EP4143279A1 - Verfahren zur herstellung von dispergierenden polyalkyl(meth)acrylatpolymeren - Google Patents
Verfahren zur herstellung von dispergierenden polyalkyl(meth)acrylatpolymerenInfo
- Publication number
- EP4143279A1 EP4143279A1 EP21720541.8A EP21720541A EP4143279A1 EP 4143279 A1 EP4143279 A1 EP 4143279A1 EP 21720541 A EP21720541 A EP 21720541A EP 4143279 A1 EP4143279 A1 EP 4143279A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- monomers
- meth
- mixture
- oil
- 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
- 238000000034 method Methods 0.000 title claims abstract description 135
- 230000008569 process Effects 0.000 title claims abstract description 82
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002270 dispersing agent Substances 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 438
- 239000000178 monomer Substances 0.000 claims description 387
- 239000003921 oil Substances 0.000 claims description 157
- -1 alkyl methacrylates Chemical class 0.000 claims description 111
- 239000002199 base oil Substances 0.000 claims description 100
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 92
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 83
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 60
- 229920002857 polybutadiene Polymers 0.000 claims description 41
- 239000005062 Polybutadiene Substances 0.000 claims description 35
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 33
- 150000002148 esters Chemical class 0.000 claims description 32
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical compound CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 claims description 16
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 15
- 238000009472 formulation Methods 0.000 abstract description 19
- 239000010705 motor oil Substances 0.000 abstract description 14
- 239000000314 lubricant Substances 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 119
- 229920000642 polymer Polymers 0.000 description 108
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 34
- 239000011541 reaction mixture Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 27
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000003999 initiator Substances 0.000 description 13
- 229920000098 polyolefin Polymers 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 239000010687 lubricating oil Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 238000013459 approach Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000001542 size-exclusion chromatography Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000001050 lubricating effect Effects 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 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 2
- 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 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 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
- 230000000994 depressogenic effect Effects 0.000 description 2
- 239000010710 diesel engine oil Substances 0.000 description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 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 2
- 239000003550 marker Substances 0.000 description 2
- 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 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 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-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
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 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 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- JVPKLOPETWVKQD-UHFFFAOYSA-N 1,2,2-tribromoethenylbenzene Chemical class BrC(Br)=C(Br)C1=CC=CC=C1 JVPKLOPETWVKQD-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical class ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical class ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- DIUOAZFIHVLGKZ-UHFFFAOYSA-N 2-methyldodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCC(C)COC(=O)C(C)=C DIUOAZFIHVLGKZ-UHFFFAOYSA-N 0.000 description 1
- NXAFRGRYHSKXJB-UHFFFAOYSA-N 2-tert-butylperoxy-3,5,5-trimethylhexanoic acid Chemical compound CC(C)(C)CC(C)C(C(O)=O)OOC(C)(C)C NXAFRGRYHSKXJB-UHFFFAOYSA-N 0.000 description 1
- CARSMBZECAABMO-UHFFFAOYSA-N 3-chloro-2,6-dimethylbenzoic acid Chemical compound CC1=CC=C(Cl)C(C)=C1C(O)=O CARSMBZECAABMO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- YQGYZMIBRAEMEI-UHFFFAOYSA-N 5-methyltridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCC(C)CCCCOC(=O)C(C)=C YQGYZMIBRAEMEI-UHFFFAOYSA-N 0.000 description 1
- GJODIXVOCRXROJ-UHFFFAOYSA-N 5-methylundecyl 2-methylprop-2-enoate Chemical compound CCCCCCC(C)CCCCOC(=O)C(C)=C GJODIXVOCRXROJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 102100040409 Ameloblastin Human genes 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101000891247 Homo sapiens Ameloblastin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 238000006887 Ullmann reaction Methods 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000020169 heat generation Effects 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
- 239000002638 heterogeneous catalyst Substances 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
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 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
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- YOTGRUGZMVCBLS-UHFFFAOYSA-N pentadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCOC(=O)C(C)=C YOTGRUGZMVCBLS-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- KRLHYNPADOCLAJ-UHFFFAOYSA-N undecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C(C)=C KRLHYNPADOCLAJ-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- SXYOAESUCSYJNZ-UHFFFAOYSA-L zinc;bis(6-methylheptoxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C.CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C SXYOAESUCSYJNZ-UHFFFAOYSA-L 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
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
- C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
- C10M145/14—Acrylate; Methacrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- 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
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
-
- 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
- C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
-
- 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
- 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
Definitions
- the present invention is directed to a novel process for the preparation of polyalkyl (meth)acrylate polymers with improved compositional distribution leading to better producibility, solubility and improved performance of the products in lubricant compositions, especially in engine oil formulations.
- Lubricants are playing an important role in reducing a vehicle's fuel consumption and there is a continuing need for improvements in fuel economy performance.
- SAE Society of Automotive Engineers
- Viscosity index (VI) improvers are generally added to a lubricant to improve its thickening efficiency and to protect the engine.
- Polyalkyl (meth)acrylate-based polymers and especially polyalkyl (meth)acrylates comprising macromonomers, are commonly used as additives, especially as viscosity index improvers. They show good viscometric properties like low KV40, HTHSso and HTHS100 values in engine oil formulations leading to good fuel economy.
- Polyalkyl (meth)acrylate polymers usually comprise short-chain alkyl (meth)acrylates and long- chain alkyl (meth)acrylates. Short-chain alkyl (meth)acrylates are more polar and contribute to the viscometric properties of the resulting polymer, whereas long-chain alkyl (meth)acrylates are less polar and provide the oil solubility of the resulting polymer.
- composition of a polyalkyl (meth)acrylate has to be well balanced between polar and apolar monomers as a raise in polarity usually comes along with poor solubility and an undesired change in the viscometric performance of the polymer.
- polar monomers like methyl (meth)acrylate (MMA), butyl (meth)acrylate (BMA), styrene or functional monomers like dimethylaminoethyl methacrylate (DMAEMA)
- DMAEMA dimethylaminoethyl methacrylate
- One typical approach to counteract this polarity increase is to balance the polymer polarity by increasing the amount of less polar comonomers like for example long-chain alkyl (meth)acrylates or macromonomers.
- the solubility of the polymer in oil can be improved this way, the drawback of this approach is that the viscometric performance measured as KV40, HTHSso, or HTHS100 values in oil is compromised. This means that increasing for example the amount of long- chain alkyl (meth)acrylates leads to an increased KV40, HTHSso and HTHS100 and therefore reduced fuel efficiency effect.
- the viscometric performance of a polyalkyl (meth)acylate based comb polymer can e.g. be improved by introducing novel monomers. It is already known in the art that a certain amount of macromonomers has a positive impact on fuel efficiency (US 2010/0190671), that the presence of alkyl acrylates improves the NOACK volatility (WO 2018/041755) and a certain amount of imide functionality has a positive impact on friction reduction (WO 2019/012031).
- the changed process conditions additionally allow the synthesis of new polymer compositions with improved viscometric properties towards fuel efficiency that were not producible before and showed an unfavorable solubility in oil.
- US 2008/0194443 and US 2010/0190671 disclose a synthesis of comb polymers wherein a mixture of all monomers is added to an apparatus and diluted with base oil. Subsequently, the reaction mixture is heated to a desired temperature and reacted while several shots of initiator are added after certain time intervals. A split of the monomers into different feeds with different compositions and concentrations of monomers is not mentioned.
- US 2011/0306533 and US 2011/0319305 disclose a method for the preparation of comb polymers wherein an initial reaction mixture is prepared comprising all of the monomers and solvent oil. This initial reaction mixture is then split into a heel (about one fifth of the initial reaction mixture) and a feed (about four fifth of the initial reaction mixture).
- the compositions of the monomers in both, heel and feed are the same as well as are the concentrations of the monomers. After reaching the reaction temperature, several shots of initiator are added after certain time intervals. A split of the monomers into different feeds with different compositions and concentrations of monomers is not mentioned.
- WO 2014/170169 discloses a method for the preparation of comb polymers wherein an initial reaction mixture is prepared comprising all the monomers and solvent oil. This initial reaction mixture is then split into a heel (about one third of the initial reaction mixture) and a feed (about two thirds of the initial reaction mixture).
- the compositions of the monomers in both, heel and feed are the same as well as are the concentrations of the monomers. After reaching the reaction temperature, several shots of initiator are added after certain time intervals. A split of the monomers into different feeds with different compositions and concentrations is not mentioned.
- WO 2019/012031 is directed to comb polymers and describes a base polymer synthesis wherein an apparatus is initially charged with a mixture of 300 g of monomers and 200 g of solvent oil. This mixture is heated, and initiator added. Subsequently, another mixture of 300 g of monomers and 200 g of solvent oil, having the same composition and concentration as the initial mixture, is added as a feed as well as further initiator shot. A split of the monomers into different feeds with different compositions and concentrations of monomers is not mentioned.
- WO 2018/114673 discloses a method for the preparation of comb polymers wherein an initial reaction mixture of different monomers and solvent oil is prepared. 50% of said mixture are charged into a beaker and the other 50% of the initial mixture fed during a time interval. Monomer composition and concentration are the same. Several shots of initiator are added after certain time intervals. A split of the monomers into different feeds having different compositions and concentrations is not mentioned.
- WO 2018/041755 discloses a method for the preparation of comb polymers wherein a heel is charged with an initial mixture of monomers and solvent oil and a feed of monomers in solvent is added.
- the composition of the monomers in heel and feed are the same, but the concentrations of heel and feed are different.
- Copolymerization parameters need to be defined for each comonomer couple individually and temperature, medium and initiator need to be considered as well because the copolymerization parameters are parameters for the relative reactivity only.
- the copolymerization parameters of such a monomer A-monomer B couple differ significantly, the first synthesized polymer molecules show a different composition than the later polymerized ones. Partial demixing is therefore a known phenomenon occurring for such polymer mixtures. Copolymers with constant composition overtime can then be obtained by adding the faster polymerizing monomer according to its conversion or working at azeotrope conditions. In technical copolymerizations and products where many comonomers are applied this becomes challenging.
- the described new process can be applied to all free radical polymerizations run in a feed process wherein at least one comonomer exhibits a copolymerization kinetics that varies significantly from the kinetics of the other comonomers.
- polyalkyl (meth)acrylates comprising monomers that show differences in polarity, reactivity and oil solubility can be prepared by the process according to the present invention.
- a first object of the present invention is therefore directed to a method for the preparation of polyalkyl (meth)acrylate polymers comprising one or more apolar monomers (a) and one or more polar monomers (b), the method comprising the steps of:
- a monomer mixture 2 comprising 50 to 60% of the targeted content of monomers (a) and 105% to 110% of the targeted content of monomers (b), the concentration of the monomers in mixture 2 being 50 to 60%; characterized in that monomer mixture comprises 50 to 60% of the total amount of monomers used in the process and monomer mixture 2 comprises 40 to 50% of the total amount of monomers used in the process.
- apolar monomers (a) are understood less reactive monomers with good oil solubility that are selected from the group consisting of polyolefin-based macromonomers and other sterically hindered monomers.
- Preferred polyolefin-based macromonomers are esters of (meth)acrylic acid and hydroxylated hydrogenated polybutadienes.
- polar monomers (b) are understood more reactive monomers with only moderate or even poor oil solubility that are selected from the group consisting of C1-30 alkyl (meth)acrylates, substituted and unsubstituted styrenes, N-functionalized monomers and O-functionalized monomers.
- Preferred polar monomers (b) are selected from the group consisting of C1-4 alkyl (meth)acrylates, C10-30 alkyl (meth)acrylates, styrene, N,N-dimethylaminoethyl methacrylate (DMAEMA), N-(3- (dimethylamino)propyl)-methacrylamide (DMAPMAm), N-vinylpyrrolidinone (NVP), 2-hydroxyethyl (meth)acrylate (HEMA) and 3-hydroxypropyl (meth)acrylate (HPMA).
- DMAEMA N,N-dimethylaminoethyl methacrylate
- DMAPMAm N-(3- (dimethylamino)propyl)-methacrylamide
- NDP N-vinylpyrrolidinone
- HEMA 2-hydroxyethyl (meth)acrylate
- HPMA 3-hydroxypropyl (meth)acrylate
- a further first object of the present invention is directed to the method for the preparation of polyalkyl (meth)acrylate polymers as described further above, wherein the monomer mixture 2 can be further split into monomer mixture 2a and monomer mixture 2b, wherein mixture 2a comprises 100% of the targeted content of monomers (a) and 100% of the targeted content of monomers (b), the concentration of the monomers in mixture 2a being 50 to 60% and monomer mixture 2b comprises 0% of the targeted content of monomers (a) and 115- 125% of the targeted content of monomers (b), the concentration of the monomers in mixture 2b being 50 to 60%, characterized in that monomer mixture 2a comprises 20 to 30% of the total amount of monomers used in the process, and monomer mixture 2b comprises 20 to 25% of the total amount of monomers used in the process.
- a further first object is directed to the method as described further above, wherein the polyalkyl
- (meth)acrylate polymer comprises:
- (b2) 10% to 30% by weight of C 10 -30 alkyl (meth)acrylates, preferably C 10-15 alkyl methacrylates, more preferably C 12-14 alkyl methacrylates;
- N-containing monomers selected from the group consisting of N,N- dimethylaminoethyl methacrylate (DMAEMA), N-(3-(dimethylamino)propyl)methacrylamide (DMAPMAm) and N-vinylpyrrolidinone (NVP), preferably DMAEMA.
- DMAEMA N,N- dimethylaminoethyl methacrylate
- DMAPMAm N-(3-(dimethylamino)propyl)methacrylamide
- NDP N-vinylpyrrolidinone
- a further first object is directed to the method as described further above, wherein the polyalkyl
- (meth)acrylate polymer comprises:
- (b2) 10% to 25% by weight of C10-30 alkyl (meth)acrylates, preferably C10-15 alkyl methacrylates, more preferably C12-14 alkyl methacrylates;
- a further first object is directed to the method as described further above, wherein the polyalkyl
- (meth)acrylate polymer comprises:
- a further first object is directed to the method as described further above, wherein the polyalkyl
- (meth)acrylate polymer consists of:
- (b2) 10% to 25% by weight of C10-30 alkyl (meth)acrylates, preferably C10-15 alkyl methacrylates, more preferably C12-14 alkyl methacrylates;
- N-containing monomers selected from the group consisting of N,N- dimethylaminoethyl methacrylate (DMAEMA), N-(3-(dimethylamino)propyl)methacrylamide (DMAPMAm) and N-vinylpyrrolidinone (NVP), preferably DMAEMA.
- DMAEMA N,N- dimethylaminoethyl methacrylate
- DMAPMAm N-(3-(dimethylamino)propyl)methacrylamide
- NDP N-vinylpyrrolidinone
- a further first object is directed to the method as described further above, wherein the polyalkyl (meth)acrylate polymer consists of:
- each component (a), (b1), (b2), (b3) and (b4) is based on the total composition of the polyalkyl (meth)acrylate polymer. ln a particular embodiment, the proportions of components (a), (b1), (b2), (b3) and (b4) add up to 100% by weight.
- the weight-average molecular weight of the polyalkyl(meth)acrylate polymers according to the present invention is preferably in the range of 100,000 to 1 ,000,000 g/mol, more preferably in the range of 400,000 to 700,000 g/mol.
- the number-average molecular weight of the polyalkyl(meth)acrylate polymers according to the present invention is preferably in the range of 60,000 to 300,000 g/mol, more preferably in the range of 100,000 to 200,000 g/mol.
- the polyalkyl(meth)acrylate polymers according to the present invention have a polydispersity index (PDI) M /M n in the range of 2 to 10, more preferably in the range of 2 to 6.
- PDI polydispersity index
- Mw and M n are determined by size exclusion chromatography (SEC) using commercially available polymethylmethacrylate standards. The determination is affected by gel permeation chromatography with THF as eluent.
- a polyalkyl(meth)acrylate polymer in the context of this invention comprises a first polymer, which is also referred to as backbone or main chain, and a multitude of further polymers which are referred to as side chains and are bonded covalently to the backbone.
- the backbone of the polyalkyl(meth)acrylate polymer is formed by the interlinked unsaturated groups of the mentioned (meth)acrylates.
- the ester groups of the (meth)acrylic esters, the phenyl radicals of the styrene monomers and the substituents of the further free-radically polymerizable comonomers form the side chains of the comb polymer.
- (meth)acrylate refers to both, esters of acrylic acid and esters of methacrylic acid. Methacrylates are preferred over acrylates.
- Polyolefin-based macromonomers comprise at least one group which is derived from polyolefins.
- Polyolefins are known in the technical field and can be obtained by polymerizing alkenes and/or alkadienes which consist of the elements carbon and hydrogen, for example C2-C10-alkenes such as ethylene, propylene, n-butene, isobutene, norbornene, and/or C4-C10-alkadienes such as butadiene, isoprene, norbornadiene.
- the repeating units derived from polyolefin-based macromonomers comprise preferably at least 70% by weight and more preferably at least 80% by weight and most preferably at least 90% by weight of groups which are derived from alkenes and/or alkadienes, based on the weight of the repeating units derived from polyolefin-based macromonomers.
- the polyolefinic groups may in particular also be present in hydrogenated form.
- the repeating units derived from polyolefin-based macromonomers may comprise further groups. These include small proportions of copolymerizable monomers. These monomers are known perse and include, among other monomers, alkyl (meth)acrylates, styrene monomers, fumarates, maleates, vinyl esters and/or vinyl ethers. The proportion of these groups based on copolymerizable monomers is preferably at most 30% by weight, more preferably at most 15% by weight, based on the weight of the repeat units derived from polyolefin-based macromonomers.
- repeating units derived from polyolefin-based macromonomers may comprise starting groups and/or end groups which serve for functionalization or are caused by the preparation of the repeat units derived from polyolefin-based macromonomers.
- the proportion of these starting groups and/or end groups is preferably at most 30% by weight, more preferably at most 15% by weight, based on the weight of the repeat units derived from polyolefin-based macromonomers.
- Preferred polyolefin-based macromonomers are esters of (meth)acrylic acid and a hydroxylated hydrogenated polybutadiene.
- the hydroxylated hydrogenated polybutadiene for use in accordance with the invention has a number-average molar mass M n of 4,000 to 6,000 g/mol, preferably 4,500 to 5,000 g/mol. Because of their high molar mass, the hydroxylated hydrogenated polybutadienes can also be referred to as macroalcohols in the context of this invention.
- the number-average molar mass M n is determined by size exclusion chromatography using commercially available polybutadiene standards. The determination is affected to DIN 55672-1 by gel permeation chromatography with THF as eluent.
- the hydroxylated hydrogenated polybutadiene has a hydrogenation level of at least 99%.
- An alternative measure of the hydrogenation level which can be determined on the copolymer of the invention is the iodine number.
- the iodine number refers to the number of grams of iodine which can be added onto 100 g of copolymer.
- the copolymer of the invention has an iodine number of not more than 5 g of iodine per 100 g of copolymer.
- the iodine number is determined by the Wijs method according to DIN 53241-1 :1995-05.
- Preferred hydroxylated hydrogenated polybutadienes can be obtained according to GB 2270317.
- the hydroxylated hydrogenated polybutadiene is a hydroxyethyl- or hydroxypropyl-terminated hydrogenated polybutadiene. Particular preference is given to hydroxypropyl-terminated polybutadienes.
- These monohydroxylated hydrogenated polybutadienes can be prepared by first converting butadiene monomers by anionic polymerization to polybutadiene. Subsequently, by reaction of the polybutadiene monomers with ethylene oxide or propylene oxide, a hydroxy-functionalized polybutadiene can be prepared. This hydroxylated polybutadiene can be hydrogenated in the presence of a suitable transition metal catalyst.
- esters of (meth)acrylic acid for use in accordance with the invention and a hydroxylated hydrogenated polybutadiene described are also referred to as macromonomers in the context of this invention because of their high molar mass.
- the macromonomers for use in accordance with the invention can be prepared by transesterification of alkyl (meth)acrylates. Reaction of the alkyl (meth)acrylate with the hydroxylated hydrogenated polybutadiene forms the ester of the invention. Preference is given to using methyl (meth)acrylate or ethyl (meth)acrylate as reactant.
- This transesterification is widely known.
- a heterogeneous catalyst system such as lithium hydroxide/calcium oxide mixture (LiOH/CaO), pure lithium hydroxide (LiOH), lithium methoxide (LiOMe) or sodium methoxide (NaOMe) or a homogeneous catalyst system such as isopropyl titanate (Ti(OiPr) 4 ) or dioctyltin oxide (Sn(0Ct) 2 0).
- the reaction is an equilibrium reaction. Therefore, the low molecular weight alcohol released is typically removed, for example by distillation.
- the macromonomers can be obtained by a direct esterification proceeding, for example, from (meth)acrylic acid or (meth)acrylic anhydride, preferably under acidic catalysis by p- toluenesulfonic acid or methanesulfonic acid, or from free methacrylic acid by the DCC method (dicyclohexylcarbodiimide).
- the present hydroxylated hydrogenated polybutadiene can be converted to an ester by reaction with an acid chloride such as (meth)acryloyl chloride.
- polymerization inhibitors are used, for example the 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl radical and/or hydroquinone monomethyl ether.
- Ci-3o 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 30 carbon atoms.
- the term "C1-30 alkyl methacrylates” 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 C1-30 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, fe/f-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, 2-butyloctyl (meth)acrylate, 2-hexyloctyl (meth)acrylate, decyl (meth)acrylate, 2-butyldecyl (meth)acrylate, 2-hexyldecyl (meth)acrylate, 2-octyldecyl (meth
- Suitable styrene monomers are selected from the group consisting of styrene, substituted styrenes having an alkyl substituent in the side chain, for example alpha-methylstyrene and alpha- ethylstyrene, substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene and para-methylstyrene, halogenated styrenes, for example monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes; styrene being preferred.
- N-functionalized monomers for use in accordance with the invention are selected from the group consisting of aminoalkyl (meth)acrylates, such as N,N-dimethylaminoethyl (meth)acrylate (DMAEMA), N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopentyl (meth)acrylate or N,N-dibutylaminohexadecyl (meth)acrylate, aminoalkyl(meth)acrylamides, such as N-(3- (dimethylamino)propyl-(meth)acrylamide (DMAPMAm), and heterocyclic vinyl compounds, such as N-vinylpyrrolidinone (NVP).
- N,N-dimethylaminoethyl methacrylate, N-(3- (dimethylamino)propyl)-methacrylamide and N-vinylpyrrolidinone are preferred.
- the O-functionalized monomers for use in accordance with the invention are derived from hydroxyalkyl (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate (HEMA) and 3-hydroxypropyl (meth)acrylate (HPMA).
- HEMA 2-hydroxyethyl (meth)acrylate
- HPMA 3-hydroxypropyl (meth)acrylate
- Ci- 4 -alkyl (meth)acrylates for use in accordance with the invention are esters of (meth)acrylic acid and straight chained or branched alcohols having 1 to 4 carbon atoms.
- the term "Ci- 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 (meth)acrylate, n-propyl (meth)acrylate), /so-propyl (meth)acrylate, n-butyl (meth)acrylate, /so-butyl (meth)acrylate and fe/f-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 C 10 -30 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 30 carbon atoms.
- the term "C10-30 alkyl methacrylates” 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 C10-30 alkyl (meth)acrylates include, for example, 2-butyloctyl (meth)acrylate, 2-hexyloctyl (meth)acrylate, decyl (meth)acrylate, 2-butyldecyl (meth)acrylate, 2-hexyldecyl (meth)acrylate, 2-octyldecyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, 2-hexyldodecyl (meth)acrylate, 2-octyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, 2-decyltetradecyl (meth)acrylate,
- C10-15 alkyl methacrylates for use in accordance with the invention are esters of methacrylic acid and alcohols having 10 to 15 carbon atoms.
- the term "C10-15 alkyl methacrylates” encompasses individual methacrylic esters with an alcohol of a particular length, and likewise mixtures of methacrylic esters with alcohols of different lengths.
- Suitable C10-15 alkyl methacrylates include, for example, decyl methacrylate, undecyl methacrylate, 5-methylundecyl methacrylate, dodecyl methacrylate, 2-methyldodecyl methacrylate, tridecyl methacrylate, 5-methyltridecyl methacrylate, tetradecyl methacrylate and/or pentadecyl methacrylate.
- Particularly preferred C10-15 alkyl methacrylates are methacrylic esters of a linear C12-14 alcohol mixture (C12-14 alkyl methacrylate).
- the method according to the present invention is a free-radical polymerization.
- Customary free- radical polymerization is explained, inter alia, in Ullmanns’s Encylopedia of Industrial Chemistry, Sixth Edition.
- a polymerization initiator and a chain transfer agent are used for this purpose.
- the use of chain transfer agents is not necessary.
- an initiator is added to monomer mixtures 1 , 2, 2a and 2b in amounts of 0.1% to 0.5% by weight, preferably 0.1% to 0.3% by weight, based on the total amount of monomers used in the reaction.
- a further amount of 0.05% to 0.25% by weight, based on the total amount of monomers, of an initiator can optionally be added at the end of the reaction.
- the initiator may be selected from the group consisting of azo initiators, such as azobis- isobutyronitrile (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN) and 1 ,1- azobiscyclohexanecarbonitrile, and peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, fe/f-butyl per-2-ethylhexanoate, ketone peroxide, tert- butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropylcarbonate, 2,5-bis(2-ethylhexanoylperoxy)-2,5- dimethylhexane, tert-butyl per
- Preferred initiators are selected from the group consisting of 2,2'-azobis(2-methylbutyronitrile), tert- butylperoxy-2-ethylhexanoate, 1 ,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexan, tert-butyl- peroxybenzoate and tert-butylperoxy-3,5,5-trimethylhexanoat.
- tert- butylperoxy-2-ethylhexanoate is especially preferred.
- the polymerization may be carried out at standard pressure, reduced pressure or elevated pressure.
- the polymerization temperature is generally in the range of 20° to 200°C, preferably 90° to 100°C.
- the polymerization is carried out with a solvent.
- solvent is to be understood here in a broad sense.
- the solvent is selected according to the polarity of the monomers used, preference being given to using API group III oil, relatively light gas oil and/or aromatic hydrocarbons, for example toluene or xylene.
- the polymerization is carried out in a suitable reaction vessel that is equipped with a stirrer and a temperature control system under nitrogen atmosphere.
- the base oil to be used in the present invention comprises an oil of lubricating viscosity.
- oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof.
- the base oil may also be 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
- API 1509 Annex E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils, September 2011.
- 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;
- Group V are all others, including e.g. ester oils.
- the table below illustrates these API classifications.
- the kinematic viscosity at 100°C (KV100) 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 3 mm 2 /s to 10 mm 2 /s, more preferably in the range of 4 mm 2 /s to 8 mm 2 /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.
- 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 0668 342, WO 97/21788, WO 00/15736, WO 00/14188, WO 00/14187, WO 00/14183, WO 00/14179, WO 00/08115, WO 99/41332, EP 1 029 029, WO 01/18156, WO 01/57166 and WO 2013/189951.
- base oils of API Group III, API Group V and mixtures thereof are used base oils of API Group III, API Group V and mixtures thereof; preferred are mixtures of API Group III and API Group V base oils.
- Group V base oils are preferably be used dioctylsebacate (DIOS) or Berylane.
- a further object of the present invention is therefore directed to a method for preparing the polyalkyl (meth)acrylates as outlined further above, wherein mixture 1 comprises 60% to 75% by weight of API Group III oil or mixtures thereof and 25% to 40% by weight of Group V base oil and mixtures thereof, based on the total amount of base oil used in mixture 1 ; and mixture 2 comprises 75% to 85% by weight of API Group III oil or mixtures thereof and 15% to 25% by weight of Group V base oil and mixtures thereof, based on the total amount of base oil used in mixture 2; or mixture 1 comprises 65% to 75% by weight of API Group III oil or mixtures thereof and 25% to 35% by weight of Group V base oil and mixtures thereof, based on the total amount of base oil used in mixture 1 ; mixture 2a comprises 65% to 75% by weight of API Group III oil or mixtures thereof and 25% to 35% by weight of Group V base oil and mixtures thereof, based on the total amount of base oil used in mixture 2a; and mixture 2b comprises 65% to 75% by weight of API Group
- a further object of the present invention is directed to a method for the preparation of polyalkyl (meth)acrylate polymers, wherein the polyalkyl (meth)acrylate polymer comprises:
- (b2) 10% to 30% by weight of C10-30 alkyl (meth)acrylates, preferably C10-15 alkyl methacrylates, more preferably C12-14 alkyl methacrylates;
- N-containing monomers selected from the group consisting of N,N- dimethylaminoethyl methacrylate (DMAEMA), N-(3-(dimethylamino)propyl)methacrylamide (DMAPMAm) and N-vinylpyrrolidinone (NVP), preferably DMAEMA, based on the total amount of the polyalkyl (meth)acrylate polymers, the method comprising the steps of: (i) preparing a monomer mixture L comprising 130 to 145% of the targeted content of monomers (a) and 90% to 96% of the targeted content of monomers (b), the concentration of the monomers in mixture being 50 to 60%; and
- a monomer mixture 2 comprising 50 to 60% of the targeted content of monomers (a) and 105% to 110% of the targeted content of monomers (b), the concentration of the monomers in mixture 2 being 50 to 60%; characterized in that monomer mixture comprises 50 to 60% of the total amount of monomers used in the process and monomer mixture 2 comprises 40 to 50% of the total amount of monomers used in the process, or
- a further object of the present invention is directed to a method for the preparation of polyalkyl (meth)acrylate polymers, wherein the polyalkyl (meth)acrylate polymer comprises:
- (b2) 10% to 30% by weight of C 10 -30 alkyl (meth)acrylates, preferably C 10-15 alkyl methacrylates, more preferably C 12-14 alkyl methacrylates;
- N-containing monomers selected from the group consisting of N,N- dimethylaminoethyl methacrylate (DMAEMA), N-(3-(dimethylamino)propyl)methacrylamide (DMAPMAm) and N-vinylpyrrolidinone (NVP), preferably DMAEMA, based on the total amount of the polyalkyl (meth)acrylate polymers, the method comprising the steps of:
- a monomer mixture 2 comprising 50 to 60% of the targeted content of monomers (a) and 105% to 110% of the targeted content of monomers (b), the concentration of the monomers in mixture 2 being 50 to 60%; characterized in that monomer mixture comprises 50 to 60% of the total amount of monomers used in the process and monomer mixture 2 comprises 40 to 50% of the total amount of monomers used in the process, wherein mixture 1 comprises 60% to 75% by weight of API Group III oil or mixtures thereof and 25% to 40% by weight of Group V base oil and mixtures thereof, based on the total amount of base oil used in mixture 1 ; and mixture 2 comprises 75% to 85% by weight of API Group III oil or mixtures thereof and 15% to 25% by weight of Group V base oil and mixtures thereof, based on the total amount of base oil used in mixture 2.
- a further object of the present invention is directed to a method for the preparation of polyalkyl (meth)acrylate polymers, wherein the polyalkyl (meth)acrylate polymer comprises:
- (b2) 10% to 30% by weight of C10-30 alkyl (meth)acrylates, preferably C10-15 alkyl methacrylates, more preferably C12-14 alkyl methacrylates;
- N-containing monomers selected from the group consisting of N,N- dimethylaminoethyl methacrylate (DMAEMA), N-(3-(dimethylamino)propyl)methacrylamide (DMAPMAm) and N-vinylpyrrolidinone (NVP), preferably DMAEMA, based on the total amount of the polyalkyl (meth)acrylate polymers, the method comprising the steps of: (i) preparing a monomer mixture L comprising 18 to 23% by weight of monomers (a), 45% to 52% by weight of monomers (b1), 14% to 18% by weight of monomers (b2), 9% to 11% by weight of monomers (b3) and 2.5 to 6.5% by weight of monomers (b4), based on the total amount of monomers in mixture 1_, in a base oil, the concentration of the monomers in mixture being 50 to 60%; and
- DMAEMA N,N- dimethylaminoethyl methacrylate
- DMAPMAm N
- a monomer mixture 2 comprising 6 to 11 % by weight of monomers (a), 53% to 60% by weight of monomers (b1), 16 to 20% by weight of monomers (b2), 10 to 13% by weight of monomers (b3) and 3 to 7% by weight of monomers (b4), based on the total amount of monomers in mixture 2, in a base oil, the concentration of the monomers in mixture 2 being 50 to 60%; characterized in that monomer mixture comprises 54 to 59% of the total amount of monomers used in the process and monomer mixture 2 comprises 41 to 46% of the total amount of monomers used in the process, or
- a monomer mixture 2b comprising 0 to 1% by weight of monomers (a), 58% to 65% by weight of monomers (b1), 18 to 22% by weight of monomers (b2), 12 to 14% by weight of monomers (b3) and 3 to 8% by weight of monomers (b4), based on the total amount of monomers in mixture 2b, in a base oil, the concentration of the monomers in mixture 2b being 51 to 55%.
- monomer mixture 2a comprises 23 to 27% of the total amount of monomers used in the process and monomer mixture 2b comprises 20 to 24% of the total amount of monomers used in the process wherein mixture 1 comprises 60% to 75% by weight of API Group III oil or mixtures thereof and 25% to 40% by weight of Group V base oil and mixtures thereof, based on the total amount of base oil used in mixture 1 ; and mixture 2 comprises 75% to 85% by weight of API Group III oil or mixtures thereof and 15% to 25% by weight of Group V base oil and mixtures thereof, based on the total amount of base oil used in mixture 2; or mixture 1 comprises 65% to 75% by weight of API Group III oil or mixtures thereof and 25% to 35% by weight of Group V base oil and mixtures thereof, based on the total amount of base oil used in mixture 1 ; mixture 2a comprises 65% to 75% by weight of API Group III oil or mixtures thereof and 25% to 35% by weight of Group V base oil and mixtures thereof, based on the total amount of base oil used in mixture 2a; and mixture 2
- a further object of the present invention is directed to a method for the preparation of polyalkyl (meth)acrylate polymers, wherein the polyalkyl (meth)acrylate polymer comprises:
- (b2) 10% to 30% by weight of C10-30 alkyl (meth)acrylates, preferably C10-15 alkyl methacrylates, more preferably C12-14 alkyl methacrylates;
- N-containing monomers selected from the group consisting of N,N- dimethylaminoethyl methacrylate (DMAEMA), N-(3-(dimethylamino)propyl)methacrylamide (DMAPMAm) and N-vinylpyrrolidinone (NVP), preferably DMAEMA, based on the total amount of the polyalkyl (meth)acrylate polymers, the method comprising the steps of:
- a monomer mixture 2 comprising 6 to 11 % by weight of monomers (a), 53% to 60% by weight of monomers (b1), 16 to 20% by weight of monomers (b2), 10 to 13% by weight of monomers (b3) and 3 to 7% by weight of monomers (b4), based on the total amount of monomers in mixture 2, in a base oil, the concentration of the monomers in mixture 2 being 50 to 60%; characterized in that monomer mixture comprises 54 to 59% of the total amount of monomers used in the process and monomer mixture 2 comprises 41 to 46% of the total amount of monomers used in the process, wherein mixture 1 comprises 60% to 75% by weight of API Group III oil or mixtures thereof and 25% to 40% by weight of Group V base oil and mixtures thereof, based on the total amount of base oil used in mixture 1 ; and mixture 2 comprises 75% to 85% by weight of API Group III oil or mixtures thereof and 15% to 25% by weight of Group V base oil and mixtures thereof, based on the total amount of base oil used in mixture 2.
- (b2) 10% to 25% by weight of C10-30 alkyl (meth)acrylates, preferably C10-15 alkyl methacrylates, more preferably C12-14 alkyl methacrylates;
- N-containing monomers selected from the group consisting of N,N- dimethylaminoethyl methacrylate (DMAEMA), N-(3-(dimethylamino)propyl)methacrylamide
- DMAPMAm N-vinylpyrrolidinone
- NVP N-vinylpyrrolidinone
- a further first object is directed to the method as described further above, wherein the polyalkyl (meth)acrylate polymer comprises:
- a further first object is directed to the method as described further above, wherein the polyalkyl (meth)acrylate polymer consists of: (a) 10 to 20% by weight of esters of (meth)acrylic acid and a hydroxylated hydrogenated polybutadiene;
- N-containing monomers selected from the group consisting of N,N- dimethylaminoethyl methacrylate (DMAEMA), N-(3-(dimethylamino)propyl)methacrylamide (DMAPMAm) and N-vinylpyrrolidinone (NVP), preferably DMAEMA.
- DMAEMA N,N- dimethylaminoethyl methacrylate
- DMAPMAm N-(3-(dimethylamino)propyl)methacrylamide
- N-vinylpyrrolidinone N-vinylpyrrolidinone
- a further first object is directed to the method as described further above, wherein the polyalkyl (meth)acrylate polymer consists of:
- each component (a), (b1), (b2), (b3) and (b4) is based on the total composition of the polyalkyl (meth)acrylate polymer.
- the proportions of components (a), (b1), (b2), (b3) and (b4) add up to 100% by weight.
- a second object of the present invention is directed to the polyalkyl (meth)acrylates prepared according to the method as outlined further above.
- the polymers prepared according to the method of the present invention are characterized by their contribution to low KV40, HTHSso and HTHS100 values (e.g. at a given HTHS150 of 2.6 mPas or 2.9 mPas) of lubricating oil compositions comprising them.
- the polyalkyl(meth)acrylate polymers prepared according to the method of the present invention can therefore be used in all common grades of motor oils having the viscosity characteristics defined in the document SAE J300.
- a third object of the present invention is therefore directed to the use of polyalkyl(meth)acrylate polymers prepared according to the method of the present invention to improve the kinematic viscosity and HTHS performance of lubricating oil compositions, especially of engine oil formulations.
- a fourth object of the present invention is directed to an additive composition comprising:
- each component (A1), (A2) and (B) is based on the total composition of the additive composition.
- the proportions of components (A1), (A2) and (B) add up to 100% by weight.
- the base oil to be used in the additive composition comprises an oil of lubricating viscosity as described further above.
- a fifth object of the present invention is directed to the use of an additive composition comprising at least one polyalkyl(meth)acrylate polymer prepared according to the method of the present invention and a base oil to improve the kinematic viscosity and HTHS performance of lubricating oil compositions, especially of engine oil formulations.
- the invention has been illustrated by the following non-limiting examples.
- DMAEMA dimethylaminoethyl methacrylate HTHSso high-temperature high-shear viscosity @80°C, measured according to CEC L-036 HTHS100 high-temperature high-shear viscosity @100°C, measured according to CEC L-036 HTHS150 high-temperature high-shear viscosity @150°C, measured according to CEC L-036 KV kinematic viscosity measured according to ASTM D445 KV40 kinematic viscosity @40°C, measured according to ISO 3104 KV100 kinematic viscosity @100°C, measured according to ISO 3104 LMA lauryl methacrylate; MM macromonomer MMA methyl methacrylate Mn number-average molecular weight Mw weight-average molecular weight NB 3020 Nexbase® 3020, Group III base oil from Neste with a KV100 of 2.2 cSt NB 3043 Nexbase® 3043,
- VPL® 1-358 pour point depressant commercially available from Evonik Yubase 4+ Group III base oil from SK Lubricants with a KV100 of 4.2 cSt
- the polyalkyl (meth)acrylate polymers according to the present invention and the comparative examples were characterized with respect to their molecular weight and PDI.
- Molecular weights were determined by size exclusion chromatography (SEC) using commercially available polymethylmethacrylate (PMMA) standards. The determination is affected by gel permeation chromatography with THF as eluent (flow rate: 1 mL/min; injected volume: 100 pi).
- the additive compositions including the polyalkyl (meth)acrylate polymers according to the present invention and comparative examples were characterized with respect to their viscosity index (VI) to ASTM D 2270, kinematic viscosity at 40°C (KV 4 o) and 100°C (KV100) to ASTM D445 and with respect to their solubility.
- VI viscosity index
- KV 4 o kinematic viscosity at 40°C
- KV100 100°C
- the lubricating oil compositions including the comb polymers according to the present invention and comparative examples were characterized with respect to kinematic viscosity at 40°C (KV 4 o) and 100°C (KV100) to ASTM D445, the viscosity index (VI) to ASTM D 2270, high-temperature high- shear viscosity at 80°C, 100°C and 150°C to CEC L-036 and with respect to their solubility.
- PSSI Permanent Shear Stability Index
- the macroalcohol was synthesized by an anionic polymerization of 1 ,3-butadiene with butyllithium at 20-45°C. On attainment of the desired degree of polymerization, the reaction was stopped by adding propylene oxide and lithium was removed by precipitation with methanol. Subsequently, the polymer was hydrogenated under a hydrogen atmosphere in the presence of a noble metal catalyst at up to 140°C and pressure of 200 bar. After the hydrogenation had ended, the noble metal catalyst was removed, and organic solvent was drawn off under reduced pressure. Finally, the base oil NB 3020 was used for dilution to a polymer content of 70% by weight.
- the vinyl content of the macroalcohol was 61%, the hydrogenation level > 99% and the OH functionality > 98%. These values were determined by H-NMR (nuclear resonance spectroscopy).
- An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 55%.
- the resulting reaction mixture contained 45% of an oil mixture comprising 9.6% by weight of NB3020, 61.6% by weight of NB3043 and 28.8% by weight of Group V oil, based on the total amount of the oil composition.
- the monomer concentration of mixture 2 was 55% and the base oil was a mixture of 9.6% by weight of NB3020, 61.6% by weight of NB3043 and 28.8% of Group V oil, based on the total amount of the oil composition.
- the reaction mixture obtained was further maintained at 95°C for another hour. Subsequently, another 0.2%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate was added and the resulting reaction mixture was diluted to 40% solids with NB3043 within 3 hours.
- reaction mixture received was again maintained at 95°C for further 2 hours and after this, another 0.1%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate was added and the mixture was stirred at 95°C overnight. The next day, the mixture was diluted to 25% polymer with NB3043.
- Table 1.1 Composition of monomer mixtures used for the preparation of Polymer 1.1.
- An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 55.8%.
- the resulting reaction mixture contained 44.2% of an oil mixture comprising 11.3% by weight of NB3020, 61 % by weight of NB3043 and 27.7% by weight of Group V oil, based on the total amount of the oil composition.
- Monomer mixture 2 contained 55% of monomers and 45% of an oil mixture comprising 7.9% by weight of NB3020, 63.3% by weight of NB3043 and 28.8% by weight of Group V oil, based on the total amount of the oil composition.
- Monomer mixture 3 contained 53% of monomers and 47% of an oil mixture comprising 68.8% by weight of NB3043 and 31.2% by weight of Group V oil, based on the total amount of the oil composition. After that, the reaction was maintained at 95°C for another hour.
- reaction mixture was diluted to 40% solids with NB3043 and 0.2%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate within 3 hours. Then the reaction was again maintained at 95°C for another 2 h and after this another 0.1%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate was added and the mixture was stirred at 95°C overnight. The next day, the mixture was diluted to 25% solids with NB3043. Table 1.2: Composition of monomer mixtures used for the preparation of Polymer 1.2.
- An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 52.6%.
- the resulting reaction mixture contained 47.4% of an oil mixture comprising 10% by weight of NB3020, 53.5% by weight of NB3043 and 36.5% by weight of Group V oil, based on the total amount of the oil composition.
- Monomer mixture 2 contained 58% of monomers and 42% of an oil mixture comprising 4.8% by weight of NB3020, 77.6% by weight of NB3043 and 17.6% by weight of Group V oil, based on the total amount of the oil composition. The resulting reaction mixture was then maintained at 95°C for another hour.
- reaction mixture was diluted to 40% solids with NB3043 and 0.2%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate within one hour. Then the reaction was again maintained at 95°C for another hour and after this, another 0.1%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate was added and the mixture was stirred at 95°C overnight. The next day, the mixture was diluted to 25% solids with NB3043.
- Table 1.3 Composition of monomer mixtures used for the preparation of Polymer 1.3.
- the resulting reaction mixture contained an oil mixture comprising 10.4% by weight of NB3020, 60.8% by weight of NB3043 and 28.8% by weight of Group V oil, based on the total amount of the base oil composition. After heating to 95°C under nitrogen, 0.18%, based on the total amount of monomers, oftert- butylperoxy-2-ethyl-hexanoate was added and the temperature maintained.
- Monomer mixture 2 contained 55% of monomers and 45% of an oil mixture comprising 4.5% by weight of NB3020, 76.1% by weight of NB3043 and 19.4% by weight of Group V oil, based on the total amount of the oil composition. The resulting reaction mixture was then maintained at 95°C for another hour.
- reaction mixture was diluted to 40% solids with NB3043 and 0.2%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate within 3 hours. Then the reaction was again maintained at 95°C for another 2 hours and after this another 0.1%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate was added and the mixture was stirred at 95°C overnight. The next day, the mixture was diluted to 25% solids with NB3043.
- Table 1.4 Composition of monomer mixtures used for the preparation of Polymer 1.4.
- Table 1.5 shows the molecular weights, polydispersity and HAZE values of Polymers 1.
- Table 1.5 Characteristics of Polymers 1.
- the haze values of all products from the 4 runs were well below 5.
- the haze value of the polymer of the 4 th batch was reduced from 14 (comparative example 1.1) to 4.1. That ensures the applicability of the polymers in engine oil formulations.
- a kettle needs to be cleaned as soon as the product haze raises to 10. That means that for the split-feed processes 1.2, 1 .3 and 1.4 at least four batches can be produced in a row before cleaning the kettle. This is not possible for the process 1 .1 , where the kettle would have to be cleaned latest after the third batch.
- the method according to the present invention allows the upscaled production of Polymers 1 in a plant.
- Table 1.6 the HAZE values and viscosities of 3.75% Polymers 1 in oil are disclosed.
- Table 1.6 Viscosities of 3.75% Polymers 1 in a Group III base oil mixture (NB 3043 and NB 3080 from Neste) with KV100 of 4.9 cSt.
- An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 55%.
- the resulting reaction mixture contained 45% of an oil mixture comprising 7.9% by weight of NB3020, 63.3% by weight of NB3043 and 28.8% by weight of Group V oil, based on the total amount of the oil composition.
- Monomer mixture 2 contained 55% of monomers and 45% of an oil mixture comprising 7.9% by weight of NB3020, 63.3% by weight of NB3043 and 28.8% by weight of Group V oil, based on the total amount of the oil composition.
- the reaction was further maintained at 95°C for another hours. Subsequently, the reaction mixture was diluted to 40% solids with NB3043 and 0.2%, based on the total amount of monomers, of tert- butylperoxy-2-ethyl-hexanoate within 3 hours.
- Table 2.1 Composition of monomer mixtures used for the preparation of Polymer 2.1.
- An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 55.8%.
- the resulting reaction mixture contained 44.2% of an oil mixture comprising 11.3% by weight of NB3020, 61 % by weight of NB3043 and 27.2% by weight of Group V oil, based on the total amount of the oil composition.
- Monomer mixture 2 contained 55% of monomers and 45% of an oil mixture comprising 7.9% by weight of NB3020, 36.3% by weight of NB3043 and 28.8% by weight of Group V oil, based on the total amount of the oil composition.
- Monomer mixture 3 contained 53% of monomers and 47% of an oil mixture comprising 68.8% by weight of NB3043 and 31.2% by weight of Group V oil, based on the total amount of the oil composition. After that, the reaction was maintained at 95°C for another hour.
- reaction mixture was diluted to 40% solids with NB3043 and 0.2%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate within 3 hours. Then the reaction was again maintained at 95°C for another 2 h and after this another 0.1%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate was added and the mixture was stirred at 95°C overnight. The next day, the mixture was diluted to 25% solids with NB3043.
- Table 2.2 Composition of monomer mixtures used for the preparation of Polymer 2.2.
- An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 52.6%.
- the resulting reaction mixture contained an oil mixture comprising 10% by weight of NB3020, 53.5% by weight of NB3043 and 36.5% by weight of Group V oil, based on the total amount of the oil composition.
- Monomer mixture 2 contained 58% of monomers and 42% of an oil mixture comprising 4.8% by weight of NB3020, 77.6% by weight of NB3043 and 17.6% by weight of Group V oil, based on the total amount of the oil composition.
- the resulting reaction mixture was then maintained at 95°C for another hour. Subsequently, the reaction mixture was diluted to 40% solids with NB3043 and 0.2%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate within 3 hours.
- Table 2.3 Composition of monomer mixtures used for the preparation of Polymer 2.3.
- An oil mixture of NB3043 and Group V oil was added to achieve a concentration of monomers in oil of 60%.
- the resulting reaction mixture contained an oil mixture comprising 12.7% by weight of NB3020, 58.7% by weight of NB3043 and 28.6% by weight of Group V oil, based on the total amount of the oil composition.
- Monomer mixture 2 contained 60% of monomers and 40% of an oil mixture comprising 5.6% by weight of NB3020, 75% by weight of NB3043 and 19.4% by weight of Group V oil, based on the total amount of the oil composition.
- the resulting reaction mixture was then maintained at 95°C for another hour. Subsequently, the reaction mixture was diluted to 40% solids with NB3043 and 0.2%, based on the total amount of monomers, of tert-butylperoxy-2-ethyl-hexanoate within 3 hours.
- Table 2.4 Composition of monomer mixtures used for the preparation of Polymer 2.4.
- CE comparative example It can be seen that the HAZE values of the polymers retrieved out of the different syntheses are well below 5. That means that the polymers are soluble in oil, i.e. the solution appears clear.
- Table 2.6 Viscosities of 3.75% Polymers 2 in a Group III base oil mixture (NB 3043 and NB
- reaction mixtures used to prepare commonly known polyalkyl (meth)acrylates contain monomers with different reactivities leading to polymers with an inhomogenous distribution of the apolar and polar monomers. If one monomer is more reactive than another second monomer, this monomer will be copolymerized in a higher amount in the beginning of the monomer feed leading to polymer compositions with increased amounts of this monomer at the beginning, while the second monomer will be enriched in the polymers formed during a later time in the feed process.
- the final product then contains a mixture of all the different fractions of the polymer compositions formed during the whole process, from more polar to less polar fractions as compared to the average polymer composition.
- Table 3 Composition of generated and accumulated Polymer 1.1 overtime.
- Table 4 shows the polymerization kinetics of Polymer 1.2 having the same total composition as Polymer 1.1 but was produced using the "split-feed" process 1.2. The composition of generated and accumulated polymer is shown over the time.
- compositional differences of the product fractions prepared via the different processes becomes visible when both sets of kinetics data are compared.
- Table 4 Composition of generated and accumulated Polymer 1.2 over time.
- This ratio can be used as an estimate for the overall polarity of the polymer in each fraction prepared in the respective time intervals and is therefore used as an estimate for the solubility/HAZE of the polymer in this fraction. Comparing the polarity ratios of the two process variants leads to the result that for the original process larger deviations from the average polarity ratio of the polymer exist.
- the kinetics can be calculated via the residual monomer contends).
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- Macromonomer-Based Addition Polymer (AREA)
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| Application Number | Priority Date | Filing Date | Title |
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| EP20172357 | 2020-04-30 | ||
| PCT/EP2021/061045 WO2021219679A1 (en) | 2020-04-30 | 2021-04-28 | Process for the preparation of dispersant polyalkyl (meth)acrylate polymers |
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| EP4143279A1 true EP4143279A1 (de) | 2023-03-08 |
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| EP21720541.8A Pending EP4143279A1 (de) | 2020-04-30 | 2021-04-28 | Verfahren zur herstellung von dispergierenden polyalkyl(meth)acrylatpolymeren |
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| EP (1) | EP4143279A1 (de) |
| JP (1) | JP2023523755A (de) |
| CN (1) | CN115485354B (de) |
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| US4048413A (en) * | 1975-12-08 | 1977-09-13 | Scm Corporation | High-conversion drift-free batch-type addition copolymerization |
| FI924730A (fi) * | 1992-03-20 | 1993-09-21 | Rohm & Haas | Foerfarande foer reglering av molekylviktsfoerdelningen i polymerer |
| US5393843A (en) | 1992-08-31 | 1995-02-28 | Shell Oil Company | Butadiene polymers having terminal functional groups |
| EP0668342B1 (de) | 1994-02-08 | 1999-08-04 | Shell Internationale Researchmaatschappij B.V. | Verfahren zur Herstellung von Basisschmieröl |
| EP0776959B1 (de) | 1995-11-28 | 2004-10-06 | Shell Internationale Researchmaatschappij B.V. | Verfahren zur Herstellung von Schmierölen |
| EP1389635A1 (de) | 1995-12-08 | 2004-02-18 | ExxonMobil Research and Engineering Company | Bioabbaubare Hochleistungskohlenwasserstoffbasisöle |
| US6140431A (en) * | 1997-02-27 | 2000-10-31 | Rohm And Haas Company | Process for preparing continuously variable-composition copolymers |
| US6090989A (en) | 1997-10-20 | 2000-07-18 | Mobil Oil Corporation | Isoparaffinic lube basestock compositions |
| EP1029030B1 (de) * | 1997-10-21 | 2003-01-15 | Solutia Inc. | Schaumarme kohlenwasserstoffölzusammensetzungen |
| US6059955A (en) | 1998-02-13 | 2000-05-09 | Exxon Research And Engineering Co. | Low viscosity lube basestock |
| US6008164A (en) | 1998-08-04 | 1999-12-28 | Exxon Research And Engineering Company | Lubricant base oil having improved oxidative stability |
| US6165949A (en) | 1998-09-04 | 2000-12-26 | Exxon Research And Engineering Company | Premium wear resistant lubricant |
| US6475960B1 (en) | 1998-09-04 | 2002-11-05 | Exxonmobil Research And Engineering Co. | Premium synthetic lubricants |
| US6103099A (en) | 1998-09-04 | 2000-08-15 | Exxon Research And Engineering Company | Production of synthetic lubricant and lubricant base stock without dewaxing |
| US6080301A (en) | 1998-09-04 | 2000-06-27 | Exxonmobil Research And Engineering Company | Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins |
| US6332974B1 (en) | 1998-09-11 | 2001-12-25 | Exxon Research And Engineering Co. | Wide-cut synthetic isoparaffinic lubricating oils |
| FR2798136B1 (fr) | 1999-09-08 | 2001-11-16 | Total Raffinage Distribution | Nouvelle huile de base hydrocarbonee pour lubrifiants a indice de viscosite tres eleve |
| US7067049B1 (en) | 2000-02-04 | 2006-06-27 | Exxonmobil Oil Corporation | Formulated lubricant oils containing high-performance base oils derived from highly paraffinic hydrocarbons |
| DE102005031244A1 (de) | 2005-07-01 | 2007-02-15 | Rohmax Additives Gmbh | Öllösliche Kammpolymere |
| MX2009013917A (es) | 2007-07-09 | 2010-03-10 | Evonik Rohmax Additives Gmbh | Uso de polímeros tipo peine para reducir el consumo de combustible. |
| DE102009001446A1 (de) | 2009-03-10 | 2010-09-23 | Evonik Rohmax Additives Gmbh | Verwendung von Kammpolymeren als Antifatigue-Additive |
| DE102009001447A1 (de) | 2009-03-10 | 2010-09-16 | Evonik Rohmax Additives Gmbh | Verwendung von Kammpolymeren zur Verbesserung des Lasttragevermögens |
| WO2013189951A1 (en) | 2012-06-21 | 2013-12-27 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
| JP6218924B2 (ja) | 2013-04-18 | 2017-10-25 | エボニック オイル アディティヴス ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｏｉｌ Ａｄｄｉｔｉｖｅｓ ＧｍｂＨ | 燃料消費量を減少させるためのギヤーオイル配合物 |
| MX2019002413A (es) * | 2016-08-31 | 2019-07-04 | Evonik Oil Additives Gmbh | Polimeros de tipo peine para mejorar la perdida de evaporacion de noack de formulaciones de aceite para motor. |
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| BR112020000774A2 (pt) | 2017-07-14 | 2020-07-14 | Evonik Operations Gmbh | polímero em pente à base de polialquil(met)acrilato enxertado, copolímero à base de polialquil(met)acrilato e seu uso, composição aditiva, método de redução do coeficiente de atrito de uma composição de óleo lubrificante, composição de óleo lubrificante e método de redução de atrito em um veículo automotivo |
| EP3450527B1 (de) * | 2017-09-04 | 2020-12-02 | Evonik Operations GmbH | Neue viskositätsindexverbesserer mit definierten molekulargewichtsverteilungen |
| JP6456468B1 (ja) * | 2017-12-13 | 2019-01-23 | エボニック オイル アディティヴス ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｖｏｎｉｋ Ｏｉｌ Ａｄｄｉｔｉｖｅｓ ＧｍｂＨ | 改善された低温粘度および剪断抵抗を有する粘度指数向上剤 |
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