EP3898907A1 - Use of associative triblockcopolymers as viscosity index improvers - Google Patents
Use of associative triblockcopolymers as viscosity index improversInfo
- Publication number
- EP3898907A1 EP3898907A1 EP19809873.3A EP19809873A EP3898907A1 EP 3898907 A1 EP3898907 A1 EP 3898907A1 EP 19809873 A EP19809873 A EP 19809873A EP 3898907 A1 EP3898907 A1 EP 3898907A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- meth
- acrylates
- alkyl
- group
- 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.)
- Pending
Links
- 229920000428 triblock copolymer Polymers 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 127
- 239000010687 lubricating oil Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 72
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 58
- 239000000178 monomer Substances 0.000 claims description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 33
- -1 polyethylene Polymers 0.000 claims description 31
- 239000002199 base oil Substances 0.000 claims description 28
- 229920000098 polyolefin Polymers 0.000 claims description 20
- 229920000728 polyester Polymers 0.000 claims description 15
- 238000005227 gel permeation chromatography Methods 0.000 claims description 12
- 229920002857 polybutadiene Polymers 0.000 claims description 12
- 239000005062 Polybutadiene Substances 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 150000002596 lactones Chemical class 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920002367 Polyisobutene Polymers 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 73
- 239000003921 oil Substances 0.000 description 24
- 229920001400 block copolymer Polymers 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 230000000694 effects Effects 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 18
- 230000008719 thickening Effects 0.000 description 17
- 238000009472 formulation Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 230000007246 mechanism Effects 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- AHLWZBVXSWOPPL-RGYGYFBISA-N 20-deoxy-20-oxophorbol 12-myristate 13-acetate Chemical compound C([C@]1(O)C(=O)C(C)=C[C@H]1[C@@]1(O)[C@H](C)[C@H]2OC(=O)CCCCCCCCCCCCC)C(C=O)=C[C@H]1[C@H]1[C@]2(OC(C)=O)C1(C)C AHLWZBVXSWOPPL-RGYGYFBISA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000000693 micelle Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 6
- 230000001050 lubricating effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 241001602688 Pama Species 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000010705 motor oil Substances 0.000 description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 4
- 150000003440 styrenes Chemical class 0.000 description 4
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 3
- IURGWERPLNHEGY-UHFFFAOYSA-L 2-[4-[4-[3,5-bis(4-nitrophenyl)tetrazol-2-ium-2-yl]-3-methoxyphenyl]-2-methoxyphenyl]-3,5-bis(4-nitrophenyl)tetrazol-2-ium;ethanol;dichloride Chemical compound [Cl-].[Cl-].CCO.CCO.COC1=CC(C=2C=C(OC)C(=CC=2)[N+]=2N(N=C(N=2)C=2C=CC(=CC=2)[N+]([O-])=O)C=2C=CC(=CC=2)[N+]([O-])=O)=CC=C1[N+]1=NC(C=2C=CC(=CC=2)[N+]([O-])=O)=NN1C1=CC=C([N+]([O-])=O)C=C1 IURGWERPLNHEGY-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JJTUDXZGHPGLLC-QWWZWVQMSA-N (3r,6r)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@@H](C)OC1=O JJTUDXZGHPGLLC-QWWZWVQMSA-N 0.000 description 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 2
- LOKPJYNMYCVCRM-UHFFFAOYSA-N 16-Hexadecanolide Chemical compound O=C1CCCCCCCCCCCCCCCO1 LOKPJYNMYCVCRM-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- ZPBJLEZUJMQIHC-UHFFFAOYSA-N 2-(2-bromo-2-methylpropanoyl)oxyethyl 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C(=O)OCCOC(=O)C(C)(C)Br ZPBJLEZUJMQIHC-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VGHBEMPMIVEGJP-UHFFFAOYSA-N 4-methyl-2h-furan-5-one Chemical compound CC1=CCOC1=O VGHBEMPMIVEGJP-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- FKUPPRZPSYCDRS-UHFFFAOYSA-N Cyclopentadecanolide Chemical compound O=C1CCCCCCCCCCCCCCO1 FKUPPRZPSYCDRS-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- SIFBVNDLLGPEKT-UHFFFAOYSA-N alpha'-angelica lactone Chemical compound C=C1CCC(=O)O1 SIFBVNDLLGPEKT-UHFFFAOYSA-N 0.000 description 2
- GSLDEZOOOSBFGP-UHFFFAOYSA-N alpha-methylene gamma-butyrolactone Chemical compound C=C1CCOC1=O GSLDEZOOOSBFGP-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000010710 diesel engine oil Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- DQGSJTVMODPFBK-UHFFFAOYSA-N oxacyclotridecan-2-one Chemical compound O=C1CCCCCCCCCCCO1 DQGSJTVMODPFBK-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
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- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
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- RZTOWFMDBDPERY-UHFFFAOYSA-N Delta-Hexanolactone Chemical compound CC1CCCC(=O)O1 RZTOWFMDBDPERY-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- WNVCMFHPRIBNCW-UHFFFAOYSA-N Quercuslactone a Chemical compound CCCCC1OC(=O)CC1C WNVCMFHPRIBNCW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OIRDTQYFTABQOQ-UHTZMRCNSA-N Vidarabine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@@H]1O OIRDTQYFTABQOQ-UHTZMRCNSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- QOTQFLOTGBBMEX-UHFFFAOYSA-N alpha-angelica lactone Chemical compound CC1=CCC(=O)O1 QOTQFLOTGBBMEX-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 210000000617 arm Anatomy 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012711 chain transfer polymerization Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 239000011557 critical solution Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- FYTRVXSHONWYNE-UHFFFAOYSA-N delta-octanolide Chemical compound CCCC1CCCC(=O)O1 FYTRVXSHONWYNE-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- PHXATPHONSXBIL-JTQLQIEISA-N gamma-Undecalactone Natural products CCCCCCC[C@H]1CCC(=O)O1 PHXATPHONSXBIL-JTQLQIEISA-N 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 229940020436 gamma-undecalactone Drugs 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- LVECZGHBXXYWBO-UHFFFAOYSA-N pentadecanolide Natural products CC1CCCCCCCCCCCCC(=O)O1 LVECZGHBXXYWBO-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
-
- 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
- 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
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
-
- 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
- C10M2205/024—Propene
-
- 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
- C10M2205/026—Butene
-
- 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
-
- 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
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/102—Polyesters
-
- 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
- C10M2209/10—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
-
- 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
- C10M2209/10—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
-
- 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
- C10M2209/10—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
-
- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/68—Shear stability
Definitions
- the present invention is directed to a process for improving the viscosity index of a lubricating oil composition by adding a triblock copolymer.
- Viscosity index is a commonly used method of measuring a fluid's change of viscosity in relation to temperature. The higher the VI, the smaller the relative change in viscosity with temperature. VI improvers (also known as viscosity modifiers) are additives that increase the viscosity of the fluid throughout its useful temperature range.
- Viscosity modifiers are polymeric molecules that are sensitive to temperature. At elevated temperatures, the polymeric chain is better solvated by the solvent that leads to an increase in hydrodynamic radius of the polymer in solution. Higher hydrodynamic radius equals an increase in thickening power and therefore an increase in VI.
- each individual polymer strand is separated from its neighbours and in solution exists in isolation.
- the polymer is fully solvated by the oil, but still retains a coiled structured, with oil solvent molecules filling the empty spaces within the loosened coil.
- the polymer then adopts an ellipsoid or spherical form and occupies a discrete volume known as the hydrodynamic volume of the polymer coil (see Scheme 1 below).
- Dissolving polymer in a solvent such as oil is accompanied by a large increase viscosity, and this is due to the presence of these larger scale hydrodynamic spheres.
- the size of the hydrodynamic sphere volume determines the magnitude of the viscosity increase.
- Polymers yielding a high hydrodynamic volume, either due to a high molecular weight or strong associating with the oil solvent, give a relatively higher increases in the viscosity of the solution.
- the hydrodynamic volume of a polymer in solution depends on many parameters, such as for example the polymer chain length and composition. At low temperatures, the long-chained fiberlike polymers are more tightly coiled and contribute relatively little to viscosity. The polymers uncoil at higher temperatures, occupying a larger hydrodynamic volume and increasingly boosting viscosity as shown in the following Scheme 1.
- OCP olefin copolymers
- PAMAs polyalkyl(meth)acrylates
- WO 2005/056739 describes the use of (meth)acrylate block copolymers as VI improvers.
- the block copolymers consist of oil soluble and insoluble blocks and mainly diblock and triblock structures are reported. In case of triblock copolymers, the oil-insoluble part is in the middle and the outer parts are oil-soluble.
- the working examples comprise at least 90 mol% of acrylic monomers and show number-average molecular weight between 20,000 and 80,000 g/mol.
- the use of triblock copolymers according to the present invention with a weight-average molecular weight of 3,000 to 30,000 g/mol for improving the viscosity index of lubricating oil compositions is not disclosed.
- Diblock polymers consisting of a hydrogenated diene and a styrene block (also described as HSDs) are commonly used in the lubricant field (Rudnick; Lubricant Additives: Chemistry and Applications, 3rd Edition, p.263-276). These polymers form micelles in solution which provide a huge thickening effect even at very low treat rates. These aggregates are known to lose their thickening power under shear which is used to reach low HTHS values with rather thick oils. Their permanent shear loss is quite low relative to their thickening power (see US4036910); if temperature is raised too much the aggregates break down and the thickening effect is lost. No exceptional VI effect is provided by these polymers (see US 5,209,862).
- the oil soluble part can also be polyisobutylene (see US 9,428,709).
- the use of triblock copolymers according to the present invention with a weight-average molecular weight of 3,000 to 30,000 g/mol for improving the viscosity index of lubricating oil compositions is not disclosed.
- EP431706 and EP0298578 describe methacrylate blocks which are used to replace the insoluble styrene block or the oil soluble hydrogenated diene block.
- WO 2014/105290 describes diblock polymers including PAMA blocks which are prepared in combination with polypropylene and micelle formation in PA04 of these polymers was investigated.
- the use of triblock copolymers according to the present invention with a weight-average molecular weight of 3,000 to 30,000 g/mol for improving the viscosity index of lubricating oil compositions is not disclosed.
- triblock copolymers comprising at least one oil-soluble part and at least one oil-insoluble part and having a relatively low molecular weight show an associative mechanism at higher temperatures and can be used as viscosity index improvers in lubricating oil compositions.
- Associative mechanism in this connection means that relatively small molecules self-organize at elevated temperature in order to form bigger structures with an increased hydrodynamic radius. In this way, thickening contribution at low temperatures can be minimized. As the small molecules are too small to be destroyed by mechanical shear, the bigger assemblies could reform after destruction by shear forces.
- One embodiment of the present invention is therefore directed to a process for improving the viscosity index of lubricating oil compositions by adding a triblock copolymer of general formula (I) A-B-A (I), wherein each A denotes an oil-insoluble residue and B denotes an oil-soluble residue, characterized in that the weight-average molecular weight of the triblock copolymer is in the range of 3,000 to 30,000 g/mol, preferably 3,500 to 25,000 g/mol, more preferably 4,000 to 20,000 g/mol.
- the weight-average molecular weight is determined by gel permeation chromatography against polymeric standards.
- styrene or polyalkylmethacrylates are used as corresponding standard.
- the triblock copolymers can be derived from different polymer classes as long as the outer segments A are polar and oil-insoluble and the inner segment B is apolar and oil-soluble.
- Each segment A can be selected from the group consisting of polyesters, polyalkylene glycols, polystyrenes, polyalkyl(meth)acrylates or mixtures thereof.
- Preferred segments A are selected from the group consisting of polyesters, polyalkylene glycols, polyalkyl(meth)acrylates or mixtures thereof.
- Suitable polyalkylene glycols are selected from the group consisting of polyethylene glycol (also known as polyethylene oxide), polypropylene glycol and mixtures thereof. They are derived from ethylene oxide or propylene oxide.
- Polyethylene glycol is produced by the interaction of ethylene oxide with ethylene glycol or ethylene glycol oligomers.
- the reaction is catalyzed by acidic or basic catalysts. Usually, the mechanism is a ring-opening polymerization which is catalyzed by an alcoholate. Polymer chain length depends on the ratio of reactants. Depending on the catalyst type, the mechanism of polymerization can be cationic or anionic. The anionic mechanism is preferable because PEG with a low polydispersity can be obtained.
- Polyethylene oxide, or high-molecular weight polyethylene glycol is synthesized by suspension polymerization. It is necessary to hold the growing polymer chain in solution in the course of the polycondensation process.
- the reaction is catalyzed by magnesium-, aluminium-, or calcium-organoelement compounds. To prevent coagulation of polymer chains from solution, chelating additives such as dimethylglyoxime are used.
- Alkaline catalysts such as sodium hydroxide (NaOH), potassium hydroxide (KOH), or sodium carbonate (Na 2 CC>3) are used to prepare low-molecular-weight polyethylene glycol.
- Polypropylene glycol is produced by ring-opening polymerization of propylene oxide.
- the initiator is an alcohol and the catalyst a base, usually potassium hydroxide.
- the initiator is ethylene glycol or water the polymer is linear.
- a multifunctional initiator like glycerine, pentaerythritol or sorbitol the polymer branches out.
- Polystyrene is prepared by the polymerization of styrene monomers.
- Suitable styrene monomers can be selected from the group consisting of styrene and substituted styrenes having an alkyl substituent in the side chain, such as, for example, alpha-methylstyrene and alpha-ethylstyrene, or substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene and p- methylstyrene.
- unsubstituted styrene is preferred.
- Suitable polyalkyl(meth)acrylates to be used as segments A have to be oil-insoluble. They can be prepared from monomer mixtures, comprising:
- C5-3 2 -alkyl (meth)acrylates preferably Cio-i6-alkyl (meth)acrylates.
- each component (A1 ) and (A2) is based on the total composition of segments A.
- the proportions of components (A1 ) and (A2) add up to 100% by weight.
- (meth)acrylate refers to both, esters of acrylic acid and esters of methacrylic acid. Methacrylates are preferably used in accordance with the present invention.
- Ci- 4 -alkyl (meth)acrylates for use in accordance with the invention are esters of (meth)acrylic acid and straight chain or branched alcohols having 1 to 4 carbon atoms.
- the term "C-i- 4 -alkyl (meth)acrylates” encompasses individual (meth)acrylic esters with an alcohol of a particular length, and likewise mixtures of (meth)acrylic esters with alcohols of different lengths.
- Ci- 4 -alkyl (meth)acrylates include, for example, methyl (meth)acrylate, ethyl
- Ci- 4 -alkyl (meth)acrylates are methyl (meth)acrylate and n-butyl (meth)acrylate; methyl methacrylate and n-butyl methacrylate are especially preferred.
- the C5-3 2 -alkyl (meth)acrylates for use in accordance with the invention are esters of (meth)acrylic acid and straight chain or branched alcohols having 5 to 32 carbon atoms.
- the term "Cs-3 2 -alkyl (meth)acrylates” encompasses individual (meth)acrylic esters with an alcohol of a particular length, and likewise mixtures of methacrylic esters with alcohols of different lengths.
- Suitable Cs-3 2 -alkyl (meth)acrylates include, for example, pentyl (meth)acrylate, hexyl
- (meth)acrylate 1 ,2-octyl-1 -dodecyl (meth)acrylate, 2-tetradecyl-octadecyl (meth)acrylate, 1 ,2- tetrad ecyl-octadecy I (meth)acrylate and 2-hexadecyl-eicosyl (meth)acrylate.
- Cio-16-alkyl (meth)acrylates for use in accordance with the invention are esters of (meth)acrylic acid and straight chain or branched alcohols having 10 to 16 carbon atoms.
- the term "Cio-i6-alkyl (meth)acrylates” encompasses individual (meth)acrylic esters with an alcohol of a particular length, and likewise mixtures of methacrylic esters with alcohols of different lengths.
- Cio-i6-alkyl (meth)acrylates include, for example, decyl (meth)acrylate, undecyl
- (meth)acrylate tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate and hexadecyl (meth)acrylate.
- methacrylic esters of a linear Ci 2 -i 4 -alcohol mixture (Ci 2 -i 4 -alkyl-methacrylate).
- Segment B can be selected from the group consisting of polyolefins, polyalkyl(meth)acrylates or mixtures thereof.
- polyolefins are understood to mean polymers which are based on alkenes and/or polyenes as monomers.
- the repeating units of the polyolefins consist exclusively of the elements carbon and hydrogen and do not include any aromatic structures.
- the polyolefins may contain any desired proportion of double bonds, but they are preferably mainly hydrogenated.
- the polyolefin residue of segment B can be selected from the group consisting of polyethylene, polypropylene, polyisobutylene, poly-n-butene, polybutadiene, polyisoprene, polyfarnesene and mixtures thereof.
- One preferred olefin is derived from hydrogenated polybutadiene (hPBD). In order to initiate the polyester polymerization on both sides, the hPBD needs to be OH-terminated at both ends of the molecule.
- the hydrogenated polybutadiene is preferably characterized by a number-average molecular weight M n in the range of 1 ,000 to 4,000 g/mol, preferably in the range of 1 ,500 to 3,500 g/mol, more preferably in the range of 1 ,500 to 2,500, determined by gel permeation chromatography to DIN 55672-1 in tetrahydrofuran as eluent and polystyrene for calibration.
- Suitable polyalkyl(meth)acrylates to be used as segment B have to be oil-soluble. They can be prepared from monomer mixtures, comprising:
- (B1 ) 80 to 100% by weight of, preferably 85 to 100% by weight, more preferably 90 to 100% by weight, monomers being selected from the group consisting of Cs-3 2 -alkyl (meth)acrylates, preferably Cio-i6-alkyl (meth)acrylates; and
- (B2) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight, of monomers being selected from the group consisting of Ci- 4 -alkyl (meth)acrylates, styrene, benzyl (meth)acrylate and mixtures thereof, preferably Ci- 4 -alkyl (meth)acrylates.
- each component (B1 ) and (B2) is based on the total composition of segments B.
- the proportions of components (B1 ) and (B2) add up to 100% by weight.
- the C5-3 2 -alkyl (meth)acrylates, Cio-i6-alkyl (meth)acrylates, Ci- 4 -alkyl (meth)acrylates and styrenes for use in accordance with the invention are as defined further above.
- the triblock copolymers of general formula (I) consist preferably of:
- segment B 15 to 70% by weight, preferably 15 to 55% by weight, of segment B.
- each component (a) and (b) is based on the total composition of the triblock copolymer.
- the proportions of components (a) and (b) add up to 100% by weight.
- the amount of the oil-soluble segment B is dependent on the nature of B.
- Polyolefins, for example, have different solubilities in oil than polyalkyl(meth)acrylates. This leads to different ratios of A:B as outlined further below.
- the triblock copolymers of general formula (I) consist preferably of:
- segment B which is a polyolefin
- the triblock copolymers of general formula (I) consist preferably of:
- segment B which is a polyalkyl(meth)acrylate
- each component (a) and (b) is based on the total composition of the triblock copolymer.
- the proportions of components (a) and (b) add up to 100% by weight.
- Another embodiment of the present invention is directed to a process for improving the viscosity index of lubricating oil compositions by adding a triblock copolymer of general formula (la)
- each segment A denotes a polyester residue prepared from at least two different monomers 1 and 2, where monomer 1 is selected from a lactone and monomer 2 is selected from the group consisting of lactide and glycolide, and the two monomers are block-wise or randomly distributed over each polyester residue A, and the segment B is derived from a polyolefin residue.
- lactones examples include C3 lactones such as beta-propiolactone, C4 lactones such as beta-butyrolactone or gamma-butyrolactone, Cs lactones such as 4-hydroxy-3-pentenoic acid-gamma-lactone, alpha-methylene-gamma-butyrolactone, gamma-methylene-gamma- butyrolactone, 3-methyl-2(5H)-furanone, gamma-valerolactone, delta-valerolactone, C6 lactones such as delta-hexalactone, epsilon-caprolactone or gamma-hexalactone, or further lactones such as 5-butyl-4-methyldihydro-2(3H)-furanone, delta-octanolactone, gamma-phenyl-epsilon-capro- lactone, oxacyclododecan-2-one, oxacyclotri
- Lactides in the context of the present invention are understood to mean cyclic esters of lactic acid which can occur in three isomers: (S,S)-3,6-dimethyl-1 ,4-dioxane-2,5-dione (CAS No. 451 1-42-6), (R,R)-3,6-dimethyl-1 ,4-dioxane-2,5-dione (CAS No. 25038-75-9) and (meso)-3,6-dimethyl-1 ,4- dioxane-2,5-dione (CAS No. 13076-19-2). No isomeric form is particularly preferred here.
- each polyester residue A is prepared from epsilon-caprolactone as monomer 1 and lactide as monomer 2 and monomers 1 and 2 are randomly distributed over each polyester residue
- the ratio of epsilon-caprolactone to lactide is in the range of 12: 1 to 1 :3, preferably in the range of 6: 1 to 1 :2.
- the resulting triblock copolymers of general formula (la) are characterized in that the polyester residue A can be the same or different and has the general formula (II)
- R 1 is hydrogen or Ch , preferably Ch ,
- a is an integer of 3 to 50
- b is an integer of 5 to 60
- n is an integer of 3 or 4, preferably 4, and
- the a and b moieties may be randomly bonded or block-bonded and are preferably randomly bonded.
- suitable polyolefin residues are selected from the group consisting of polyethylene, polypropylene, polyisobutylene, poly-n-butene, polybutadiene, polyisoprene, polyfarnesene and mixtures thereof and is preferably derived from hydrogenated polybutadiene (hPBD).
- hPBD hydrogenated polybutadiene
- the hydrogenated polybutadiene residue of segment B consists preferably of:
- (b) 0 to 40% by weight, preferably 0 to 35% by weight, more preferably 0 to 15% by weight of monomer units (IVb) based on the total weight of the segment B and with the proviso that the monomer units (IVa) and (IVb) may be arranged in blocks or in random distribution.
- the degree of hydrogenation of the hydrogenated polybutadiene residue of segment B is at least 80%, preferably at least 90%.
- monomer 1 and monomer 2 are mixed with the polyolefin of segment B as starter and the ring-opening polymerization is conducted at elevated temperatures in pure substance using small amounts of a catalyst.
- the catalyst to be used in the present invention can be selected from the group consisting of tin(ll)- ethylhexanoate, dibutyltin dilaurate, 1 , 8-diazabicyclo [5.4.0] undec-7-ene, 1 , 5-diazabicyclo [4.3.0] non-5- ene, 1 , 4-diazabicyclo [2.2.2] octane, 1 , 5,7-triazabicyclo [4.4.0] dec-5-ene, titanium tetramethanolate, titanium tetraethanloate, titanium tetrapropylate, titanium tetraisopropylate, titanium tetra-n-butylate, titanium tetra-ferf-butylate, titanium tetraphenylate, titanium
- Preferred catalysts are selected from the group consisting of titanium tetramethanolate, titanium tetraethanolate, titanium tetrapropylate, titanium tetra-/so-propylate, titanium tetra-n-butylate, titanium tetra-ferf-butylate, titanium tetraphenylate, titanium oxidacetylacetonate and titanium acetylacetonate.
- Preferred triblock copolymers of general formula (la) to be used in accordance with the present invention comprise:
- each component (a) and (b) is based on the total composition of the block copolymer.
- the proportions of components (a) and (b) add up to 100% by weight.
- M w is in the range of 3,000 to 30,000 g/mol, determined by gel permeation chromatography to DIN 55672-1 in tetrahydrofuran as eluent and polystyrene for calibration.
- the polydispersity index PDI of the block polymers according to the present invention is in the range of 1 to 5.
- the hydrogenated polybutadienes usable with preference in the context of the present invention are commercially available.
- Another embodiment of the present invention is directed to a process for improving the viscosity index of lubricating oil compositions by adding a triblock copolymer of general formula (lb),
- each segment A is prepared from a monomer mixture comprising:
- (A1 ) 80 to 100% by weight, preferably 85 to 100% by weight, more preferably 90 to 100% by weight, of monomers being selected from the group consisting of Ci- 4 -alkyl (meth)acrylates, styrene, benzyl (meth)acrylate and mixtures thereof, preferably C-i- 4 -alkyl (meth)acrylates; and
- segment B is prepared from a monomer mixture comprising:
- (B1 ) 80 to 100% by weight, preferably 85 to 100% by weight, more preferably 90 to 100% by weight, of monomers being selected from the group consisting of Cs-3 2 -alkyl
- (meth)acrylates preferably Cio-i6-alkyl (meth)acrylates.
- (B2) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight, of monomers being selected from the group consisting of Ci- 4 -alkyl (meth)acrylates, styrene, benzyl (meth)acrylate and mixtures thereof, preferably Ci- 4 -alkyl (meth)acrylates.
- each component (A1 ) and (A2) is based on the total composition of segments A.
- the proportions of components (A1 ) and (A2) add up to 100% by weight.
- each component (B1 ) and (B2) is based on the total composition of segments B.
- the proportions of components (B1 ) and (B2) add up to 100% by weight.
- Preferred triblock copolymers of general formula (lb) to be used in accordance with the present invention comprise:
- the resulting polymers are characterized by a number-average molecular weight M n in the range of 2,000 to 8,000 g/mol, determined by gel permeation chromatography to DIN 55672-1 in tetrahydrofuran as eluent and PMMA for calibration.
- M w is in the range of 3,000 to 30,000 g/mol, determined by gel permeation chromatography to DIN 55672-1 in tetrahydrofuran as eluent and PMMA for calibration.
- the polydispersity index PDI of the block polymers according to the present invention is in the range of 1 to 5.
- Triblock polymers of general formula (lb) can be generally prepared by any living or controlled polymerization technique.
- the block copolymers of the present invention are preferably prepared by controlled radical polymerization.
- These processes generally combine a typical free-radical initiator with a free radical stabilizing compound to control the polymerization process and produce polymers of a specific composition, and having a controlled molecular weight and narrow molecular weight range.
- the free-radical initiators used may be those known in the art, including, but not limited to peroxy compounds, peroxides, hydroperoxides and azo compounds which decompose thermally to provide free radicals.
- controlled radical polymerization techniques include, but are not limited to, atom transfer radical polymerization (ATRP), reversible addition fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP), boron-mediated polymerization, and catalytic chain transfer polymerization (CCT).
- ATRP atom transfer radical polymerization
- RAFT reversible addition fragmentation chain transfer polymerization
- NMP nitroxide-mediated polymerization
- boron-mediated polymerization boron-mediated polymerization
- CCT catalytic chain transfer polymerization
- Another embodiment of the present invention is directed to a lubricating oil composition, comprising:
- each A denotes an oil-insoluble residue and B denotes an oil-soluble residue, characterized in that the weight-average molecular weight of the triblock copolymer is in the range of 3,000 to 30,000 g/mol, determined by gel permeation chromatography;
- each component (A) and (B) is based on the total weight of the additive
- the proportions of components (A) and (B) add up to 100% by weight.
- the lubricating oil composition is characterized by a VI of at least 300, preferably at least 400, determined to ASTM D2270, and a kinematic viscosity at 40°C of 4 to 30 mm 2 /s, preferably 5 to 25 mm 2 /s, determined to ASTM D445.
- the base oil to be used in the additive composition comprises an oil of lubricating viscosity.
- Such base oils are defined as specified by the American Petroleum Institute (API) (see April 2008 version of "Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock Categories").
- API American Petroleum Institute
- the API currently defines five groups of lubricant base stocks (API 1509, Annex E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils, September 201 1 ).
- Groups I, II and III are mineral oils which are classified by the amount of saturates and sulphur they contain and by their viscosity indices; Group IV are polyalphaolefins; and Group V are all others, including e.g. ester oils. The table below illustrates these API classifications.
- the kinematic viscosity at 40°C (KV40) of appropriate apolar base oils used to prepare an additive composition or lubricating composition in accordance with the present invention is preferably in the range of 1 mm 2 /s to 25 mm 2 /s, more preferably in the range of 2 mm 2 /s to 20 mm 2 /s, according to ASTM D445.
- Fischer-Tropsch derived base oils are known in the art.
- Fischer-Tropsch derived is meant that a base oil is, or is derived from, a synthesis product of a Fischer-Tropsch process.
- a Fischer-Tropsch derived base oil may also be referred to as a GTL (Gas-To-Liquids) base oil.
- GTL Gas-To-Liquids
- Suitable Fischer-Tropsch derived base oils that may be conveniently used as the base oil in the lubricating composition of the present invention are those as for example disclosed in EP 0 776 959, EP 0 668 342, WO 97/21788, WO 00/15736, WO 00/14188, WO 00/14187, WO 00/14183,
- Another embodiment of the present invention is directed to a lubricating oil composition, comprising:
- each A denotes an oil-insoluble residue and B denotes an oil-soluble residue, characterized in that the weight-average molecular weight of the triblock copolymer is in the range of 3,000 to 30,000 g/mol, determined by gel permeation chromatography; (B) 90 to 98% by weight of a base oil selected from the group consisting of API Group II, II, III,
- each component (A) and (B) is based on the total weight of the lubricating oil composition.
- the proportions of components (A) and (B) add up to 100% by weight.
- the lubricating oil composition is further characterized in that the base oil (B) comprises:
- (B2) 0 to 100 % by weight, preferably 0 to 50% by weight, of a base oil selected from the group consisting of API Group I, II, III, IV oils and mixtures thereof.
- each component (B1 ) and (B2) is based on the total weight of the base oil (B).
- the proportions of components (B1 ) and (B2) add up to 100% by weight.
- the lubricating oil composition is characterized by a VI of at least 300, preferably at least 400, determined to ASTM D2270, and a kinematic viscosity at 40°C of 4 to 30 mm 2 /s, preferably 5 to 25 mm 2 /s, determined to ASTM D445.
- the lubricating oil composition according to the invention may also contain, as component (C), further additives selected from the group consisting of pour point depressants, dispersants, defoamers, detergents, demulsifiers, antioxidants, antiwear additives, extreme pressure additives, friction modifiers, anticorrosion additives, dyes and mixtures thereof.
- component (C) further additives selected from the group consisting of pour point depressants, dispersants, defoamers, detergents, demulsifiers, antioxidants, antiwear additives, extreme pressure additives, friction modifiers, anticorrosion additives, dyes and mixtures thereof.
- Triblock polymers with insoluble outer parts are known in the art for their ability to aggregate in special micelles. These micelles are described as flower-like as both ends of the polymer are shielded from the solvent in the inner part of the micelle. This is illustrated by the following Scheme 2.
- a special feature of these micelles is that the polymer ends can also be part of two different micelles, which is called bridging.
- the thermodynamic balance in between bridging and nonbridging polymer chains is very complex.
- the triblock polymers according to the present invention show a very pronounced thickening behavior which is not typical for polymers of such low molecular weight indicating an associative thickening mechanism. Another indicator for this hypothesis is that thickening power increases strongly with higher polymer concentration.
- the described polymer solutions are usually clear and flowable over the whole relevant temperature range. Neither precipitation at low temperatures nor at high temperatures is observed. For a few polymer compositions precipitation at elevated temperatures can be observed dependent on the solvent. This may be an indicator that the general mechanism is based on reduced miscibility at elevated temperatures which can result in a miscibility gap for some solvent/polymer combinations.
- formulations with exceptional Vis can be generated.
- Another embodiment of the present invention is directed to the use of block copolymers as outlined further above to provide a positive VI effect in lubricating oil compositions, characterized in that the lubricating oil compositions have a VI of 300 or greater, preferably of 400 or greater, determined to ASTM D2270.
- Another embodiment of the present invention is directed to a method for improving the viscosity index (VI) of a lubricating oil composition, the method comprising the step of adding a block copolymer of general formula (I) to a lubricating oil composition.
- a further object of the present invention is directed to the use of the above-described lubricating oil composition as hydraulic fluid, transmission fluid, gear oil or motor oil.
- the triblock copolymers according to the present invention and the comparative examples were characterized with respect to their molecular weight, PDI and thermal properties (differential scanning calorimetry - DSC).
- the number-average molecular weights M n and the weight-average molecular weights M w were determined by gel permeation chromatography (GPC) to DIN 55672-1 in tetrahydrofuran as eluent and polymeric standards like polystyrene or polymethylmethacrylate (PMMA) for calibration.
- the block copolymers and the statistical polyester-copolymer prepared have hydroxyl groups as end groups.
- the concentration of OH groups is determined titrimetrically in mg KOH/g polymer according to DIN 53240-2.
- the additive compositions including the block copolymers according to the present invention and comparative examples were characterized with respect to their viscosity index (VI) to ASTM D2270 and their kinematic viscosity at 40°C (KV40) and 100°C (KV100) to ASTM D445.
- VI viscosity index
- KV40 kinematic viscosity at 40°C
- KV100 100°C
- the lubricating oil compositions including the block copolymers according to the present invention and comparative examples were characterized with respect to kinematic viscosity at -20°C (KV-20), 40°C (KV 4 o) and 100°C (KV100) to ASTM D445, their viscosity index (VI) to ASTM D2270, their cloud point to ASTM D5771 and their pour point to ASTM D5950.
- Table 1 lists the polyolefins which were used in accordance with the present invention to produce the working examples and comparative examples.
- Table 1 Dihydroxyl-functionalized polybutadienes used according to the present invention.
- titanium tetra-n-butanolate (TYTAN TNBT ® , commercially available from Borica Company, Ltd.) were added and the resulting mixture heated to 160°C until complete monomer conversion was determined by GPC. After a polymerization degree of 99.5% or higher was achieved, the melt was transferred to a steel drum and stored under a nitrogen atmosphere at room temperature.
- Synthesis 2 Synthesis of a block copolymer based on polyalkyl methacrylates by ATRP
- Synthesis 3 Synthesis of a random polymer based on polyalkyl methacrylates by RAFT
- Synthesis 4 Synthesis of a random polymer based on polyalkyl methacrylate
- a round-bottom flask equipped with a glass stir rod, nitrogen inlet, reflux condenser and thermometer was charged with 94.3 g of Chevron 100R oil, 50.4 g lauryl methacrylate, 49.6 g methyl methacrylate and 3.75 g DDM.
- the mixture was heated up to 1 10°C while stirring and nitrogen bubbling for inertion.
- 3-stage feed for 3 hours feed of a mixture consisting of 0.25 g tert-butyl-perhexanoate and 5.7 g Chevron 100R oil was started. After the feed end the mixture was stirred for an additional 60 minutes. The colorless viscous liquid was used without further purification.
- Synthesis 5 Synthesis of a random polymer based on hPBD and Polyester
- the reaction was ended when no acid end groups are present any longer (acid number ⁇ 1 mgKOH/g Polymer) and a concentration of hydroxyl end groups of 10 mg KOH/g Polymer had been attained.
- the co-polyester had a glass transition temperature of -47°C and an average molecular weight of 8.6 kDa with a PDI of 3.3.
- Table 2 shows the reaction mixtures used to prepare examples 1-14 by following the protocol as described in Synthesis 1.
- the monomer components do in each case add up to 750 g.
- As initiator was always used titanium tetra-n-butanolate (TYTAN TNBT ® , commercially available by Borica Company, Ltd.) in an amount of 0.75 g (0.1 % by weight, based on the total amount of the monomers used).
- Comparative example 15 is a random copolymer based on hPBD and polyester and was prepared by following the protocol as described in Synthesis 5.
- Table 3a Net compositions of the block copolymers 1-15 prepared according to the present invention.
- Examples 1-12 are polyolefin-based triblock copolymers A-B-A according to general formula (la). These block copolymers are all non-crystalline and show glass transition temperatures of below 0°C. It can be seen that their weight-average molecular weights are within the claimed range of 3,000 to 30,000 g/mol.
- Examples 13 and 14 are comparative examples as their polyolefin content is outside the claimed range.
- Example 15 is a comparative example as the polymer has a random distribution and is therefore not an A-B-A triblock copolymer.
- Table 4 shows the reaction mixtures used to prepare examples 16-20 which are PAMA-based triblock copolymers A-B-A according to general formula (lb) and comparative examples. The reaction was carried out by using Chevron 100R as base oil.
- Example 16 is a comparative example because the content of segments A (MMA) is lower than the ranges described in the present invention.
- Examples 17 and 18 are in accordance with the present invention and were prepared by following the protocol as described in Synthesis 2.
- Example 19 is a comparative example as it is an A-B diblock copolymer.
- monofunctional initiator was used ethyl-alpha-bromoisobutyrate.
- Example 20 is a comparative example as it is an inverse triblock copolymer B-A-B; i.e. the oil- soluble segment B forms the outer parts and the oil-insoluble segment A forms the inner part.
- the inner block A was synthesized first, the synthesis was performed in toluene because the A- block alone was insoluble in oil. After polymerization, the whole amount of toluene was exchanged by the same amount of Chevron 100R oil.
- weight-average molecular weights are within the claimed range of 3,000 to 30,000 g/mol.
- Table 6 shows the reaction mixtures used to prepare examples 21-24 which are PAMA-based block copolymers A-B-A according to general formula (lb). They were prepared by following the protocol of Synthesis 3. Table 6: Reaction mixtures used to prepare examples 21-24.
- Examples 21-24 are all in accordance with the present invention.
- the synthesis was performed in toluene as solvent. After polymerization, the whole amount of toluene was exchanged by the same amount of NB3020.
- Examples 21-24 are all prepared by RAFT polymerization, the different blocks A and B are built up consecutively. That means that for each block A half of the corresponding monomer mixture is added to the reaction mixture. Regarding the initiator, for each block A and B is added one third of the whole amount.
- the net compositions of the resulting block copolymers 21-24 are shown in the following Table 7 together with their characteristic weight-average molecular weights M w , number-average molecular weights M n as well as polydispersity indices.
- weight-average molecular weights are within the claimed range of 3,000 to 30,000 g/mol.
- Table 8 shows that the triblock polymers according to the present invention provide a very strong VI lift in lubricating oil compositions. This origin of the effect is the high thickening power at elevated temperatures. Contrary to standard VI improver technology, this effect can be achieved at comparably low viscosities at 40°C which is highly desirable for modern low viscosity lubricants. Another important factor compared to the existing VI improver technology is that the effect is achieved with low molecular weight polymers which are known to be more resistant to mechanical shear forces. Adjustment of the polymer parameters allows fine-tuning of the desired thickening power at 40°C.
- Comparative example 16 demonstrates how the effect vanishes when the apolar A segments become too short.
- the size of the aggregates was investigated by dynamic light scattering (DLS).
- the data were determined to DIN ISO 13321 by using a Zetasizer ® Nano ZS (Malvern Instruments GmbH).
- the pore size of the nozzle filter was 0.45 pm.
- the samples were first measured at 40°C, then heated to 80°C and finally cooled down to 40°C again. The samples were kept at the temperature for 30 minutes prior to the measurement.
- Table 9 DLS measurements of polymer solutions in NS8.
- Lubricating compositions will contain a range of other polar additives, which may influence the performance of an associative VI improver. Data for a hydraulic fluid formulation are shown in Table 10.
- Table 10 Formulation data of Example 2 with Dl Package (composition HF-2) and without Dl package (composition HF-1 ).
- pour point (PP) stays almost the same for both formulations, with and without Dl package. That means that neither turbidity nor separation of the block copolymer is observed and the formulation remains stable even at low temperatures.
- Table 12 Advanced performance testing of a formulation based on Example 3.
Abstract
The present invention is directed to a process for improving the viscosity index of a lubricating oil composition by adding a triblock copolymer.
Description
Use of Associative Triblockcopolymers as Viscosity Index Improvers
The present invention is directed to a process for improving the viscosity index of a lubricating oil composition by adding a triblock copolymer.
Viscosity index (VI) is a commonly used method of measuring a fluid's change of viscosity in relation to temperature. The higher the VI, the smaller the relative change in viscosity with temperature. VI improvers (also known as viscosity modifiers) are additives that increase the viscosity of the fluid throughout its useful temperature range.
Viscosity modifiers are polymeric molecules that are sensitive to temperature. At elevated temperatures, the polymeric chain is better solvated by the solvent that leads to an increase in hydrodynamic radius of the polymer in solution. Higher hydrodynamic radius equals an increase in thickening power and therefore an increase in VI.
When linear polymers are dissolved in a solvent such as oil, each individual polymer strand is separated from its neighbours and in solution exists in isolation. The polymer is fully solvated by the oil, but still retains a coiled structured, with oil solvent molecules filling the empty spaces within the loosened coil. The polymer then adopts an ellipsoid or spherical form and occupies a discrete volume known as the hydrodynamic volume of the polymer coil (see Scheme 1 below).
Dissolving polymer in a solvent such as oil is accompanied by a large increase viscosity, and this is due to the presence of these larger scale hydrodynamic spheres. The size of the hydrodynamic sphere volume determines the magnitude of the viscosity increase. Polymers yielding a high hydrodynamic volume, either due to a high molecular weight or strong associating with the oil solvent, give a relatively higher increases in the viscosity of the solution.
Increasing temperature increases the solvency of the oil, which, in turn, promotes the uncoiling of the polymer and results in a larger hydrodynamic volume.
The hydrodynamic volume of a polymer in solution depends on many parameters, such as for example the polymer chain length and composition. At low temperatures, the long-chained fiberlike polymers are more tightly coiled and contribute relatively little to viscosity. The polymers uncoil at higher temperatures, occupying a larger hydrodynamic volume and increasingly boosting viscosity as shown in the following Scheme 1.
Scheme 1 : Polymer deformation and decomposition under stress
Main disadvantage of the coiling/uncoiling mechanism is that the VI effect is strongly dependent on the molecular weight of the polymer. In addition, shear stability and thickening effect are linked to the molecular weight. Shear stability limits have always been a challenge for high VI formulations, but requirements are getting constantly more demanding. A more recent challenge are low viscosity formulations that do not leave much space for thickening polymer species. Therefore, a decoupling of VI effect, shear stability and thickening would be highly desirable. The use of a viscosity index improver in an oil of lubricating viscosity to impart desired low and high temperature viscometrics and other viscosity properties is well known. Some of the most commonly used polymers in lubricating oils include olefin copolymers (OCP), polyalkyl(meth)acrylates (PAMAs) and hydrogenated poly-(styrene-co-conjugated dienes).
The widely reported mechanism of how polymers improve VI is that polymers raise the viscosity of the fluid proportionately more at higher temperatures than at lower temperatures due to expansion of the polymer coil with increasing temperature. Not much is known in the art about other mechanisms that could be used to provide a VI effect.
Armes et al. (Angew. Chem. Int. Ed. 2017, 56, 1746-1750) describes a transition of specific diblock PAMA polymer aggregates from vesicles to worms. This transition occurs around 120°C and drastically increases the viscosity of the solutions which are conducted in dodecane as a lubricant model system. Armes does not disclose the use of triblock copolymers according to the present invention with a weight-average molecular weight of 3,000 to 30,000 g/mol for improving the viscosity index of lubricating oil compositions.
WO 2005/056739 describes the use of (meth)acrylate block copolymers as VI improvers. The block copolymers consist of oil soluble and insoluble blocks and mainly diblock and triblock structures are reported. In case of triblock copolymers, the oil-insoluble part is in the middle and the outer parts are oil-soluble. The working examples comprise at least 90 mol% of acrylic monomers and show number-average molecular weight between 20,000 and 80,000 g/mol. The use of triblock copolymers according to the present invention with a weight-average molecular weight of 3,000 to 30,000 g/mol for improving the viscosity index of lubricating oil compositions is not disclosed.
Diblock polymers consisting of a hydrogenated diene and a styrene block (also described as HSDs) are commonly used in the lubricant field (Rudnick; Lubricant Additives: Chemistry and Applications, 3rd Edition, p.263-276). These polymers form micelles in solution which provide a huge thickening effect even at very low treat rates. These aggregates are known to lose their thickening power under shear which is used to reach low HTHS values with rather thick oils. Their permanent shear loss is quite low relative to their thickening power (see US4036910); if temperature is raised too much the aggregates break down and the thickening effect is lost. No exceptional VI effect is provided by these polymers (see US 5,209,862). The oil soluble part can also be polyisobutylene (see US 9,428,709). The use of triblock copolymers according to the present invention with a weight-average molecular weight of 3,000 to 30,000 g/mol for improving the viscosity index of lubricating oil compositions is not disclosed.
EP431706 and EP0298578 describe methacrylate blocks which are used to replace the insoluble styrene block or the oil soluble hydrogenated diene block.
WO 2014/105290 describes diblock polymers including PAMA blocks which are prepared in combination with polypropylene and micelle formation in PA04 of these polymers was investigated. The use of triblock copolymers according to the present invention with a weight-average molecular weight of 3,000 to 30,000 g/mol for improving the viscosity index of lubricating oil compositions is not disclosed.
Pure PAMA diblocks with a dispersant block are described in WO2010/053890 and the use of these polymers as emulsifiers in engine oils was investigated. The use of triblock copolymers according to the present invention with a weight-average molecular weight of 3,000 to 30,000 g/mol for improving the viscosity index of lubricating oil compositions is not disclosed.
It was now surprisingly found that triblock copolymers comprising at least one oil-soluble part and at least one oil-insoluble part and having a relatively low molecular weight show an associative mechanism at higher temperatures and can be used as viscosity index improvers in lubricating oil compositions.
Associative mechanism in this connection means that relatively small molecules self-organize at elevated temperature in order to form bigger structures with an increased hydrodynamic radius. In this way, thickening contribution at low temperatures can be minimized. As the small molecules are too small to be destroyed by mechanical shear, the bigger assemblies could reform after destruction by shear forces.
One embodiment of the present invention is therefore directed to a process for improving the viscosity index of lubricating oil compositions by adding a triblock copolymer of general formula (I)
A-B-A (I), wherein each A denotes an oil-insoluble residue and B denotes an oil-soluble residue, characterized in that the weight-average molecular weight of the triblock copolymer is in the range of 3,000 to 30,000 g/mol, preferably 3,500 to 25,000 g/mol, more preferably 4,000 to 20,000 g/mol. The weight-average molecular weight is determined by gel permeation chromatography against polymeric standards. Depending on the nature and composition of the copolymer, either styrene or polyalkylmethacrylates (PMMA) are used as corresponding standard. The triblock copolymers can be derived from different polymer classes as long as the outer segments A are polar and oil-insoluble and the inner segment B is apolar and oil-soluble.
Each segment A can be selected from the group consisting of polyesters, polyalkylene glycols, polystyrenes, polyalkyl(meth)acrylates or mixtures thereof. Preferred segments A are selected from the group consisting of polyesters, polyalkylene glycols, polyalkyl(meth)acrylates or mixtures thereof.
Suitable polyalkylene glycols are selected from the group consisting of polyethylene glycol (also known as polyethylene oxide), polypropylene glycol and mixtures thereof. They are derived from ethylene oxide or propylene oxide.
Polyethylene glycol is produced by the interaction of ethylene oxide with ethylene glycol or ethylene glycol oligomers. The reaction is catalyzed by acidic or basic catalysts. Usually, the mechanism is a ring-opening polymerization which is catalyzed by an alcoholate. Polymer chain length depends on the ratio of reactants. Depending on the catalyst type, the mechanism of polymerization can be cationic or anionic. The anionic mechanism is preferable because PEG with a low polydispersity can be obtained. Polyethylene oxide, or high-molecular weight polyethylene glycol, is synthesized by suspension polymerization. It is necessary to hold the growing polymer chain in solution in the course of the polycondensation process. The reaction is catalyzed by magnesium-, aluminium-, or calcium-organoelement compounds. To prevent coagulation of polymer chains from solution, chelating additives such as dimethylglyoxime are used.
Alkaline catalysts such as sodium hydroxide (NaOH), potassium hydroxide (KOH), or sodium carbonate (Na2CC>3) are used to prepare low-molecular-weight polyethylene glycol.
Polypropylene glycol is produced by ring-opening polymerization of propylene oxide. The initiator is an alcohol and the catalyst a base, usually potassium hydroxide. When the initiator is ethylene glycol or water the polymer is linear. With a multifunctional initiator like glycerine, pentaerythritol or sorbitol the polymer branches out.
Polystyrene is prepared by the polymerization of styrene monomers. Suitable styrene monomers can be selected from the group consisting of styrene and substituted styrenes having an alkyl substituent in the side chain, such as, for example, alpha-methylstyrene and alpha-ethylstyrene, or substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene and p- methylstyrene. In accordance with the present invention, unsubstituted styrene is preferred.
Suitable polyalkyl(meth)acrylates to be used as segments A have to be oil-insoluble. They can be prepared from monomer mixtures, comprising:
(A1 ) 80 to 100% by weight, preferably 85 to 100% by weight, more preferably 90 to 100% by weight, of monomers being selected from the group consisting of Ci-4-alkyl
(meth)acrylates, styrene, benzyl (meth)acrylate and mixtures thereof, preferred Ci-4-alkyl (meth)acrylates; and
(A2) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight, of
C5-32-alkyl (meth)acrylates, preferably Cio-i6-alkyl (meth)acrylates.
The content of each component (A1 ) and (A2) is based on the total composition of segments A.
In a particular embodiment, the proportions of components (A1 ) and (A2) add up to 100% by weight.
The term "(meth)acrylate" refers to both, esters of acrylic acid and esters of methacrylic acid. Methacrylates are preferably used in accordance with the present invention.
The Ci-4-alkyl (meth)acrylates for use in accordance with the invention are esters of (meth)acrylic acid and straight chain or branched alcohols having 1 to 4 carbon atoms. The term "C-i-4-alkyl (meth)acrylates" encompasses individual (meth)acrylic esters with an alcohol of a particular length, and likewise mixtures of (meth)acrylic esters with alcohols of different lengths.
Suitable Ci-4-alkyl (meth)acrylates include, for example, methyl (meth)acrylate, ethyl
(meth)acrylate, n-propyl (meth)acrylate), /'so-propyl (meth)acrylate, n-butyl (meth)acrylate, /'so-butyl (meth)acrylate and tert- butyl (meth)acrylate. Particularly preferred Ci-4-alkyl (meth)acrylates are methyl (meth)acrylate and n-butyl (meth)acrylate; methyl methacrylate and n-butyl methacrylate are especially preferred.
The C5-32-alkyl (meth)acrylates for use in accordance with the invention are esters of (meth)acrylic acid and straight chain or branched alcohols having 5 to 32 carbon atoms. The term "Cs-32-alkyl (meth)acrylates" encompasses individual (meth)acrylic esters with an alcohol of a particular length, and likewise mixtures of methacrylic esters with alcohols of different lengths.
Suitable Cs-32-alkyl (meth)acrylates include, for example, pentyl (meth)acrylate, hexyl
(meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2 tert-butylheptyl (meth)acrylate,
octyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, 2- dodecylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-isopropylheptadecyl (meth)acrylate, 4-ferf-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl (meth)acrylate, octadecyl (meth)acrylate, 2-decyloctadecyl (meth)acrylate, 2-tetrad ecyloctadecy I (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, cetyleicosyl (meth)acrylate, stearyleicosyl (meth)acrylate, docosyl (meth)acrylate and/or eicosyltetratriacontyl (meth)acrylate. 2- decyl-tetradecyl (meth)acrylate, 2-decyloctadecyl (meth)acrylate, 2-dodecyl-1 -hexadecyl
(meth)acrylate, 1 ,2-octyl-1 -dodecyl (meth)acrylate, 2-tetradecyl-octadecyl (meth)acrylate, 1 ,2- tetrad ecyl-octadecy I (meth)acrylate and 2-hexadecyl-eicosyl (meth)acrylate.
The Cio-16-alkyl (meth)acrylates for use in accordance with the invention are esters of (meth)acrylic acid and straight chain or branched alcohols having 10 to 16 carbon atoms. The term "Cio-i6-alkyl (meth)acrylates" encompasses individual (meth)acrylic esters with an alcohol of a particular length, and likewise mixtures of methacrylic esters with alcohols of different lengths.
Suitable Cio-i6-alkyl (meth)acrylates include, for example, decyl (meth)acrylate, undecyl
(meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl
(meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate and hexadecyl (meth)acrylate.
Amongst these, particularly preferred are methacrylic esters of a linear Ci2-i4-alcohol mixture (Ci2-i4-alkyl-methacrylate).
Segment B can be selected from the group consisting of polyolefins, polyalkyl(meth)acrylates or mixtures thereof.
In the context of the present invention, polyolefins are understood to mean polymers which are based on alkenes and/or polyenes as monomers. The repeating units of the polyolefins consist exclusively of the elements carbon and hydrogen and do not include any aromatic structures. The polyolefins may contain any desired proportion of double bonds, but they are preferably mainly hydrogenated.
The polyolefin residue of segment B can be selected from the group consisting of polyethylene, polypropylene, polyisobutylene, poly-n-butene, polybutadiene, polyisoprene, polyfarnesene and mixtures thereof. One preferred olefin is derived from hydrogenated polybutadiene (hPBD). In order to initiate the polyester polymerization on both sides, the hPBD needs to be OH-terminated at both ends of the molecule.
The hydrogenated polybutadiene is preferably characterized by a number-average molecular weight Mn in the range of 1 ,000 to 4,000 g/mol, preferably in the range of 1 ,500 to 3,500 g/mol, more preferably in the range of 1 ,500 to 2,500, determined by gel permeation chromatography to DIN 55672-1 in tetrahydrofuran as eluent and polystyrene for calibration.
Suitable polyalkyl(meth)acrylates to be used as segment B have to be oil-soluble. They can be prepared from monomer mixtures, comprising:
(B1 ) 80 to 100% by weight of, preferably 85 to 100% by weight, more preferably 90 to 100% by weight, monomers being selected from the group consisting of Cs-32-alkyl (meth)acrylates, preferably Cio-i6-alkyl (meth)acrylates; and
(B2) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight, of monomers being selected from the group consisting of Ci-4-alkyl (meth)acrylates, styrene, benzyl (meth)acrylate and mixtures thereof, preferably Ci-4-alkyl (meth)acrylates.
The content of each component (B1 ) and (B2) is based on the total composition of segments B.
In a particular embodiment, the proportions of components (B1 ) and (B2) add up to 100% by weight.
The C5-32-alkyl (meth)acrylates, Cio-i6-alkyl (meth)acrylates, Ci-4-alkyl (meth)acrylates and styrenes for use in accordance with the invention are as defined further above.
The triblock copolymers of general formula (I) consist preferably of:
(a) 30 to 85% by weight, preferably 45 to 85% by weight, of segments A and
(b) 15 to 70% by weight, preferably 15 to 55% by weight, of segment B.
The content of each component (a) and (b) is based on the total composition of the triblock copolymer.
In a particular embodiment, the proportions of components (a) and (b) add up to 100% by weight.
The amount of the oil-soluble segment B is dependent on the nature of B. Polyolefins, for example, have different solubilities in oil than polyalkyl(meth)acrylates. This leads to different ratios of A:B as outlined further below.
The triblock copolymers of general formula (I) consist preferably of:
(a) 55 to 85% by weight of segments A and
(b) 15 to 45% by weight of segment B which is a polyolefin,
based on the total composition of the triblock copolymer.
The triblock copolymers of general formula (I) consist preferably of:
(a) 45 to 70% by weight of segments A and
(b) 30 to 55% by weight of segment B which is a polyalkyl(meth)acrylate,
based on the total composition of the triblock copolymer.
The content of each component (a) and (b) is based on the total composition of the triblock copolymer.
In a particular embodiment, the proportions of components (a) and (b) add up to 100% by weight.
Another embodiment of the present invention is directed to a process for improving the viscosity index of lubricating oil compositions by adding a triblock copolymer of general formula (la)
A-B-A (la),
wherein each segment A denotes a polyester residue prepared from at least two different monomers 1 and 2, where monomer 1 is selected from a lactone and monomer 2 is selected from the group consisting of lactide and glycolide, and the two monomers are block-wise or randomly distributed over each polyester residue A, and the segment B is derived from a polyolefin residue.
Examples of suitable lactones are especially C3 lactones such as beta-propiolactone, C4 lactones such as beta-butyrolactone or gamma-butyrolactone, Cs lactones such as 4-hydroxy-3-pentenoic acid-gamma-lactone, alpha-methylene-gamma-butyrolactone, gamma-methylene-gamma- butyrolactone, 3-methyl-2(5H)-furanone, gamma-valerolactone, delta-valerolactone, C6 lactones such as delta-hexalactone, epsilon-caprolactone or gamma-hexalactone, or further lactones such as 5-butyl-4-methyldihydro-2(3H)-furanone, delta-octanolactone, gamma-phenyl-epsilon-capro- lactone, oxacyclododecan-2-one, oxacyclotridecan-2-one, pentadecanolide, 16-hexadecanolide, gamma-undecalactone, delta-undecalactone, gamma-methylene-gamma-butyrolactone and mixtures thereof.
Lactides in the context of the present invention are understood to mean cyclic esters of lactic acid which can occur in three isomers: (S,S)-3,6-dimethyl-1 ,4-dioxane-2,5-dione (CAS No. 451 1-42-6), (R,R)-3,6-dimethyl-1 ,4-dioxane-2,5-dione (CAS No. 25038-75-9) and (meso)-3,6-dimethyl-1 ,4- dioxane-2,5-dione (CAS No. 13076-19-2). No isomeric form is particularly preferred here.
Preferably, each polyester residue A is prepared from epsilon-caprolactone as monomer 1 and lactide as monomer 2 and monomers 1 and 2 are randomly distributed over each polyester residue
A.
The ratio of epsilon-caprolactone to lactide is in the range of 12: 1 to 1 :3, preferably in the range of 6: 1 to 1 :2.
The resulting triblock copolymers of general formula (la) are characterized in that the polyester residue A can be the same or different and has the general formula (II)
wherein
R1 is hydrogen or Ch , preferably Ch ,
a is an integer of 3 to 50,
b is an integer of 5 to 60, and
n is an integer of 3 or 4, preferably 4, and
the a and b moieties may be randomly bonded or block-bonded and are preferably randomly bonded.
Examples of suitable polyolefin residues are selected from the group consisting of polyethylene, polypropylene, polyisobutylene, poly-n-butene, polybutadiene, polyisoprene, polyfarnesene and mixtures thereof and is preferably derived from hydrogenated polybutadiene (hPBD).
The hydrogenated polybutadiene residue of segment B consists preferably of:
(a) 60 to 100% by weight, preferably 65 to 100%, more preferably 85 to 100% of monomer units (
(b) 0 to 40% by weight, preferably 0 to 35% by weight, more preferably 0 to 15% by weight of monomer units (IVb)
based on the total weight of the segment B and with the proviso that the monomer units (IVa) and (IVb) may be arranged in blocks or in random distribution.
The degree of hydrogenation of the hydrogenated polybutadiene residue of segment B is at least 80%, preferably at least 90%.
In order to obtain such a block copolymer, monomer 1 and monomer 2 are mixed with the polyolefin of segment B as starter and the ring-opening polymerization is conducted at elevated temperatures in pure substance using small amounts of a catalyst.
The catalyst to be used in the present invention can be selected from the group consisting of tin(ll)- ethylhexanoate, dibutyltin dilaurate, 1 , 8-diazabicyclo [5.4.0] undec-7-ene, 1 , 5-diazabicyclo [4.3.0] non-5- ene, 1 , 4-diazabicyclo [2.2.2] octane, 1 , 5,7-triazabicyclo [4.4.0] dec-5-ene, titanium tetramethanolate, titanium tetraethanloate, titanium tetrapropylate, titanium tetraisopropylate, titanium tetra-n-butylate, titanium tetra-ferf-butylate, titanium tetraphenylate, titanium
oxidacetylacetonate and titanium acetylacetonate. Preferred catalysts are selected from the group consisting of titanium tetramethanolate, titanium tetraethanolate, titanium tetrapropylate, titanium tetra-/so-propylate, titanium tetra-n-butylate, titanium tetra-ferf-butylate, titanium tetraphenylate, titanium oxidacetylacetonate and titanium acetylacetonate.
Preferred triblock copolymers of general formula (la) to be used in accordance with the present invention comprise:
(a) 55 to 85% by weight, of polyester residues A; and
(b) 15 to 45% by weight, of hydrogenated polybutadiene residues B.
The content of each component (a) and (b) is based on the total composition of the block copolymer.
In a particular embodiment, the proportions of components (a) and (b) add up to 100% by weight.
They are further characterized by a weight-average molecular weight Mw is in the range of 3,000 to 30,000 g/mol, determined by gel permeation chromatography to DIN 55672-1 in tetrahydrofuran as eluent and polystyrene for calibration.
The polydispersity index PDI of the block polymers according to the present invention is in the range of 1 to 5.
The hydrogenated polybutadienes usable with preference in the context of the present invention are commercially available.
Another embodiment of the present invention is directed to a process for improving the viscosity index of lubricating oil compositions by adding a triblock copolymer of general formula (lb),
A-B-A (lb),
wherein each segment A is prepared from a monomer mixture comprising:
(A1 ) 80 to 100% by weight, preferably 85 to 100% by weight, more preferably 90 to 100% by weight, of monomers being selected from the group consisting of Ci-4-alkyl
(meth)acrylates, styrene, benzyl (meth)acrylate and mixtures thereof, preferably C-i-4-alkyl (meth)acrylates; and
(A2) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight, of
C5-32-alkyl (meth)acrylates, preferably Cio-i6-alkyl (meth)acrylates; and segment B is prepared from a monomer mixture comprising:
(B1 ) 80 to 100% by weight, preferably 85 to 100% by weight, more preferably 90 to 100% by weight, of monomers being selected from the group consisting of Cs-32-alkyl
(meth)acrylates, preferably Cio-i6-alkyl (meth)acrylates; and
(B2) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight, of monomers being selected from the group consisting of Ci-4-alkyl (meth)acrylates, styrene, benzyl (meth)acrylate and mixtures thereof, preferably Ci-4-alkyl (meth)acrylates.
The content of each component (A1 ) and (A2) is based on the total composition of segments A.
In a particular embodiment, the proportions of components (A1 ) and (A2) add up to 100% by weight.
The content of each component (B1 ) and (B2) is based on the total composition of segments B.
In a particular embodiment, the proportions of components (B1 ) and (B2) add up to 100% by weight.
Preferred triblock copolymers of general formula (lb) to be used in accordance with the present invention comprise:
(a) 45 to 70% by weight, of PAMA residues A; and
(b) 30 to 55% by weight, of PAMA residues B.
The resulting polymers are characterized by a number-average molecular weight Mn in the range of 2,000 to 8,000 g/mol, determined by gel permeation chromatography to DIN 55672-1 in tetrahydrofuran as eluent and PMMA for calibration.
They are further characterized by a weight-average molecular weight Mw is in the range of 3,000 to 30,000 g/mol, determined by gel permeation chromatography to DIN 55672-1 in tetrahydrofuran as eluent and PMMA for calibration.
The polydispersity index PDI of the block polymers according to the present invention is in the range of 1 to 5.
Triblock polymers of general formula (lb) can be generally prepared by any living or controlled polymerization technique. To synthesize copolymers with segments of different polarity, the block copolymers of the present invention are preferably prepared by controlled radical polymerization.
These processes generally combine a typical free-radical initiator with a free radical stabilizing compound to control the polymerization process and produce polymers of a specific composition, and having a controlled molecular weight and narrow molecular weight range. The free-radical initiators used may be those known in the art, including, but not limited to peroxy compounds, peroxides, hydroperoxides and azo compounds which decompose thermally to provide free radicals.
Examples of controlled radical polymerization techniques are generally known the person skilled in the art and include, but are not limited to, atom transfer radical polymerization (ATRP), reversible addition fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP), boron-mediated polymerization, and catalytic chain transfer polymerization (CCT).
Descriptions and comparisons of these types of polymerizations are described in the ACS
Symposium Series 768, entitled "Controlled/Living Radical Polymerization: Process in ATRP, NMP, and RAFT", edited by Krystof Matyjaszewski, American Chemical Society, Washington D.C., 2000.
Another embodiment of the present invention is directed to a lubricating oil composition, comprising:
(A) 2 to 20% by weight, preferably 5 to 15% by weight, of a triblock copolymer of general formula (I)
A-B-A (I),
wherein each A denotes an oil-insoluble residue and B denotes an oil-soluble residue, characterized in that the weight-average molecular weight of the triblock copolymer is in the range of 3,000 to 30,000 g/mol, determined by gel permeation chromatography; and
(B) 80 to 98% by weight, preferably 85 to 95% by weight, of a base oil.
The content of each component (A) and (B) is based on the total weight of the additive
composition.
In a particular embodiment, the proportions of components (A) and (B) add up to 100% by weight.
The lubricating oil composition is characterized by a VI of at least 300, preferably at least 400, determined to ASTM D2270, and a kinematic viscosity at 40°C of 4 to 30 mm2/s, preferably 5 to 25 mm2/s, determined to ASTM D445.
The base oil to be used in the additive composition comprises an oil of lubricating viscosity. Such base oils are defined as specified by the American Petroleum Institute (API) (see April 2008 version of "Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", section 1.3 Sub-heading 1.3. "Base Stock Categories").
The API currently defines five groups of lubricant base stocks (API 1509, Annex E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils, September 201 1 ). Groups I, II and III are mineral oils which are classified by the amount of saturates and sulphur they contain and by their viscosity indices; Group IV are polyalphaolefins; and Group V are all others, including e.g. ester oils. The table below illustrates these API classifications.
The kinematic viscosity at 40°C (KV40) of appropriate apolar base oils used to prepare an additive composition or lubricating composition in accordance with the present invention is preferably in the range of 1 mm2/s to 25 mm2/s, more preferably in the range of 2 mm2/s to 20 mm2/s, according to ASTM D445.
Further base oils which can be used in accordance with the present invention are Group ll-lll Fischer-Tropsch derived base oils.
Fischer-Tropsch derived base oils are known in the art. By the term "Fischer-Tropsch derived" is meant that a base oil is, or is derived from, a synthesis product of a Fischer-Tropsch process. A Fischer-Tropsch derived base oil may also be referred to as a GTL (Gas-To-Liquids) base oil. Suitable Fischer-Tropsch derived base oils that may be conveniently used as the base oil in the lubricating composition of the present invention are those as for example disclosed in EP 0 776 959, EP 0 668 342, WO 97/21788, WO 00/15736, WO 00/14188, WO 00/14187, WO 00/14183,
WO 00/14179, WO 00/081 15, WO 99/41332, EP 1 029 029, WO 01/18156, WO 01/57166 and WO 2013/189951.
Another embodiment of the present invention is directed to a lubricating oil composition, comprising:
(A) 2 to 20% by weight, preferably 5 to 15% by weight, of a triblock copolymer of general formula (I)
A-B-A (I),
wherein each A denotes an oil-insoluble residue and B denotes an oil-soluble residue, characterized in that the weight-average molecular weight of the triblock copolymer is in the range of 3,000 to 30,000 g/mol, determined by gel permeation chromatography;
(B) 90 to 98% by weight of a base oil selected from the group consisting of API Group II, II, III,
IV, V and mixtures thereof.
The content of each component (A) and (B) is based on the total weight of the lubricating oil composition.
In a particular embodiment, the proportions of components (A) and (B) add up to 100% by weight.
The lubricating oil composition is further characterized in that the base oil (B) comprises:
(B1 ) 0 to 100% by weight, preferably 50 to 100% by weight, of a Group V base oil; and
(B2) 0 to 100 % by weight, preferably 0 to 50% by weight, of a base oil selected from the group consisting of API Group I, II, III, IV oils and mixtures thereof.
The content of each component (B1 ) and (B2) is based on the total weight of the base oil (B).
In a particular embodiment, the proportions of components (B1 ) and (B2) add up to 100% by weight.
The lubricating oil composition is characterized by a VI of at least 300, preferably at least 400, determined to ASTM D2270, and a kinematic viscosity at 40°C of 4 to 30 mm2/s, preferably 5 to 25 mm2/s, determined to ASTM D445.
The lubricating oil composition according to the invention may also contain, as component (C), further additives selected from the group consisting of pour point depressants, dispersants, defoamers, detergents, demulsifiers, antioxidants, antiwear additives, extreme pressure additives, friction modifiers, anticorrosion additives, dyes and mixtures thereof.
Triblock polymers with insoluble outer parts are known in the art for their ability to aggregate in special micelles. These micelles are described as flower-like as both ends of the polymer are shielded from the solvent in the inner part of the micelle. This is illustrated by the following Scheme 2.
A special feature of these micelles is that the polymer ends can also be part of two different micelles, which is called bridging. The thermodynamic balance in between bridging and nonbridging polymer chains is very complex.
Scheme 2: Schematic illustration of the expected association pattern of the investigated
triblock polymers in solution.
oil insoluble 0il soluble
very polar apolar
When dissolved in apolar fluids such as mineral oils, the triblock polymers according to the present invention show a very pronounced thickening behavior which is not typical for polymers of such low molecular weight indicating an associative thickening mechanism. Another indicator for this hypothesis is that thickening power increases strongly with higher polymer concentration.
Surprisingly, this thickening effect becomes even stronger at elevated temperatures, completely opposite to what was expected. Using this effect oils with very exceptional temperature/viscosity behavior can be formulated. Formulations with extremely high Vis can be formulated in this way. Even behavior that cannot be described by the VI anymore due to lack of definition can be generated in this way. For example, it is possible to generate oil formulations with a higher viscosity at 100°C than at 40°C.
As the effect is based on self-organization of low-molecular weight polymers the system is less susceptible to destruction by mechanical shear. In fact no permanent shear loss was observed in standard industry tests.
The described polymer solutions are usually clear and flowable over the whole relevant temperature range. Neither precipitation at low temperatures nor at high temperatures is observed. For a few polymer compositions precipitation at elevated temperatures can be observed dependent on the solvent. This may be an indicator that the general mechanism is based on reduced miscibility at elevated temperatures which can result in a miscibility gap for some solvent/polymer combinations. By application of the triblock copolymers of the present invention in lubricating oil compositions, formulations with exceptional Vis can be generated.
Another embodiment of the present invention is directed to the use of block copolymers as outlined further above to provide a positive VI effect in lubricating oil compositions, characterized in that the
lubricating oil compositions have a VI of 300 or greater, preferably of 400 or greater, determined to ASTM D2270.
Another embodiment of the present invention is directed to a method for improving the viscosity index (VI) of a lubricating oil composition, the method comprising the step of adding a block copolymer of general formula (I) to a lubricating oil composition.
A further object of the present invention is directed to the use of the above-described lubricating oil composition as hydraulic fluid, transmission fluid, gear oil or motor oil.
The invention has been further illustrated by the following non-limiting examples.
Experimental Part Abbreviations
BnMA benzyl methacrylate
Chevron 100R Group II base oil from Chevron with a KV100 of 4.1 cSt
CP cloud point
DDM 1-dodecyl mercaptane
EBIB ethyl alpha-bromoisobutyrate (monofunctional)
e-CL epsilon-caprolactone
2fBiB ethylene bis(2-bromoisobutyrate) (bifunctional)
HITEC521® hydraulic Dl package from Afton
hPBD hydrogenated polybutadiene
IR8080 lrgalube®8080, ashless hydraulic Dl package from BASF
KRL Kegelrollenlager (tapered roller bearing)
KV kinematic viscosity measured according to ASTM D445
KV-20 kinematic viscosity @-20°C, measured according to ASTM D445
KV40 kinematic viscosity @40°C, measured according to ASTM D445
KV100 kinematic viscosity @100°C, measured according to ASTM D445
LCST lower critical solution temperature
LMA lauryl methacrylate, 73% C12, 27% C14, all linear
MMA methyl methacrylate
Mn number-average molecular weight
Mw weight-average molecular weight
NB3020 Nexbase® 3020, Group III base oil from Neste with a KV100 of 2.2 cSt
NB3043 Nexbase® 3043, Group III base oil from Neste with a KV100 of 4.3 cSt
NB3060 Nexbase® 3060, Group III base oil from Neste with a KV100 of 5.9 cSt
NS3® naphthenic base oil from Nynas with a KV100 of 1.1 cSt
NS8® naphthenic base oil from Nynas with a KV100 of 2.1 cSt
PDI polydispersity index
PMDETA pentamethyldiethylenetriamine
PP pour point
RC9300® ashless hydraulic Dl package from Rheinchemie
Tg glass transition temperature
Tm melting point
VI viscosity index
Test methods
The triblock copolymers according to the present invention and the comparative examples were characterized with respect to their molecular weight, PDI and thermal properties (differential scanning calorimetry - DSC).
The number-average molecular weights Mn and the weight-average molecular weights Mw were determined by gel permeation chromatography (GPC) to DIN 55672-1 in tetrahydrofuran as eluent and polymeric standards like polystyrene or polymethylmethacrylate (PMMA) for calibration.
Determining the thermal properties (Tg and Tm) of the block copolymers employed in the present invention was carried out by differential scanning calorimetry (DSC) according to DSC method DIN 1 1357-1.
The block copolymers and the statistical polyester-copolymer prepared have hydroxyl groups as end groups. The concentration of OH groups is determined titrimetrically in mg KOH/g polymer according to DIN 53240-2.
The additive compositions including the block copolymers according to the present invention and comparative examples were characterized with respect to their viscosity index (VI) to ASTM D2270 and their kinematic viscosity at 40°C (KV40) and 100°C (KV100) to ASTM D445.
The lubricating oil compositions including the block copolymers according to the present invention and comparative examples were characterized with respect to kinematic viscosity at -20°C (KV-20), 40°C (KV4o) and 100°C (KV100) to ASTM D445, their viscosity index (VI) to ASTM D2270, their cloud point to ASTM D5771 and their pour point to ASTM D5950.
KRL measurements to determine the shear loss were also done to CEC L-45-A-99 (20 hours, 60°C and 5kN).
In connection with the evaluation of hydraulic formulations, foam tests to ASTM D892 were run, air release was determined to DIN ISO 9120.
The Brookfield viscosity was determined to DIN 51398.
OH-functionalized polyolefins
The following Table 1 lists the polyolefins which were used in accordance with the present invention to produce the working examples and comparative examples.
Table 1 : Dihydroxyl-functionalized polybutadienes used according to the present invention.
As shown in Table 1 , the degree of branching is higher in the material from Nippon Soda. Synthesis 1: General synthesis of the polyolefin-based block copolymers
The in Table 2 mentioned amounts of OH-functional polyolefin, epsilon-caprolactone and lactide were mixed in a 1 L multi-neck flask with reflux condenser and continuous nitrogen flow.
Afterwards, 0.75 g (0.1 % by weight based on the total amount of 750 g starting materials) titanium tetra-n-butanolate (TYTAN TNBT®, commercially available from Borica Company, Ltd.) were added and the resulting mixture heated to 160°C until complete monomer conversion was determined by GPC. After a polymerization degree of 99.5% or higher was achieved, the melt was transferred to a steel drum and stored under a nitrogen atmosphere at room temperature.
Synthesis 2: Synthesis of a block copolymer based on polyalkyl methacrylates by ATRP
polymerization
1.36 g of pentamethyldiethylenetriamine (PMDETA), 0.56 g CuBr and 55.0 g of lauryl methacrylate (LMA) were dissolved in 98.8 g of Chevron 100R oil. The solution was purged with nitrogen for 30 minutes and heated to 65°C. After addition of 2.83 g of ethylene bis(2-bromoisobutyrate) the reaction mixture was heated to 95°C. 45.0 g of methyl methacrylate were added after 3 h and another 3 h later 0.80 g DDM were added. The mixture was stirred for 2 h, cooled to room temperature and purified by pressure filtration. After filtration, a clear and slightly yellow colored highly viscous liquid was obtained which was applied without further purification.
Synthesis 3: Synthesis of a random polymer based on polyalkyl methacrylates by RAFT
polymerization
27.5 g methyl methacrylate and 3.13 g 2-cyanobutanyl-2-yl 3,5-dimethyl-1 H-pyrazole-1- carbodithioate were dissolved in 98.8 g of toluene and purged with nitrogen for 30 minutes. The mixture was heated to 80°C and 0.48 g 2,2'-azobis(2-methylbutyronitrile) was added. After 2 h,
0.48 g 2,2'-azobis(2-methylbutyronitrile) dissolved in 45.0 g lauryl methacrylate was added and
after stirring for another 2 h 0.48 g 2,2'-azobis(2-methylbutyronitrile) dissolved in 27.5 g methyl methacrylate was added. The mixture was stirred overnight. The toluene was removed by vacuum distillation and replaced by 98.8 g of Nexbase 3020. The highly viscous yellow liquid was used without further purification.
Synthesis 4: Synthesis of a random polymer based on polyalkyl methacrylate
(comparative example)
A round-bottom flask equipped with a glass stir rod, nitrogen inlet, reflux condenser and thermometer was charged with 94.3 g of Chevron 100R oil, 50.4 g lauryl methacrylate, 49.6 g methyl methacrylate and 3.75 g DDM. The mixture was heated up to 1 10°C while stirring and nitrogen bubbling for inertion. Then 3-stage feed for 3 hours feed of a mixture consisting of 0.25 g tert-butyl-perhexanoate and 5.7 g Chevron 100R oil was started. After the feed end the mixture was stirred for an additional 60 minutes. The colorless viscous liquid was used without further purification.
Synthesis 5: Synthesis of a random polymer based on hPBD and Polyester
(comparative example)
512 g of NISSO GI 1000 (0.29 mol) were melted together with 122 g neopentyl glycol (1.17 mol) and 194 g adipic acid (1 .32 mol) in a 1 L flask with a distillation attachment under nitrogen. At a temperature of 240°C, the majority of the water of the reaction was formed and distilled off within about four to six hours. Subsequently, 1 g (0.1 wt%) of TYTAN TNBT® was added and the pressure in the apparatus was lowered stepwise down to 10 mbar. The reaction was ended when no acid end groups are present any longer (acid number < 1 mgKOH/g Polymer) and a concentration of hydroxyl end groups of 10 mg KOH/g Polymer had been attained. The co-polyester had a glass transition temperature of -47°C and an average molecular weight of 8.6 kDa with a PDI of 3.3.
Table 2 shows the reaction mixtures used to prepare examples 1-14 by following the protocol as described in Synthesis 1. The monomer components do in each case add up to 750 g. As initiator was always used titanium tetra-n-butanolate (TYTAN TNBT®, commercially available by Borica Company, Ltd.) in an amount of 0.75 g (0.1 % by weight, based on the total amount of the monomers used).
Comparative example 15 is a random copolymer based on hPBD and polyester and was prepared by following the protocol as described in Synthesis 5.
Table 2: Reaction mixtures used to prepare examples 1-15.
comparative example
The net compositions of the resulting block copolymers 1-15 are shown in the following Table 3a whereas the characteristic weight-average molecular weights Mw, number-average molecular weights Mn as well as polydispersity indices (PDI), glass transition temperatures and melting points are summarized in Table 3b.
Table 3a: Net compositions of the block copolymers 1-15 prepared according to the present invention.
** comparative example
Table 3b: Characteristics of block copolymers 1-15 prepared according to the present invention.
** comparative example
Examples 1-12 are polyolefin-based triblock copolymers A-B-A according to general formula (la). These block copolymers are all non-crystalline and show glass transition temperatures of below 0°C. It can be seen that their weight-average molecular weights are within the claimed range of 3,000 to 30,000 g/mol.
Examples 13 and 14 are comparative examples as their polyolefin content is outside the claimed range.
Example 15 is a comparative example as the polymer has a random distribution and is therefore not an A-B-A triblock copolymer. Table 4 shows the reaction mixtures used to prepare examples 16-20 which are PAMA-based triblock copolymers A-B-A according to general formula (lb) and comparative examples. The reaction was carried out by using Chevron 100R as base oil.
Table 4. Reaction mixtures used to prepare examples 18-22.
comparative example
*** toluene was used for the synthesis instead of 100R oil
Example 16 is a comparative example because the content of segments A (MMA) is lower than the ranges described in the present invention.
Examples 17 and 18 are in accordance with the present invention and were prepared by following the protocol as described in Synthesis 2.
Example 19 is a comparative example as it is an A-B diblock copolymer. As monofunctional initiator was used ethyl-alpha-bromoisobutyrate.
Example 20 is a comparative example as it is an inverse triblock copolymer B-A-B; i.e. the oil- soluble segment B forms the outer parts and the oil-insoluble segment A forms the inner part. As the inner block A was synthesized first, the synthesis was performed in toluene because the A- block alone was insoluble in oil. After polymerization, the whole amount of toluene was exchanged by the same amount of Chevron 100R oil.
The net compositions of the resulting block copolymers 16-20 are shown in the following Table 5 together with their characteristic weight-average molecular weights Mw, number-average molecular weights Mn as well as polydispersity indices. Table 5: Net compositions and characteristics of block copolymers 16-20 prepared
according to the present invention.
It can be seen that their weight-average molecular weights are within the claimed range of 3,000 to 30,000 g/mol.
Table 6 shows the reaction mixtures used to prepare examples 21-24 which are PAMA-based block copolymers A-B-A according to general formula (lb). They were prepared by following the protocol of Synthesis 3.
Table 6: Reaction mixtures used to prepare examples 21-24.
Examples 21-24 are all in accordance with the present invention. The synthesis was performed in toluene as solvent. After polymerization, the whole amount of toluene was exchanged by the same amount of NB3020.
As Examples 21-24 are all prepared by RAFT polymerization, the different blocks A and B are built up consecutively. That means that for each block A half of the corresponding monomer mixture is added to the reaction mixture. Regarding the initiator, for each block A and B is added one third of the whole amount.
The net compositions of the resulting block copolymers 21-24 are shown in the following Table 7 together with their characteristic weight-average molecular weights Mw, number-average molecular weights Mn as well as polydispersity indices.
Table 7: Net compositions and characteristics of block copolymers 21-24 prepared
according to the present invention.
It can be seen that their weight-average molecular weights are within the claimed range of 3,000 to 30,000 g/mol.
Evaluation of the properties of solutions comprising inventive triblock copolymers
To demonstrate the thickening effect of triblock copolymers according to the present invention on the viscosity of base oils, solutions with different polymer content were prepared and corresponding KV40 and KV100 values as well as viscosity indices were measured. The results are shown in the following Table 8.
Table 8: Thickening effect of triblock copolymers.
** comparative example
*** not soluble
n.d. = not defined
Table 8 shows that the triblock polymers according to the present invention provide a very strong VI lift in lubricating oil compositions. This origin of the effect is the high thickening power at elevated temperatures. Contrary to standard VI improver technology, this effect can be achieved at comparably low viscosities at 40°C which is highly desirable for modern low viscosity lubricants. Another important factor compared to the existing VI improver technology is that the effect is achieved with low molecular weight polymers which are known to be more resistant to mechanical
shear forces. Adjustment of the polymer parameters allows fine-tuning of the desired thickening power at 40°C.
Such an effect is not known for previously reported triblock systems in the patent literature as they do not match the requirements for geometry and polarity of the claimed polymers, which is required for aggregates that show this unusual effect.
Comparative example 16 demonstrates how the effect vanishes when the apolar A segments become too short.
Also, different block structures such as A-B (comparative example 19), B-A-B (comparative example 20) or a multiblock structure (comparative example 15) do not provide the effect.
The size of the aggregates was investigated by dynamic light scattering (DLS). The data were determined to DIN ISO 13321 by using a Zetasizer® Nano ZS (Malvern Instruments GmbH). The pore size of the nozzle filter was 0.45 pm.
The samples were first measured at 40°C, then heated to 80°C and finally cooled down to 40°C again. The samples were kept at the temperature for 30 minutes prior to the measurement.
The values determined for the polymers in accordance with the present invention are summarized in Table 9.
Table 9: DLS measurements of polymer solutions in NS8.
All samples were filtered prior to the measurements to remove dust and impurities. Polymer concentrations are given in % by weight.
What can be concluded is that rather big polymer aggregates exist in solution and that the aggregation process is reversible which is in line with the viscometric results. Further investigation of the particles was done by transmission electron microscopy, similar as reported in Angew. Chem. Int. Ed. 2017, 56, 1746-1750. The investigation indicates a spherical shape of the particles, but the polymer distribution in the particles is inhomogeneous. No further conclusion can be drawn
due to the limitations of the available methods, but a complex mechanism seems to be at work to generate this inverse temperature effect.
Lubricating Compositions
Lubricating compositions will contain a range of other polar additives, which may influence the performance of an associative VI improver. Data for a hydraulic fluid formulation are shown in Table 10.
Table 10: Formulation data of Example 2 with Dl Package (composition HF-2) and without Dl package (composition HF-1 ).
It can be seen that the used package has a detrimental effect on the VI performance of the polymer in this formulation.
It is further shown that the pour point (PP) stays almost the same for both formulations, with and without Dl package. That means that neither turbidity nor separation of the block copolymer is observed and the formulation remains stable even at low temperatures.
The data presented in Table 10 further show the shear stability performance. The polymer is too small to be impacted by KRL; i.e. no permanent shear loss is observed. This is a significant advantage compared to common VI improvers in the market for which a high VI lift is always coupled to a significant loss in performance after severe mechanical shear.
Further application tests were run on formulations comprising Example 12 without Dl package and with different Dl packages as presented in following Table 1 1.
Table 1 1 : Formulation data of Example 12.
n.d. = not defined
Further application tests were run on the formulations as presented in following Table 12.
Table 12: Advanced performance testing of a formulation based on Example 3.
Due to the high polarity of some of the polymer blocks an impact on performance tests involving interfaces was expected. For the air release and foam tests no strong effect was observed. Filtration of the fluid is no problem at all which confirms the visual observation that the polymer is completely dissolved in the oil phase.
Claims
1. Process for improving the viscosity index of lubricating oil compositions by adding a triblock copolymer of general formula (I)
A-B-A (I), wherein each A denotes an oil-insoluble residue selected from the group consisting of polyesters, polyalkylene glycols, polystyrenes, polyalkyl(meth)acrylates or mixtures thereof, and B denotes an oil-soluble residue selected from the group consisting of polyolefins,
polyalkyl(meth)acrylates or mixtures thereof,
characterized in that the weight-average molecular weight of the triblock copolymer is in the range of 3,000 to 30,000 g/mol, preferably 3,500 to 25,000 g/mol, more preferably 4,000 to 20,000 g/mol, determined by gel permeation chromatography against polymeric standards (polystyrene or PMMA).
2. The process according to any one of claim 1 , characterized in that each segment A is a polyester residue derived from at least two different monomers 1 and 2, where monomer 1 is selected from a lactone and monomer 2 is selected from the group consisting of lactide and glycolide.
3. The process according to claim 1 , characterized in that the polyalkylene glycols are selected from the group consisting of polyethylene glycol (also known as polyethylene oxide), polypropylene glycol and mixtures thereof.
4. The process according to claim 1 , characterized in that the polystyrenes are selected from the group consisting of styrene, alpha-methylstyrene, alpha-ethylstyrene, vinyltoluene, p- methylstyrene and mixtures thereof; preferably styrene.
5. The process according to claim 1 , characterized in that the polyalkyl(meth)acrylates to be used as segments A are prepared from monomer mixtures, comprising:
(A1 ) 80 to 100% by weight, preferably 85 to 100% by weight, more preferably 90 to 100% by weight, of monomers being selected from the group consisting of C-i-4-alkyl
(meth)acrylates, styrene, benzyl (meth)acrylate and mixtures thereof, preferred Ci-4-alkyl (meth)acrylates; and
(A2) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight, of
C5-32-alkyl (meth)acrylates, preferably Cio-i6-alkyl (meth)acrylates,
based on the total composition of segments A.
6. The process according to claim 1 , characterized in that the polyolefin can be selected from the group consisting of polyethylene, polypropylene, polyisobutylene, poly-n-butene, polybutadiene, polyisoprene, polyfarnesene and mixtures thereof.
7. The process according to claim 1 , characterized in that the polyalkyl(meth)acrylates to be used as segment B are prepared from monomer mixtures, comprising:
(B1 ) 80 to 100% by weight of, preferably 85 to 100% by weight, more preferably 90 to 100% by weight, monomers being selected from the group consisting of Cs-32-alkyl (meth)acrylates, preferably Cio-i6-alkyl (meth)acrylates; and
(B2) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight, of monomers being selected from the group consisting of C-i-4-alkyl (meth)acrylates, styrene, benzyl (meth)acrylate and mixtures thereof, preferably Ci-4-alkyl (meth)acrylates, based on the total composition of segments B.
8. The process according to any one of claims 1 to 7, characterized in that the triblock copolymer of general formula (I) consists of:
(a) 45 to 85% by weight of segments A and
(b) 15 to 55% by weight of segment B,
based on the total composition of the triblock copolymer.
9. The process according to any one of claims 1 to 7, characterized in that the triblock copolymer of general formula (I) consists of:
(a) 45 to 85% by weight of segments A and
(b) 15 to 45% by weight of segment B which is a polyolefin,
based on the total composition of the triblock copolymer.
10. The process according to any one of claims 1 to 7, characterized in that the triblock copolymer of general formula (I) consists of:
(a) 45 to 70% by weight of segments A and
(b) 30 to 55% by weight of segment B which is a polyalkyl(meth)acrylate,
based on the total composition of the triblock copolymer.
1 1. The process according to claim 1 , characterized in that the triblock copolymer is of general formula (la)
A-B-A (lb),
wherein each segment A is prepared from a monomer mixture comprising:
(A1 ) 80 to 100% by weight, preferably 85 to 100% by weight, more preferably 90 to
100% by weight, of monomers being selected from the group consisting of
C-i-4-alkyl (meth)acrylates, styrene, benzyl (meth)acrylate and mixtures thereof, preferably Ci-4-alkyl (meth)acrylates; and
(A2) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight, of Cs-32-alkyl (meth)acrylates, preferably Cio-i6-alkyl (meth)acrylates, based on the total weight of segments A, and segment B is prepared from a monomer mixture comprising:
(B1 ) 80 to 100% by weight, preferably 85 to 100% by weight, more preferably 90 to
100% by weight, of monomers being selected from the group consisting of C5-32-alkyl (meth)acrylates, preferably Cio-i6-alkyl (meth)acrylates; and
(B2) 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight, of monomers being selected from the group consisting of Ci-4-alkyl (meth)acrylates, styrene, benzyl (meth)acrylate and mixtures thereof, preferably Ci-4-alkyl (meth)acrylates,
based on the total weight of segments B.
12. The process according to any one of the preceding claims, characterized in that the lubricating oil composition has a VI of 300 or greater, determined to ASTM D2270.
13. Lubricating oil composition, comprising:
(A) 2 to 20% by weight of a triblock copolymer of general formula (I)
A-B-A (I),
wherein each A denotes an oil-insoluble residue selected from the group consisting of polyesters, polyalkylene glycols, polystyrenes,
polyalkyl(meth)acrylates or mixtures thereof, and B denotes an oil-soluble residue selected from the group consisting of polyolefins, polyalkyl(meth)acrylates or mixtures thereof, characterized in that the weight-average molecular weight of the triblock copolymer is in the range of 3,000 to 30,000 g/mol, determined by gel permeation chromatography; and
(B) 80 to 98% by weight of a base oil,
characterized in that the lubricating oil compositions has a VI of at least 300, determined to ASTM
D2270.
14. Lubricating oil composition according to claim 13, characterized in that the triblock copolymer (A) consists of:
(a) 45 to 85% by weight of segments A and
(b) 15 to 55% by weight of segment B,
based on the total composition of the triblock copolymer.
15. Lubricating oil composition according to claim 13 or 14, characterized in that it has a VI of 300 or greater, determined to ASTM D2270.
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| EP18213836 | 2018-12-19 | ||
| PCT/EP2019/083623 WO2020126494A1 (en) | 2018-12-19 | 2019-12-04 | Use of associative triblockcopolymers as viscosity index improvers |
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2019
- 2019-12-04 EP EP19809873.3A patent/EP3898907A1/en active Pending
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