EP0418610A1 - Viscosity index improver, with a dispersant activity - Google Patents
Viscosity index improver, with a dispersant activity Download PDFInfo
- Publication number
- EP0418610A1 EP0418610A1 EP90116624A EP90116624A EP0418610A1 EP 0418610 A1 EP0418610 A1 EP 0418610A1 EP 90116624 A EP90116624 A EP 90116624A EP 90116624 A EP90116624 A EP 90116624A EP 0418610 A1 EP0418610 A1 EP 0418610A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- monomers
- parts
- meth
- acrylates
- 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.)
- Granted
Links
- 230000000694 effects Effects 0.000 title description 6
- 239000002270 dispersing agent Substances 0.000 title description 2
- 239000000654 additive Substances 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 19
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000003599 detergent Substances 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 239000000839 emulsion Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 8
- 229920001195 polyisoprene Polymers 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical class CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 claims 1
- 239000002480 mineral oil Substances 0.000 description 69
- 235000010446 mineral oil Nutrition 0.000 description 68
- 230000000996 additive effect Effects 0.000 description 28
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 26
- 239000003921 oil Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 25
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 24
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 21
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 12
- 239000010802 sludge Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007046 ethoxylation reaction Methods 0.000 description 7
- 150000002191 fatty alcohols Chemical class 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 5
- 229920005601 base polymer Polymers 0.000 description 4
- 101150017210 ccmC gene Proteins 0.000 description 4
- 230000003749 cleanliness Effects 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 3
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical compound CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 230000001236 detergent effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000004324 sodium propionate Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- DWFUTNJGNBYHNN-UHFFFAOYSA-N 2,2,4-trimethylhexanedioic acid Chemical compound OC(=O)CC(C)CC(C)(C)C(O)=O DWFUTNJGNBYHNN-UHFFFAOYSA-N 0.000 description 1
- WFTWWOCWRSUGAW-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CCOCCOCCOC(=O)C(C)=C WFTWWOCWRSUGAW-UHFFFAOYSA-N 0.000 description 1
- XVTPGZQPUZSUKS-UHFFFAOYSA-N 2-(2-oxopyrrolidin-1-yl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCN1CCCC1=O XVTPGZQPUZSUKS-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- WNWVKZTYMQWFHE-UHFFFAOYSA-N 4-ethylmorpholine Chemical group [CH2]CN1CCOCC1 WNWVKZTYMQWFHE-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- 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
- C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
-
- 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
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
-
- 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
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
- C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
- C10M145/14—Acrylate; Methacrylate
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
-
- 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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
-
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
- C10M2217/023—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group the amino group containing an ester bond
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- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
-
- 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
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol-fuelled engines
-
- 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
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
-
- 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
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
- C10N2040/253—Small diesel engines
-
- 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
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
-
- 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
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B1/00—Engines characterised by fuel-air mixture compression
- F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
- F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
- F02F7/00—Casings, e.g. crankcases or frames
- F02F7/006—Camshaft or pushrod housings
Definitions
- the invention relates to viscosity index (VI) improvers with good shear stability and good dispersing detergent action in lubricating oils, in particular for diesel and gasoline engines.
- VI viscosity index
- N-vinylpyrrolidone is particularly suitable as a dispersing monomer in addition to N-vinylimidazole.
- graft products based on OCP or PAMA as base polymers or as constituents of concentrated polymer emulsions which are composed of both polymer classes have gained practical importance.
- the object was therefore to provide polyalkyl (meth) acrylates, in particular in the form of highly concentrated polymer emulsions with sufficient dispersing action and detergent action, the other properties of which, in particular the ratio "thickening action to shear stability", meet modern requirements. It has now been found that the additives according to the present invention meet the requirements of technology to an outstanding degree.
- the poly (meth) acrylates are in combination with olefin copolymers (OCP) and / or hydrogenated isoprene or butadiene-styrene copolymers (HSD) and / or hydrogenated polyisoprene or polybutadiene in the form of concentrated polymer emulsions.
- OCP olefin copolymers
- HSD hydrogenated isoprene or butadiene-styrene copolymers
- polyisoprene or polybutadiene in the form of concentrated polymer emulsions.
- the present application furthermore relates to a process for the preparation of concentrated polymer emulsions from poly (meth) acrylates and olefin copolymers suitable for improving the viscosity index in liquid carrier media for use as oil additives with improved dispersing and detergent action in diesel and gasoline engines, with monomers 80 to 99.5 parts by weight of alkyl (meth) acrylates of the formula I.
- the polymerization of the monomers I, II, IIA, IIB and III can be carried out with the addition of 0.1 to 2.0% by weight of radical initiator and with the simultaneous presence of 0.05 up to 0.5% by weight of molecular weight regulators, in each case based on the total of the monomers.
- the usual sulfur regulators cf. Th.Völker, H.Rauch-Puntigam, acrylic and methacrylic compounds, Springer-Verlag 1968
- the concentrations of the monomers and polymers are preferably such that the total of the monomers and polymers present in the liquid carrier medium TM is 40 to 75% by weight, preferably 55 to 70% by weight, based on the overall system.
- the polymerization batch is followed by At the end of the polymerization, further olefin copolymers were added in amounts such that the olefin copolymer content in the total polymer present was 31 to 80% by weight.
- the olefin copolymer can advantageously be added tel quel, ie in undiluted form, it being advantageously emulsified using shear forces.
- the additional olefin copolymer can also be added in the form of a solution, for example a 10-20% solution in the liquid carrier medium.
- VI improvers namely olefin copolymers (OCP), polyalkyl (meth) acrylates (PAMA) and the aforementioned “mixed polymers” serve e.g. according to EP 14 746 as base polymers for the process according to the invention.
- the polyalkyl (meth) acrylates are primarily those with alkyl radicals with 6-24 carbon atoms, which lead to solubility in mineral oil. Shorter alkyl residues and those with polar substituents that do not impart solubility in the mineral oil can be present to a certain extent.
- the molecular weights M w are between 5,000 and 1,000,000, preferably between 50,000 and 500,000. Such products are described in GB-C 1 068 938, US Pat. No. 3,732,334, US Pat. No. 4,149,984, US Pat.
- the monomers to be used in the process according to the invention are illustrated below.
- alkyl (meth) acrylates of the formula I are copolymerized in proportions of 80 to 99.5, preferably 90 to 98.5, parts by weight.
- monomers of the formula I are (meth) acrylic acid esters of tallow fatty alcohols (for example in the C number range 14-20, on average approx. 17.3), of coconut fatty alcohols (C number range 10 -16, on average approx. 12.6) ) or of synthetic alcohols such as Dobanol 25 R (C number range 11 - 16, on average 13.5).
- Examples of functionalized monomers of the formula II are those with an OH group in the alkyl radical, in particular in the u-position of the alkyl radical, for example the 2-hydroxyethyl methacrylate and the -acrylate, the 3-hydroxypropyl methacrylate and -acrylate, and also the 2-position or double methyl-substituted derivatives, 4-hydroxybutyl methacrylate and acrylate, but also the 2-hydroxypropyl methacrylate and acrylate.
- the monomers of the formula II in which R 2 stands for a frequently alkoxylated, in particular ethoxylated radical, for example 2- (2-ethoxyethoxy) ethyl methacrylate and - are of particular interest because of their low other aggressiveness under practical conditions in motor testing.
- R 7 represents an alkylene dialkylamino group
- R 7 represents an alkylene dialkylamino group
- the corresponding amides especially the N- (3-dimethylaminopropyl) methacrylamide.
- These comonomers can be copolymerized, for example by copolymerization, together with compounds of the formula II, but also at a later point in time.
- the formula IIA also includes heterocyclically substituted monomers, such as, for example, the 2- (1-imidazolyl) ethyl methacrylate and acrylate, the 2- (4-morpholinyl) ethyl methacrylate and acrylate and the 1- (2-methylacryloyloxyethyl) -2-pyrrolidone, as well as the corresponding amides.
- heterocyclically substituted monomers such as, for example, the 2- (1-imidazolyl) ethyl methacrylate and acrylate, the 2- (4-morpholinyl) ethyl methacrylate and acrylate and the 1- (2-methylacryloyloxyethyl) -2-pyrrolidone, as well as the corresponding amides.
- the monomers of the formula IIB are of particular importance, especially N-vinylpyrrolidone-2.
- the olefin copolymers to be used according to the invention are known per se. It is primarily composed of ethylene, propylene, butylene and / or other ⁇ -olefins with 5 to 200 carbon atoms built-up polymers, as have already been recommended as VI improvers.
- the molecular weight M w is in general from 10,000 to 300,000, preferably between 50,000 and 150,000.
- Such olefin copolymers are described, for example, in German Offenlegungsschriften DE-A 16 44 941, DE-A 17 69 834, DE-A 19 39 037 , DE-A 19 63 039 and DE-A 20 59 981.
- the base copolymer consists of a hydrogenated polyisoprene or copolymer with styrene
- commercially available hydrogenated products for example commercial products SHELLVIS 50, 200 or 250 @ are preferred.
- Ethylene-propylene copolymers are particularly useful, and terpolymers with the known tercomponents, such as ethylidene Norbornen (cf. Macromolecular Reviews, Vol. 10 (1975)) is possible, but their tendency to cross-link during the aging process must be taken into account.
- the distribution can be largely statistical, but sequence polymers with ethylene blocks can also be used with advantage
- the ratio of the monomers ethylene-propylene is variable within certain limits, which can be set as the upper limit at around 75% for ethylene and around 80% for propylene.As a result of its reduced tendency to solubility in oil, polypropylene is already less suitable than ethylene-propylene copolymers .
- the solvents therefore fall e.g. in the group of hydrocarbons such as kerosene (boiling range 180-210 degrees C), the naphthenic oils, the paraffin-based oils or the gas oils. (Cf. Ullmanns Enzyklopadie der Techn. Chemie, 4th edition, vol. 10, pp. 641-714.
- carrier media are advantageously used which only solve OCP to a limited extent or are only swelling agents, as described in detail in "USP 4,677,151 and US Pat. No. 4,622,358.
- phthalic esters such as dibutyl phthalate and esters of 2,2,4-trimethyladipic acid, for example with a mixture of octanol / decanol.
- the mono- or multifunctional alcohols themselves are also suitable.
- *** for example hexadecanol, octadecanol, diethylene glycol, tetraethylene glycol and methoxypolyethylene glycols with degrees of ethoxylation of approx. 2-50.
- the polymerization of the alkyl (meth) acrylates is generally carried out as a monomer feed polymerization at 80-100 ° C. in a liquid carrier medium with the addition of peroxidic initiators such as t-butyl peroctoate. In the case of the production of concentrated polymer emulsions, this is done in the presence of a small amount of dissolved OCP. The polymerization is usually complete after about 8 hours. Subsequently, further monomers can be graft-polymerized at 130 ° C. with the addition of t-butyl perbenzoate. Finally, the desired final composition is then set by adding further OCP and, if appropriate, solvent or carrier medium.
- the VI-improving additives according to the invention with dispersing / detergent action are generally available as relatively concentrated polymer solutions in the carrier media.
- the polymer content in the concentrates is 30 to 75% by weight, preferably 40 to 70%.
- oils or fractions are advantageously added to the oils or fractions, the viscosity indices of which are to be improved, in such amounts that they preferably contain 1 to 10% by weight of the polymeric additives according to the present invention.
- the advantage of the additives according to the invention is an excellent dispersing and detergent effect in Otto and diesel engines with completely neutral behavior against sealing materials such as e.g. Viton ®.
- Polymer content 60% by weight
- Table 2 shows results of the M-102-E black sludge test.
- Additive 4 (example 5) containing OH groups is rated significantly better than additive 5 with vinylpyrrolidone (example 6). Both additives are present as a concentrated polymer emulsion.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Detergent Compositions (AREA)
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Abstract
Description
Die Erfindung betrifft Viskositätsindex (VI)-Verbesserer mit guter Scherstabilität und guter Dispergier- Detergenzwirkung in Schmierölen, insbesondere für Diesel-und Otto-Motoren.The invention relates to viscosity index (VI) improvers with good shear stability and good dispersing detergent action in lubricating oils, in particular for diesel and gasoline engines.
Moderne Hochleistungsmotoren stellen zunehmend höhere Anforderungen an das Dispergier- und Detergenzvermögen der Motoren-Schmieröle.Modern high-performance engines place increasing demands on the dispersing and detergent properties of engine lubricating oils.
Im Bereich der Otto-Motoren dienen Motorentests in den dafür ausgewählten Motoren (DB-M 102 E oder Sequence VE-Test) zur Beurteilung der Schlamm-Dispergierwirkung. Auf der Seite der Diesel-Motoren wird die Neigung zur Bildung von Ablagerungen, die u.a. zu Ringstecken führen, im Motor-Test (VW-TD oder MWM-B) beurteilt.In the field of Otto engines, engine tests in the engines selected for this purpose (DB-M 102 E or Sequence VE test) are used to assess the sludge dispersing effect. On the side of diesel engines, the tendency to form deposits, which i.a. lead to ring sticking, judged in the engine test (VW-TD or MWM-B).
Der Gesamtheit der Anforderungen kann in der Regel nur mit Mehrbereichsölen, die neben entsprechend abgestimmten Detergent-Inhibitor (DI)-Paketen in der Dispergier/Detergenzwirkung optimierte VI-Verbesserer enthalten, entsprochen werden.The entirety of the requirements can generally only be met with multigrade oils which, in addition to correspondingly coordinated detergent inhibitor (DI) packages, contain optimized VI improvers in the dispersing / detergent effect.
Daß spezielle Dispergierwirkung durch polare, insbesondere basische Comonomere, beispielsweise N-Vinylheterocyclen oder Dialkylaminoalkyl(meth)acrylate in polymere VI-Verbesserer eingebracht werden kann, ist schon seit langem bekannt (vgl. H. Rauch-Puntigam, Th. Völker, Acryl- und Methacrylverbindungen, p. 314 - 318, Springer-Verlag, Berlin 1967; Ullmanns Encyclopädie der technischen Chemie, 4. Auflage, Bd. 20, pg 547 - 550, Verlag Chemie 19 81)It has long been known that special dispersing effects can be introduced into polymeric VI improvers by means of polar, in particular basic comonomers, for example N-vinyl heterocycles or dialkylaminoalkyl (meth) acrylates (cf. H. Rauch-Puntigam, Th. Völker, Acryl- and Methacrylic compounds, p. 314 - 318, Springer-Verlag, Berlin 1967; Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, Vol. 20, pg 547 - 550, Verlag Chemie 19 81)
Als technisch besonders interessant hat sich die Pfropfung von Basispolymerisaten vom Typ der Olefincopolymerisate (OCP) und der Polyalkyl(meth)acrylate (PAMA) mit den dispergierwirksamen polaren Monomeren erwiesen, für die im Laufe der Zeit verschiedene Verfahrensvarianten vorgeschlagen wurden. (Vgl. DE-A 12 35 491, BE-A 592 880, US-A 4 281 081, US-A 4 338 418, US-A 4 290 025).The grafting of base polymers of the olefin copolymer (OCP) and polyalkyl (meth) acrylate (PAMA) type with the dispersing polar monomers has proven to be of particular technical interest, for which various process variants have been proposed over time. (See DE-A 12 35 491, BE-A 592 880, US-A 4 281 081, US-A 4 338 418, US-A 4 290 025).
Nach vorliegenden Erfahrungen eignet sich N-Vinylpyrrolidon neben N-Vinylimidazol besonders als dispergierwirksames Monomer. Insbesondere haben Pfropfprodukte auf OCP oder PAMA als Basispolymere, beziehungsweise als Bestandteile von konzentrierten Polymeremulsionen, die aus beiden Polymerklassen aufgebaut sind (sogenannte "Mixed Polymers", vgl. EP 14 746) praktische Bedeutung erlangt. Konzentrierte Emulsionen von Olefincopolymerisaten mit einem Pfropf- oder Blockcopolymerisat aus Olefincopolymerisat-sequenzen und Poly(meth)acrylat-sequenzen als Emulgator in einem Tragermedium, welches die Olefincopolymerisate im wesentlichen nicht löst, die Poly(meth)acrylat-sequenzen jedoch löst, wobei die Olefincopolymerisate unter Anwendung von Scherkräften bei 40 - 150 Grad C im Trägermedium emulgiert werden, sind in dem EP 88 904 beschrieben.Experience has shown that N-vinylpyrrolidone is particularly suitable as a dispersing monomer in addition to N-vinylimidazole. In particular, graft products based on OCP or PAMA as base polymers or as constituents of concentrated polymer emulsions which are composed of both polymer classes (so-called "mixed polymers", cf. EP 14 746) have gained practical importance. Concentrated emulsions of olefin copolymers with a graft or block copolymer of olefin copolymer sequences and poly (meth) acrylate sequences as an emulsifier in a carrier medium which essentially does not dissolve the olefin copolymers, but does dissolve the poly (meth) acrylate sequences, the olefin copolymers are emulsified in the carrier medium using shear forces at 40-150 degrees C are described in EP 88 904.
Andererseits hat sich erwiesen, daß in vielen Fällen eine ausreichende Dispergier-/Detergenzwirkung dann erzielt werden kann, wenn die Pfropfausbeute bei der Pfropfung von N-Vinylpyrrolidon von ca. 60 % auf ca. 75 % gesteigert wird. Die Steigerung der Pfropfausbeute läßt sich zwar in naheliegender Weise durch Erhöhung der Pfropfkomponente von ca. 58 % auf ca. 70 % bezogen auf das PAMA-Basispolymerisat erreichen, man handelt sich aber dafür so schwerwiegende Nachteile ein, daß diese Maßnahme keinen echten Fortschritt bringt. So wird das Molekulargewicht durch vernetzende Nebenreaktionen der Basisketten (sogenannten Pfropfanstieg des Mw) in der Pfropfstufe mit N-Vinylpyrrolidon unverhältnismäßig erhöht, mit der Folge, daß die Scherstabilität drastisch abfällt. Die Relation "Verdickungswirkung zu Scherstabilität" genügt dann längst nicht den herrschenden Anforderungen.On the other hand, it has been found that in many cases a sufficient dispersing / detergent effect can be achieved if the grafting yield is increased from approximately 60% to approximately 75% when grafting N-vinylpyrrolidone. Although the increase in the grafting yield can be achieved in an obvious manner by increasing the grafting component from approximately 58% to approximately 70% based on the PAMA base polymer, the disadvantages involved are so serious that this measure does not bring any real progress. The molecular weight is increased disproportionately by crosslinking side reactions of the base chains (so-called graft increase in Mw) in the grafting stage with N-vinylpyrrolidone, with the result that the shear stability drops drastically. The relation "thickening effect to shear stability" then does not meet the prevailing requirements.
Es bestand daher die Aufgabe, Polyalkyl(meth)acrylate, insbesondere in Form von hochkonzentrierten Polymeremulsionen mit ausreichender Dispergierwirkung und Detergenzwirkung zur Verfügung zu stellen, deren übrige Eigenschaften, insbesondere das Verhältnis "Verdickungswirkung zu Scherstabilität" den modernen Anforderungen genügen. Es wurde nun gefunden, daß die Additive gemäß vorliegender Erfindung den Anforderungen der Technik in hervorragendem Maße gerecht werden.The object was therefore to provide polyalkyl (meth) acrylates, in particular in the form of highly concentrated polymer emulsions with sufficient dispersing action and detergent action, the other properties of which, in particular the ratio "thickening action to shear stability", meet modern requirements. It has now been found that the additives according to the present invention meet the requirements of technology to an outstanding degree.
Gegenstand der Erfindung sind zur Verbesserung des Viskositätsindex geeignete Polyalkyl(meth)-acrylate (PAMA) und/oder konzentrierte Polymeremulsionen aus Polyalkyl(meth)acrylaten und Olefin-copolymerisaten (OCP) in flüssigen Trägermedien (TM) zur Verwendung als Öladditive mit verbesserter Dispergier-und Detergenzwirkung in Diesel- und Otto-Motoren, wobei die Polyalkyl(meth)acrylate aufgebaut sind aus 80 - 99,5 Gew.-Teilen Alkyl(meth)acrylaten der Formel
- R für Wasserstoff oder Methyl und R1 für einen Alkylrest mit 6 bis 24 Kohlenstoffatomen, vorzugsweise 8 bis 20 Kohlenstoffatomen steht,
zusammen mit 0,5 - 20 Gew.-Teilen mindestens eines funktionalisierten Alkylmethacrylats der Formel II
- R' für Wasserstoff oder Methyl steht und R2 für einen mit mindestens einer OH-Gruppe substituierten Alkylrest mit 2 - 6 Kohlenstoffatomen oder für einen mehrfach alkoxylierten Rest
gegebenenfalls 0 - 20 Gew.-Teile eines oder mehrerer Monomeren der Formel III
- R für Wasserstoff oder Methyl und
- R6 für einen Alkylrest mit 1 bis 5 Kohlenstoffatomen steht
- als Comonomeren.
- R represents hydrogen or methyl and R 1 represents an alkyl radical having 6 to 24 carbon atoms, preferably 8 to 20 carbon atoms,
together with 0.5-20 parts by weight of at least one functionalized alkyl methacrylate of the formula II - R 'represents hydrogen or methyl and R 2 represents an alkyl radical having 2 to 6 carbon atoms substituted by at least one OH group or a polyalkoxylated radical
optionally 0-20 parts by weight of one or more monomers of the formula III - R represents hydrogen or methyl and
- R 6 represents an alkyl radical with 1 to 5 carbon atoms
- as comonomers.
Neben den Monomeren der Formel II bzw. III können weiterhin noch zusätzlich 0 - 20 Gew.-Teile, vorzugsweise 0,5 bis 15 Gew.-Teile funktionalisierte Alkyl(meth)acrylate der Formel IIA
- X für Sauerstoff oder
- R"' für Wasserstoff oder Methyl steht und R7 für einen mit mindestens einer Gruppe -NR8R9 substituierten, gegebenenfalls verzweigten Alkylrest mit 2 bis 20, vorzugsweise 2 bis 6 Kohlenstoffatomen, wobei R8 und R9 unabhängig voneinander für einen Alkylrest mit 1 bis 20, vorzugsweise 1 bis 6 Kohlenstoffatomen stehen oder worin R8 und Rs unter Einbeziehung des Stickstoffatoms und gegebenenfalls eines weiteren Stickstoff-oder Sauerstoffatoms einen 5- oder 6-gliedrigen Ring bilden, der gegebenenfalls mit C1-C6-Alkyl substituiert sein kann und worin R'6 dieselbe Bedeutung wie R6 besitzt und/oder eine vinylische heterocyclische Verbindung der Formel IIB
- Bs einen fünf- oder sechsgliedrigen Heterocyclus, insbesondere einen N-Heterocyclus, vorzugsweise aus der Gruppe in der Bs für einen Pyridin-, Carbazol-, Imidazol- und insbesondere einen Pyrrolidon-Rest steht, copolymerisiert werden.
- X for oxygen or
- R "'represents hydrogen or methyl and R 7 represents an optionally branched alkyl radical having 2 to 20, preferably 2 to 6 carbon atoms substituted by at least one group -NR 8 R 9 , R 8 and R 9 independently of one another having an alkyl radical 1 to 20, preferably 1 to 6 carbon atoms or in which R 8 and Rs, including the nitrogen atom and optionally a further nitrogen or oxygen atom, form a 5- or 6-membered ring which is optionally substituted by C 1 -C 6 -alkyl and where R ' 6 has the same meaning as R 6 and / or a vinyl heterocyclic compound of the formula IIB
- Bs a five- or six-membered heterocycle, in particular an N-heterocycle, preferably from the group in which Bs represents a pyridine, carbazole, imidazole and in particular a pyrrolidone radical.
Bei einer besonderen Ausgestaltung der Erfindung sind im Anschluß an die Polymerisation der Monomeren der Formeln I, II, IIA, IIB und gegebenenfalls III noch weitere 0,5 bis 15 Gew.-Teile Monomere der Formel IIA und/oder IIB, gegebenenfalls zusammen mit 1 bis 30 Gew.-Teilen Monomeren der Formel I und III zugegeben und polymerisiert worden. In einer weiteren besonderen Ausgestaltung der Erfindung liegen die Poly(meth)acrylate in Kombination mit Olefincopolymeren (OCP) und/oder hydrierten Isopren-oder Butadien-Styrol-Copolymeren (HSD) und/oder hydriertem Polyisopren oder Polybutadien in Form von konzentrierten Polymerisatemulsionen vor.In a special embodiment of the invention, after the polymerization of the monomers of the formulas I, II, IIA, IIB and, if appropriate, III, a further 0.5 to 15 parts by weight of monomers of the formula IIA and / or IIB, optionally together with 1 up to 30 parts by weight of monomers of the formula I and III have been added and polymerized. In a further particular embodiment of the invention, the poly (meth) acrylates are in combination with olefin copolymers (OCP) and / or hydrogenated isoprene or butadiene-styrene copolymers (HSD) and / or hydrogenated polyisoprene or polybutadiene in the form of concentrated polymer emulsions.
Gegenstand der vorliegenden Anmeldung ist weiterhin ein Verfahren zur Herstellung von konzentrierten Polymerisatemulsionen aus zur Verbesserung des Viskositatsindex geeigneten Poly(meth)acrylaten und Olefincopolymerisaten in flüssigen Trägermedien zur Verwendung als Öladditive mit verbesserter Dispergier- und Detergenzwirkung in Diesel- und Ottomotoren, wobei als Monomere 80 bis 99,5 Gew.-Teile Alkyl(meth)acrylate der Formel I
In einer besonderen Ausgestaltung des Verfahrens zur Herstellung von konzentrierten Polymerisatemulsionen kann die Polymerisation der Monomeren I, II, IIA, IIB und III unter Zusatz von 0,1 bis 2,0 Gew.-% Radikal-Initiator und bei gleichzeitiger Anwesenheit von 0,05 bis 0,5 Gew.-% Molekulargewichtsreglern, jeweils bezogen auf die Gesamtheit der Monomeren durchgeführt werden. Als Regler können an sich übliche Schwefelregler (vgl. Th.Völker, H.Rauch-Puntigam, Acryl- und Methacrylverbindungen, Springer-Verlag 1968) dienen, aber auch Produkte wie Terpinolen und dessen Derivate.In a particular embodiment of the process for the preparation of concentrated polymer emulsions, the polymerization of the monomers I, II, IIA, IIB and III can be carried out with the addition of 0.1 to 2.0% by weight of radical initiator and with the simultaneous presence of 0.05 up to 0.5% by weight of molecular weight regulators, in each case based on the total of the monomers. The usual sulfur regulators (cf. Th.Völker, H.Rauch-Puntigam, acrylic and methacrylic compounds, Springer-Verlag 1968) can serve as regulators, but also products such as terpinolene and its derivatives.
Vorzugsweise werden die Konzentrationen der Monomeren und Polymeren so bemessen, daß die Gesamtheit der in dem flüssigen Trägermedium TM vorhandenen Monomeren und Polymeren 40 bis 75 Gew.-%, vorzugsweise 55 bis 70 Gew.-% bezogen auf das Gesamtsystem beträgt.The concentrations of the monomers and polymers are preferably such that the total of the monomers and polymers present in the liquid carrier medium TM is 40 to 75% by weight, preferably 55 to 70% by weight, based on the overall system.
Bei einer weiteren, vorteilhaften Ausgestaltung des Verfahrens wird zu dem Polymerisationsansatz nach Abschluß der Polymerisation noch weiteres Olefincopolymerisat in solchen Mengen zugegeben, daß der Olefincopolymerisatanteil am gesamten vorhandenen Polymerisat 31 bis 80 Gew.-% ausmacht. Das Olefincopolymerisat kann vorteilhafterweise tel quel, d.h. in unverdünnter Form zugesetzt werden, wobei man es vorteilhafterweise unter Anwendung von Scherkräften einemulgiert.In a further, advantageous embodiment of the method, the polymerization batch is followed by At the end of the polymerization, further olefin copolymers were added in amounts such that the olefin copolymer content in the total polymer present was 31 to 80% by weight. The olefin copolymer can advantageously be added tel quel, ie in undiluted form, it being advantageously emulsified using shear forces.
Alternativ kann das zusätzliche Olefincopolymerisat auch in Form einer Lösung, beispielsweise einer 10 - 20 %-igen Lösung in dem flüssigen Trägermedium zugesetzt werden.Alternatively, the additional olefin copolymer can also be added in the form of a solution, for example a 10-20% solution in the liquid carrier medium.
Wie bereits aus dem Vorstehenden hervorgeht, dienen an sich bekannte VI-Verbesserer, nämlich Olefincopolymerisate (OCP), Polyalkyl(meth)acrylate (PAMA) sowie die vorstehend genannten "Mixed Polymers" z.B. gemäß EP 14 746 als Basispolymerisate für das erfindungsgemäße Verfahren.As can already be seen from the above, known VI improvers, namely olefin copolymers (OCP), polyalkyl (meth) acrylates (PAMA) and the aforementioned "mixed polymers" serve e.g. according to EP 14 746 as base polymers for the process according to the invention.
Bei den Polyalkyl(meth)acrylaten handelt es sich in erster Linie um solche mit Alkylresten mit 6-24 Kohlenstoffatomen, die zu einer Löslichkeit im Mineralöl führen. Kürzere Alkylreste und solche mit polaren Substituenten, die keine Löslichkeit im Mineralöl vermitteln, können bis zu einem bestimmten Anteil vorhanden sein. Die Molekulargewichte M w liegen zwischen 5 000 und 1 000 000, bevorzugt zwischen 50 000 und 500 000. Derartige Produkte sind in den Druckschriften GB-C 1 068 938, US-A 3 732 334, US-A 4 149 984, US-A 4 229 311, US-A 4 281 081, US-A 4 338 418, US-A 4 290 925, DE-A 3 339 103, DE-A 3 607 444, DE-A 3 613 992, sowie US-A 4 677 151, US-A 4 622 358, US-A 4 822 508 beschrieben. Die bei dem erfindungsgemäßen Verfahren anzuwendenden Monomeren seien im folgenden erläuternd dargestellt.The polyalkyl (meth) acrylates are primarily those with alkyl radicals with 6-24 carbon atoms, which lead to solubility in mineral oil. Shorter alkyl residues and those with polar substituents that do not impart solubility in the mineral oil can be present to a certain extent. The molecular weights M w are between 5,000 and 1,000,000, preferably between 50,000 and 500,000. Such products are described in GB-C 1 068 938, US Pat. No. 3,732,334, US Pat. No. 4,149,984, US Pat. A 4 229 311, US-A 4 281 081, US-A 4 338 418, US-A 4 290 925, DE-A 3 339 103, DE-A 3 607 444, DE-A 3 613 992, and US A 4 677 151, US-A 4 622 358, US-A 4 822 508. The monomers to be used in the process according to the invention are illustrated below.
Erfindungsgemäß werden obligatorisch Alkyl(meth)acrylate der Formel I in Anteilen von 80 bis 99,5, vorzugsweise 90 bis 98,5 Gew.-Teilen copolymerisiert. Als Monomere der Formel I seien z.B. (Meth)-acrylsäureester von Talgfettalkoholen (z.B. im C-Zahlbereich 14 - 20, im Mittel ca. 17,3), von Kokosfettalkoholen (C-Zahlbereich 10 -16, im Mittel ca. 12,6) oder von Synthesealkoholen wie Dobanol 25 R (C-Zahlbereich 11 - 16, im Mittel 13,5) genannt.According to the invention, alkyl (meth) acrylates of the formula I are copolymerized in proportions of 80 to 99.5, preferably 90 to 98.5, parts by weight. Examples of monomers of the formula I are (meth) acrylic acid esters of tallow fatty alcohols (for example in the C number range 14-20, on average approx. 17.3), of coconut fatty alcohols (C number range 10 -16, on average approx. 12.6) ) or of synthetic alcohols such as Dobanol 25 R (C number range 11 - 16, on average 13.5).
Als funktionalisierte Monomere der Formel II seien einmal diejenigen mit einer OH-Gruppe im Alkylrest, insbesondere in u-Stellung des Alkylrests genannt z.B. das 2-Hydroxyethylmethacrylat und das -acrylat, das 3-Hydroxypropylmethacrylat und -acrylat, sowie die in 2-Stellung einfach oder doppelt methylsubstituierten Derivate, 4-Hydroxybutylmethacrylat und -acrylat, aber auch das 2-Hydroxypropylmethacrylat und -acrylat. Spezifisches Interesse wegen ihrer geringen sonstigen Aggressivität unter Praxis-Bedingungen in der motorischen Prüfung kommen den Monomeren der Formel II zu, in denen R2für einen vielfach alkoxylierten, insbesondere ethoxylierten Rest steht, beispielsweise 2-(2-Ethoxyethoxy)ethyl-methacrylat und -acrylat bis zu (Meth)acrylsäureestern von C1-C18-Fettalkoholgemischen mit mittleren Ethoxylierungsgraden I bis 60, z.B. mit einem mittleren Ethoxylierungsgrad 11 bzw. 25, ausgehend von entsprechenden industriellen Produkten. Genannt seien (Meth)acrylsäureester von Carbowax 550 @, Marlipal 1618/11 ®, Marlipal 1618/25 @, Carbowax 2000 0 und Carbowax 750 @.Examples of functionalized monomers of the formula II are those with an OH group in the alkyl radical, in particular in the u-position of the alkyl radical, for example the 2-hydroxyethyl methacrylate and the -acrylate, the 3-hydroxypropyl methacrylate and -acrylate, and also the 2-position or double methyl-substituted derivatives, 4-hydroxybutyl methacrylate and acrylate, but also the 2-hydroxypropyl methacrylate and acrylate. The monomers of the formula II in which R 2 stands for a frequently alkoxylated, in particular ethoxylated radical, for example 2- (2-ethoxyethoxy) ethyl methacrylate and - are of particular interest because of their low other aggressiveness under practical conditions in motor testing. Acrylate up to (meth) acrylic acid esters of C 1 -C 18 fatty alcohol mixtures with medium degrees of ethoxylation I to 60, for example with a medium degree of ethoxylation 11 or 25, starting from corresponding industrial products. Examples include (meth) acrylic acid esters from Carbowax 550 @, Marlipal 1618/11 ®, Marlipal 1618/25 @, Carbowax 2000 0 and Carbowax 750 @.
Zu nennen sind weiterhin die funktionalisierten Monomeren der Formel IIA, worin R7 für eine Alkylendialkylaminogruppe steht, insbesondere das 2-Dimethylamino- und das 2-Diethylaminoethylmethacrylat und -acrylat, 3-Dimethylaminopropylmethacrylat und -acrylat und die entsprechenden Diethylaminoverbindungen, sowie die entsprechenden Amide, insbesondere das N-(3-dimethylaminopropyl)-methacrylamid. Diese Comonomeren können beispielsweise durch Copolymerisation zusammen mit Verbindungen der Formel II einpolymerisiert werden aber auch zu einem späteren Zeitpunkt. Weiter fallen unter die Formel IIA heterocyclisch substituierte Monomere wie z.B. das 2-(1-Imidazolyl) ethylmethacrylat und -acrylat, das 2-(4-Morpholinyl)ethylmethacrylat und -acrylat und das 1-(2-Methylacryloyloxyethyl)-2-pyrrolidon, sowie die entsprechenden Amide.Also to be mentioned are the functionalized monomers of the formula IIA, in which R 7 represents an alkylene dialkylamino group, in particular the 2-dimethylamino and 2-diethylaminoethyl methacrylate and acrylate, 3-dimethylaminopropyl methacrylate and acrylate and the corresponding diethylamino compounds, and the corresponding amides, especially the N- (3-dimethylaminopropyl) methacrylamide. These comonomers can be copolymerized, for example by copolymerization, together with compounds of the formula II, but also at a later point in time. The formula IIA also includes heterocyclically substituted monomers, such as, for example, the 2- (1-imidazolyl) ethyl methacrylate and acrylate, the 2- (4-morpholinyl) ethyl methacrylate and acrylate and the 1- (2-methylacryloyloxyethyl) -2-pyrrolidone, as well as the corresponding amides.
Weiter kommt den Monomeren der Formel IIB besondere Bedeutung zu, vor allem dem N-Vinylpyrrolidon-2.Furthermore, the monomers of the formula IIB are of particular importance, especially N-vinylpyrrolidone-2.
Die erfindungsgemäß zur verwendenden Olefincopolymerisate sind an sich bekannt. Es handelt sich in erster Linie um aus Ethylen-, Propylen-, Butylen- und/oder weiteren a-Olefinen mit 5 bis 200 C-Atomen aufgebaute Polymerisate, wie sie bereits als VI-Verbesserer empfohlen worden sind. Das Molekulargewicht M w liegt im allgemeinen bei 10 000 bis 300 000, vorzugsweise zwischen 50 000 und 150 000. Derartige Olefincopolymerisate sind beispielsweise in den deutschen Offenlegungsschriften DE-A 16 44 941, DE-A 17 69 834, DE-A 19 39 037, DE-A 19 63 039 und DE-A 20 59 981 beschrieben. Sofern das Basiscopolymerisat aus einem hydrierten Polyisopren oder Copolymerisat mit Styrol besteht, sind käufliche hydrierte Produkte (z.B. Handelsprodukte SHELLVIS 50, 200 oder 250 @ bevorzugt. Besonders gut brauchbar sind Ethylen-Propylen-Copolymere, ebenfalls sind Terpolymere mit den bekannten Terkomponenten, wie Ethyliden-Norbornen (vgl. Macromolecular Reviews, Vol. 10 (1975)) möglich, e's ist jedoch deren Neigung zur Vernetzung beim Alterungsprozeß mit einzukalkulieren. Die Verteilung kann dabei weitgehend statistisch sein, es können aber auch mit Vorteil-Sequenzpolymere mit Ethylenblöcken angewendet werden. Das Verhältnis der Monomeren Ethylen-Propylen ist dabei innerhalb gewisser Grenzen variabel, die bei etwa 75 % für Ethylen und etwa 80 % für Propylen als obere Grenze angesetzt werden können. Infolge seiner verminderten Löslichkeitstendenz in Öl ist bereits Polypropylen weniger geeignet als Ethylen-Propylen-Copolymere.The olefin copolymers to be used according to the invention are known per se. It is primarily composed of ethylene, propylene, butylene and / or other α-olefins with 5 to 200 carbon atoms built-up polymers, as have already been recommended as VI improvers. The molecular weight M w is in general from 10,000 to 300,000, preferably between 50,000 and 150,000. Such olefin copolymers are described, for example, in German Offenlegungsschriften DE-A 16 44 941, DE-A 17 69 834, DE-A 19 39 037 , DE-A 19 63 039 and DE-A 20 59 981. If the base copolymer consists of a hydrogenated polyisoprene or copolymer with styrene, commercially available hydrogenated products (for example commercial products SHELLVIS 50, 200 or 250 @ are preferred. Ethylene-propylene copolymers are particularly useful, and terpolymers with the known tercomponents, such as ethylidene Norbornen (cf. Macromolecular Reviews, Vol. 10 (1975)) is possible, but their tendency to cross-link during the aging process must be taken into account. The distribution can be largely statistical, but sequence polymers with ethylene blocks can also be used with advantage The ratio of the monomers ethylene-propylene is variable within certain limits, which can be set as the upper limit at around 75% for ethylene and around 80% for propylene.As a result of its reduced tendency to solubility in oil, polypropylene is already less suitable than ethylene-propylene copolymers .
Als Lösungsmittel bzw. Tragermedium TM wird zweckmäßig ein mit der nachfolgenden Anwendung compatibles inertes Lösungsmittel mit einem Siedepunkt von mindestens 300 Grad C bei 760 mm, zweckmäßigerweise ein Mineralöl angewendet. Die Lösungsmittel fallen demnach z.B. in die Gruppe der Kohlenwasserstoffe wie Kerosin (Siedebereich 180 -210 Grad C), der napthenbasischen Öle, der paraffinbasischen Öle oder der Gasöle. (Vgl. Ullmanns Enzyklopädie der Techn. Chemie, 4. Auflage, Bd. 10, S.641 - 714. Bei der Herstellung von konzentrierten Polymerisatemulsionen werden vorteilhaft Trägermedien eingesetzt, die OCP nur begrenzt lösen bzw. nur Quellungsmittel sind, wie sie ausführlich in USP 4 677 151 und US-P 4 622 358 beschrieben worden sind. Insbesondere sind dies Phthalsäureester wie Dibutylphthalat und Ester der 2,2,4-Trimethyladipinsäure z.B. mit einem Gemisch Octanol/Decanol. Auch die mono- oder multifunktionellen Alkohole selbst kommen in Frage, z.B. Hexadecanol, Octadecanol, Diäthylenglykol, Tetraäthylenglykol und Methoxypolyäthylenglykole mit Äthoxylierungsgraden von ca. 2 - 50.A solvent which is compatible with the following application and which has a boiling point of at least 300 ° C. at 760 mm, advantageously a mineral oil, is expediently used as the solvent or carrier medium TM. The solvents therefore fall e.g. in the group of hydrocarbons such as kerosene (boiling range 180-210 degrees C), the naphthenic oils, the paraffin-based oils or the gas oils. (Cf. Ullmanns Enzyklopadie der Techn. Chemie, 4th edition, vol. 10, pp. 641-714. In the production of concentrated polymer emulsions, carrier media are advantageously used which only solve OCP to a limited extent or are only swelling agents, as described in detail in "USP 4,677,151 and US Pat. No. 4,622,358. These are, in particular, phthalic esters such as dibutyl phthalate and esters of 2,2,4-trimethyladipic acid, for example with a mixture of octanol / decanol. The mono- or multifunctional alcohols themselves are also suitable. ***" , for example hexadecanol, octadecanol, diethylene glycol, tetraethylene glycol and methoxypolyethylene glycols with degrees of ethoxylation of approx. 2-50.
Die Polymerisation der Alkyl(meth)acrylate wird im allgemeinen als Monomerzulaufpolymerisation bei 80 -100 Grad C im flüssigen Trägermedium unter Zusatz von peroxidischen Initiatoren wie t-Butylperoctoat durchgeführt. Im Falle der Herstellung von konzentrierten Polymerisatemulsionen geschieht dies im Anwesenheit von einer kleinen Menge gelöstem OCP. Die Polymerisation ist üblicherweise nach ca. 8 Stunden beendet. Anschließend können weitere Monomere bei 130 Grad C unter Zusatz von t- Butylperbenzoat pfropfend aufpolymerisiert werden. Abschließend wird dann durch Zugabe von weiterem OCP und gegebenenfalls Lösungsmittel bzw. Trägermedium die gewünschte Endzusammensetzung eingestellt.The polymerization of the alkyl (meth) acrylates is generally carried out as a monomer feed polymerization at 80-100 ° C. in a liquid carrier medium with the addition of peroxidic initiators such as t-butyl peroctoate. In the case of the production of concentrated polymer emulsions, this is done in the presence of a small amount of dissolved OCP. The polymerization is usually complete after about 8 hours. Subsequently, further monomers can be graft-polymerized at 130 ° C. with the addition of t-butyl perbenzoate. Finally, the desired final composition is then set by adding further OCP and, if appropriate, solvent or carrier medium.
Die erfindungsgemäßen VI-verbessernden Additive mit Dispergier-/Detergenzwirkung stehen in der Regel als relativ konzentrierte Polymerlösungen in den Trägermedien zur Verfügung. Im allgemeinen beträgt der Gehalt an Polymerisat in den Konzentraten 30 bis 75 Gew.-%, bevorzugt 40 bis 70 %.The VI-improving additives according to the invention with dispersing / detergent action are generally available as relatively concentrated polymer solutions in the carrier media. In general, the polymer content in the concentrates is 30 to 75% by weight, preferably 40 to 70%.
Man setzt sie vorteilhaft den Ölen bzw. Fraktionen, deren Viskositätsindices zu verbessern sind, in solchen Mengen zu, daß diese vorzugsweise 1 bis 10 Gew.-% an den polymeren Additiven gemäß der vorliegenden Erfindung enthalten.They are advantageously added to the oils or fractions, the viscosity indices of which are to be improved, in such amounts that they preferably contain 1 to 10% by weight of the polymeric additives according to the present invention.
Der Vorteil der erfindungsgemaßen Additive besteht in einer hervorragenden Dispergier- und Detergenzwirkung in Otto- und Diesel-Motoren bei vollständig neutralem Verhalten gegen Dichtungsmaterialien wie z.B. Viton ®.The advantage of the additives according to the invention is an excellent dispersing and detergent effect in Otto and diesel engines with completely neutral behavior against sealing materials such as e.g. Viton ®.
Die Prüfung erfolgt nach
- 1. CCMC European Oil Sequence For Service - Fill Oils For Gasoline Engines, Classes G4 and G5: Low Temperature Sludge nach ASTM 315 H, Part 111, Seq. VE. Black Sludge M 102 E: nach CEC L-41-T-88
- 2. CCMC European Oil Sequence For Service - Fill Oils For Diesel Engines, Classes D4, D5 and PD2: Ring Sticking and Piston Cleanliness VW 1,6 TC Diesel nach CEC L-35-T-84.
- 3. Screening-Test For Bore Polishing and Piston Cleanliness For Diesel Engines: MWM B nach CEC-L-12-A-76
- 4. VW-Elastomer-Test TL-VW 521 v. 07.10.1988, FKM-E-281.
- 5. Viskositätsbestimmung nach DIN 51562 (Ubbelohde-Viskosimeter).
- 1. CCMC European Oil Sequence For Service - Fill Oils For Gasoline Engines, Classes G4 and G5: Low Temperature Sludge according to ASTM 315 H, Part 111, Seq. VE. Black Sludge M 102 E: according to CEC L-41-T-88
- 2. CCMC European Oil Sequence For Service - Fill Oils For Diesel Engines, Classes D4, D5 and PD2: Ring Sticking and Piston Cleanliness VW 1.6 TC Diesel according to CEC L-35-T-84.
- 3. Screening Test For Bore Polishing and Piston Cleanliness For Diesel Engines: MWM B according to CEC-L-12-A-76
- 4. VW elastomer test TL-VW 521 v. 07.10.1988, FKM-E-281.
- 5. Determination of viscosity according to DIN 51562 (Ubbelohde viscometer).
Die folgenden Beispiele dienen zur Erläuterung der Erfindung.The following examples serve to illustrate the invention.
SSI = Scherstabilitätsindex: Verlust an Verdickungswirkung in % bei Scherstabilitätsprüfung nach DIN 51382SSI = shear stability index: loss of thickening effect in% with shear stability test according to DIN 51382
Ferner wurden folgende Abkürzungen verwendet:
- "Di-Paket A" ist ein handelsübliches DI-Paket der API-Leistungsklasse SF/CC.
- "DI-Paket B" ist ein handelsübliches DI-Paket der API-Leistungsklasse, SF/CD.
- "Di-Paket A" is a commercially available DI package of the API performance class SF / CC.
- "DI Package B" is a commercially available DI package of the API performance class, SF / CD.
In einem 2 1-Vierhalsrundkolben mit Rührer, Thermometer, Rückflußkühler und Dosierleitung wird folgende Mischung vorgelegt:
- 400,00 g Mineralöl (η 100 Grad C = 3,9 mm2/s)
- 4,44 g 2-Hydroxyethylmethacrylat
- 39,96 g Methacrylsäureester eines C12-C18-Alkoholgemisches
- 0,35 g Dodecylmercaptan
- 1,00 g tert.-Butylperoctoat
- 400.00 g mineral oil (η 100 degrees C = 3.9 mm 2 / s)
- 4.44 g of 2-hydroxyethyl methacrylate
- 39.96 g methacrylic acid ester of a C12-C18 alcohol mixture
- 0.35 g dodecyl mercaptan
- 1.00 g of tert-butyl peroctoate
Nach Lösen der Komponenten wird bei 90 Grad C nachstehendes Gemisch über einen Zeitraum von 3,5 Stunden gleichmäßig zudosiert:
- 55,56 g 2-Hydroxyethylmethacrylat
- 500,04 g Methacrylsäureester eines C12-C18-Alkoholgemisches
- 4,44 g Dodecylmercaptan
- 1,67 g tert.-Butylperoctoat
- 55.56 g of 2-hydroxyethyl methacrylate
- 500.04 g of methacrylic acid ester of a C 12 -C 18 alcohol mixture
- 4.44 g dodecyl mercaptan
- 1.67 g of tert-butyl peroctoate
Zwei Stunden nach Zulaufende wird mit 1,2 g tert.-Butylperoctoat nachgefüttert. Gesamtpolymerisationszeit 8 Stunden. Es wird eine klare, viskose Lösung erhalten.
- Polymerisatgehalt = 60 Gew.-%
- Viskosität (100 Grad C, 60 Gew.-%ig) = 1 300 mm2/s
- Viskosität (100 Grad C, 6 Gew.-%ig in Mineralöl mit η 100 Grad C = 5,4 mm2/s) = 9,7 mm2/s
- SSI (6 Gew.-%ig in Mineralöl mit η 100 Grad C = 6,4 mm2/s) = 3,6
- Polymer content = 60% by weight
- Viscosity (100 degrees C, 60% by weight) = 1 300 mm 2 / s
- Viscosity (100 degrees C, 6% by weight in mineral oil with η 100 degrees C = 5.4 mm 2 / s) = 9.7 mm 2 / s
- SSI (6% by weight in mineral oil with η 100 degrees C = 6.4 mm 2 / s) = 3.6
Apparatur und Durchführung wie Beispiel 1; vorgelegt werden:
- 400,0 g Mineralöl (η 100 Grad C = 3,9 mm2/s)
- 5,73 g Methacrylsäureester eines ethoxylierten C16-C18-Fettalkoholgemisches, mittlerer Ethoxylierungsgrad = 25
- 3,86 g Methylmethacrylat
- 34,81 g Methacrylsäureester eines C12-C15-Alkoholgemisches
- 0,35 g Dodecylmercaptan
- 1,00 g tert.-Butylperoctoat
- zudosiert werden:
- 71,67 g Methacrylsaureester eines ethoxylierten C16-C18-Fettalkoholgemisches, mittlerer Ethoxylierungsgrad = 25
- 48,33 g Methylmethacrylat
- 435,60 g Methacrylsäureester eines C12-C15-Alkoholgemisches
- 4,44 g Dodecylmercaptan
- 1,67 g tert.-Butylperoctoat
- 400.0 g mineral oil ( η 100 degrees C = 3.9 mm 2 / s)
- 5.73 g of methacrylic acid ester of an ethoxylated C16-C18 fatty alcohol mixture, average degree of ethoxylation = 25
- 3.86 g of methyl methacrylate
- 34.81 g methacrylic acid ester of a C12-C15 alcohol mixture
- 0.35 g dodecyl mercaptan
- 1.00 g of tert-butyl peroctoate
- be added:
- 71.67 g of methacrylic acid ester of an ethoxylated C16-C18 fatty alcohol mixture, average degree of ethoxylation = 25
- 48.33 g of methyl methacrylate
- 435.60 g methacrylic acid ester of a C12-C15 alcohol mixture
- 4.44 g dodecyl mercaptan
- 1.67 g of tert-butyl peroctoate
Zwei Stunden nach Zulaufende wird mit 1,2 g tert.-Butylperoctoat nachgefüttert. Gesamtpolymerisationszeit 8 Stunden. Es wird eine klare, viskose Lösung erhalten.
- Polymerisatgehalt = 60 Gew.-%
- Viskosität (100 Grad C, 60 Gew.-%ig) = 270 mm2/s
- Viskosität (100 Grad C, 6 Gew.-%ig in Mineralöl mit η 100 Grad C = 5,4 mm2/s) = 9,7 mm2/s.
- SSI (6 Gew.-%ig in Mineralöl mit η 100 Grad C = 5,4 mm2/s) = 3,6
- Polymer content = 60% by weight
- Viscosity (100 degrees C, 60% by weight) = 270 mm 2 / s
- Viscosity (100 degrees C, 6% by weight in mineral oil with η 100 degrees C = 5.4 mm 2 / s) = 9.7 mm 2 / s.
- SSI (6% by weight in mineral oil with η 100 degrees C = 5.4 mm 2 / s) = 3.6
Apparatur und Durchführung wie Beispiel 1; vorgelegt werden:
- 360,0 g Mineralöl ( 100 Grad C = 5,4 mm2/s)
- 42,0 g Ethylen-Propylen-Copolymerisat (50 Gew.-% Ethylen; SSI (1 %ig in Mineralöl 100 Grad C = 5,4 mm2/s) = 24)
- 5,5 g Methacrylsäureester eines ethoxylierten C16-C18-Fettalkoholgemisches; mittlerer Ethoxylierungsgrad = 25
- 2,5 g Methylmethacrylat
- 36,7 g Methacrylsäureester eines C12-C15-Alkoholgemisches
- 0,05 g Terpinolen
- 0,61 g tert.-Butylperoctoat
- zudosiert werden:
- 92,7 g Methacrylsäureester eines ethoxylierten C16-C18-Fettalkoholgemisches, mittlerer Ethoxylierungsgrad = 25
- 42,2 g Methylmethacrylat
- 618,6 g Methacrylsäureester eines C12-C15-Alkoholgemisches
- 0,75 g Terpinolen
- 3.39 g tert-Butylperoctoat
- 360.0 g mineral oil (100 degrees C = 5.4 mm 2 / s)
- 42.0 g ethylene-propylene copolymer (50% by weight ethylene; SSI (1% in mineral oil 100 degrees C = 5.4 mm 2 / s) = 24)
- 5.5 g methacrylic acid ester of an ethoxylated C16-C18 fatty alcohol mixture; average degree of ethoxylation = 25
- 2.5 g methyl methacrylate
- 36.7 g methacrylic acid ester of a C12-C15 alcohol mixture
- 0.05 g terpinolene
- 0.61 g of tert-butyl peroctoate
- be added:
- 92.7 g methacrylic acid ester of an ethoxylated C16-C18 fatty alcohol mixture, average degree of ethoxylation = 25
- 42.2 g methyl methacrylate
- 618.6 g of methacrylic acid ester of a C12-C15 alcohol mixture
- 0.75 g terpinolene
- 3.39 g of tert-butyl peroctoate
2 Stunden nach Zulaufende wird mit 1,6 g tert.-Butylperoctoat nachgefüttert. Gesamtpolymerisationszeit 8 Stunden. Es wird eine leicht trübe, viskose Lösung erhalten.2 hours after the end of the feed, 1.6 g of tert-butyl peroctoate are added. Total polymerization time 8 hours. A slightly cloudy, viscous solution is obtained.
Diese Lösung wird in einen 4 I-Dreihalskolben mit Rührer, Thermometer und Rückflußkühler gegeben und auf 100 Grad C gebracht.This solution is placed in a 4 I three-necked flask with stirrer, thermometer and reflux condenser and brought to 100 degrees C.
Danach Zugabe von:
- 384,5 g Ethylen-Propylen-Copolymerisat (50 Gew.-% Ethylen; SSI (1 %ig in Mineralöl η 100 Grad C = 5,4 mm2/s) = 24)
- 384.5 g ethylene-propylene copolymer (50% by weight ethylene; SSI (1% in mineral oil η 100 degrees C = 5.4 mm 2 / s) = 24)
Nach Auflösen bei 100 Grad C innerhalb 8 Stunden wird eine trübe, viskose Emulsion erhalten. 1 476,7 g Mineralöl (71100 Grad C = 5,4 mm2/s)After dissolving at 100 degrees C within 8 hours, a cloudy, viscous emulsion is obtained. 1 476.7 g mineral oil ( 71 100 degrees C = 5.4 mm 2 / s)
Polymerisatgehalt: 40 Gew.-% Viskosität (100 Grad C, 40 Gew.-%ig) = 2 800 mm2/s Viskosität (100 Grad C, 3 Gew.-%ig in Mineralöl mit η 100 Grad C = 5,4 mm2/s) = 14,1 mm2/s SSI (3 Gew.-%ig in Mineralöl mit η 100 Grad C = 5,4 mm2/s) = 24Polymer content: 40% by weight viscosity (100 degrees C, 40% by weight) = 2 800 mm 2 / s viscosity (100 degrees C, 3% by weight in mineral oil with η 100 degrees C = 5.4 mm 2 / s) = 14.1 mm 2 / s SSI (3% by weight in mineral oil with η 100 degrees C = 5.4 mm 2 / s) = 24
Apparatur und Durchführung wie Beispiel 1; vorgelegt werden:
- 360,0 g Mineralöl (71 100 Grad C = 5,4 mm2/s)
- 42,0 g Ethylen-Propylen-Copolymerisat (50 Gew.-% Ethylen; SSI (1 %ig in Mineralöl n 100 Grad C = 5,4 mm2/s) = 24)
- 2,24 g 2-Hydroxyethylmethacrylat
- 42,46 g Methacrylsäureester eines C12-C18-Alkoholgemisches
- 0,05 g Terpinolen
- 2,10 g tert.-Butylperoctoat
- zudosiert werden:
- 37,7 g 2-Hydroxyethylmethacrylat
- 715,8 g Methacrylsäureester eines C12-18-Alkoholgemisches
- 0,75 g Terpinolen
- 3,39 g tert.-Butylperoctoat
- 360.0 g mineral oil ( 71 100 degrees C = 5.4 mm 2 / s)
- 42.0 g of ethylene-propylene copolymer (50 wt .-% of ethylene; SSI (1% in mineral oil n 100 degrees C = 5.4 mm 2 / s) = 24)
- 2.24 g of 2-hydroxyethyl methacrylate
- 42.46 g methacrylic acid ester of a C12-C18 alcohol mixture
- 0.05 g terpinolene
- 2.10 g of tert-butyl peroctoate
- be added:
- 37.7 g of 2-hydroxyethyl methacrylate
- 715.8 g methacrylic acid ester of a C12-18 alcohol mixture
- 0.75 g terpinolene
- 3.39 g of tert-butyl peroctoate
2 Stunden nach Zulaufende wird mit 1,6 g tert.-Butylperoctoat nachgefüttert. Gesamtpolymerisationszeit 8 Stunden. Es wird eine leicht trübe, hochviskose Lösungen erhalten.2 hours after the end of the feed, 1.6 g of tert-butyl peroctoate are added. Total polymerization time 8 hours. A slightly cloudy, highly viscous solution is obtained.
Diese Lösung wird in einen 4 I-Dreihalskolben mit Rührer, Thermometer und Rückflußkühler gegeben und auf 100 Grad C gebracht.This solution is placed in a 4 I three-necked flask with stirrer, thermometer and reflux condenser and brought to 100 degrees C.
Danach Zugabe von:
- 384,5 g Ethylen-Propylen-Copolymerisat (50 Gew.-% Ethylen, SSI (1 %ig in Mineralöl η 100 Grad C = 5,4 mm2/s) = 24)
- 1 476,7 g Mineralöl (η 100 Grad C = 5,4 mm2/s)
- 384.5 g ethylene-propylene copolymer (50% by weight ethylene, SSI (1% in mineral oil η 100 degrees C = 5.4 mm 2 / s) = 24)
- 1 476.7 g mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
Nach Auflösen bei 100 Grad C innerhalb 8 Stunden wird eine trübe, viskose Emulsion erhalten.After dissolving at 100 degrees C within 8 hours, a cloudy, viscous emulsion is obtained.
Polymerisatgehalt: 40 Gew.-% Viskosität (100 Grad C, 40 Gew.-%ig) = 2 800 mm2/s Viskosität (100 Grad C, 3 Gew.-%ig in Mineralöl mit η 100 Grad C = 5,4 mm2/s) = 14,1 mm2/s SSI (3 Gew.-%ig in Mineralöl mit 100 Grad C = 5,4 mm2/s) = 24Polymer content: 40% by weight viscosity (100 degrees C, 40% by weight) = 2 800 mm 2 / s viscosity (100 degrees C, 3% by weight in mineral oil with η 100 degrees C = 5.4 mm 2 / s) = 14.1 mm 2 / s SSI (3% by weight in mineral oil with 100 degrees C = 5.4 mm 2 / s) = 24
Apparatur und Durchführung wie Beispiel 1; vorgelegt werden:
- 360,0 g Mineralöl (η 100 Grad C = 5,4 mm2/s)
- 42,0 g Ethylen-Propylen-Copolymerisat ( 50 Gew.-% Ethylen; SSI (1 %ig in Mineralöl η 100 Grad C = 5,4 mm2/s) = 24
- 0,22 g 2-Dimethylaminoethylmethacrylat
- 2,60 g Methylmethacrylat
- 41,88 g Methacrylsäureester eines C12-C18-Alkoholgemisches
- 0,05 g Terpinolen
- 2,40 g tert.-Butylperoctoat
- zudosiert werden:
- 3,77 g 2-Dimethylaminoethylmethacrylat
- 43,70 g Methylmethacrylat
- 706,03 g Methacrylsäureester eines C12-C18-Alkoholgemisches
- 0,75 g Terpinolen
- 7,50 g tert.-Butylperoctoat
- 360.0 g mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
- 42.0 g ethylene-propylene copolymer (50% by weight ethylene; SSI (1% in mineral oil η 100 degrees C = 5.4 mm 2 / s) = 24
- 0.22 g of 2-dimethylaminoethyl methacrylate
- 2.60 g methyl methacrylate
- 41.88 g methacrylic acid ester of a C12-C18 alcohol mixture
- 0.05 g terpinolene
- 2.40 g of tert-butyl peroctoate
- be added:
- 3.77 g of 2-dimethylaminoethyl methacrylate
- 43.70 g methyl methacrylate
- 706.03 g of methacrylic acid ester of a C12-C18 alcohol mixture
- 0.75 g terpinolene
- 7.50 g of tert-butyl peroctoate
2 Stunden nach Zulaufende wird mit 1,6 g tert.-Butylperoctoat nachgefüttert. Gesamtpolymerisationszeit 8 Stunden.2 hours after the end of the feed, 1.6 g of tert-butyl peroctoate are added. Total polymerization time 8 hours.
Danach Zugabe von:
- 26,0 g N-Vinylpyrrolidon-2
- 11,0 g Mineralöl (η 100 Grad C = 5,4 mm2/s)
- und Aufheizen auf 130 Grad C.
- 26.0 g of N-vinyl pyrrolidone-2
- 11.0 g mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
- and heating to 130 degrees C.
Nach Erreichen der Temperatur erfolgt die Zugabe von 1,95 g tert.-Butylperbenzoat, wobei jeweils nach 1 und 2 Stunden mit weiteren 0,94 g tert.-Butylperbenzoat nachgefüttert wird. Gesamtdauer der Pfropfung 6 Stunden. Es wird eine leicht trübe, viskose Lösung erhalten. Diese Lösung wird in einem 1 I-Dreihalskolben mit Rührer, Thermometer und Rückflußkühler gegeben und auf 100 Grad C gebracht.After the temperature has been reached, 1.95 g of tert-butyl perbenzoate are added, with a further 0.94 g of tert-butyl perbenzoate being added after 1 and 2 hours. Total grafting time 6 hours. A slightly cloudy, viscous solution is obtained. This solution is placed in a 1 liter three-necked flask with a stirrer, thermometer and reflux condenser and brought to 100 ° C.
Danach Zugabe von:
- 384,5 g Ethylen-Propylen-Copolymerisat (50 Gew.-% Äthylen; SSI (1 %ig in Mineralöl η 100 Grad C = 5,4 mm2/s) = 24) 1 476,7 g Mineralöl (» 100 Grad C = 5,4 mm2/s)
- 384.5 g ethylene-propylene copolymer (50% by weight ethylene; SSI (1% in mineral oil η 100 degrees C = 5.4 mm 2 / s) = 24) 1 476.7 g mineral oil (»100 degrees C = 5.4 mm 2 / s)
Nach Auflösen bei 100 Grad C innerhalb 8 Stunden wird eine trübe, viskose Emulsion erhalten. Polymerisatgehalt: 40 Gew.-% Viskosität (100 Grad C, 40 Gew.-%ig) = 2 800 mm2/s Viskosität (100 Grad C, 3 Gew.-%ig in Mineralöl mit η 100 Grad C = 5,4 mm2/s) = 14,1 mm2/s SSI (3 Gew.-%ig in Mineralöl mit η 100 Grad C = 5,4 mm2/s) = 24After dissolving at 100 degrees C within 8 hours, a cloudy, viscous emulsion is obtained. Polymer content: 40% by weight viscosity (100 degrees C, 40% by weight) = 2 800 mm 2 / s viscosity (100 degrees C, 3% by weight in mineral oil with η 100 degrees C = 5.4 mm 2 / s) = 14.1 mm 2 / s SSI (3% by weight in mineral oil with η 100 degrees C = 5.4 mm 2 / s) = 24
Apparatur und Durchführung wie Beispiel 1; vorgelegt werden:
- 417,0 g Mineralöl (η 100 Grad C = 5,4 mm2/s)
- 29,15 g Ethylen-Propylen-Copolymerisat (50 Gew.-% Ethylen, SSI (1 %ig in Mineralöl 100 Grad C = 5,4
- mm2/s) = 24)
- 2,87 g Methylmethacrylat
- 46,70 g Methacrylsäureester eines C12-C18-Alkoholgemisches
- 3,0 g tert.-Butylperoctoat
- zudosiert werden:
- 29,25 g Methylmethacrylat
- 475,13 g Methacrylsäureester eines C12-C18-Alkoholgemisches
- 5,00 g tert.-Butylperoctoat
- 417.0 g mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
- 29.15 g of ethylene-propylene copolymer (50% by weight of ethylene, SSI (1% in mineral oil at 100 degrees C = 5.4
- mm 2 / s) = 24)
- 2.87 g methyl methacrylate
- 46.70 g methacrylic acid ester of a C12-C18 alcohol mixture
- 3.0 g of tert-butyl peroctoate
- be added:
- 29.25 g methyl methacrylate
- 475.13 g methacrylic acid ester of a C12-C18 alcohol mixture
- 5.00 g of tert-butyl peroctoate
2 Stunden nach Zulaufende wird mit 1,1 g tert.-Butylperoctoat nachgefüttert. Gesamtpolymerisationszeit 8 Stunden.2 hours after the end of the feed, 1.1 g of tert-butyl peroctoate are added. Total polymerization time 8 hours.
danach Zugabe von:
- 18,03 g N-Vinylpyrrolidon-2
- 12,90 g Mineralöl (η 100 Grad C = 5,4 mm2/s)
- und Aufheizen auf 130 Grad C
- 18.03 g of N-vinyl pyrrolidone-2
- 12.90 g mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
- and heating to 130 degrees C.
Nach Erreichen der Temperatur erfolgt die Zugabe von 1,5 g tert.-Butylperbenzoat, wobei jeweils nach 1 und 2 Stunden mit weiteren 0,72 g tert.-Butylperbenzoat nachgefüttert wird. Gesamtdauer der Pfropfung 6 Stunden. Es wird eine leicht trübe, viskose Lösung erhalten.After the temperature has been reached, 1.5 g of tert-butyl perbenzoate are added, with a further 0.72 g of tert-butyl perbenzoate being added after 1 and 2 hours. Total grafting time 6 hours. A slightly cloudy, viscous solution is obtained.
Diese Lösung wird in einen 4 I-Dreihalskolben mit Rührer, Thermometer und Rückflußkühler gegeben und auf 100 Grad C gebracht.This solution is placed in a 4 I three-necked flask with stirrer, thermometer and reflux condenser and brought to 100 degrees C.
Danach Zugabe von:
- 266,88 g Ethylen-Propylen-Copolymerisat
- (50 Gew.-% Ethylen; SSI (1 %ig in Mineralöl 100 Grad C = 5,4 mm2/s) = 24) 857,90 g Mineralöl ( 100 Grad C = 5,4 mm2/s)
- 266.88 g of ethylene-propylene copolymer
- (50% by weight ethylene; SSI (1% in mineral oil 100 degrees C = 5.4 mm 2 / s) = 24) 857.90 g mineral oils (100 degrees C = 5.4 mm 2 / s)
Nach Auflösen bei 100 Grad C innerhalb 8 Stunden wird eine trübe, viskose Emulsion erhalten.After dissolving at 100 degrees C within 8 hours, a cloudy, viscous emulsion is obtained.
Polymerisatgehalt: 40 Gew.-% Viskosität (100 Grad C, 40 Gew.-%ig) = 2 800 mm2/s Viskosität (100 Grad C, 3 Gew.-%ig in Mineralöl mit η 100 Grad C = 5,4 mm2/s) = 24Polymer content: 40% by weight viscosity (100 degrees C, 40% by weight) = 2 800 mm 2 / s viscosity (100 degrees C, 3% by weight in mineral oil with η 100 degrees C = 5.4 mm 2 / s) = 24
Apparatur und Durchführung wie Beispiel 1; vorgelegt werden:
- 400,00 g Mineralöl (17 100 Grad C = 3,9 mm2/s)
- 1,55 g N-Dimethylaminopropylmethacrylamid
- 4,44 g Methylmethacrylat
- 38,45 g Methacrylsäureester eines C12-C18-Alkoholgemisches
- 0,35 g Dodecylmercaptan
- 1,00 g tert.-Butylperoctoat
- zudosiert werden:
- 19,44 g N-Dimethylaminopropylmethacrylamid
- 55,56 g Methylmethacrylat
- 480,56 g Methacrylsäureester eines C12-C18-Alkoholgemisches
- 4,44 g Dodecylmercaptan
- 1,67 g tert.-Butylperoctoat
- 400.00 g mineral oil ( 17 100 degrees C = 3.9 mm 2 / s)
- 1.55 g of N-dimethylaminopropyl methacrylamide
- 4.44 g of methyl methacrylate
- 38.45 g methacrylic acid ester of a C12-C18 alcohol mixture
- 0.35 g dodecyl mercaptan
- 1.00 g of tert-butyl peroctoate
- be added:
- 19.44 g of N-dimethylaminopropyl methacrylamide
- 55.56 g of methyl methacrylate
- 480.56 g methacrylic acid ester of a C12-C18 alcohol mixture
- 4.44 g dodecyl mercaptan
- 1.67 g of tert-butyl peroctoate
Zwei Stunden nach Zulaufende wird mit 1,2 g tert.-Butylperoctoat nachgefüttert. Gesamtpolymerisationszeit 8 Stunden. Es wird eine klare, viskose Lösung erhalten.Two hours after the end of the feed, 1.2 g of tert-butyl peroctoate are added. Total polymerization time 8 hours. A clear, viscous solution is obtained.
Polymerisatgehalt = 60 Gew.-%Polymer content = 60% by weight
Viskosität (100 Grad C, 60 Gew.-%ig) = 500 mm2/s Viskosität (100 Grad C, 6 Gew.-%ig in Mineralöl mit 100 Grad C = 5,4 mm2/s) = 9,8 mm2/sViscosity (100 degrees C, 60% by weight) = 500 mm 2 / s Viscosity (100 degrees C, 6% by weight in mineral oil with 100 degrees C = 5.4 mm 2 / s) = 9.8 mm 2 / s
SSI (6 Gew.-%ig in Mineralöl mit η 100 Grad C = 5,4 mm2/s) = 3,6SSI (6% by weight in mineral oil with η 100 degrees C = 5.4 mm 2 / s) = 3.6
Apparatur und Durchführung wie Beispiel 1;. vorgelegt werden:
- 400,0 g Mineralöl ( 100 Grad C = 3,9 mm2/s)
- 2,0 g N-Vinylpyrrolidon-2
- 4,44 g Methylmethacrylat
- 38,00 g Methacrylsäureester eines C12-C18-Alkoholgemisches
- 0,35 g Dodecylmercaptan
- 1,00 g tert.-Butylperoctoat
- zudosiert werden:
- 25,00 g N-Vinylpyrrolidon-2
- 55,56 g Methylmethacrylat
- 475,00 g Methacrylsäureester eines C12-C18-Alkoholgemisches
- 4,44 g Dodecylmercaptan
- 1,67 g tert.-Butylperoctoat
- 400.0 g mineral oil (100 degrees C = 3.9 mm 2 / s)
- 2.0 g of N-vinyl pyrrolidone-2
- 4.44 g of methyl methacrylate
- 38.00 g methacrylic acid ester of a C12-C18 alcohol mixture
- 0.35 g dodecyl mercaptan
- 1.00 g of tert-butyl peroctoate
- be added:
- 25.00 g of N-vinyl pyrrolidone-2
- 55.56 g of methyl methacrylate
- 475.00 g methacrylic acid ester of a C12-C18 alcohol mixture
- 4.44 g dodecyl mercaptan
- 1.67 g of tert-butyl peroctoate
Zwei Stunden nach Zulaufende wird mit 1,2 g tert.-Butylperoctoat nachgefüttert. Gesamtpolymerisationszeit 8 Stunden. Es wird eine klare, viskose Lösung erhalten.Two hours after the end of the feed, 1.2 g of tert-butyl peroctoate are added. Total polymerization time 8 hours. A clear, viscous solution is obtained.
Polymerisatgehalt = 60 Gew.-%ig Viskosität (100 Grad C, 60 Gew.-%ig) = 980 mm2/s Viskosität (100 Grad C, 6 Gew.-%ig in Mineralöl mit η 100 Grad C = 5,4 mm2/s) = 9,8 mm2/s SSI (6 Gew.-%ig in Mineralöl mit η 100 Grad C = 5,4 mm2/s) = 3,6Polymer content = 60% by weight viscosity (100 degrees C, 60% by weight) = 980 mm 2 / s viscosity (100 degrees C, 6% by weight in mineral oil with η 100 degrees C = 5.4 mm 2 / s) = 9.8 mm 2 / s SSI (6% by weight in mineral oil with η 100 degrees C = 5.4 mm 2 / s) = 3.6
In einem 20 I-VA-Behälter, versehen mit Heizung, Rührung und Thermometer werden bei 65 Grad C folgende Komponenten zu einem 10 W-30-Mehrbereichsöl aufgemischt:
- 331,5 g Additiv 1
- 975,0 g Ethylen-Propylen-Copolymerisat (50 Gew.-% Ethylen, SSI (1 %ig in Mineralöl 100 Grad C = 5,4 mm2/s) = 24) Das Copolymerisat lag als 11 Gew.-%ige Lösung in Mineralöl (n 100 Grad C = 5,4 mm2/s) vor
- 1 280,0 g DI-Paket A 1 300,0 g Poly-a-olefin (η 100 Grad C = 4 mm2/s)
- 4 550,0 g Mineralöl (η 100 Grad C = 3,9 mm2/s)
- 4 563,0 g Mineralöl (η 100 Grad C = 6,2 mm2/s)
- 331.5 g of additive 1
- 975.0 g of ethylene-propylene copolymer (50% by weight of ethylene, SSI (1% in mineral oil at 100 ° C. = 5.4 mm 2 / s) = 24) The copolymer was in the form of an 11% by weight solution in mineral oil (n 100 degrees C = 5.4 mm 2 / s)
- 1 280.0 g DI package A 1 300.0 g poly-a-olefin ( η 100 degrees C = 4 mm 2 / s)
- 4 550.0 g mineral oil ( η 100 degrees C = 3.9 mm 2 / s)
- 4 563.0 g mineral oil ( η 100 degrees C = 6.2 mm 2 / s)
Apparatur und Durchführung wie Beispiel 1. Folgende Komponenten werden zu einen 10 W-30-Mehrbereichsöl aufgemischt:
- 331,5 g Additiv 2
- 975,0 g Ethylen-Propylen-Copolymerisat (50 Gew.-% Ethylen, SSI (1 %ig in Mineralöl η 100 Grad C = 5,4 mm2/s) = 24) Das Copolymerisat lag als 11 Gew.-%ige Lösung in Mineralöl (η 100 Grad C = 5,4 mm2/s) vor
- 1 280,5 g DI-paket A
- 1 399,9 g Poly-a-olefin (η 100 Grad C = 4 mm2/s)
- 4 550,0 g Mineralöl (η 100 Grad C = 3,9 mm2/s)
- 4 563,0 g Mineralöl (η 100 Grad C = 6,2 mm2/s)
- 331.5 g of additive 2
- 975.0 g of ethylene-propylene copolymer (50% by weight of ethylene, SSI (1% in mineral oil η 100 degrees C = 5.4 mm 2 / s) = 24) The copolymer was 11% by weight Solution in mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
- 1 280.5 g DI package A
- 1 399.9 g poly-a-olefin ( η 100 degrees C = 4 mm 2 / s)
- 4 550.0 g mineral oil ( η 100 degrees C = 3.9 mm 2 / s)
- 4 563.0 g mineral oil ( η 100 degrees C = 6.2 mm 2 / s)
Apparatur und Durchführung wie Beispiel 1. Folgende Komponenten werden zu einem 10 W-30-Mehrbereichsöl aufgemischt:
- 762,8 g Additiv 3
- 1 280,5 g DI-Paket A
- 1 300,0 g Poly-a-olefin (η 100 Grad C = 4 mm2/s)
- 407,2 g Mineralöl (η 100 Grad C = 5,4 mm2/s)
- 4 550,0 g Mineralöl (η 100 Grad C = 3,9 mm2/s)
- 4 699,5 g Mineralöl (17 100 Grad C = 6,2 mm2/s)
- 762.8 g additive 3
- 1 280.5 g DI package A
- 1 300.0 g poly-a-olefin ( η 100 degrees C = 4 mm 2 / s)
- 407.2 g mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
- 4 550.0 g mineral oil ( η 100 degrees C = 3.9 mm 2 / s)
- 4,699.5 g mineral oil ( 17 100 degrees C = 6.2 mm 2 / s)
Apparatur und Durchführung wie Beispiel 1. Folgende Komponenten werden zu einem 10 W-30-Mehrbereichsöl aufgemischt:
- 762,8 g Additiv 5
- 1 280,5 g DI-Paket A
- 1 300,0 g Poly-a-olefin (η 100 Grad C = 4 mm2/s)
- 407,2 g Mineralöl (η 100 Grad C = 5,4 mm2/s)
- 4 550,0 g Mineralöl (η 100 Grad C = 3,9 mm2/s)
- 4 699,5 g Mineralöl (η 100 Grad C = 6,2 mm2/s)
- 762.8 g additive 5
- 1 280.5 g DI package A
- 1 300.0 g poly-a-olefin ( η 100 degrees C = 4 mm 2 / s)
- 407.2 g mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
- 4 550.0 g mineral oil ( η 100 degrees C = 3.9 mm 2 / s)
- 4,699.5 g mineral oil ( η 100 degrees C = 6.2 mm 2 / s)
Apparatur und Durchführung wie Beispiel 1. Folgende Komponenten werden zu einem 10 W-30-Mehrbereichsöl aufgemischt:
- 688,5 g Additiv 4
- 1 447,5 g DI-Paket A
- 5 250,0 g Mineralöl (η 100 Grad C = 10,5 mm2/s)
- 7 584,0 g Mineralöl (η 100 Grad C = 5,4 mm2/s)
- 688.5 g of additive 4
- 1 447.5 g DI package A
- 5 250.0 g mineral oil ( η 100 degrees C = 10.5 mm 2 / s)
- 7 584.0 g mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
Apparatur und Durchführung wie Beispiel 1. Folgende Komponenten werden zu einem 15 W-40-Mehrbereichsöl aufgemischt:
- 688,5 g Additiv 5
- 1 477,5 g DI-Paket A 5 250,0 g Mineralöl (η 100 Grad C = 10,5 mm2/s)
- 7 584,0 g Mlneralöl (η 100 Grad C = 5,4 mm2/s)
- 688.5 g of additive 5
- 1 477.5 g DI package A 5 250.0 g mineral oil ( η 100 degrees C = 10.5 mm 2 / s)
- 7 584.0 g of mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
Apparatur und Durchführung wie Beispiel 1. Folgende Komponenten werden zu einem 15 W-30-Mehrbereichsö aufgemischt:
- 130,0 g Additiv 2
- 539,5 g DI-Paket B
- 975,0 g Mineralöl (η 100 Grad C = 10,5 mm2/s)
- 4 855,5 g Mineralöl (η 100 Grad C = 5,4 mm2/s)
- 130.0 g additive 2
- 539.5 g DI package B
- 975.0 g mineral oil ( η 100 degrees C = 10.5 mm 2 / s)
- 4 855.5 g mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
Apparatur und Durchführung wie Beispiel 1. Folgende Komponenten werden zu einem 15 W-30-Mehrbereichsöl aufgemischt:
- 130,0 g Additiv 1
- 539,5 g DI-Paket B
- 975,0 g Mineralöl (η 100 Grad C = 10,5 mm2/s)
- 4 855,5 g Mineralöl (η 100 Grad C = 5,4 mm2/s)
- 130.0 g additive 1
- 539.5 g DI package B
- 975.0 g mineral oil ( η 100 degrees C = 10.5 mm 2 / s)
- 4 855.5 g mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
Apparatur und Durchführung wie Beipsiel 1. Folgende Komponenten werden zu einem 10 W-30-Mehrbereichsöl aufgemischt:
- 762,8 g Additiv 6
- 1 280,5 g DI-Paket A
- 467,2 g Mineralöl (η 100 Grad C = 5,4 mm2/s)
- 1 300,0 g Poly-a-olefin (n 100 Grad C = 4 mm2/s)
- 4 550,0 g Mineralöl (η 100 Grad C = 3,9 mm2/s) 4 639,5 g Mineralöl (11 100 Grad C = 6,2 mm2/s)
- 762.8 g additive 6
- 1 280.5 g DI package A
- 467.2 g mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
- 1 300.0 g poly-a-olefin (n 100 degrees C = 4 mm 2 / s)
- 4 550.0 g mineral oil ( η 100 degrees C = 3.9 mm 2 / s) 4 639.5 g mineral oil ( 11 100 degrees C = 6.2 mm 2 / s)
Apparatur und Durchführung wie Beispiel 1. Folgende Komponenten wurden zu einem 15 W-30-Mehrbereichsöl aufgemischt.
- 130,0 g Additiv 7
- 539,5 g DI-Paket B
- 975,0 g Mineralöl (η 100 Grad C = 10,5 mm2/s)
- 4 855,5 g Mineralöl (η 100 Grad C = 5,4 mm2/s)
- 130.0 g additive 7
- 539.5 g DI package B
- 975.0 g mineral oil ( η 100 degrees C = 10.5 mm 2 / s)
- 4 855.5 g mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
Apparatur und Durchführung wie Beispiel 1. Folgende Komponenten werden zu einem 15 W-30-Mehrbereichsöl aufgemischt:
- 130,0 g Additiv 8
- 539,5 g DI-Paket B
- 975,0 g Mineralöl (η 100 Grad C = 10,5 mm2/s)
- 4 855,5 g Mineralöl (η 100 Grad C = 5,4 mm2/s)
- 130.0 g additive 8
- 539.5 g DI package B
- 975.0 g mineral oil ( η 100 degrees C = 10.5 mm 2 / s)
- 4 855.5 g mineral oil ( η 100 degrees C = 5.4 mm 2 / s)
In der folgenden Tabelle 1 werden die folgenden gebräuchlichen Abkürzungen verwendet:
- AS = Average Sludge
- RCS = Rocker Cover Sludge
- PSV = Piston Skirt Varnish
- AV = Average Varnish
- CW = Cam Wear [10-3 inches]
- AS = Average Sludge
- RCS = Rocker Cover Sludge
- PSV = Piston Skirt Varnish
- AV = Average Varnish
- CW = C on Wear [10- 3 inches]
Für die Bewertung in Tabelle gilt "10 = clean".
Aus Tabelle 1 (siehe Beispiele) ist zu ersehen, daß sowohl Additive mit OH-Gruppen (Beisp. 1) als auch Additive mit Ether-Gruppen (Beisp. 2 und 3) im Seq. VE-Test zu einer verbesserten Schlamm- und Lackbewertung führen. Verglichen wird mit dem Stand der Technik, der durch ein Additiv mit Vinylpyrrolidon (Vergleichsbeispiel 1) dargestellt wird. Beispiel 4 zeigt, daß ein ebenfalls erfindungsgemäßes Additiv, welches als konzentrierte Polymerisatemulsion vorliegt und in Gegenwart von Regler hergestellt worden ist (s. Anspruch) in der Bewertung dazwischen liegt.From Table 1 (see examples) it can be seen that both additives with OH groups (Ex. 1) and additives with ether groups (Ex. 2 and 3) in Seq. VE test lead to improved sludge and paint evaluation. A comparison is made with the prior art, which is represented by an additive with vinylpyrrolidone (comparative example 1). Example 4 shows that an additive likewise according to the invention, which is present as a concentrated polymer emulsion and has been prepared in the presence of a regulator (see claim), lies in between in the evaluation.
Die Tabelle 2 zeigt Ergebnisse des M-102-E-Schwarzschlammtestes. Das OH-Gruppen-haltige Additiv 4 (Beisp. 5) ist deutlich besser bewertet als Additiv 5 mit Vinylpyrrolidon (Beisp. 6). Beide Additive liegen als konzentrierte Polymerisatemulsion vor.Table 2 shows results of the M-102-E black sludge test. Additive 4 (example 5) containing OH groups is rated significantly better than additive 5 with vinylpyrrolidone (example 6). Both additives are present as a concentrated polymer emulsion.
In Tabelle 3 wird das Ether-Gruppen-haltige Additiv 2 (Beisp. 7) und das OH-Gruppen-haltige Additiv 1 (Beisp. 8) mit den nicht erfindungsgemäßen Additiven 7 und 8 (Vergleichsbeispiele 2 und 3), die Dimethylamino-Gruppen (Vergleichsbeispiel 2) bzw. Pyrrolidon-Gruppen (Vergleichsbeispiel 3) enthalten, verglichen. Während im MWMB-Screening-Motortest keine markant verschiedene Kohlenbewertung zu erkennen ist, sind aber deutliche Unterschiede im VW-Elastomer-Test vorhanden. Die erfindungsgemäßen Additive 2 und 1 haben das bessere Verhalten, wobei Additiv 1 (OH-Gruppen) dem Additiv 2 (Ethergruppen) sogar überlegen ist.In Table 3, the ether group-containing additive 2 (Ex. 7) and the OH group-containing additive 1 (Ex. 8) with the additives 7 and 8 not according to the invention (Comparative Examples 2 and 3), the dimethylamino groups (Comparative example 2) or pyrrolidone groups (comparative example 3) included, compared. While the MWMB screening engine test does not show any markedly different coal ratings, there are clear differences in the VW elastomer test. Additives 2 and 1 according to the invention have better behavior, additive 1 (OH groups) even being superior to additive 2 (ether groups).
Claims (11)
dadurch gekennzeichnet,
daß die Polyalkyl(meth)acrylate Copolymerisate aus 80 - 99,5 Gew.-Teilen Alkyl(meth)acrylate der Formel
zusammen mit 0,5 - 20 Gew.-Teilen mindestens eines funktionalisierten Alkylmethacrylats der Formel 11
steht,
und die Summe aus den Monomeren der Formeln (I) und (II) 100 Gew.-Teile beträgt,
und gegebenenfalls 0 - 20 Gew.-Teile eines oder mehrerer Monomeren der Formel III
darstellen.1. Polyalkyl (meth) acrylates suitable for improving the viscosity index for use as oil additives with improved dispersing and detergent action in diesel and Otto engines,
characterized,
that the polyalkyl (meth) acrylate copolymers of 80-99.5 parts by weight of alkyl (meth) acrylates of the formula
together with 0.5-20 parts by weight of at least one functionalized alkyl methacrylate of the formula 11
stands,
and the sum of the monomers of the formulas (I) and (II) is 100 parts by weight,
and optionally 0-20 parts by weight of one or more monomers of the formula III
represent.
worin X für Sauerstoff oder -NH oder -NR6'
und/oder vinylische heterocyclische Verbindungen der Formel (IIB)
copolymerisiert worden sind.2. To improve the viscosity index, suitable polyalkyl (meth) acrylates according to claim 1, characterized in that additionally 0-20 parts by weight of functionalized alkyl (meth) acrylates of the formula IIA as monomers
where X is oxygen or -NH or -NR 6 '
and / or vinylic heterocyclic compounds of the formula (IIB)
have been copolymerized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT90116624T ATE100489T1 (en) | 1989-09-09 | 1990-08-30 | DISPERSING EFFECTIVE VISCOSITY INDEX IMPROVERS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3930142 | 1989-09-09 | ||
| DE3930142A DE3930142A1 (en) | 1989-09-09 | 1989-09-09 | DISPERGING VISCOSITY INDEX IMPROVERS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0418610A1 true EP0418610A1 (en) | 1991-03-27 |
| EP0418610B1 EP0418610B1 (en) | 1994-01-19 |
Family
ID=6389077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90116624A Expired - Lifetime EP0418610B1 (en) | 1989-09-09 | 1990-08-30 | Viscosity index improver, with a dispersant activity |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5188770A (en) |
| EP (1) | EP0418610B1 (en) |
| JP (1) | JP2941392B2 (en) |
| AT (1) | ATE100489T1 (en) |
| DE (2) | DE3930142A1 (en) |
| DK (1) | DK0418610T3 (en) |
| ES (1) | ES2062234T3 (en) |
| HK (1) | HK155396A (en) |
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| EP0708170A1 (en) * | 1994-10-19 | 1996-04-24 | AGIP PETROLI S.p.A. | Multi functional additive for lubricating oils compatible with fluoroelastomers |
| WO1999027037A1 (en) * | 1997-11-21 | 1999-06-03 | Rohmax Additives Gmbh | Additive for biodiesel and biofuel oils |
| EP1808476A1 (en) * | 2004-10-22 | 2007-07-18 | Nippon Oil Corporation | Lubricant composition for transmission |
| EP2235149A1 (en) * | 2007-12-10 | 2010-10-06 | Chevron U.S.A. Inc. | Method for forming finished lubricants |
| DE102010001040A1 (en) | 2010-01-20 | 2011-07-21 | Evonik RohMax Additives GmbH, 64293 | (Meth) acrylate polymers for improving the viscosity index |
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- 1990-08-30 AT AT90116624T patent/ATE100489T1/en not_active IP Right Cessation
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0644252A3 (en) * | 1993-09-20 | 1995-06-28 | Rohm & Haas | Compatibilizer for a viscosity index improving polymer blend. |
| EP0691355A3 (en) * | 1994-07-04 | 1996-04-10 | Roehm Gmbh | Cooligomers and copolymers with dispersant activity |
| EP0697457A1 (en) * | 1994-08-03 | 1996-02-21 | Röhm GmbH | Motor oil with high dispersing capacity and with good wear protection |
| EP0708170A1 (en) * | 1994-10-19 | 1996-04-24 | AGIP PETROLI S.p.A. | Multi functional additive for lubricating oils compatible with fluoroelastomers |
| WO1999027037A1 (en) * | 1997-11-21 | 1999-06-03 | Rohmax Additives Gmbh | Additive for biodiesel and biofuel oils |
| EP1808476A1 (en) * | 2004-10-22 | 2007-07-18 | Nippon Oil Corporation | Lubricant composition for transmission |
| EP1808476A4 (en) * | 2004-10-22 | 2008-12-03 | Nippon Oil Corp | Lubricant composition for transmission |
| US8846589B2 (en) | 2004-10-22 | 2014-09-30 | Nippon Oil Corporation | Lubricating oil composition for transmission |
| US8728997B2 (en) | 2006-04-20 | 2014-05-20 | Nippon Oil Corporation | Lubricating oil composition |
| EP2235149A4 (en) * | 2007-12-10 | 2012-10-31 | Chevron Usa Inc | Method for forming finished lubricants |
| US8540869B2 (en) | 2007-12-10 | 2013-09-24 | Chevron U.S.A. Inc. | Method for forming finished lubricants |
| EP2235149A1 (en) * | 2007-12-10 | 2010-10-06 | Chevron U.S.A. Inc. | Method for forming finished lubricants |
| WO2011088929A1 (en) | 2010-01-20 | 2011-07-28 | Evonik Rohmax Additives Gmbh | (meth)acrylate polymers for improving the viscosity index |
| DE102010001040A1 (en) | 2010-01-20 | 2011-07-21 | Evonik RohMax Additives GmbH, 64293 | (Meth) acrylate polymers for improving the viscosity index |
| US9200233B2 (en) | 2010-01-20 | 2015-12-01 | Evonik Rohmax Additives Gmbh | (Meth)acrylate polymers for improving the viscosity index |
| RU2749905C2 (en) * | 2016-08-15 | 2021-06-18 | Эвоник Оперейшнс Гмбх | Functional groups containing polyalkyl (meth) acrylates with improved demulsifying ability |
Also Published As
| Publication number | Publication date |
|---|---|
| US5188770A (en) | 1993-02-23 |
| EP0418610B1 (en) | 1994-01-19 |
| JP2941392B2 (en) | 1999-08-25 |
| HK155396A (en) | 1996-08-23 |
| JPH03100099A (en) | 1991-04-25 |
| ATE100489T1 (en) | 1994-02-15 |
| DK0418610T3 (en) | 1994-04-11 |
| DE3930142A1 (en) | 1991-03-21 |
| ES2062234T3 (en) | 1994-12-16 |
| DE59004308D1 (en) | 1994-03-03 |
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| Date | Code | Title | Description |
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