PL127691B1 - Lubricating oil with improving additive - Google Patents
Lubricating oil with improving additive Download PDFInfo
- Publication number
- PL127691B1 PL127691B1 PL1980226207A PL22620780A PL127691B1 PL 127691 B1 PL127691 B1 PL 127691B1 PL 1980226207 A PL1980226207 A PL 1980226207A PL 22620780 A PL22620780 A PL 22620780A PL 127691 B1 PL127691 B1 PL 127691B1
- Authority
- PL
- Poland
- Prior art keywords
- lubricating oil
- carbon atoms
- weight
- copper
- additive
- Prior art date
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- 239000000654 additive Substances 0.000 title claims description 78
- 239000010687 lubricating oil Substances 0.000 title claims description 62
- 230000000996 additive effect Effects 0.000 title claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 48
- -1 alkenyl acid Chemical class 0.000 claims description 46
- 239000010949 copper Substances 0.000 claims description 46
- 229910052802 copper Inorganic materials 0.000 claims description 44
- 239000002270 dispersing agent Substances 0.000 claims description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 42
- 229910052749 magnesium Inorganic materials 0.000 claims description 25
- 239000011777 magnesium Substances 0.000 claims description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 24
- 239000011701 zinc Substances 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 22
- 239000003963 antioxidant agent Substances 0.000 claims description 22
- 229910052791 calcium Inorganic materials 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 22
- 150000002148 esters Chemical class 0.000 claims description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 20
- 150000001880 copper compounds Chemical class 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- 239000005749 Copper compound Substances 0.000 claims description 19
- 230000003078 antioxidant effect Effects 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 14
- 150000002989 phenols Chemical class 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 12
- 150000001298 alcohols Chemical class 0.000 claims description 11
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 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 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229940014800 succinic anhydride Drugs 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004018 acid anhydride group Chemical group 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 230000004936 stimulating effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 38
- 239000003921 oil Substances 0.000 description 37
- 235000019198 oils Nutrition 0.000 description 37
- 229910052751 metal Inorganic materials 0.000 description 29
- 239000002184 metal Substances 0.000 description 29
- 230000003647 oxidation Effects 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 18
- 239000000314 lubricant Substances 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 13
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 229920000768 polyamine Polymers 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 150000008064 anhydrides Chemical class 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical class C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000010688 mineral lubricating oil Substances 0.000 description 4
- 125000005609 naphthenate group Chemical group 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 4
- 150000003752 zinc compounds Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920002367 Polyisobutene Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical class CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 230000001458 anti-acid effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- SVOAENZIOKPANY-UHFFFAOYSA-L copper;octadec-9-enoate Chemical compound [Cu+2].CCCCCCCCC=CCCCCCCCC([O-])=O.CCCCCCCCC=CCCCCCCCC([O-])=O SVOAENZIOKPANY-UHFFFAOYSA-L 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 3
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002103 osmometry Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000006294 amino alkylene group Chemical group 0.000 description 2
- 239000007866 anti-wear additive Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000021523 carboxylation Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000001177 diphosphate Substances 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- KVXBYLVNWBOBOK-UHFFFAOYSA-N hexan-2-yloxy-hexan-2-ylsulfanyl-hydroxy-sulfanylidene-lambda5-phosphane Chemical compound CCCCC(C)OP(O)(=S)SC(C)CCCC KVXBYLVNWBOBOK-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000003879 lubricant additive Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 125000005608 naphthenic acid group Chemical group 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000004707 phenolate Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- GPTFURBXHJWNHR-UHFFFAOYSA-N protopine acetate Natural products C1=C2C(=O)CC3=CC=C4OCOC4=C3CN(C)CCC2=CC2=C1OCO2 GPTFURBXHJWNHR-UHFFFAOYSA-N 0.000 description 2
- 150000003873 salicylate salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- ZGXMNEKDFYUNDQ-GQCTYLIASA-N (5e)-hepta-1,5-diene Chemical compound C\C=C\CCC=C ZGXMNEKDFYUNDQ-GQCTYLIASA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- SIQZJFKTROUNPI-UHFFFAOYSA-N 1-(hydroxymethyl)-5,5-dimethylhydantoin Chemical compound CC1(C)N(CO)C(=O)NC1=O SIQZJFKTROUNPI-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- DJABNVJZYFGAJE-UHFFFAOYSA-N 1-ethenyl-5-ethylpyrrolidin-2-one Chemical compound CCC1CCC(=O)N1C=C DJABNVJZYFGAJE-UHFFFAOYSA-N 0.000 description 1
- UDJZTGMLYITLIQ-UHFFFAOYSA-N 1-ethenylpyrrolidine Chemical compound C=CN1CCCC1 UDJZTGMLYITLIQ-UHFFFAOYSA-N 0.000 description 1
- PPWUTZVGSFPZOC-UHFFFAOYSA-N 1-methyl-2,3,3a,4-tetrahydro-1h-indene Chemical compound C1C=CC=C2C(C)CCC21 PPWUTZVGSFPZOC-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
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- 150000007525 superbases Chemical class 0.000 description 1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Description
***** Twórcy wynalazku: Terence Colclough, Frederick Alastair Gibson, John Frederick Marsh Uprawniony z patentu: Exxon Research and Enginnering Company, Florham Park (Stany Zjednoczone Ameryki) Olej smarowy z dodatkiem uszlachetniajacym Przedmiotem wynalazku jest olej smarowy z dodatkiem uszlachetniajacym, zwlaszcza olej smarowy do silników samochodów osobowych i ciezarowych, zawierajacy miedz w ilosci do¬ statecznej do opózniania lub hamowania utlenia¬ nia w trakcie uzytkowania oleju smarowego, bez wywierania niekorzystnego wplywu na inne jego skladniki.Aktualnie istnieje wielka potrzeba poprawy wy¬ dajnosci i czasokresu przydatnosci olejów smaro¬ wych, zwlaszcza smarów silnikowych stosowanych w silnikach spalinowych samochodów osobowych i ciezarowych. Ograniczone zasoby i rosnace ceny surowej ropy naftowej spowodowaly koniecznosc wytwarzania smarów trwalszych o dluzszym okre¬ sie przydatnosci.Jednym z istotnych czynników, które w sposób zasadniczy skracaja okres przydatnosci smarów jest utlenianie sie skladnika olejowego. Utlenianie powoduje zwiekszenie sie kwasowosci smaru co prowadzi do wiekszej korozji elementów silnika i niepozadanego wzrostu lepkosci obnizajacego wlasnosci smarowe.Chociaz sam olej wysokojakosciowy jest stosun¬ kowo odporny na utlenianie, to takie zanieczysz¬ czenia jak zelazo, które w sposób nieunikniony jest obecne w silnikach spalinowych, i dodatki zwykle stosowane w substancjach smarujacych takie jak detergenty magnezowe i wapniowe oraz dyspergatory, takie jak polimery kwasu poliizo- butenylobursztynowego z poliamina lub poliestrem wywierajace niepozadane dzialanie, znacznie przy¬ spieszajac proces utleniania do takiego zakresu, ze staje sie on glównym czynnikiem skracania okresu przydatnosci smaru. Ponadto, w miare jak ubo¬ zeja pola naftowe dajace olej o wyzszej jakosci wzrasta potrzeba wykorzystania olejów smarowych o nizszej jakosci. Oleje o nizszej jakosci maja wieksza tendencje do utleniania sie.Od pewnego czasu wiadomo, ze niektóre zwiaz¬ ki maja zdolnosc wstrzymywania lub opózniania utleniania, jesli zostana wlaczone do smaru. W tym celu stosuje sie na przyklad blokowane fenole lub sulfuryzowane fenole oraz dwutiofosforany dwualkilowocynkowe, które w pierwszym rzedzie sa srodkami stosowanymi przeciw zuzyciu, ale równiez dzialaja jako utleniacze.Dla uzyskania pozadanego efektu znane srodki stosuje sie zazwyczaj w duzych ilosciach, co zwieksza koszty mieszaniny, a w przypadku dwu- tiofosforanu dwualkilowocynkowego prowadzi do niepozadanie wysokiego poziomu fosforu w oleju.Nawet w tak duzych ilosciach mozna nie uzyskac 25 adekwatnego dzialania przeciwutlendajacego, gdy mieszanina zawiera inne dodatki, które moga byc promotorami utleniania.Ponadto, nowoczesne dodatki uszlachetniajace do olejów smarowych sa mieszaninami zlozonymi 30 z róznych dodatków, z których kazdy sluzy jakie- 15 20 127 691127 8 mus celowi. Moga one zawierac na przyklad jeden lub wiecej modyfikatorów lepkosci, detergentów, dyspergatorów, srodków przeciw kwasowych, in¬ hibitorów korozji, srodków przeciw rdzewieniu i przeciw zuzyciu oraz srodków dla ochrony 5 i zwiekszania sprawnosci silnika, w którym zasto¬ suje sie mieszanine. Skuteczny przeciwutleniacz powinien opózniac utlenianie nie zaklócajac jed¬ nakze dzialania innych dodatków i nie powinien zawierac niepozadanych zanieczyszczen. Oczywis- 10 cie, wydluzenie okresu przydatnosci przez opóznia¬ nie utleniania bedzie bezwartosciowe, jesli towa¬ rzyszyc mu bedzie uszkadzanie silnika na skutek zwiajksaoaej_ korozji lub zuzycia.Uprzednio ukazS^raly sie pojedyncze publikacje w dotyczace wlaczania^-zwiazków miedzi do olejów smarowych, ale zadna, z nich nie dotyczyla do- dalfcu "tis~zlactfetmajacego podobnego do kompozy¬ cji*ive4Lu£j#yttalazku.; W opisach patentowych Stanów Zjedn. Ameryki *° nr nr 2 343 756 i 2 356 662 opisano dodatek do ole¬ jów smarowych w postaci zwiazków miedzi, lacz¬ nie ze zwiazkami siarki. W opisie patentowym Stanów Zjedn. Ameryki nr 2 $52 580 opisano do¬ dawanie do smaru stosunkowo duzych ilosci tio- M fosforanów miedziawych, które powoduja niepo¬ zadanie wysokie zawartosci popiolu siarczano¬ wego.W opisie patentowym Stanów Zjedn. Ameryki nr 3 346 493 opisano wiele polimerycznych reagen¬ tów amino-metalicznych stosowanych w olejach smarowych jako detergentów. W dwóch pojedyn¬ czych przypadkach, w których metalem byla miedz, a smar zawieral dwutiofosforan dwuweglo- wodorowo-cynkowy, ilosc dodanej miedzi znajdo¬ wala sie poza zakresem wystepujacym w oleju smarowym wedlug wynalazku, badz wyste¬ powal warunek, zeby nierozpuszczalny w oleju zwiazek miedzi tworzyl kompleks z substancja dyspergujaca.W opisie patentowym Stanów Zjedn. Ameryki nr 3 652 616 opisano wiele róznych polimerycznych reagentów amino-metalicznych jako dodatków do smarów. W opisie patentowym Stanów Zjedn.Ameryki nr 4 122 033 opisano cala grupe zwiazków metali przejsciowych jako dodatków do smarów.Obecnie okazalo sie, ze mozliwe jest opóznianie lub hamowanie utleniania smaru zawierajacego dyspergator i dodatek przeciw zuzyciu bez szkód- 50 liwego wplywu na dzialanie tych dodatków, przez wlaczenie w sklad kompozycji smarowej rozpusz¬ czalnego w oleju zwiazku miedzi w ponizej po¬ danym zakresie stezen.Nowy odporny na utlenianie olej smarowy 56 z dodatkiem uszlachetniajacym wedlug wynalaz¬ ku zawiera w przewazajacej czesci oleju smaro¬ wego dodatki obejmujace dodatek dyspergujacy zlozony z 1—10% wagowych bezpopiolowych zwiaz¬ ków dyspergujacych i 0,3—10% wagowych polime- w rycznego dodatku zmniejszajacego zaleznosc lep¬ kosci od temperatury a jako dalsze dodatki dwu¬ tiofosforan dwuwejjffiowodorowo-cyfrkowy w ilosci odpowiadajacej 0,01—5,0% wagowych fosforu i 0,01 —5,0% wagowych cynku, oraz 5—500 czesci na mi- «5 4 lion miedzi w postaci rozpuszczalnego w oleju zwiazku miedzi. Ilosci te podane sa w stosunku do calkowitego ciezaru kompozycji. Dwutiofosfo¬ ran dwuweglowodorowo-cynkowy jest srodkiem przeciw zuzyciu mechanizmów przenoszacych du¬ ze obciazenia jednostkowe.W szczególnie korzystnym wykonaniu olej sma¬ rowy z dodatkiem uszlachetniajacym wedlug wy¬ nalazku zawiera równiez jeden lub kilka nadza- sadowych dodatków o dzialaniu przeciw kwaso¬ wym i przeciw rdzewieniu, na przyklad nadza- sadowe sulfoniany i fenolany wapnia lub magnezu.W oleju smarowym z dodatkiem uszlachetniaja¬ cym wedlug wynalazku ilosc zwiazku miedzi jest krytyczna. Przy zbyt niskich stezeniach nie uzy¬ ska sie dostatecznego dzialania przeciwutleniaja- cego. Przy zbyt wysokich stezeniach moze wysta¬ pic zaklócenie dzialania dodatku przeciw zuzyciu a w punktach wysokich nacisków, takich jak wal rozrzadczy czy dzwignie, moga wystapic objawy wiekszego zuzycia.Jak wspomniano, ilosc zwiazków miedzi wyno¬ si 5—500 czesci na milion (ippm) miedzi w prze¬ liczeniu na calkowity ciezar kompozycji, a korzyst¬ nie 10—200, np. 60—200 ppm miedzi, 80—180 ppm, 90—120 ppm. Ilosc stosowanego zwiazku miedzi w podanych powyzej zakresach korzystnie powin¬ na byc równiez skorelowana z iloscia dwutiofos- foranu dwuweglowodorowo-cynkowego, co wynika- z podanego stezenia fosforu.Zdolnosc zwiazku miedzi rozpuszczalnego w ole¬ ju do dzialania jako przeciwutleniacz w oleju smarowym z dodatkiem uszlachetniajacym we¬ dlug wynalazku jest nieoczekiwana. Wiadomo, ze miedz w wielu przypadkach dziala jako promotor utleniania lub katalizator. Ponadto, blisko spo¬ krewnione metale, takie jak kobalt czy chrom, nie sa skuteczne jako przeciwutleniacze w sma¬ rze. Ilosc miedzi dodawana do swiezego, nieuzy¬ wanego jeszcze oleju smarowego jest okreslona oddzielnie i odrózniana od zanieczyszczen miedzia, które moga pojawiac sie w trakcie stosowania oleju w silniku, np. na skutek korozji lub zuzy¬ cia metalowych czesci zawierajacych miedz. Miedz, dodaje sie do kompozycji w postaci zwiazku mie¬ dzi rozpuszczalnego w olcju.Nieoczekiwane jest równiez, ze zwiazek miedzi dziala skutecznie w kompozycjach, które zawie¬ raja inne zwiazki metali, takie jak dwutiofosfo- rany dwualkilo-cynkowe i nadzasadowe dodatki, zwiazków wapnia lub magnezu, co do których mozna byloby oczekiwac, ze beda dezaktywowaly miedz poprzez wymiane skladników metalicznych.Przeciwutleniacze miedziowe wchodzace w sklad, oleju smarowego z dodatkiem uszlachetniajacym wedlug wynalazku sa niedrogie i skuteczne w nis¬ kich stezeniach, a zatem nie zwiekszaja w zasa¬ dzie kosztu produktu. Otrzymywane wyniki czesto sa lepsze niz uzyskiwane przy zastosowaniu po¬ przednio stosowanych antyutleniaczy, które sa drogie i które stosuje sie w wyzszych stezeniach.W stosowanych ilosciach zwiazki miedzi nie koli¬ duja z dzialaniem innych skladników i w wielu-127 691 6 przypadkach uzyskuje sie calkowicie zadawalajace wyniki, gdy zwiazek miedzi jest jedynym utle¬ niaczem w dodatku do dwutiofosforanu dwualkilo- ^cynkowego.Zwiazki miedzi moga byc stosowane w celu za- 5 stapienia czesci lub calego potrzebnego dodatko¬ wo przeciwutleniacza. W szczególnie surowych wa¬ runkach pozadane moze byc wlaczenie dodatko¬ wego, tradycyjnego przeciwutleniacza, jednakze wymagane ilosci dodatkowego przeciwutleniacza io sa male, znacznie mniejsze niz ilosci potrzebne w przypadku nieobecnosci zwiazku miedzi.Reasumujac, nalezy zaznaczyc, ze zadna z omó¬ wionych wczesniej publikacji nie ujawniala za¬ stosowania zwiazków miedzi rozpuszczalnych 15 w oleju per se w ilosci 5—500 ppm w polaczeniu z dwutiofosforanem dwuweglowodorowo-cynkowym i bezpopiolowym srodkiem dyspergujacym osad lub polimerycznym dodatkiem dyspergujacym zmniejszajacym zaleznosc lepkosci od tempera- w tury.Zadna z publikacji nie sugerowala mozliwosci -sporzadzenia smaru z miedzia ani w formie kom¬ pleksu z substancja dyspergujaca ani w zwiazku niekompleksowym, w korzystnej ilosci 10—200 25 ppm. Zadna z publikacji nie' wskazywala na zdol¬ nosc takiej kompozycji do poprawienia odpornos¬ ci na utlenianie przy dobrych wlasnosciach prze¬ ciw zuzyciowych, zadna tez nie ujawniala ze mozna stosowac równiez kompozycje zawierajace 3D zasadowe dodatki bez pogorszenia odpornosci na utlenianie.Okreslenie olej smarowy dotyczy mineralnego oleju smarowego i syntetycznego oleju smarowego a takze ich mieszanin. Oleje syntetyczne obejmu- & ja oleje dwuestrowe, takie jak dwu(2-etyloheksy- .lo)sebacynian, azelainian i adypinian, kompleksy estrowe olejów takie jak kompleksy utworzone z kwasów dwukarboksylowych, glikoli albo jedno- zasadowych kwasów lub alkoholi jednowodorotle- 40 nowych, olejów silikonowych, estrów siarczkowych, weglanów organicznych, olejów weglowodorowych i innych znanych olejów syntetycznych.W kompozycji wedlug wynalazku szczególnie od¬ powiednie sa mineralne oleje smarowe. Ma to te ^ dodatkowa zalete, ze pozwala na zuzywanie za¬ pasów olejów o gorszych wlasnosciach przeciw- utleniajaceych niz oleje stosowane obecnie.Olej smarowy z dodatkiem uszlachetniajacym wedlug wynalazku zawiera dwutiofosforan dwu- 50 weglowodorowo-cynkowy w ilosci odpowiadajacej 0,01—5,0% wagowych fosforu i 0,01—5,0% wago¬ wych cynku, korzystnie 0,03—0,3% wagowych, a najkorzystniej 0,04—0,14% wagowych tych pier¬ wiastków. % wagowe i wszystkie wartosci w % 53 wagowych o ile nie zaznaczono inaczej, podane sa w przeliczeniu na 100 czesci wagowych cale¬ go oleju smarowego z dodatkiem uszlachetniaja¬ cym. Fosfor i cynk najdogodniej dostarcza sie w postaci dwutiofosforanu dwuweglowodorowo- «o -cynkowego.Na ogól dwutiofosforan cynkowy stosuje sie w ilosci 0,01—5 czesci, korzystnie 0,2—2,0 czesci, a korzystniej 0,5—1,5 czesci wagowych na 100 cze¬ sci kompozycji. M Dwutiofosforany dwuweglowodorowo-cynkowe stosowane jako skladnik oleju smarowego z dodat¬ kiem uszlachetniajacym wedlug wynalazku mozna sporzadzac w znany sposób, najpierw przez wy¬ twarzanie kwasu dwutiofosforowegó zazwyczaj przez reakcje alkoholu lub fenolu w P2ss a nas¬ tepnie przez zobojetnienie kwasu dwutiofosforo¬ wegó odpowiednim zwiazkiem cynku.Mozna stosowac mieszaniny alkoholi lacznie z mieszaninami alkoholi pierwszo- i drugorzedo- wych. Alkohole drugorzedowe na ogól wprowadza sie w celu nadania lepszych wlasnosci przeciw zuzyciu, zas pierwszorzedowe zapewniaja lepsza trwalosc termiczna. Mieszaniny tych dwóch ro¬ dzajów alkoholi sa szczególnie uzyteczne. Na ogól moze byc uzyty dowolny zasadowy lub obojetny zwiazek cynku, ale najczesciej stosowane sa tlen¬ ki, wodorotlenki i weglany. Dodatki dostepne w handlu czesto zawieraja nadmiar cynku z uwa¬ gi na stosowanie nadmiaru zasadowego zwiazku cynku w reakcji zobojetniania.Dwutiofosforany dwuweglowodorowo-cynkowe odpowiednie do stosowania w oleju smarowym z dodatkiem uszlachetniajacym wedlug wynalazku sa rozpuszczalnymi w oleju solami dwuweglowo¬ dorowych estrów kwasów fosforowych i moga byc przedstawione wzorem ogólnym 1, w którym R i R' moga byc takie same lub rózne i oznaczaja rodniki weglowodorowe zawierajace 1—18 a ko¬ rzystnie 2—12 atomów wegla, takie jak rodnik alkilowy, alkenyIowy, aryIowy, aralkilowy, alki- loarylowy i cykloalifatyczne.Szczególnie korzystnymi grupami R i R' sa grupy alkilowe o 2—8 atomach wegla. Tak wiec, rodnikami moga byc na przyklad rodniki etylo¬ wy, n-propylowy, izopropylowy, n-butylowy, izo- butylowy, Il-rz. butylowy, amylowy, n-heksylo- wy, izoljeksylowy, n-heptylowy, n-oktylowy, decy- lowy, dodecylowy, oktadecylowy, 2-etyloheksylowy, fenylowy, butylofenylowy, cykloheksylowy, mety- locyklopentylowy, propenylowy, butenylowy itd.W celu zapewnienia rozpuszczalnosci w olejach, calkowita ilosc atomów wegla w rodnikach R i R' w kwasie dwutiofosforowym powinna na ogól wynosic 5 lub wiecej.Jak podano powyzej, miedz moze byc mieszana z olejem w postaci dowolnego zwiazku rozpusz¬ czalnego w alej u, przy czym przez okreslenie roz¬ puszczalny olej nalezy rozumiec, ze zwiazek jest rozpuszczalny w oleju w normalnych warunkach mieszania w oleju lub w opakowaniach, Zwiazek miedzi moze byc w postaci zwiazku miedziowego lub miedziawego. Miedz moze byc w postaci dwuweglowodorotio- lub dwutiofosfo- ranów miedzi, w których miedz zastepuje cynk w zwiazkach i reakcjach opisanych powyzej. Je¬ den mol tlenku miedziowego lub miedziawego mozna poddac reakcji z jednym lub dwoma mo- , lami kwasu dwutiofosforowegó. Mozna ewentual¬ nie dodac miedz w postaci soli miedzi z synte¬ tycznym lub naturalnym kwasem karboksylowym.Moga to byc na przyklad kwasy tluszczowe o 10— —18 atomach wegla, takie jak kwas stearynowy lub palmitynowy, ale korzystniejsze sa kwasy7 nienasycone, takie jak kwas oleinowy lub rozga¬ lezione kwasy karboksylowe, takie jak kwasy naf¬ tenowe o ciezarze czasteczkowym 200—500 badz syntetyczne kwasy karboksylowe, z uwagi na po¬ prawione wlasnosci otrzymanych karboksylanów miedzi przelewania i rozpuszczalnosci.Moga równiez byc stosowane rozpuszczalne w oleju dwutiokarbaminiany miedzi o wzorze ogólnym (RR'NCiSS)pCu, w którym n jest równe 1 lub 2 a R i R' takie same lub rózne, maja zna¬ czenie podane powyzej $\a dwutiofosforanów dwu- weg}owodorowQ-cynkowych, sulfoniany miedzi, fe- nolany i acetyloacetoniany. Stwierdzono, ze ilosc miedzi w polaczeniu z dwualkilodwutiofosforana- mi w oleju jest istotna dla otrzymania wlasnosci antyutleniajacyeh i przeciw zuzyciu.Olej smarowy z dodatkiem uszlachetniajacym zawiera korzystnie 60^200, zwlaszcza 80—180, a najkorzystniej 90—120 czesci na milion miedzi, chociaz na ogól zawiera 5—500, korzystnie 10—200, korzystniej 10—180 a zwlaszcza 20^130 czesci na milion, miedzi w przeliczeniu na caly ciezar kom¬ pozycji. Korzystna ilosc moze zalezec miedzy in¬ nymi czynnikami od jakosci oleju z zapasu pod¬ stawowego/ Olej smarowy z dodatkiem uszlachetniajacym wedlug wynalazku moze i zazwyczaj zawiera in¬ ne tradycyjne dodatki do smarów, takie jak inhi¬ bitory rdzewienia, jak lecytyna, monooleinian sor- bitanu, bezwodnik doc(ecylobursztyriowy lub eto- ksylowane alkilofenole, srodki obnizajace tempe¬ rature plynnosci, takie jak kopolimery octanu winylu z estrami kwasu fumarowego z alkohola¬ mi oleju kokosowego, dodatki zmniejszajace za¬ leznosc lepkosci od temperatury, jak kopolimery olefin, polimetakrylany itd.Dla poprawienia odpornosci przeciw utlenianiu w tradycyjnych olejach nie zawierajacych miedzi wymagane sa czasami, poza dwutiofosforanem dwualkilowo-cynkowym dodatkowe przeciwutle- niacze. Te dodatkowe przeciwutleniacze dodaje sie zwlaszcza wtedy, gdy olej z zapasu podstawowe¬ go ma zla trwalosc tlenowa.Zazwyczaj dodatkowy przeciwutleniacz dodaje sie do oleju w ilosciach 0,5—2,5% wagowych. Ja¬ ko dodatkowe przeciwutleniacze stosuje sie feno¬ le, fenole a przeszkodami; bis-fenole, fenole siar¬ kowane, katechol, katechole alkilowano i siarkowa¬ ne alkilokatechole, dwufenyjoamina i alkilodwu- fenyloaminy, fenyio-1-naftyloamina i jej alkilowa- ne pochodne, alkiloborany i aryloborany, alkilo- fctsfpryny i alkilofpsforany, arylolosforyny i ary- lofpsforany, dwutiofosforany Q,0,S-trójalkilowe, dwutiofojaforanj 0,Q,S-trójacyIowe oraz dwutio- fosforany 0,QtS-tr$jpod$iawione zawierajace gru¬ py zarcww alkWoW* JaH. * arylowe. Mala ilosc miedzi aa ogól eliminuje zapotrzebowanie na ten dodatkowy przeciwutleniacz. Do oleju smarowego z dodatkiem uszlachetniajacyro wedlug wynalazku moga byc jednakze wlaczone pewne ilosci dodat¬ kowego przeciwutleniacza, zwlaszcza do olejów pracujacych W szczególnie surowych warunkach, «dy ich obecni mi#e byc ba^z#.korzystna.Glówna zaleca kompozycji wedlug wynalazku jest to, ze miedz zastepuje czesc lub caly potrzeb- 691 8 ny dodatkowy przeciwutleniacz, to znaczy prze¬ ciwutleniacz dodatkowy dwutiofosforan dwuweglo- wodorowo-cynkowy. Czesto umozliwia to uzys^ kanie pozadanych wlasnosci przeciwutleniajacych * albo bez dalszego dodatku przeciwutleniajacego^ albo z ilosciami znacznie mniejszymi niz normal¬ nie, na przyklad mniejszym od 0,5% wagowych a czesto mniejszymi od okolo 0,3% wagowych do¬ datkowego przeciwutleniacza, Obecnosc malych w ilosci miedzi ma jeszcze te zalete, ze mozna sto¬ sowac mniejsze ilosci dwutiofosforanu dwualkilo- wocynkowego.Dyspergowalnoic zapewnia tradycyjny bezpopio^ lowy srodek dyspergujacy taki jak dlugolancu- 15 chowe pochodne weglowodorowe podstawione kwa¬ sami karboksylowymi, w których grupy weglo¬ wodorowe zawieraja 50-^*00 atomów wegla. Beda to na ogól zawierajace azot bezpopiolowe zwiazki dyspergujace majace przylaczone do nich alifa- 20 tyczne grupy o stosunkowo wysokim ciezarze cza¬ steczkowym, solubUisujace olej weglowodorowy lub ester kwasu (bezwodnika bursztynowego ma¬ jacy przylaczony weglowodór alifatyczny o wyso¬ kim ciezarze czasteczkowym i pochodzacy od mo- * no- i wielowodorotjenpwych alkoholi, fenoli lub naftoli.Zawierajace azot dodatki dyspergujace znane sa jako dyspergatory osadu w olejach) silnikowych.Dyspergatory te obejmuja rozpuszczalne w oleju mineralnym sole, amidy, oksazoliny i estry kwa¬ sów jedno- i dwukarboksylowych, a tam gdzie ist¬ nieja, odpowiadajacych kwasom bezwodników, róz¬ nych amin i substancji zawierajacych azot, maja¬ cych azot aminowy lub azot heterocykliczny i co najmniej jedna grupe amidowa lub hydroksylowa zdolna do tworzenia soli, amidów, imidów, oksa¬ zoliny lub estru.Stosowane dodatki dyspergujace zawierajace 40 azot obejmuja te zwiazki, w których poliamina zawierajaca azot przylaczona jest bezposrednio do dlugolancuchowego weglowodoru alifatycznego i opisane sa w opisach patentowych Stanów Zjedn. .Ameryki nr nr 3 275 554 i 3 565 804, w których jak 4ft podano grupa halogenkowa chlorowcowanego we¬ glowodoru zastapiona jest róznymi alkilenopoli- aminami.Inna klasa dyspergato.row zawierajacych azot, które moga byc stosowane w oleju smarowym io z dodatkiem, uszlachetniajacym wedlug wynalaz¬ ku sa znane zwiazki dyspergujace zawierajace za¬ sade Mannicha lub produkty kondensacji Manni- cha. Takie produkty kodensacji Mannicha sporza¬ dza sie na ogól przez kondensacje ojcolo 1 mola u fenolu podstawionego alkilem z okolo 1—2,5 mo¬ la formaldehydu i okolo 0,5—2 moli polialkileno- poliaminy, wedlug opisu patentowego Stanów Zjedn. Ameryki nr 3 442 808.Wymienione produkty kondensacji Mannicha •° moga obejmowac dlugolancuchowe weglowodory o wysokim ciezarze czasteczkowym na grupach fenyIowyeh lub moga Wc poddane reakcji ze zwiazkiem zawierajacym weglowodór np. z. bez¬ wodnikiem alkenylobursztynowym co. podano*- 13 w wyzej wymienionym opisie 3 442 808.127 691 9 10 10 20 19 Monokarboksylowe dyspergatory opisano w opi¬ sie patentowym W. Brytanii nr 983 040. Wymie¬ nione w tym opisie wysokoczasteczkowe kwasy monokarboksylowe moga byc otrzymywane z po- liolefin takich jak poliizobutylen, przez utlenianie • kwasem azotowym lub tlenem lub przez dodanie do poliolefiny halogenku i nastepna hydrolize i utlenienie.Inny sposób podano w "belgijskim opisie paten¬ towym nr 658 236 wedlug którego chlorowcuje sie np. chloruje poliolefiny takie jak polimery olefin o 2—5 atomach wegla np. polipropylen lub poli¬ izobutylenu, a nastepnie kondensuje sie z alfa- beta- nienasyconym kwasem monokarboksylowym zawierajacym 3—8 atomów wegla, korzystnie 3—4 w atomów wegla np. z kwasem akrylowym, kwasem alfa-metyloakrylowym itd. W miejsce wolnych kwasów moga byc ewentualnie uzyte estry tych kwasów np. metakrylan etylu.Najpowszechniej stosowanym kwasem dwukar- boksylowym iest bezwodnik alkenylobursztynowy, którego grupy alkenylowe zawieraja okolo 50— —400 atomów wegla. Glównie z powodu latwej dostepnosci i niskiej ceny, czesc weglowodorowa kwasu mono- lub dwukarboksylowego lub innej podstawionej grupy, korzystnie pochodzi od poli¬ meru monoolefiny o 2—«5 atomach wegla, przy czym polimer na ogól ma ciezar czasteczkowy okolo 700 do okolo 5000. Szczególnie korzystny jest poliizobutylen.Aminami stosowanymi do wytwarzania dysper- gatora sa zazwyczaj polialkilenoamkiy. Polialkile- noaminy takie moga byc przedstawione wzorem ogólnym H2N(CH2)n...[NH w którym n oznacza 2 lub 3 a m oznacza 0—10.Przykladami takich polialfcilenoamin sa dwuety- lenotrójamina, tetraetylenopentamina, oktaetyleno- nonamina, tetrapropylenopentamina jak równiez inne cykliczne pólialkenoaminy. 40 Zwiazki dyspergujace tworzone przez reakcje bezwodnika alkenylobursztynowego np. bezwodni¬ ka poliizobutenylobursztynowego i aminy opisano w opisach patentowych Stanów Zjedn. Ameryki nr nr 3 202 678, 3154 560, 3172 892, 3 024195, 3 024 237, 45 3 219 666, 3 216 936.Alternatywnie bezpopiolowymi dodatkami dys¬ pergujacymi moga byc estry pochodzace od do¬ wolnego z wyzej wymienionych dlugolancuchowych weglowodorów podstawionych kwasami karboksy- lowymi i od zwiazków hydroksylowych takich jak jedno- i wielowodorotlenowe alkohole lub zwiaz¬ ki aromatyczne takie jka fenole i naftole itd.Najkorzystniejszymi hydroksy zwiazkami sa al- 55 kohole poliwodorotlenowe i które korzystnie za¬ wieraja 2—10 grup hydroksylowych, na przyklad, glikol etylenowy, glikol dwuetylenowy, glikol trój- etylenowy, glikol tetraetylenowy, glikol dwupro- pylenowy, i inne glikole alkrlenowe, w których §o rodnik alkdlenowy zawiera 2-*€ atomów wegla.Inne przydatne alkohole poliwodorotlenowe za¬ wieraja gliceryne, monooldnian gliceryny, mono- .sterynian gliceryny, monoetylowy eter gliceryny, pentaerytrytoL * 5fl Dyspergator estrowy równiez moze pochodzic od alkoholi nienasyconych takich jak alkohol allilo- wy, alkohol cynamylowy, alkohol propargilowy, l-cykloheksanol-3 i alkohol oleilowy.Jeszcze jedna grupe alkoholi, która moze dac przydatne estry sa etero-alkohole i amino-alko- hole takie jak na przyklad oksyalkileny, ofcsy- aryleny, amino-alkileny i podstawione aminoary- lenoalkohole majace jeden lub wiecej rodników oksyalkilenowych, aminoalkilenowych lub amino- aryleno-oksy-arylenowych.Przykladami moga byc Carbltol, NJN^NMe- trahydroksy-trójmetyleno^dwuamina i podobne.W wiekszosci, korzystne sa etero-alkohole maja¬ ce do okolo 150 rodników oksyalkilenowych, w których rodnik alkilenowy zawiera 1—8 ato¬ mów wegla.Jako dodatki dyspergujace moga byc stosowane dwuestry kwasu bursztynowego lub estry kwasne np. czesciowo zestryfikowany kwas bursztynowy, jak równiez czesciowo zestryfikowane wielowodo¬ rotlenowe alkohole lub fenole np. estry majace wolne rodniki hydroksylowe alkoholowe lub feno¬ lowe. Moga byc równiez stosowane mieszaniny po¬ wyzszych estrów.Dyspergatory estrowe moga byc sporzadzone zna¬ nym sposobem np. zilustrowanym w opisie paten¬ towym Stanów Zjedn. Ameryki nr 3 522179.Hydroksyloaminami, które przy sporzadzaniu zwiazków dyspergujacych moga byc poddane re¬ akcji z dowolnym sposród wyzej wymienionych dlugolancuchowych podstawionych weglowodoro¬ wych kwasów karboksylowych sa: 2-amino-buita- nol-1, 2-amino-2-merykpropanol-l, p- ksyetylo)-anilina, 2-aminopropanol-l, 3-aminopro*- panol-1, 2-amino-2-metylo-l,3-propanodiol, 2-ami- no-2-etylo-l,3-propanodiol, N,N-(beta-hydroksypro- pylo)-NMbeta-aminoetylo)-piperazyna, tris(hydro- ksymetylo)aminometan znany równiez pod nazwa trismetyloloaminometan, 2-aminoizobutanol, etano- loamina, beta-(beta-hydroksyetoksy)e1yloeiniaa i podobne. Mozna równiez stosowac mieszaniny tych i podobnych amin.Korzystnymi dyspergatorami sa zwiazki dysper¬ gujace pochodzace od bezwodnika poliizobuteny¬ lobursztynowego i polietylenoamin np. tetraetyle- nopentaminy, amin polioksyetylenowych lub poii- oksypropylenowych np. polJoksypropylenodwuaini- ny, trismetyloloaminometanu i pentaerytrytolu oraz ich kombinacji.Jedna szczególnie korzystna ich kombinacja jest kombinacja bezwodnika poiiizobuteny^oburszrtyno- wego ze zwiazkiem hydroksylowym np. pentaery- trytolem, polioksyetylenopoliamina np. pottoksy- etylenodwuamina i poBalkilenopolianiiny, np. po- lietylenodwuaminy i tetraetylenopentaminy.Jak podano w opisie patentowym Stanów Zjada.Ameryki nr 3 884 768 stosuje sie okolo t«6i do okolo 4 równowazników zwlariku hydroksylowego i polialkilenopoliaminy oraz okolo dfil do okolo 2 równowazników polioksyalkilenoponaminy na równowaznik bezwodnika poliizobuteiyloburszty- nowego.Inny korzystny dodatek dyspergu}acy obejmuje bezwodnik poliizobutenylobursztynowy z pollalki-127 U lenopoliamina np. tetraetylenopentamina i alkoho¬ lem poliwodorotlenowym lub polihydroksypodsta- wiona alifatyczna amina pierwszorzedowa np. pen- taerytrytol lub trismeityloloaminometan wedlug opisu patentowego Stanów Zjedn. Ameryki 5 nr 3 632 511.Zwiazki dyspergujace typu poliaminy alkenylo- bursztynowej moga byc dalej modyfikowane zwiazkiem boru takim jak tlenek boru, haloge¬ nek boru, kwasy borowe i estry kwasów borowych 10 w ilosci okolo 0,1 do okolo 10 czesci boru na mol acylowanego zwiazku azotowego wedlug opisów patentowych Stanów Zjedn. Ameryki nr 3 087 936 i nr 3 254 025. Mozna równiez stosowac mieszaniny dyspergatorów takie jak opisane w opisie paten- 15 towym Stanów Zjedn. Ameryki nr 41,13 639.Oleje moga zawierac 1,0—10% wagowych, ko¬ rzystnie 2,0—7,0% wagowych tych dyspergatorów.Dyspergowalnosc zapewnia równiez 0,3—10% wagowych polimerycznego dyspergujacego dodatku 20 zmniejszajacego zaleznosc lepkosci od temperatu¬ ry. Przykladami odpowiednich dyspergujacych po¬ limerycznyeh dodatków poprawiajacych indeks lepkosci sa: a) polimery nienasyconych estrów alkoholu wi- 25 nylowego o 4—24 atomach wegla lub nienasyco¬ nych kwasów mono- lub dwukarboksylowych o 3—10 atomach wegla z nienasyconymi mono¬ merami zawierajacymi azot o 4—20 atomach we¬ gla, 30 b) polimery olefin o 2—20 atomach wegla z nie¬ nasyconymi kwasami mono- lub dwukarboksylo- wymi o 3—10 atomach wegla neutralizowanymi aminami, hydroksyaminami lub alkoholami, c) polimery etylenu z olefina zawierajace 3^20 H atomów wegla, poddane dalszej reakcji badz przez -szczepienie na nich nienasyconych monomerów zawierajacych azot, o 4—20 atomach wegla, lub przez szczepienie nienasyconego kwasu na osnowie polimeru i nastepna reakcje powyzszych grup 40 kwasowych z amina, hydroksyamina lub alkoho¬ lem.W polimerach tych amina, hydroksyamina i al¬ kohol mono- lub wielowodorotlenowy moga byc takie jak omówiono w odniesieniu do dysperga- ^ torów bezpopiolowych.Korzystnie dyspergujacy dodatek poprawiajacy indeks lepkosci ma przecietny ciezar czasteczkowy wedlug pomiaru osmometrycznego w fazie gazo¬ wej, osmometrii membranowej, lub zelowej 50 ^ romatografii przepuszczalnej, w zakresie 1000— —2 000 000 korzystnie 5000—250 000 a najkorzyst- nij 10000—200 000.Korzystnie polimery grupy (a) zawieraja wago¬ wo wieksza ilosc estrów nienasyconych i mniej- M sza .np. 0,1—40, korzystnie 1—20% wagowycli nie- nasycOnych ; mdnomerów zawierajacych azot, przy czym podane % wagowe dotycza przeliczenia na cala ilosc polimeru.Korzystnie polimery grupy (b) zawieraja 0,1—40 19 moli olefiny, korzystnie 0,2—»5 moli olefin o cze¬ sciach alifatycznych lub aromatycznych, o 2—20 atomach wegla, na mol nienasyconego kwasu kar- boksylowego przy czym 50—100% czesci kwaso¬ wych jest zneutralizowanych. 65 691 12 Korzystny polimer grupy (c) zawiera kopolimer etylenu zlozony w 25—80% wagowych z etylenu i 75—20% wagowych mono- i lub dwuolefin o 3— —20 atomach wegla, przy czym 100 czesci wago¬ wych kopolimeru jest szczepionych badz za po¬ moca 0,1—40, korzystnie 1—20 czesci wagowych nienasyconego monomeru zawierajacego azot badz za pomoca 0,01—5 czesci wagowych nienasyconego mono- lub dwukarboksylowego kwasu o 3—10 ato¬ mach wegla, przy czym kwas jest w 50% lub wiecej zobojetniony.Nienasycone kwasy karboksylowe stosowane w punkach (a), (b) i (c) zawieraja korzystnie 3—-10 czesciej 3 lub 4 atomy wegla i moga to byc kwa¬ sy monokarboksylowe takie jak kwasy metakry- lowy lub akrylowy lub dwukarboksylowe takie jak kwas maleinowy, bezwodnik maleinowy, kwas bumarowy itd- Przykladami stosowanych nienasyconych estrów sa estry zawierajace nasycone alifatyczne mono- -alkohole o co najmniej 1 atomie wegla a ko¬ rzystnie 12—20 atomów wegla takie jak aferylan dodecylu, akrylan laurylu, akrylan stearylu, akry¬ lan cikozanylu, akrylan dokozanylu, metakrylan decylu, fumarynian dwuamylu, metakrylan laury¬ lu, metakrylan cetylu, metakrylan stearylu i po¬ dobne oraz ich mieszaniny.Innymi stosowanymi estrami moga byc estry alkoholu winylowego i kwasów tluszczowych lub monokarboksylowych o 2—22 atomach wegla, ko¬ rzystnie nasyconych, takie jak octan winylu, la- urynian winylu, palmitynian winylu, stearynian winylu, oleinian winylu i podobne oraz ich mie¬ szaniny.Przykladami odpowiednich nienasyconych mo¬ nomerów zawierajacych azot o 4—20 atomach we¬ gla, które moga byc stosowane do polimerów wy¬ mienionych w punkcie (a) i (c) sa olefiny amino- podstawione takie jak p-!(beta-dwuetyloaminoety- lo)-styren, zasadowe heterocykle zawierajace, azot i ulegajace polimeryzacji etylenowo nienasycone podstawniki np. winylopirydyny i winyloalkilopiry- dyny takie jak 2-winylo-5-etylopirydyna, 2-mety- lo-5-winylopirydyna, 2-winylopirydyna, 3-winylo- pirydyna, 4-winylopirydyna, 3-metylo-5-winylopi- rydyna, 4-metylo-2-winylopirydyna, 4-etylo-2-wi- ~ 1 nylopirydyna i 2-butylo-5-winylopirydyna i po¬ dobne.Odpowiednie sa równiez N-winylolaktamy, a zwlaszcza N-winylopirolidony lub N-winylopipe- rydony. Korzystnie, rodnik winylowy jest niepod- stawiony {CI^ = CH-), ale moze byc on mono- podstawiony weglowodorem alifatycznym o 1—2 atomach wegla, np. grupa metylowa lub etylowa.Korzystna klasa N-winylolaktamów sa winylopi- rolidony na przyklad N-winylopirolidon, N-(l-me- tylowinylo)pirolido N-winylo-3,3-dwumetylopiTolin, N-winylo-5-etylo— pirolidon, N-winylo-4jbutylopirolin, N-etylo-3-wi— nylopirolidon, 5-butylo-5-winylopirolidon, 3-winy- lopirolin, 4-winylopirolin, 5-winylopirolidon i 5-cy- kloheksylo-N-winylopirolidon.Przykladami olefin, które rrioga byc stosowane- do sporzadzania kopolimerów wymienionycri13 127 691 14 15 20 30 w punktach (b) i (c) sa mono-olefiny takie jak propylen, 1-buten, 1-penten, 1-heksen, 1-heplen, 1-decen, 1-dodecen, styren itd.Przykladami dwuolefin, które moga byc stoso¬ wane w (c) sa 1,4-heksadien, 1,5-heptadien, 1,6- 5 -oktadien, 5-metylo-l,4-heksadien, 1,4-cykloheksa- dien, 1,5-cyklooktadien, winylocykloheksan, dwu- cyklopentenyl i 4,4'-dwucykloheksenyl, taki jak tetrahydroinden, metylotetrahydroinden, dwucy- klopentadien, bicyklo(2.2.1)hepta-2,5-dien, alkenyl, 10 alkilidien, 5-metyleno-2-norbornen, 5-etylideno-2- -norbornen.Typowym dyspergujacym polimerycznym dodat¬ kiem poprawiajacym indeks lepkosci sa kopoli¬ mery metakrylanów alkili z N-winylopirolidonem lub dwumetyloaminoalkilometakrylan, kopolime¬ ry fumarynianu alkilu, octanu winylu i N-winy- lopirolidyny, szczepione nastepczo interpolimery etylenu — propylenu z aktywnym monomerem takim jak bezwodnik maleinowy, który mozna dalej poddac reakcji z alkoholem lub alkileno- poliamina np. tak jak podano w opisach paten¬ towych Stanów Zjedn. Ameryki nr nr 4 089 794, 4160 739 i 4 137 185, lub kopolimery etylenu i pro¬ pylenu poddane reakcji lub szczepione zwiazkiem azotowym takim jak przedstawiono w opisach pa¬ tentowych Stanów Zjedn. Ameryki nr nr 4 068 058, 4 068 056, 4146 489 i 4149 984, polimery styren /bezwodnik maleinowy poddane nastepnie reakcji z alkoholami i aminami, etoksylowane pochodne polimerów akrylanowych opisane np. w opisie pa¬ tentowym Stanów Zjedn. Ameryki nr 3 702 300.Do oleju smarowego czesto dodaje sie dodatki zawierajace magnez lub wapn w postaci soli me- talicznych kwasów sulfonowych, alkilofenoli, sali¬ cylanów alkili, naftenów i innych rozpuszczalnych w oleju kwasów mono- lub dwukarboksylowych.Wysoko zasadowe sulfoniany metali ziem alka¬ licznych wytwarza sie zazwyczaj przez ogrzewa- 40 nie mieszaniny zawierajacej rozpuszczalny w ole¬ ju kwas alkiloarylo-sulfonowy z nadmiarem zwiazku metalu ziem alkalicznych w stosunku do ilosci potrzebnej do pelnej neutralizacji kwasu sulfonowego. Nastepnie tworzy sie zdyspergowany 45 kompleks weglanowy przez reakcje nadmiaru me¬ talu z dwutlenkiem wegla, w celu otrzymania po¬ zadanej nadzasadowosci.Kwasy sulfonowe zazwyczaj otrzymuje sie przez sulfonowanie aromatycznych weglowodorów pod- 50 stawionych alkilem otrzymywanych z frakcjono¬ wania ropy naftowej przez destylacje i/lub ekstra¬ kcje lub przez alkilowanie weglowodorów aroma¬ tycznych na przyklad otrzymywanych przez al¬ kilowanie benzenu, toluenu, ksylenu, naftalenu, 55 dwufenylu i pochodnych chlorowcowych takich jak chlorobenzen, chlorotoluen i chloronaftalen.Alkilowanie mozna prowadzic w obecnosci ka¬ talizatora z czynnikiem alkilujacym zawieraja¬ cym od okolo 3 do ponad 30 atomów wegla, ta- W kim jak na przyklad chlorowcoparafiny, olefiny otrzymywane przez odwodornienie parafin, poli- olefiny na przyklad polimery etylenu, propylenu itd. Sulfoniany alkiloarylowe zazwyczaj zawiera¬ ja okolo 9—70 i wiecej atomów wegla, korzyst- * nie 16—50 a reszite aromatyczna.Do neutralizacji kwasów alkiloarylosulfonowych w celu otrzymania sulfonianów metali ziem al¬ kalicznych stosuje sie tlenki i wodorotlenki, al¬ koholany, weglany, karboksylany, siarczyny, wo- dorosiarczyny, azotany, borany i etery magnezu, wapnia i baru. Przykladowo stosuje sie tlenek wapnia, wodorotlenek wapnia, octan magnezu i boran magnezu.Jak juz podano, zwiazek metalu ziem alkalicz¬ nych stosuje sie w nadmiarze w stosunku do ilosci potrzebnej do zneutralizowania kwasów al- kiloarylosulfonowych.Na ogól stosuje sie 100—220%, chociaz korzyst¬ ne jest zuzycie co najmniej 125% stechiometrycz- nej ilosci metalu potrzebnego do kompletnej ne¬ utralizacji.Wytwarzanie wysolko zasadowych alkiloarylo- sulfonianów metali ziem alkalicznych jest znane na przyklad z opisów patentowych Stanów Zjedn.Ameryki nr 3 150 088 i nr 3 150 089, w którym zwiek¬ szona zasadowosc uzyskuje sie przez hydrolize kompleksu alkoholanu-weglanu z alkiloarylosulfo- nianem w weglowodorowym rozpuszczalniku-roz- cienczalniku. Korzystnie jest stosowac taki weglo¬ wodorowy rozpuszczalnik-rozcienczalnik, który mo¬ ze byc z latwoscia usuniety pozostawiajac jako do¬ datek inhibitor rdzewienia w nosniku np. olej smarowy Solvent 150N, odpowiedni do uzycia w kompozycji smarowej.Korzystnym sulfonianem metalu ziem alkalicz¬ nych jest alkiloaromatyczny sulfonian magnezu o calkowitej liczbie zasadowej w zakresie okolo 300—400 z zawartoscia sulfonianu magnezu w za¬ kresie 25—32% wagowych w przeliczeniu na ilosc wagowa wszystkich dodatków zdyspergowanych w obojetnym oleju Solvent 150.Alkilosalicylany i nafteniany metali wielowarto- sciowych sa znanymi dodatkami do olejów sma¬ rowych poprawiajac ich odpornosc na eksploata¬ cje w warunkach wysokich temperatur i przeciw¬ dzialajac osadzaniu sie osadów weglowych na tlo¬ kach co opisano na przyklad w opisie patento¬ wym Stanów Zjedn. Ameryki nr 2 744 069.Zwiekszenie rezerwowej zasadowosci alkilosali- cylanów i naftenianów wielowartosciowego meta¬ lu osiaga sie przez zastosowanie metali ziem al¬ kalicznych np. wapnia, soli mieszanin alkilo-sa- licylanów i fenolanów o 8—26 atomach wegla, (opis patentowy Stanów Zjedn. Ameryki nr 2 744 069) lub soli wielowartosciowych metali i kwasów alkilosalicylowych otrzymanych z alki¬ lowania fenoli i nasrtepnego fenolowania, karbo- ksylowania i hydrolizy (opis patentowy Stanów Zjedn. Ameryki nr 3 704 315), które moga byc nas¬ tepnie przeksztalcone do soli wysoko zasadowych znanymi technikami i uzyte do takich konwersji.Rezerwowa zasadowosc tych inhibitorów rdzewie¬ nia zawierajacych metal jest przydatna przy cal¬ kowitych liczbach zasadowych w zakresie okolo 60 a 150.Przydatne sa równiez salicylany i nafteniany wielowartosciowyeh metali z mostkiem metyleno¬ wym i siarkowym, które z latwoscia otrzymuje127 li sie z alkilopodstawionych kwasów salicylowych lub naftenowych lub mieszanin kazdego z nich lub mieszanin z alkilopodstawionymi fenolami.Zasadowe siarkowane salicylany i sposób ich wytwarzania znane sa z opisu patentowego Sta- ! nów Zjedn. Ameryki nr a 505 791.Stosowane jako inhibitory rdzewienia salicyla¬ ny/nafteniany metali ziem alkalicznych, zwlasz¬ cza magnezu, wapnia, strontu i baru sa solami kwasów aromatycznych o wzorze ogólnym HOOC- 1 -ArBj-KyfArl^OH),,, w którym Ar oznacza gru¬ pe arylowa o 1—6 pierscieniach, Rj oznacza gru¬ pe alkilowa o 8—50 atomach wegla, korzystnie 12—30 atomów wegla, optymalnie 12, X oznacza siarke <-S-) lub metylen (-CHj-, Y oznacza licz- w be 0—4 i n oznacza liczbe 0—4.Sól salicylanowo-fenelanowa z mostkiem mety¬ lenowym o zwiekszonej zasadowosci z latwoscia wytwarza sie technikami tradycyjnymi takimi jak alkilowanie fenolu a nastepnie fenolanowanie, kar- m boksylowanie, hydrolize, sprzeganie srodka most¬ kiem metylenowym takim jak dwuhalogenek al- kilenu i nastepnie tworzenie soli z równoczesnym nasyceniem dwutlenku wegla. Wysoce uzytecznym inhibitorem rdzewienia jest nadzasadowa sól wap- u niowa kwasu fenolo~salicykwfego z mostkiem me¬ tylenowym o wzorze 2, posiadajaca liczbe zasa¬ dowa 09—150.Siarkowane fenolany metali moga byc uwazane za sole metalu z siarczkiem fenolu, co oznacza n sól metaliczna zarówno obojetna jak i zasadowa o wzorze ogólnym 3, w którym x oznacza 1 lub 2, a n oznacza 0, 1 lub 2, lub polimeryczna po¬ stacia takiego zwiazku, w którym R oznacza gru¬ pe alkilowa, n i x oznaczaja liczby calkowite 1— n —4, przy czym przecietna liczba atomów wegla we wszystkich grupach R, aby zapewnic odpo¬ wiednia rozpuszczalnosc w oleju wynosi co naj¬ mniej 9. Poszczególne grupy R moga zawierac 5—40, korzystnie 8—20 atomów wegla. Sól meta- 41 liczna sporzadza sie przez poddanie reakcji siarcz¬ ku alkilofenolu z iloscia materialu zawierajacego metal odpowiednio do nadania pozadanej alka¬ licznosci siarkowanemu fenolowi metalu. niezaleznie od sposobu sporzadzania, odpowied- 45 nie siarkowane alkilofeaole zawieraja okolo 2— —44% wagowych, korzystnie okolo 4—12% wago¬ wych siarki w przeliczeniu na siarkowany alkilo- fenol.Siarkowany alkilofenol przeksztalca sie przez go reakcje z materialem zawierajacym metal, np tlenkami, wodorotlenkami i zwiazkami komplek¬ sowymi stosowanym w ilosci dostatecznej do zne¬ utralizowania powyzszego fenolu i ewentualnie do uzyskania oadeasadowosci produktu znanym n sposobem. Korzystny jest sposób neutralizacji z zastosowaniem roztworu metalu w eterze gli- kolowym.W obojetnych lub normainyfch siarkowanych fenolanach metali stosunek metalu do pierscieni • fenolowych wynosi oko*o 1:2. Nadzasadowe lub zasadowe siarkowane fenolany metali maja sto¬ sunek metalu do fenolu wyzszy niz stechiome- lryczny np. zasadowy siarkowany dodecylofenolan metalu ma zawartosc metalu dochodzaca do ¦ is i przewyzszajaca o 100% ilosc metalu obecnego w normalnym siarkowanym fenolanie metalu, w którym nadmiar metalu jest w postaci rozpusz¬ czalnej lub dyspergowalnej w oleju np. jak w re¬ akcji z C02.Dodatki zawierajace magnez i wapn, chociaz korzystne z innych wzgledów moga zwiekszac ten¬ dencje oleju smarowego do utleniania sie. Doty¬ czy to zwlaszcza wysoce zasadowych sulfonianów.W korzystnym wykonaniu wynalazek obejmuje silnikowy olej smarowy z dodatkiem uszlachet¬ niajacym zawierajacy wieksza ilosc oleju smaro¬ wego i dyspergator zlozony w 1—10% wagowych z bezpopiolowych zwiazków dyspergujacych i 0,3— —10% wagowych z dyspergujacego polimerycznego dodatku poprawiajacego indeks lepkosci oraz 0,01—0,5% wagowych fosforu, 0,01—0,5% wagowych cynku, 5—500 czesci na milion miedzi i 2—8 000 czesci na milion wapnia lub magnezu i ewentu¬ alnie inne dodatki takie jak opisane powyzej i in¬ ne dodatki zawierajace metale, na przyklad za¬ wierajace bar i sód.Magnez i/lub wapn na ogól obecne sa w posta¬ ci zasadowych lub obojetnych detergentów takich jak sulfoniany i fenolany. Korzystne sa obojetne lub zasadowe sulfoniany magnezu lub wapnia. Ko¬ rzystnie oleje zawieraja 500—5000, 2—8000 czesci na milion wapnia lub magnezu w postaci zasa¬ dowych sulfonianów magnezu lub wapnia.Olej smarowy z dodatkiem uszlachetniajacym wedlug wynalazku moze równiez obejmowac in¬ hibitory korozji zawierajace miedz i olów. Typo¬ wymi takimi zwiazkami sa polisiarczki tiadiazo- lu zawierajace 5—90 atomów wegla, ich pochod¬ ne i polimery.Korzystnymi, materialami sa pochodne 1,3,4-tia- diazoli takie jak opisano w opisie patentowym Stanów Zjedn. Ameryki nr nr 2 719125, 2 719126 i 3 087 932, szczególnie korzystnym zwiazkiem jest 2,5-bis-(t-oktaditio)-l,3,4-tiadiazol dostepny w han¬ dlu pod nazwa Amoco 150.Inne podobne materialy równiez dostepne w handlu opisane sa w opisach patentowych Sta¬ nów Zjedn. Ameryki nr nr 3 821238, 3 904 537, 4 097 387, 4107 059, 4136 043, 4188 299 i 4193 882.Innymi odpowiednimi dodatkami sa tio lub po- litio sulfamidy tiadiazoli takie jak opisane w opi¬ sie patentowym W. Brytanii nr 1560 830. Gdy zwiazki te wlacza sie do kompozycji w ilosci wy¬ noszacej 0,01—10 korzystnie 0,1—'5,0% wagowych w przeliczeniu na cala kompozycje, nieoczekiwa¬ nie stwierdzono, ze takie inhibitory korozji nio¬ sace miedz i olów hamuja przeciwuSleniajace dzia¬ lanie miedzi.Dodatki do smarów na ogól dostarcza sie w po¬ staci koncentratów w oleju i rozprowadza sie je do wymaganego stezenia w oleju smarowym. Wy¬ nalazek moze byc zilustrowany nastepujacymi przykladami.Przyklad I. Sporzadzono olej smarowy z dodatkiem uszlachetniajacym. Uzyto IOW/30 ole¬ ju smarowego zawierajacego wiefksza czesc mine¬ ralnego oleju smarowego i 4£% wagowych okolo 50% wagowo koncentratu gkladnika aktywnego zlozonego z mieszaniny dyspergatora z póliizobu-17 127 691 tenylowego bezwodnika bursztynowego przereago- wanego z polietylenoamina a nastepnie borano- wanego, lacznie z bezwodnikiem poliizobutenylo- bursztynowym przereagowanym z trishydroksyme- tyloaminometanem, jako opisano w opisie paten¬ towym Stanów Zjedn. Ameryki nr 4113 639, 1,0% wagowe sulfonianu magnezu o calkowitej liczbie zasadowej 400 zawierajacego 9,2% wagowych mag¬ nezu, 0,3% wagowych fenolanu wapnia o calko¬ witej liczbie zasadowej 250 zawierajacego 9,3% wapnia i 7,9% wagowych dodatku poprawiajacego indeks lepkosci zawierajacego 10% wagowych ko¬ polimeru etylen/propylen i 4% wagowych kopoli¬ meru octanu winylu/fumarynianu jako depresato- ra. Do powyzszego dodano koncentratu 75% wa¬ gowych w oleju mineralnym dwutiofosforanu dwualkilowocynkowego, w którym grupy alkilowe stanowily mieszanine grup o 4 i 5 atomach we¬ gla, sporzadzonego przez poddanie reakcji P2S3 z mieszanina okolo 65% alkoholu izobutylowego i 35% alkoholu amylowego, do uzyskania poziomu fosforu 0,1% wagowych w oleju smarowym.Trwalosc tlenowa tego oleju smarowego z dodat- Jciem uszlachetniajacym badano przez utlenianie 300 g próbki oleju zawierajacego 40 czesci na milion zelaza w postaci acetyloacetondanu zela¬ zowego przez przepuszczenie przez próbke 1,7 li¬ trów powietrza na minute w temperaturze 165°C i oznaczenie lepkosci w przedzialach czasowych do 64 godzin na wiskozymetrze Ferranti-Shirley Tabela 1 Zwiazek dodatkowy nie stosowano Alkilowana dwufeny- loamina (oktarnina) Fenylo-1-naftyloamina Fenol z mostkiem me¬ tylenowym i przesz¬ koda steryczna Siarkowany nonylo- fenol Ekstra dwualkilodwu- tiofosforan cynku Ekstra dwualkilodwu- tiofosforan cynku Dwuarylodwutiofosfo- ran miedziawy Dwu-sec-heksylodwu- tiofosforan miedziawy Dwu^izooktylodwutio- fosforan miedziawy Naftenian miedziawy Oleinian miedziowy % wago- 0,5 0,5 0,5 1,0 1,2 1,2 0,23 0,10 043 0,25 0,32 miedz | ppm Czas próby h 170 170 170 170 160 30 40 24 30 64 48 64 64 64 64 64 64 Lep¬ kosc Pa-s cialo stale cialo stale cialo stale cialo stale 0,5 0,5 cialo stale 0,37 0,31 0,31 0,33 0,3 10 15 20 40 45 fO 65 •0 1S typu stozek-na-plytce. W próbie tej smar mial konsystencje przechodzaca w stala, gdy lepkosc osiagala wartosc 0,5 Pa-s.Tlenowa trwalosc kompozycji porównano z kom¬ pozycja olejowa zawierajaca dodatki dobrze zna¬ ne jako dodatkowe przeciwutleniacze i z kompo¬ zycja olejowa zawierajaca pewne dodatki miedzio¬ we do dwualkilodwutiofosforanu cynku. Wyniki podano w tabeli 1.Przyklad II. Sporzadzono rózne oleje sma¬ rowe z dodatkiem uszlachetniajacym zlozone w wiekszosci z otrzymanego mineralnego oleju smarowego otrzymanego z zapasu podstawowego oleju o przecietnej jakosci 5,4% wagowych kon¬ centratu mieszaniny dyspergatora z przykladu I, innych dodatków z przykladu I a nastepnie ilos¬ ci zwiazku cynku z przykladu I lacznie z rózny¬ mi ilosciami zwiazków miedzi (tabela 2).Zwiazek cynku % wagowy (koncentrait) A 1,80 B 1,48 C 1,65 D 1,70 E 1,80 Tabela 2 Zwiazek miedzi Naftenian miedziowy Dwuizooktylodwutio- fosforan miedziawy jak wyzej Dwu-sec-heksylodwu- tiofosforan miedziawy Oleinian miedziowy .% wago¬ wy 1,50 0,39 0,20 0,084 0,156 ppm Cu w oleju 1200 486 240 120 f 94 Smar opisany powyzej badano w próbie sek¬ wencyjnej 3D ASTM publikacja STP 315G. Wy¬ mieniona powyzej kompoyzcja zawierajaca 1,80% wagowych zwiazku cynkowego i nie zawierajaca dodatku miedzi byla zbyt lepka do przeprowadze¬ nia pomiaru po 48 h.Przyklad III. W próbie utleniania takiej jak w przykladzie I oznaczono wplyw róznych dodatków na trwalosc tlenowa mineralnego sma¬ rowego oleju silnikowego IOW/30. Wyniki przed¬ stawiono w tabeli 3. Stosowano nastepujace do¬ datki: A) koncentrat dodatku poprawiajacego indeks lepkosci zawierajacy 10% wagowych kopolimeru etylen/propylen i 4% kopolimeru octanu winylu/ fumarynianu, B) koncentrat dyspergatora zlozony z okolo 50% wagowych oleju mineralnego i okolo 50% wa¬ gowych produktu kondensacji bezwodnika pollizo- butenylobursztynowego i poliaminy, traktowanego zwiazkiem boru tak, ze koncentrat zawieral 1,58% wagowych azotu i 0,35% wagowych boru, C) koncentrat dwutiofosforanu dwualkilocynko- wego stosowany w przykladzie I, D) sulfonian o calkowitej liczbie zasadowej •3 400, zawierajacych 9,2% wagowych magnezu,19 127 691 20 co cd Xi cd Eh ^ co 1—1 CM i—t OS CO c- co lO Tl< co CM 1-1 M v Dodat i 1 1 i i 1 l i 1 . i i i i i i 1 1 O) t^ 1 1 Xi u owy s? •s # < 1 1 1 1 1 1 1 1 1 1 1 1 1 4,5 1 1 m ^ i 1 1 Xi CJ owy 8P * # b i 1 i i i 1 i i 1 . i i i i i lO o 1 1 1 1 1 Xi o owy to cd £ # O i 1 1 1 o o 1 o 1—1 1 o 1-1 1 1 1 1 1 1 1 1 1 Xi o owy U) £ # Q o o 1—1 1 1 1 1 o l—i . 1 ' o 1 1 1 1 1 1 1 1 1 1 Xi u owy to cd * # W o CM 1 1 O CM i—i 1 1 120 120 1 1 o CM 1 1 1 1 1 . 1 1 1 3 U S O* fc i-* o 1—l o o i-H o 1 1 1 1 1 1 1 1 1 1 1 1 Xi CJ owy 00 cd £ <£ O CM CM~ O lO o" A o co °" lo o A co CM o" rr- CM o LO O A LO O A co o" 0,33 c- o o lO o A o LO o O* rT o fi ^o o Lepk CD O ^ co o ^ co CO o o tH CO CO co CM CO 1—1 CO l—l ^ » -° o Oi ania trw Czas CO C\| 1—1 1 ° 1—1 Oi co c- co LO ** CO CN »—( Dodatek I 1 " 1 ° o II ' CM 1 1 2 1 ° o 1 | 5 | 3 o LO O 1 1 °" 1 - <=» 1 1 3 | | g i-H 1 1 3 1 1 o 1 1 " 1 1 § csi 1 1 3 1 1 o i-H CO 1 I-I 1 ° 1 1 S- I Ig CM 1 1 5 1 I g 1 1 S | | o 1 1 »" 1 Ig O^ LO^ LO O^ ^ t tjT o" l-T 1 ^ A % wagowych B % wagowych C % wagowych D % wagowych E % wagowych F/ppm Cu i—* CM CO o co CO co LO^ <=T o A * co o" o co lO CM co lO o" o A * CM o ^ co CO CO LO^ cT o A ** LO A ' 1 Lepkosc/Pa* s Czas trwania próby/h127 691 21 10 15 20 E) sulfonian wapnia o calkowitej liczbie zasa¬ dowej 400, zawierajacej 15,3% wagowych wapnia, # F) oleinian miedziowy, G) 2,5-bis (T-oktadwutio)-l,3,4-tiadiazol.Przyklad IV. Stosujac dodatek wedlug przy¬ kladu II mierzono wplyw róznych stezen miedzi na trwalosc tlenowa w próbie utleniania opisanej w przykladzie I. Wyniki przedstawiono w tabli¬ cy 4.Zastrzezenia patentowe 1. Olej smarowy z dodatkiem uszlachetniaja¬ cym, znamienny tym, ze zawiera dodatek. dysper¬ gujacy zlozony z 1—10% wagowych bezpopiolowych zwiazków dyspergujacych i 0,3—10% wagowych polimerycznego dodatku zmniejszajacego zaleznosc lepkosci od temperatury a jako dalsze dodatki dwutiofosforan dwuweglowodorowo-cynkowy w ilosci odpowiadajacej 0,01—5,0% wagowych fos¬ foru i 0,01—-5,0% wagowych cynku oraz 5—500 cze¬ sci na milion miedzi w postaci rozpuszczalnego w oleju zwiazku miedzi i ewentualnie inne do¬ datki. 2. Olej smarowy wedlug zastrz.. 1, znamienny tym, ze zawiera 60—200 czesci na milion miedzi. 3. Olej smarowy wedlug zastrz. 1 aibo 2, zna¬ mienny tym, ze zawiera 80—180 czesci na milion miedza. 4. Olej smarowy wedlug zastrz. 1 albo 2, zna¬ mienny tym, ze zawiera 90—120 czesci na milion miedzi. 5. Olej smarowy wedlug zastrz. 1, znamienny ^ tym, ze zawiera 0,5—1,5% wagowych dwutiofosfora- nu dwuweglowodorowo-cynkowego. 6. Olej smarowy wedlug zastrz. 1, znamienny tym, ze zawiera ponadto ponizej 0,5% wagowych dalszego przeciwutlentiacza. *o 30 7. Olej smarowy wedlug zastrz. 1, znamienny tym, ze jako bezpopiolowy zwiazek dyspergujac^ zawiera pochodna alkenyIowa 'kwasu/bezwodnika bursztynowego^ 8., Olej smarowy wedlug zastrz, 7, znamienny tym, ze zawiera jako bezpopiolowy zwiazek dys¬ pergujacy zawierajaca azot pochodna alkenyIowa kwasu/bezwodnika bursztynowego lub ester tej alkenylowej pochodnej kwasu/bezwodnika burszty¬ nowego z jedno- lub wielowodoratlenowymi alko¬ holami, fenolami lub naftolami . 9. Olej smarowy wedlug zastrz. ,1, znamienny tym, ze ponadto zawiera dodatek zawierajacy magnez i/lub wapn w ilosci 2—8000 czesci na mi¬ lion wapnia lub magnezu. 10. Olej smarowy wedlug zastrz. 9, znamienny tym, ze jako dodatek zawierajacy magnez zawie¬ ra zasadowy fenolan lub sulfonian magnezowy. 11. Olej smarowy wedlug zastrz. 9, znamienny tym, ze jako dodatek zawierajacy wapn zawiera zasadowy fenolan lub sulfonian wapniowy. 12. Olej smarowy wedlug zasjtrz, 1 znamienny tym, ze jako polimeryczny dodatek dyspergujacy zmniejszajacy zaleznosc lepkosci od temperatury zawiera polimery skladajace sie z nienasyconych estrów o 4—24 atomach wegla, alkoholu winylo¬ wego lub nienasyconych kwasów jedno- lub dwu- karboksylowych o 3—10 atomach wegla z niena¬ syconymi monomerami zawierajacymi azot o 4— —20 atomach wegla, kopolimery olefin o 2—20 ato¬ mach wegla z nienasyconymi kwasami jedno- lub dwukarboksylowymi o 3—10 atomach wegla zobo¬ jetnione amina, hydroksyamina lub alkoholami, po¬ limery etylenu i olefiny o 3—20 atomach wegla poddane dalej reakcji badz przez szczepienie na nich monomerów nienasyconych o 4—20 atomach wegla zawierajacych azot, badz przez szczepienie do rdzenia polimeru nienasyconego kwasu i' nas¬ tepna reakcje grup karboksylowych kwasu z ami¬ na, hydroksyamina lub alkoholem.R0- S ir P-S OR' ---Z.Wzór 1127 691 OH HOOC C^25 CH2— C19H 12n25 1-4 R Sx OH mór 2 R Ó-Sx OH Wzór 3 R OH n Zaikl. Graf. Radom — 1154/87 90 egz. A4 Cena 100 zl PL
Claims (12)
- Zastrzezenia patentowe 1. Olej smarowy z dodatkiem uszlachetniaja¬ cym, znamienny tym, ze zawiera dodatek. dysper¬ gujacy zlozony z 1—10% wagowych bezpopiolowych zwiazków dyspergujacych i 0,3—10% wagowych polimerycznego dodatku zmniejszajacego zaleznosc lepkosci od temperatury a jako dalsze dodatki dwutiofosforan dwuweglowodorowo-cynkowy w ilosci odpowiadajacej 0,01—5,0% wagowych fos¬ foru i 0,01—-5,0% wagowych cynku oraz 5—500 cze¬ sci na milion miedzi w postaci rozpuszczalnego w oleju zwiazku miedzi i ewentualnie inne do¬ datki.
- 2. Olej smarowy wedlug zastrz.. 1, znamienny tym, ze zawiera 60—200 czesci na milion miedzi.
- 3. Olej smarowy wedlug zastrz. 1 aibo 2, zna¬ mienny tym, ze zawiera 80—180 czesci na milion miedza.
- 4. Olej smarowy wedlug zastrz. 1 albo 2, zna¬ mienny tym, ze zawiera 90—120 czesci na milion miedzi.
- 5. Olej smarowy wedlug zastrz. 1, znamienny ^ tym, ze zawiera 0,5—1,5% wagowych dwutiofosfora- nu dwuweglowodorowo-cynkowego.
- 6. Olej smarowy wedlug zastrz. 1, znamienny tym, ze zawiera ponadto ponizej 0,5% wagowych dalszego przeciwutlentiacza. *o 30
- 7. Olej smarowy wedlug zastrz. 1, znamienny tym, ze jako bezpopiolowy zwiazek dyspergujac^ zawiera pochodna alkenyIowa 'kwasu/bezwodnika bursztynowego^
- 8., Olej smarowy wedlug zastrz, 7, znamienny tym, ze zawiera jako bezpopiolowy zwiazek dys¬ pergujacy zawierajaca azot pochodna alkenyIowa kwasu/bezwodnika bursztynowego lub ester tej alkenylowej pochodnej kwasu/bezwodnika burszty¬ nowego z jedno- lub wielowodoratlenowymi alko¬ holami, fenolami lub naftolami .
- 9. Olej smarowy wedlug zastrz. ,1, znamienny tym, ze ponadto zawiera dodatek zawierajacy magnez i/lub wapn w ilosci 2—8000 czesci na mi¬ lion wapnia lub magnezu.
- 10. Olej smarowy wedlug zastrz. 9, znamienny tym, ze jako dodatek zawierajacy magnez zawie¬ ra zasadowy fenolan lub sulfonian magnezowy.
- 11. Olej smarowy wedlug zastrz. 9, znamienny tym, ze jako dodatek zawierajacy wapn zawiera zasadowy fenolan lub sulfonian wapniowy.
- 12. Olej smarowy wedlug zasjtrz, 1 znamienny tym, ze jako polimeryczny dodatek dyspergujacy zmniejszajacy zaleznosc lepkosci od temperatury zawiera polimery skladajace sie z nienasyconych estrów o 4—24 atomach wegla, alkoholu winylo¬ wego lub nienasyconych kwasów jedno- lub dwu- karboksylowych o 3—10 atomach wegla z niena¬ syconymi monomerami zawierajacymi azot o 4— —20 atomach wegla, kopolimery olefin o 2—20 ato¬ mach wegla z nienasyconymi kwasami jedno- lub dwukarboksylowymi o 3—10 atomach wegla zobo¬ jetnione amina, hydroksyamina lub alkoholami, po¬ limery etylenu i olefiny o 3—20 atomach wegla poddane dalej reakcji badz przez szczepienie na nich monomerów nienasyconych o 4—20 atomach wegla zawierajacych azot, badz przez szczepienie do rdzenia polimeru nienasyconego kwasu i' nas¬ tepna reakcje grup karboksylowych kwasu z ami¬ na, hydroksyamina lub alkoholem. R0- S ir P-S OR' ---Z. Wzór 1127 691 OH HOOC C^25 CH2— C19H 12n25 1-4 R Sx OH mór 2 R Ó-Sx OH Wzór 3 R OH n Zaikl. Graf. Radom — 1154/87 90 egz. A4 Cena 100 zl PL
Applications Claiming Priority (1)
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PL226207A1 PL226207A1 (pl) | 1981-04-24 |
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PL1980226207A PL127691B1 (en) | 1979-08-13 | 1980-08-13 | Lubricating oil with improving additive |
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EP (1) | EP0024146B1 (pl) |
JP (3) | JPS5653189A (pl) |
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DK (1) | DK152809C (pl) |
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GB (1) | GB2056482A (pl) |
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US20240141250A1 (en) | 2022-10-18 | 2024-05-02 | Infineum International Limited | Lubricating Oil Compositions |
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US4225448A (en) * | 1978-08-07 | 1980-09-30 | Mobil Oil Corporation | Copper thiobis(alkylphenols) and antioxidant compositions thereof |
US4175043A (en) * | 1978-09-21 | 1979-11-20 | Mobil Oil Corporation | Metal salts of sulfurized olefin adducts of phosphorodithioic acids and organic compositions containing same |
US4234435A (en) * | 1979-02-23 | 1980-11-18 | The Lubrizol Corporation | Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation |
US4417990A (en) * | 1979-05-31 | 1983-11-29 | The Lubrizol Corporation | Mixed metal salts/sulfurized phenate compositions and lubricants and functional fluids containing them |
US4308154A (en) * | 1979-05-31 | 1981-12-29 | The Lubrizol Corporation | Mixed metal salts and lubricants and functional fluids containing them |
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-
1979
- 1979-08-13 GB GB7928146A patent/GB2056482A/en not_active Withdrawn
-
1980
- 1980-08-01 EP EP80302627A patent/EP0024146B1/en not_active Expired
- 1980-08-01 DE DE8080302627T patent/DE3071168D1/de not_active Expired
- 1980-08-08 ZA ZA00804853A patent/ZA804853B/xx unknown
- 1980-08-10 DZ DZ805943A patent/DZ249A1/fr active
- 1980-08-11 MX MX183518A patent/MX155685A/es unknown
- 1980-08-12 SU SU802964803A patent/SU1630615A3/ru active
- 1980-08-12 CA CA000358102A patent/CA1170247A/en not_active Expired
- 1980-08-12 AU AU61367/80A patent/AU537461B2/en not_active Ceased
- 1980-08-12 RO RO101959A patent/RO81105B/ro unknown
- 1980-08-12 NO NO802409A patent/NO149665C/no unknown
- 1980-08-13 PL PL1980238096A patent/PL130651B1/pl unknown
- 1980-08-13 DK DK349980A patent/DK152809C/da active
- 1980-08-13 AR AR80282144A patent/AR241924A1/es active
- 1980-08-13 JP JP11156880A patent/JPS5653189A/ja active Granted
- 1980-08-13 PL PL1980226207A patent/PL127691B1/pl unknown
- 1980-08-13 BR BR8005107A patent/BR8005107A/pt not_active IP Right Cessation
-
1987
- 1987-05-12 US US07/049,712 patent/US4867890A/en not_active Expired - Lifetime
-
1988
- 1988-05-18 JP JP63121649A patent/JPH01163295A/ja active Granted
- 1988-05-18 JP JP63121650A patent/JPH01113495A/ja active Granted
-
1992
- 1992-07-30 GE GEAP1992106A patent/GEP19960322B/en unknown
Also Published As
Publication number | Publication date |
---|---|
DK152809B (da) | 1993-08-02 |
NO149665C (no) | 1984-05-30 |
EP0024146A1 (en) | 1981-02-25 |
GB2056482A (en) | 1981-03-18 |
DE3071168D1 (en) | 1985-11-14 |
JPH01113495A (ja) | 1989-05-02 |
NO802409L (no) | 1981-02-16 |
JPH0333759B2 (pl) | 1991-05-20 |
DK152809C (da) | 1993-08-02 |
BR8005107A (pt) | 1981-02-24 |
PL226207A1 (pl) | 1981-04-24 |
JPH0158239B2 (pl) | 1989-12-11 |
ZA804853B (en) | 1981-08-26 |
EP0024146B1 (en) | 1985-10-09 |
JPH01163295A (ja) | 1989-06-27 |
AU537461B2 (en) | 1984-06-28 |
JPS5653189A (en) | 1981-05-12 |
DK349980A (da) | 1981-02-14 |
US4867890A (en) | 1989-09-19 |
JPH0325477B2 (pl) | 1991-04-08 |
CA1170247A (en) | 1984-07-03 |
NO149665B (no) | 1984-02-20 |
GEP19960322B (en) | 1996-06-24 |
PL130651B1 (en) | 1984-08-31 |
AU6136780A (en) | 1981-02-19 |
DZ249A1 (fr) | 2004-09-13 |
RO81105A (ro) | 1985-04-17 |
MX155685A (es) | 1988-04-13 |
RO81105B (ro) | 1985-04-30 |
SU1630615A3 (ru) | 1991-02-23 |
AR241924A1 (es) | 1993-01-29 |
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