.It has now been found that lignosulfonates act as structure formers for water-resistant lubricating greases with simultaneous properties as solid lubricant or wear protection additive and aging stabilizer. At the same time, surprisingly synergistic effects of lignin sulfonate with other solid lubricants, e.g. observed with graphite or calcium carbonate.
Es wurde ebenfalls gefunden, dass Ligninsulfonate multifunktionale Komponenten für Schmierstoffe darstellen. Aufgrund ihrer hohen Anzahl an polaren Gruppen und aromatischen Strukturen, ihres polymeren Aufbaus und der geringen Löslichkeit in allen Arten von Schmierölen eignen sich Ligninsulfonate nicht nur als Verdickerbestandteil sondern auch als Festschmierstoffe in Schmierfetten und Schmierpasten. Zudem fördert der Schwefelanteil die EP/AW-Wirkung in den Schmierfetten und die phenolischen Strukturen sorgen für eine alterungsinhibierende Wirkung.It has also been found that lignosulfonates are multifunctional components for lubricants. Due to their high number of polar groups and aromatic structures, their polymeric structure and their low solubility in all types of lubricating oils, lignosulfonates are not only suitable as thickener constituents but also as solid lubricants in lubricating greases and lubricating pastes. In addition, the sulfur content promotes the EP / AW effect in the lubricating greases and the phenolic structures provide an age-inhibiting effect.
Es wird angenommen, dass die Ligninsulfonat - Struktur durch ihre in großer Anzahl vorhandenen polymeren und polaren aromatischen Einheiten einen überwiegend planaren Aufbau besitzt.It is believed that the lignosulfonate structure has a predominantly planar structure due to its large number of polymeric and polar aromatic units.
Somit können diese sich unter Einwirkung äußerer Reib- und Scherkräfte sehr gut in Schichtstrukturen auf Metalloberflächen ablagern, weil die aromatischen Kerne des Ligninsulfonates in eine assoziative Wechselwirkung mit der Metalloberfläche treten, und auch bei hohen Lasten bzw. Drücken metallische Reibpartner wirksam und dauerhaft voneinander trennen.Thus, under the action of external frictional and shear forces, these can deposit very well in layer structures on metal surfaces, because the aromatic nuclei of the lignin sulfonate interact in an associative manner with the metal surface and efficiently and permanently separate metallic friction partners even at high loads or pressures.
Gibt man Calcium-Ligninsulfonat bereits vor Beginn der Reaktionsphase bei der Herstellung von Seifenverdickern, insbesondere von Calciumkomplexseifen zu, so bewirken diese zum einen einen zusätzlichen Verdickungseffekt und einen hohen Tropfpunkt und zum anderen verbessern sie die Verschleißschutz- und die Schmierwirkungen entsprechender Schmierfettformulierungen. Deshalb ist es für die Verteilung und Wirkung von Additiven und Festschmierstoffen günstig, wenn diese bereits während der Reaktionsphase als zusätzliches Strukturelement in situ in die Verdickerstruktur chemisch oder mechanisch eingebunden werden.If calcium lignosulfonate is added even before the start of the reaction phase in the production of soap thickeners, in particular of calcium complex soaps, these on the one hand produce an additional thickening effect and a high dropping point and on the other hand they improve the wear protection and lubricating effects of corresponding grease formulations. Therefore, it is beneficial for the distribution and effect of additives and solid lubricants, if they are chemically or mechanically integrated during the reaction phase as an additional structural element in situ in the thickener structure.
Für die Herstellung von Seifenfetten mit hohen Tropfpunkten müssen nach dem Stand der Technik in vielen Fällen speziell behandelte und teure Fettsäuren wie z.B. 12-Hydroxistearinsäure oder spezielle Komplexbildner wie z.B. Borate oder Salze der Essigsäure, Sebacinsäure und Azelainsäure eingesetzt werden, die keine oder nur eine geringe gleichzeitige Wirkung als Verschleißschutz- und reibungsminderndes Additiv aufweisen. Durch Einsatz von Ca-Ligninsulfonaten kann der Einsatz der genannten Komponenten reduziert oder auf diese sogar verzichtet werden. Weiterhin bietet der Einsatz von Ca-Ligninsulfonaten die Möglichkeit, Hochleistungschmierfette auf Basis nachwachsender Rohstoffe zu formulieren und auf eine umweltbelastende Additivchemie zu verzichten.For the production of soap greases with high dropping points, in many cases specially treated and expensive fatty acids, e.g. 12-hydroxistearic acid or special chelating agents such as e.g. Borates or salts of acetic acid, sebacic acid and azelaic acid are used, which have no or only a small simultaneous effect as anti-wear and friction-reducing additive. By using Ca lignosulfonates, the use of said components can be reduced or even dispensed with. Furthermore, the use of Ca lignosulfonates offers the opportunity to formulate high performance lubricating fats based on renewable raw materials and to dispense with an environmentally harmful additive chemistry.
Verdickt man Öle bestehend aus unveränderten oder leicht modifizierten nativen Fettsäureestern mit Metallseifen auf Basis tierischer oder pflanzlicher Fettsäuren und verwendet man Ligninsulfonate als einzige weitere Verdicker- und gleichzeitige Additivkomponente, so erhält man Schmierfette, die bis auf das für die Metallseifen verwendete Calciumhydroxid ausschließlich auf Basis nachwachsender Rohstoffe hergestellt wurden. Diese sind alterungs- und verschleißschützend sowie freßlasterhöhend und reibungsmindernd ausgestattet durch den Einsatz von Ligninsulfonaten als Verdickerkomponente.Thickening oils consisting of unmodified or slightly modified native fatty acid esters with metal soaps based on animal or vegetable fatty acids and lignosulfonates used as the only other thickener and simultaneous additive component, we obtain greases, except for the calcium hydroxide used for metal soaps exclusively based on renewable Raw materials were produced. These are resistant to aging and wear, as well as increasing the load stress and reducing friction by the use of lignosulfonates as thickener component.
Die erfindungsgemäßen Schmierfette sind besonders geeignet zur Verwendung in oder für Gleichlaufgelenkwellen, Wälzlager und Getriebe.The greases according to the invention are particularly suitable for use in or for constant velocity universal joint, rolling bearings and gearbox.
Soweit die verwendeten Grundöle aus biologisch gut abbaubaren Estern, wie z.B. solche enthaltend überwiegend nachwachsende Rohstoffe, bestehen, sind die Schmierfette auch für die Verlustschmierung im umweltsensiblen Bereich (z.B. im Bergbau oder der Landwirtschaft) geeignet.Insofar as the base oils used are readily biodegradable esters, e.g. those containing predominantly renewable raw materials, the lubricating greases are also suitable for loss lubrication in the environmentally sensitive field (for example in mining or agriculture).
Im besonderen Falle der Schmierung wartungsfreier Gleichlaufgelenkwellen wurde unter Verwendung von Calciumligninsulfonat erstmals ein Schmierfett formuliert, das im Gegensatz zum Stand der Technik gänzlich ohne MoS2 und andere organische und anorganische Molybdänverbindungen zu hohen Lebensdauern und guten Wirkungsgraden führt.In the particular case of lubrication maintenance-free constant velocity universal joint shafts was first formulated using calcium lignosulfonate a grease, which leads in contrast to the prior art entirely without MoS 2 and other organic and inorganic molybdenum compounds to high lifetimes and good efficiencies.
Zudem bewirkt der Verzicht auf andere Additive als Reibwertminderer, Fresslast- und Verschleißschutz eine sehr gute Verträglichkeit mit handelsüblichen Gelenkwellenfaltenbalgmaterialien wie Chloroprenkautschuk und thermoplastischen Polyetherestern. Da der in Ligninsulfonat enthaltende Schwefel durch thermisch stabile Sulfonatgruppen gebunden ist, kann er im Gegensatz zu dem in herkömmlichen Additiven gebundenen Schwefel erst bei sehr hohen Temperaturen bzw. Aktivierungsenergien freigesetzt werden, wie sie in Schmierfettanwendungen nur bei hochbelasteten Tribokontakten auftreten. Somit wird eine nachträgliche Vulkanisation bzw. Vernetzung von Kautschukmaterialien durch aus dem gealterten Schmierstoff freigesetzten Schwefel weitgehend verhindert.In addition, the omission of other additives as Reibwertminderer, Fresslast- and wear protection causes a very good compatibility with commercially available Gelenkwellenfaltenbalgmaterialien such as chloroprene rubber and thermoplastic polyether esters. Since the sulfur containing lignosulfonate is bound by thermally stable sulfonate groups, unlike the sulfur bound in conventional additives, it can only be released at very high temperatures or activation energies, such as occur in grease applications only with highly loaded tribocontacts. Thus, a subsequent vulcanization or crosslinking of rubber materials is largely prevented by sulfur released from the aged lubricant.
Durch den Einsatz von Calciumligninsulfonat in einer durch überschüssiges Calciumhydroxid überbasisch eingestellten Schmierfettformulierung wird verhindert, dass freie Ligninsulfonsäure eine hydrolytische Wirkung auf Faltenbalgmaterialen wie thermoplastische Polyetherester entfalten kann.The use of calcium lignosulfonate in overbased excess calcium hydroxide grease formulation prevents free lignin sulfonic acid from exerting a hydrolytic effect on bellows materials such as thermoplastic polyether esters.
Es ist ein besonderer Aspekt der vorliegenden Erfindung, zu kostenoptimierten Schmierfettformulierungen für hochbelastete Schmierstellen wie insbesondere in Gleichlaufgelenke zu gelangen, die eine gute Verträglichkeit zu Faltenbälgen, aufgebaut aus z.B. thermoplastischen Polyetherestern (TPE) und Chloroprenen (CR) aufweisen, bei gleichzeitig hohem Wirkungsgrad, geringem Verschleiß und langer Lebensdauer.It is a particular aspect of the present invention to arrive at cost-optimized lubricating grease formulations for highly loaded lubrication points, in particular in constant velocity joints, which have good compatibility with bellows made of, for example, thermoplastic polyetheresters (TPE) and chloroprenes (CR), with high efficiency, low Wear and long life.
In einen Reaktor wurden in 12000 g einer Grundölmischung 958 g Talgfettsäure, 958g Rindertalg, 958g Calciumacetat, 27,7g Trinatriumphosphat, 27,7g Calciumborat und 358 g Calciumhydroxid vorgelegt und 150ml Wasser zugegeben. Der Ansatz wurde in einem festgelegten Temperaturprogramm auf 198°C unter Rühren erwärmt und dabei das zugegebene Wasser und das Reaktionswasser verdampft. In der Abkühlphase wurden dem Ansatz bei bestimmten Temperaturen Additive (vergleiche Tabelle) zugegeben.Into a reactor, 958 g of tallow fatty acid, 958 g of beef tallow, 958 g of calcium acetate, 27.7 g of trisodium phosphate, 27.7 g of calcium borate and 358 g of calcium hydroxide were placed in 12000 g of a base oil mixture and 150 ml of water were added. The batch was heated in a predetermined temperature program to 198 ° C with stirring while the added water and the water of reaction evaporated. In the cooling phase, additives (see table) were added to the batch at certain temperatures.
Nach der Einstellung des Ansatzes auf die gewünschte Konsistenz durch Zugabe von 3700 g der Basisölmischung wurde das Endprodukt über eine Zahnkolloidmühle homogenisiert. Das so erhaltene Fett ist z.B. als Gleichlaufgelenkwellenfett geeignet.After adjusting the batch to the desired consistency by adding 3700 g of the base oil mixture, the final product was homogenized on a toothed colloid mill. The fat thus obtained is e.g. suitable as constant velocity universal joint grease.
In einen Reaktor wurden in 14000 g einer Grundölmischung 460 g Talgfettsäure, 445g Rindertalg, 460g Calciumacetat, 27,7g Trinatriumphosphat, 27,7g Calciumborat und 168 g Calciumhydroxid und 920g Calciumligninsulfonat (Norlig 11 D Pulver von Borregard Lignotech) vorgelegt und 150ml Wasser zugegeben. Der Ansatz wurde in einem festgelegten Temperaturprogramm auf 208°C unter Rühren erwärmt und dabei das zugegebene Wasser und das Reaktionswasser verdampft. In der Abkühlphase wurden dem Ansatz bei bestimmten Temperaturen Additiv (vergleiche Tabelle) zugegeben. Nach der Einstellung des Ansatzes auf die gewünschte Konsistenz durch Zugabe von 3450 g der Grundölmischung wurde das Endprodukt über eine Zahnkolloidmühle homogenisiert. Das so erhaltene Fett ist z.B. als Gleichlaufgelenkwellenfett geeignet.Into a reactor were placed in 14000 g of a base oil mixture 460 g tallow fatty acid, 445 g beef tallow, 460 g calcium acetate, 27.7 g trisodium phosphate, 27.7 g calcium borate and 168 g calcium hydroxide and 920 g calcium lignosulfonate (Norlig 11 D powder from Borregard Lignotech) and added 150 ml of water. The batch was heated in a predetermined temperature program to 208 ° C with stirring, thereby evaporating the added water and the reaction water. In the cooling phase, additive was added to the batch at certain temperatures (see table). After setting the batch to the desired consistency by adding 3450 g of the base oil mixture, the final product was homogenized on a Zahnkolloidmühle. The fat thus obtained is e.g. suitable as constant velocity universal joint grease.
In einen Reaktor wurden in 5000 g einer Grundölmischung 800 g 12-hydroxistearinsäure, 288g Sebacinsäure, 388g Calciumacetat und 157,3g Calciumhydroxid vorgelegt. 64g LiOH x H2O wurden in 250ml Wasser aufgelöst und zugegeben. Der Ansatz wurde in einem festgelegten Temperaturprogramm auf 200°C unter Rühren erwärmt und dabei das zugegebene Wasser und das Reaktionswasser verdampft. In der Abkühlphase wurden dem Ansatz bei bestimmten Temperaturen Zusätze zugegeben.Into a reactor, 800 g of 12-hydroxystearic acid, 288 g of sebacic acid, 388 g of calcium acetate and 157.3 g of calcium hydroxide were placed in 5000 g of a base oil mixture. 64g of LiOH x H 2 O was dissolved in 250ml of water and added. The mixture was heated in a predetermined temperature program to 200 ° C with stirring, thereby evaporating the added water and the reaction water. In the cooling phase, additives were added to the batch at certain temperatures.
Nach der Einstellung des Ansatzes auf die gewünschte Konsistenz durch Zugabe von 3116 g der Grundölmischung wurde das Endprodukt über eine Zahnkolloidmühle homogenisiert. Das so erhaltene Fett ist z.B. als Wälzlagerfett geeignet.After adjusting the batch to the desired consistency by adding 3116 g of the base oil mixture, the final product was homogenized on a toothed colloid mill. The fat thus obtained is e.g. suitable as rolling bearing grease.
In einen Reaktor wurden in 5000 g einer Grundölmischung 600 g 12-hydroxistearinsäure, 216g Sebacinsäure, 291g Calciumacetat und 720g Calciumhydroxid und 300g Calciumlignin-sulfonat (Norlig 11 D Pulver von Borregard Lignotech) vorgelegt. 48g LiOH x H2O wurden in 250ml Wasser aufgelöst und zugegeben. Der Ansatz wurde in einem festgelegten Temperaturprogramm auf 200°C unter Rühren erwärmt und dabei das zugegebene Wasser und das Reaktionswasser verdampft. In der Abkühlphase wurden dem Ansatz bei bestimmten Temperaturen Zusätze zugegeben. Nach der Einstellung des Ansatzes auf die gewünschte Konsistenz durch Zugabe von 3116 g der Grundölmischung wurde das Endprodukt über eine Zahnkolloidmühle homogenisiert. Das so erhaltene Fett ist z.B. als Wälzlagerfett geeignet.Into a reactor were placed in 5000 g of a base oil mixture 600 g of 12-hydroxistearic acid, 216 g sebacic acid, 291 g calcium acetate and 720 g calcium hydroxide and 300 g calcium lignin sulfonate (Norlig 11 D powder from Borregard Lignotech). 48 g of LiOH x H 2 O was dissolved in 250 ml of water and added. The mixture was heated in a predetermined temperature program to 200 ° C with stirring, thereby evaporating the added water and the reaction water. In the cooling phase, additives were added to the batch at certain temperatures. After adjusting the batch to the desired consistency by adding 3116 g of the base oil mixture, the final product was homogenized on a toothed colloid mill. The resulting grease is suitable as a rolling bearing grease, for example.
In einen Reaktor wurden in 12000 g einer Grundölmischung 1380 g Talgfettsäure, 1360g Rindertalg, 80g Trinatriumphosphat, 80g Calciumborat, 1400g Calciumacetat und 493 g Calciumhydroxid vorgelegt und 150ml Wasser zugegeben. Der Ansatz wurde in einem festgelegten Temperaturprogramm auf 230°C unter Rühren erwärmt und dabei das zugegebene Wasser und das Reaktionswasser verdampft. In der Abkühlphase wurden dem Ansatz bei bestimmten Temperaturen Zusätze zugegeben. Nach der Einstellung des Ansatzes auf die gewünschte Konsistenz durch Zugabe von 3125 g der Grundölmischung wurde das Endprodukt über eine Zahnkolloidmühle homogenisiert. Das so erhaltene Fett ist z.B. als Wälzlagerfett geeignet.Into a reactor, 1380 g of tallow fatty acid, 1360 g of beef tallow, 80 g of trisodium phosphate, 80 g of calcium borate, 1400 g of calcium acetate and 493 g of calcium hydroxide were placed in 12000 g of a base oil mixture and 150 ml of water were added. The batch was heated in a predetermined temperature program to 230 ° C with stirring, thereby evaporating the added water and the water of reaction. In the cooling phase, additives were added to the batch at certain temperatures. After adjusting the batch to the desired consistency by adding 3125 g of the base oil mixture, the final product was homogenized on a Zahnkolloidmühle. The fat thus obtained is e.g. suitable as rolling bearing grease.
In einen Reaktor wurden in 12000 g einer Grundölmischung 1260 g Talgfettsäure, 1240g Rindertalg, 80g Trinatriumphosphat, 80g Calciumborat,1278g Calciumacetat, 493 g Calciumhydroxid und 885g Calciumligninsulfonat (Norlig 11 D Powder von Borregard Lignotech) vorgelegt und 150ml Wasser zugegeben.Into a reactor 1260 g of tallow fatty acid, 1240 g beef tallow, 80 g trisodium phosphate, 80 g calcium borate, 1278 g calcium acetate, 493 g calcium hydroxide and 885 g calcium lignosulfonate (Norlig 11 D Powder from Borregard Lignotech) were initially charged in 12000 g of a base oil mixture and 150 ml of water were added.
Der Ansatz wurde in einem festgelegten Temperaturprogramm auf 225°C unter Rühren erwärmt und dabei das zugegebene Wasser und das Reaktionswasser verdampft. In der Abkühlphase wurden dem Ansatz bei bestimmten Temperaturen Zusätze zugegeben. Nach der Einstellung des Ansatzes auf die gewünschte Konsistenz durch Zugabe von 3125 g der Grundölmischung wurde das Endprodukt über eine Zahnkolloidmühle homogenisiert. Das so erhaltene Fett ist z.B. als Wälzlagerfett geeignet.The batch was heated in a predetermined temperature program to 225 ° C with stirring, thereby evaporating the added water and the water of reaction. In the cooling phase, additives were added to the batch at certain temperatures. After adjusting the batch to the desired consistency by adding 3125 g of the base oil mixture, the final product was homogenized on a Zahnkolloidmühle. The fat thus obtained is e.g. suitable as rolling bearing grease.
In einen Reaktor wurden in 3500g Methyloleat-Ester, 975g Calcium-12-hydroystearat, 225g Calciumacetat und 15g Calciumborat vorgelegt. Der Ansatz wurde in einem festgelegten Temperaturprogramm auf 200°C unter Rühren erwärmt. In der Abkühlphase wurden dem Ansatz bei bestimmten Temperaturen Additive zugegeben. Nach der Einstellung des Ansatzes auf die gewünschte Konsistenz durch Zugabe von 180 g Methyloleat-Ester wurde das Endprodukt über einen 3-Walzenstuhl homogenisiert. Das so gewonnene Schmierfett ist auf Basis überwiegend nachwachsender Rohstoffe aufgebaut.Into a reactor, 3500 g of methyl oleate ester, 975 g of calcium 12-hydroystearate, 225 g of calcium acetate and 15 g of calcium borate were charged. The batch was heated in a predetermined temperature program to 200 ° C with stirring. In the cooling phase, additives were added to the batch at certain temperatures. After adjusting the batch to the desired consistency by adding 180 g of methyl oleate ester, the final product was homogenized on a 3-roll mill. The resulting grease is based on predominantly renewable raw materials.
In einen Reaktor wurden in 1965g Methyloleat-Ester, 841g Calcium-12-hydroystearat, 219,5g Calciumacetat, 15g Calciumborat und 418g Calciumligninsulfonat (Norlig 11 D Pulver von Borregard Lignotech) vorgelegt. Der Ansatz wurde in einem festgelegten Temperaturprogramm auf 200°C unter Rühren erwärmt. In der Abkühlphase wurden dem Ansatz bei bestimmten Temperaturen Additive zugegeben. Nach der Einstellung des Ansatzes auf die gewünschte Konsistenz durch Zugabe von 1684 g Trimethylolproprantrioleat-Ester wurde das Endprodukt über einen 3-Walzenstuhl homogenisiert. Das so gewonnene Schmierfett ist auf Basis überwiegend nachwachsender Rohstoffe aufgebaut.Methyloleate ester, 841 g calcium 12-hydroystearate, 219.5 g calcium acetate, 15 g calcium borate and 418 g calcium lignosulfonate (Norlig 11 D powder from Borregard Lignotech) were introduced into a reactor in 1965 g. The batch was heated in a predetermined temperature program to 200 ° C with stirring. In the cooling phase, additives were added to the batch at certain temperatures. After adjusting the batch to the desired consistency by adding 1684 g of trimethylolproprantrioleate ester, the final product was homogenized on a 3-roll mill. The resulting grease is based on predominantly renewable raw materials.
Die Herstellungen der Beispielformulierungen I und J entsprechen der Herstellung des Beispieles H unter Verwendung unterschiedlicher Mengen an Calcium-12-hydroxistearat, Calciumacetat und Calciumligninsulfonat sowie unterschiedlicher Zusammensetzungen an Ester-Grundölen. Die so gewonnenen Schmierfette sind auf Basis überwiegend nachwachsender Rohstoffe aufgebaut.
Claims (24)
- Method for manufacturing lubricating greases that contain lignosulfonate comprisinga) the step of bringing together:- at least one base oil,- at least one calcium soap of a saturated or unsaturated monocarboxylic acid with 10 to 32 carbon atoms, optionally substituted,- at least one complexing agent, selected from:(i) an alkali salt, with the exception of sodium salt, an alkaline earth salt or aluminium salt, a saturated or unsaturated monocarboxylic acid or hydroxycarboxylic acids with 2 to 8, a dicarboxylic acid with 2 to 16 carbon atoms, each of which is optionally substituted,(ii) an alkali and/or alkaline earth salt of boric acid and/or phosphoric acid, including their reaction products with LiOH and/or Ca(OH)2 and(iii) mixtures thereof, and- at least calcium lignosulfonate having mean molecular weights as weight average of greater than 10,000 g/mol,
heating to greater than 120°C for reacting and driving out low-boiling components to manufacture a base grease andb) the step of cooling and adding base oil and optionally additives while mixing. - Method according to claim 1, characterised in that in step a) calcium hydroxide is added optionally in addition to other alkaline earth hydroxides.
- Method according to claim 1, characterised in that lubricating grease is rendered alkaline, particularly by addition of excess calcium hydroxide.
- Method according to claim 1, characterised in that heating to temperatures exceeding 180°C is performed.
- Method according to claim 1, characterised in that in addition to calcium hydroxide in step a), lithium hydroxide, magnesium hydroxide and/or aluminium hydroxide and/or aluminium alcoholates and/or aluminium oxoalcoholates and/or lithium, magnesium and/or aluminium soaps of a saturated or unsaturated monocarboxylic acid with 10 to 32 carbon atoms, optionally substituted, are used.
- Method according to claim 1, characterised in that the lubricating grease comprises, independently of each other:- 55 to 92 % by weight, particularly 70 to 85 % by weight, of the base oil,- 0 to 40 % by weight, particularly 2 to 10 % by weight of additives,- 3 to 40 % by weight, particularly 5 to 20 % by weight of the calcium soaps, and- 0.5 to 10 % by weight of the complexing agents, and- optionally excess Ca(OH)2, preferably 0.01 to 2 % by weight, and- 0.5 to 15 % by weight and particularly preferably 4 to 8 % by weight of calcium lignosulfonate, optionally in addition to other alkaline earth lignosulfonates, relative in each case to the total composition of the lubricating grease.
- Method according to claim 1, characterised in that the base grease in step a) can be manufactured using- 40 to 70 % by weight, particularly 45 to 60 % by weight, of the base oil,- 10 to 60 % by weight, particularly 15 to 50 % by weight of the calcium soaps and- 5 to 30 % by weight of complexing agents and- optionally excess Ca(OH)2, preferably 0.02 to 4 % by weight and- 0.7 to 30 % by weight of calcium lignosulfonate, optionally in addition to other alkaline earth lignosulfonates,
relative in each case to the composition of the base grease. - Method according to claim 1 or 4, characterised in that the lubricating grease comprises independently of each other 0.2 - 5 % by weight of graphite and/or no solid lubricant or less than < 1 % by weight of solid lubricant, particularly no MoS2.
- Method according to claim 1, characterised in that the calcium soap is manufactured in situ as a reaction product of calcium hydroxide with a saturated or unsaturated monocarboxylic acid having 10 to 32 carbon atoms, particularly with 16 to 20 carbon atoms, optionally substituted, for example by hydroxy, as ester or anhydride.
- Method according to claim 1, characterised in that the complexing agent as a reaction product of a calcium salt, particularly calcium hydroxide, with a saturated or unsaturated monocarboxylic acid having 2 to 8, particularly having 2 to 4, carbon atoms or a dicarboxylic acid having 2 to 16, particularly 2 to 12 carbon atoms, each of which is optionally substituted, for example by hydroxy, as ester or anhydride, is added during step a).
- Method according to claim 1, characterised in that the complexing agent is a calcium salt of a carboxylic acid and is manufactured in situ during step a) by addition of a saturated or unsaturated monocarboxylic acid having 2 to 8, particularly 2 to 4, carbon atoms or a dicarboxylic acid having 2 to 16, particularly 2 to 12 carbon atoms, each of which is optionally substituted, for example by hydroxy, as ester or anhydride.
- Method according to at least one of claims 1 to 11, characterised in that the calcium lignosulfonate is dehydrated before addition to values of less than 0.5 % by weight of water, e.g. by heating in the base oil to more than 95°C, particularly to more than 100°C up to for example 120°C.
- Method according to at least one of claims 1 to 12, characterised in that the composition comprises complexing agents at between 0.5 and 10 % by weight.
- Lubricating grease composition, comprising- 55 to 92 % by weight, particularly 70 to 85 % by weight, of the base oil,- 0 to 40 % by weight, particularly 2 to 10 % by weight of additives,- 3 to 40 % by weight, particularly 5 to 20 % by weight of calcium soaps of a saturated or unsaturated monocarboxylic acid with 10 to 32 carbon atoms, optionally substituted,- 0.5 to 10 % by weight of complexing agents, selected from:(i) an alkali salt, with the exception of sodium salt, an alkaline earth salt or aluminium salt, a saturated or unsaturated monocarboxylic acid or hydroxycarboxylic acids with 2 to 8, a dicarboxylic acid with 2 to 16 carbon atoms, each of which is optionally substituted,(ii) an alkali and/or alkaline earth salt of boric acid and/or phosphoric acid, including their reaction products with LiOH and/or Ca(OH)2, optionally excess Ca(OH)2, preferably 0.01 to 2 % by weight, and(iii) mixtures thereof and- 0.5 to 15 % by weight and particularly preferably 2 to 8 % by weight of calcium lignosulfonate, optionally in addition to other alkaline earth lignosulfonates,
relative in each case to the total composition of the lubricating grease, wherein the composition has a cone penetration value (worked penetration) of between 265 and 385 mm/10 at 25°C determined according to ISO 2137. - Composition according to claim 14, characterised in that the composition has a cone penetration value (worked penetration) of between 285 and 355 mm/10, determined according to ISO 2137.
- Composition according to at least one of claims 14 or 15, characterised in that the base oil has a kinematic viscosity of between 20 and 2500 mm2/sec., preferably between 40 and 500 mm2/sec., at 40°C.
- Composition according to at least one of claims 14 to 16, characterised in that the complexing agent consists of:- an alkali salt, preferably lithium salt, an alkaline earth salt, preferably calcium salts or an aluminium salt of a saturated or unsaturated monocarboxylic acid with 2 to 8, particularly 2 to 4, carbon atoms or a dicarboxylic acid with 2 to 16, particularly 2 to 12 carbon atoms, each optionally substituted.
- Composition according to at least one of claims 14 to 17, characterised in that the additive comprises one or several members selected from the following group:- amine compounds, phenol compounds, sulphur-containing antioxidants, zinc dithiocarbamate or zinc dithiophosphate as antioxidants;- organic chlorine compounds, sulphur, phosphorus or calcium borate, zinc dithiophosphate, organic bismuth compounds as high-pressure additives;- C2 to C6 polyols, fatty acids, fatty acid esters or animal or vegetable oils;- petroleum sulfonate, dinonylnaphthalene sulfonate or sorbitol esters as anticorrosion agents;- benzotriazole or sodium nitrite as metal deactivators;- polymethacrylate, polyisobutylene, oligo-Dec-1-ene and polystyrenes as viscosity improvers;- molybdenum dialkyldithiocarbamate or molybdenum sulphide dialkyl dithiocarbamate or aromatic amines as anti-wear additives;- functional polymers such as oleylamides, organic polyether- and amide-based compounds or molybdenum dithiocarbamate as friction modifiers; and- polymer powders such as polyamides, polyimides or PTFE, graphite, metal oxides, boron nitride, metal sulphides such as molybdenum disulphide, tungsten disulphide or tungsten-, molybdenum-, bismuth-, tin- and zinc-based mixed sulphides, inorganic salts of alkali and alkaline earth metals, such as calcium carbonate, sodium phosphates and calcium phosphates, as solid lubricants.
- Composition according to at least one of claims 14 to 18, characterised in that the lubricating grease is water-resistant, i.e.a) according to the test in accordance with DIN 51807-1 of assessment level 1-90 and/orb) according to the test in accordance with DIN 51807-2 of assessment level 1-80.
- Composition according to at least one of claims 14 to 19, characterised in that the calcium lignosulfonate has a mean molecular weight (Mw, weight average) greater than 10,000, in particular greater than 12,000 or even greater than 15,000 g/mol,
which independently thereof comprises 2 to 12 % by weight, particularly 4 to 10 % by weight of sulphur (calculated as elemental sulphur) and/or also indenpendently comprises 5 to 15 % by weight, particularly 8 to 15 % by weight of calcium. - Composition according to at least one of claims 14 to 20, characterised in that the lubricating grease comprises a base oil based on sustainable raw materials and/or is formed by a percentage greater than 95% on a basis of sustainable raw materials.
- Composition according to at least one of claims 14 to 20, characterised in that the composition has a drop point greater than 200°C according to DIN ISO 2176.
- Use of the composition according to at least one of claims 14 to 22 for lubricating at least one gear.
- Use of the composition according to at least one of claims 14 to 22 for lubricating lubrication points in constant velocity joints with a drive shaft boot, formed of thermoplastic polyether esters as the drive shaft boot material.
Priority Applications (3)
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PL11711018T PL2531587T3 (en) | 2010-02-02 | 2011-01-31 | Lubricating greases containing lignosulfonate, the production thereof, and the use thereof |
SI201130721T SI2531587T1 (en) | 2010-02-02 | 2011-01-31 | Lubricating greases containing lignosulfonate, the production thereof, and the use thereof |
HRP20160072TT HRP20160072T1 (en) | 2010-02-02 | 2016-01-22 | Lubricating greases containing lignosulfonate, the production thereof, and the use thereof |
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Application Number | Priority Date | Filing Date | Title |
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DE102010006745A DE102010006745A1 (en) | 2010-02-02 | 2010-02-02 | Greases containing lignosulfonate, their preparation and use |
PCT/DE2011/000087 WO2011095155A1 (en) | 2010-02-02 | 2011-01-31 | Lubricating greases containing lignosulfonate, the production thereof, and the use thereof |
Publications (3)
Publication Number | Publication Date |
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EP2531587A1 EP2531587A1 (en) | 2012-12-12 |
EP2531587B1 EP2531587B1 (en) | 2015-11-04 |
EP2531587B9 true EP2531587B9 (en) | 2016-10-05 |
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EP11711018.9A Active EP2531587B9 (en) | 2010-02-02 | 2011-01-31 | Lubricating greases containing lignosulfonate, the production thereof, and the use thereof |
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US (1) | US20120302472A1 (en) |
EP (1) | EP2531587B9 (en) |
JP (1) | JP5856078B2 (en) |
KR (1) | KR101833854B1 (en) |
CN (1) | CN102770513B (en) |
AU (1) | AU2011212763B2 (en) |
BR (1) | BR112012019181B1 (en) |
CA (1) | CA2788157C (en) |
DE (1) | DE102010006745A1 (en) |
DK (1) | DK2531587T3 (en) |
ES (1) | ES2561821T3 (en) |
HR (1) | HRP20160072T1 (en) |
HU (1) | HUE026690T2 (en) |
MX (1) | MX2012008960A (en) |
PL (1) | PL2531587T3 (en) |
PT (1) | PT2531587E (en) |
RS (1) | RS54610B1 (en) |
RU (1) | RU2554873C2 (en) |
SI (1) | SI2531587T1 (en) |
WO (1) | WO2011095155A1 (en) |
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US9228151B1 (en) * | 2012-11-07 | 2016-01-05 | Rand Innovations, Llc | Lubricant additive composition, lubricant, and method of preparing the same |
JP5916654B2 (en) * | 2013-03-28 | 2016-05-11 | 住鉱潤滑剤株式会社 | Grease composition for constant velocity joint and constant velocity joint |
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DE102015103440A1 (en) * | 2015-03-09 | 2016-09-15 | Fuchs Petrolub Se | Process for the preparation of polyurea-thickened lubricating greases based on lignin derivatives, greases of this kind and their use |
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CN105441166A (en) * | 2015-11-27 | 2016-03-30 | 蚌埠海明压铸机有限公司 | Lubricating oil for engine |
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CN105419912A (en) * | 2015-11-27 | 2016-03-23 | 蚌埠海明压铸机有限公司 | Anti-wear lubricating oil |
CN105441165A (en) * | 2015-11-27 | 2016-03-30 | 蚌埠海明压铸机有限公司 | Durable lubricating oil for engine |
CN105441170A (en) * | 2015-11-30 | 2016-03-30 | 蚌埠市华科机电有限责任公司 | Rust-proof lubricating oil |
CN105441169A (en) * | 2015-11-30 | 2016-03-30 | 蚌埠市华科机电有限责任公司 | Lubricating oil for anti-wear engine |
JP2016084483A (en) * | 2016-02-16 | 2016-05-19 | 住鉱潤滑剤株式会社 | Grease composition and constant velocity joint |
JP2016130318A (en) * | 2016-03-16 | 2016-07-21 | 住鉱潤滑剤株式会社 | Grease composition, as well as constant velocity joint |
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US10626343B1 (en) * | 2017-11-17 | 2020-04-21 | Brave Response Shooting, LLC | Animal-based hydrocarbon firearm lubricant |
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RU2688928C1 (en) * | 2018-10-01 | 2019-05-23 | Федеральное государственное бюджетное образовательное учреждение высшего образования Иркутский государственный университет путей сообщения (ФГБОУ ВО ИрГУПС) | Method of producing anti-tearing additive for heavily loaded friction assemblies |
CN109825345B (en) * | 2019-02-19 | 2021-12-24 | 上海金兆节能科技有限公司 | High-temperature-resistant lubricant and preparation method thereof |
RU2698457C1 (en) * | 2019-06-21 | 2019-08-27 | Публичное акционерное общество "НК "Роснефть" - МЗ "Нефтепродукт" | Multipurpose complex grease |
DE102020008047A1 (en) | 2020-07-03 | 2022-01-05 | Fuchs Petrolub Se | Polyurea lubricating greases containing carbonates and their use |
DE102020117671B4 (en) | 2020-07-03 | 2022-06-09 | Fuchs Petrolub Se | Lubrication points comprising a polyurea grease composition and a seal comprising a fluorinated elastomer sealing material and the use of the polyurea grease composition for a lubrication point comprising such a seal |
CN112410101A (en) * | 2020-11-30 | 2021-02-26 | 新乡市恒星科技有限责任公司 | Precise high-molecular special lubricating grease and preparation method thereof |
CN113122354B (en) * | 2021-04-20 | 2023-08-15 | 中国石油化工股份有限公司 | Composite calcium-based lubricating grease and preparation method thereof |
CN113355148B (en) * | 2021-05-28 | 2022-12-20 | 中国石油化工股份有限公司 | Lubricant for automobile driving shaft hub bearing joint surface and preparation method thereof |
CN113403127A (en) * | 2021-06-08 | 2021-09-17 | 郑州市欧普士科技有限公司 | Environment-friendly anti-corrosion grease for overhead conductor and preparation method thereof |
DE102021133469B3 (en) | 2021-12-16 | 2022-08-25 | Fuchs Petrolub Se | Process for preparing lithium complex soap and lithium calcium complex soap greases |
CN114540106A (en) * | 2022-03-02 | 2022-05-27 | 北京市政建设集团有限责任公司 | Sealing grease for main bearing of shield tunneling machine and preparation method thereof |
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RU2224011C1 (en) * | 2002-12-02 | 2004-02-20 | Федеральное государственное унитарное предприятие "Московское машиностроительное производственное предприятие "Салют" | Hot or half-hot metal forming grease |
CN100404655C (en) * | 2003-11-13 | 2008-07-23 | 中国石油化工股份有限公司 | Composite lithium base lubricant and its preparing method |
CN100549147C (en) * | 2006-07-31 | 2009-10-14 | 中国石油化工股份有限公司 | Grease composition |
JP5101374B2 (en) * | 2008-04-02 | 2012-12-19 | 中央油化株式会社 | Calcium complex grease |
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2010
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2011
- 2011-01-31 KR KR1020127023089A patent/KR101833854B1/en active IP Right Grant
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- 2011-01-31 JP JP2012550318A patent/JP5856078B2/en active Active
- 2011-01-31 HU HUE11711018A patent/HUE026690T2/en unknown
- 2011-01-31 RU RU2012136909/04A patent/RU2554873C2/en active
- 2011-01-31 PT PT117110189T patent/PT2531587E/en unknown
- 2011-01-31 BR BR112012019181A patent/BR112012019181B1/en active IP Right Grant
- 2011-01-31 EP EP11711018.9A patent/EP2531587B9/en active Active
- 2011-01-31 WO PCT/DE2011/000087 patent/WO2011095155A1/en active Application Filing
- 2011-01-31 ES ES11711018.9T patent/ES2561821T3/en active Active
- 2011-01-31 CN CN201180008171.3A patent/CN102770513B/en active Active
- 2011-01-31 PL PL11711018T patent/PL2531587T3/en unknown
- 2011-01-31 DK DK11711018.9T patent/DK2531587T3/en active
- 2011-01-31 RS RS20160037A patent/RS54610B1/en unknown
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- 2011-01-31 CA CA2788157A patent/CA2788157C/en active Active
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BR112012019181A2 (en) | 2018-03-27 |
EP2531587B1 (en) | 2015-11-04 |
JP5856078B2 (en) | 2016-02-09 |
CN102770513B (en) | 2015-09-30 |
HRP20160072T1 (en) | 2016-04-08 |
AU2011212763A1 (en) | 2012-09-06 |
DK2531587T3 (en) | 2016-01-25 |
ES2561821T3 (en) | 2016-03-01 |
DE102010006745A1 (en) | 2011-08-04 |
US20120302472A1 (en) | 2012-11-29 |
CA2788157A1 (en) | 2011-08-11 |
BR112012019181B1 (en) | 2018-09-11 |
RU2012136909A (en) | 2014-03-10 |
HUE026690T2 (en) | 2016-07-28 |
RS54610B1 (en) | 2016-08-31 |
MX2012008960A (en) | 2012-10-15 |
PL2531587T3 (en) | 2016-06-30 |
PT2531587E (en) | 2016-02-26 |
KR20120139730A (en) | 2012-12-27 |
CN102770513A (en) | 2012-11-07 |
CA2788157C (en) | 2018-06-26 |
KR101833854B1 (en) | 2018-03-05 |
SI2531587T1 (en) | 2016-04-29 |
WO2011095155A1 (en) | 2011-08-11 |
EP2531587A1 (en) | 2012-12-12 |
JP2013518929A (en) | 2013-05-23 |
AU2011212763B2 (en) | 2013-10-17 |
RU2554873C2 (en) | 2015-06-27 |
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