CA3026812C - Lubricant spray polymers - Google Patents
Lubricant spray polymers Download PDFInfo
- Publication number
- CA3026812C CA3026812C CA3026812A CA3026812A CA3026812C CA 3026812 C CA3026812 C CA 3026812C CA 3026812 A CA3026812 A CA 3026812A CA 3026812 A CA3026812 A CA 3026812A CA 3026812 C CA3026812 C CA 3026812C
- Authority
- CA
- Canada
- Prior art keywords
- monomers
- copolymer
- methacrylate
- weight
- alkyl methacrylate
- 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.)
- Active
Links
- 239000000314 lubricant Substances 0.000 title description 30
- 229920000642 polymer Polymers 0.000 title description 21
- 239000007921 spray Substances 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims abstract description 166
- 229920001577 copolymer Polymers 0.000 claims abstract description 124
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 46
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims abstract description 30
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 54
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical group CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 238000000569 multi-angle light scattering Methods 0.000 claims description 8
- 229920005604 random copolymer Polymers 0.000 claims description 6
- 229920001400 block copolymer Polymers 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 32
- 229910052757 nitrogen Inorganic materials 0.000 description 32
- 239000003921 oil Substances 0.000 description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 25
- 238000010926 purge Methods 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 20
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 20
- 239000003999 initiator Substances 0.000 description 15
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 13
- 229960005055 sodium ascorbate Drugs 0.000 description 13
- 235000010378 sodium ascorbate Nutrition 0.000 description 12
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 12
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 210000003811 finger Anatomy 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- WVLDCUJMGWFHGE-UHFFFAOYSA-L iron(2+);sulfate;hexahydrate Chemical compound O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O WVLDCUJMGWFHGE-UHFFFAOYSA-L 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002199 base oil Substances 0.000 description 6
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 210000003813 thumb Anatomy 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 210000005224 forefinger Anatomy 0.000 description 3
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012966 redox initiator Substances 0.000 description 3
- 238000000518 rheometry Methods 0.000 description 3
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- RNAMYOYQYRYFQY-UHFFFAOYSA-N 2-(4,4-difluoropiperidin-1-yl)-6-methoxy-n-(1-propan-2-ylpiperidin-4-yl)-7-(3-pyrrolidin-1-ylpropoxy)quinazolin-4-amine Chemical compound N1=C(N2CCC(F)(F)CC2)N=C2C=C(OCCCN3CCCC3)C(OC)=CC2=C1NC1CCN(C(C)C)CC1 RNAMYOYQYRYFQY-UHFFFAOYSA-N 0.000 description 2
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000010710 diesel engine oil Substances 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical class [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 1
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- PSMAFHYZQLOGMG-MDZDMXLPSA-N 2-[(e)-2-aminopropan-2-yldiazenyl]propan-2-amine Chemical compound CC(C)(N)\N=N\C(C)(C)N PSMAFHYZQLOGMG-MDZDMXLPSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 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
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229940072107 ascorbate Drugs 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000010727 cylinder oil Substances 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- VYMDGNCVAMGZFE-UHFFFAOYSA-N phenylbutazonum Chemical compound O=C1C(CCCC)C(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 VYMDGNCVAMGZFE-UHFFFAOYSA-N 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 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
- 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
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
- C08F220/68—Esters
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10N2020/02—Viscosity; Viscosity index
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- 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
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- C10N2020/04—Molecular weight; Molecular weight distribution
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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Abstract
Disclosed are copolymers of alkyl methacrylate monomers wherein said alkyl methacrylate monomers comprise at least: a. Monomers (A) selected from C6-C10 alkyl methacrylate monomers, and b. Monomers (B) selected from C10-C18 alkyl methacrylate monomers, wherein the mass ratio of Monomers (B) in the copolymer to Monomers (A) in the copolymer is about 99:1 to about 60:40 by weight. In some cases, the copolymers are of lauryl methacrylate and C8alkyI methacrylate. Also disclosed are methods for the preparation of the copolymers.
Description
2 PCT/EP2017/064756 LUBRICANT SPRAY POLYMERS
Field of Invention [0001] This invention relates to a copolymer, its synthesis and methods of using it.
Technical Background [0002] The primary function of lubricants is to decrease friction.
Frequently, however, lubricating oils need additional properties to be used effectively.
For example, lubricants used in the crankcases of large diesel engines, such as, for example, marine diesel engines, are often subjected to operating conditions requiring special considerations.
Field of Invention [0001] This invention relates to a copolymer, its synthesis and methods of using it.
Technical Background [0002] The primary function of lubricants is to decrease friction.
Frequently, however, lubricating oils need additional properties to be used effectively.
For example, lubricants used in the crankcases of large diesel engines, such as, for example, marine diesel engines, are often subjected to operating conditions requiring special considerations.
[0003] Marine diesel engines may generally be classified as slow-speed, medium-speed, or high-speed engines, with the slow-speed variety being used for the largest, deep shaft marine vessels and certain other industrial applications. Slow-speed diesel engines are unique in size and method of operation. The larger units may approach 200 tons in weight and be upward of 10 feet wide and 45 feet high. The output of these engines can be as high as 100,000 horsepower with engine revolutions of 60 to about 200 revolutions per minute. They are typically of crosshead design and operate on a two-stroke cycle.
[0004] In large diesel engines of the crosshead type used in marine and heavy stationary applications, the piston cylinders are lubricated separately from the other engine components. The cylinders are lubricated on a total loss basis with the cylinder oil being injected separately into each cylinder by means of lubricators positioned around the cylinder liner. Oil is distributed to the lubricators by means of pumps, which are, in modern engine designs, actuated to apply the oil directly onto the rings to reduce oil wastage.
[0005] The unique design of these engines creates the need for lubricants with enhanced rheology properties. Because slow-speed engines run at a lower temperature than mid- or fast-speed engines, they are more prone to corrosion.
Accordingly, lubricants used in a marine engine must protect the engine parts from corrosion, especially rust. Rust is produced when ferrous metal engine components come in contact with water, which is typically produced by the internal combustion process or from external sources. Regardless of the source, rust and corrosion reduce engine efficiency and lifetime.
Accordingly, lubricants used in a marine engine must protect the engine parts from corrosion, especially rust. Rust is produced when ferrous metal engine components come in contact with water, which is typically produced by the internal combustion process or from external sources. Regardless of the source, rust and corrosion reduce engine efficiency and lifetime.
[0006] Also, the fuels commonly used in these diesel engines typically contain significant quantities of sulfur. During the combustion process, the sulfur can combine with water to form sulfuric acid, the presence of which leads to corrosive wear. In particular, in two-stroke engines for ships, areas around the cylinder liners and piston rings can be corroded and worn by the acid.
Therefore, it is important for diesel engine to resist such corrosion and wear by being properly lubricated.
Therefore, it is important for diesel engine to resist such corrosion and wear by being properly lubricated.
[0007] To prevent corrosion, the lubricant must be applied to the cylinder wall, typically by a pulse lubricating system or by spraying the lubricant onto the cylinder wall through an injector. In marine engines the lubricant is injected or sprayed on the cylinder liner and spread horizontally by the sprayer or injector and vertically by the piston rings when the piston is in its upward motion.
The lubricant is not used in a circulating system; when the excess lubricant comes to the bottom of cylinder it is discarded. Typically fresh lubricant is injected every four to eight strokes depending on the engine speed.
The lubricant is not used in a circulating system; when the excess lubricant comes to the bottom of cylinder it is discarded. Typically fresh lubricant is injected every four to eight strokes depending on the engine speed.
[0008] Thus, there is a need for a lubricant additive that will provide effective oxidation and corrosion resistance without posing the environmental hazards and cost of other oxidation and corrosion inhibitors. Additionally, because the lubricating oil is not circulated in marine engines, any rheology improvements that enhance lubricating efficacy or reduce the amount of oil used could significantly increase engine life and decrease costs.
SUMMARY
SUMMARY
[0009] We have found new copolymers that can modify the rheology of a marine lubricant to provide enhanced lubrication properties. In particular, marine engine lubricating oils comprising the copolymers of the disclosure as an additive surprisingly cover marine engine piston cylinder walls more completely than prior art oils (with or without additional additives), thereby leading to better lubrication and less engine cylinder wear and corrosion.
[0 0 1 0] We have also recognized that the method in which the copolymer is made can control the properties of the copolymer.
[0011] In a first aspect, the present disclosure provides a copolymer of alkyl methacrylate monomers wherein said alkyl methacrylate monomers comprise at least:
a. Monomers (A) selected from 06-010 alkyl methacrylate monomers, and b. Monomers (B) selected from 010-018 alkyl methacrylate monomers. The ratio of Monomers (B) in the copolymer to Monomers (A) in the copolymer is about 99:1 to about 10:90 by weight. In an embodiment, A is selected from 06-09 alkyl methacrylate monomers. In another embodiment, B is selected from 011-018 alkyl methacrylate monomers. In another embodiment, the ratio of Monomers (B) in the copolymer to Monomers (A) in the copolymer is about 99:1 to about 60:40 by weight.
[0012] In a second aspect, the present disclosure provides a copolymer obtained by combining at least Monomers (A) and Monomers (B) in a mixture and co-polymerizing the monomers, wherein the monomers are present in a mass ratio of about 99:1 to about 10:90, preferably about 99:1 to about 60:40, Monomers (B) to Monomers (A), and wherein Monomers (A) and Monomers (B) are distinct from one another.
[0013] In a third aspect, the present disclosure provides a method of making a copolymer as described above.
[0014] All publications referenced herein are incorporated by reference in their entirety to the extent they are not inconsistent with the teachings presented herein.
DETAILED DESCRIPTION
[0015] In the first aspect, the present disclosure provides a copolymer of alkyl methacrylate monomers wherein said alkyl methacrylate monomers comprise at least:
[0016] a. Monomers (A) selected from 06-010 alkyl methacrylate monomers, and b. Monomers (B) selected from 010-018 alkyl methacrylate monomers, wherein the mass ratio of Monomers (B) in the copolymer to Monomers (A) in the copolymer is about 99:1 to about 10:90, preferably 99:1 to 60:40, by weight.
[0017] The ratio of monomers in all aspects of the disclosure can be adjusted to manipulate the characteristics of the copolymer as desired. For example, the monomers can be present in ratios of Monomers (B) to Monomers (A) of 10:90, 15;85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, and 99:1. In one embodiment, the monomers are present in ratios of Monomers (B) to Monomers (A) of 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, and 99:1.
[0018] In some embodiments of all aspects of the disclosure, the Monomers (A) are linear or branched C8alkyl. In some embodiments, Monomers (A) are 2-ethylhexyl methacrylate.
[0019] In some embodiments of all aspects of the disclosure, the copolymer used in the lubricant composition according to the invention is prepared from a mixture of monomers that comprises at least two monomers: one monomer (A) and one monomer (B), distinct from one another. The monomers are preferably chosen from monomers which, when polymerized, form a copolymer that is soluble in liquid, preferably in oil, more preferably in marine diesel engine oil lubricants.
[0020] In another embodiment of all aspects of the disclosure, the copolymer is a copolymer of a mixture of monomers comprising at least: a 08 alkyl methacrylate, a 012 alkyl methacrylate, a 014 alkyl methacrylate, and a 016 alkyl methacrylate, and they are present in the mixture in weight ratio of:
- from 5 to 30 (:)/0 08 alkyl methacrylate, - from 40 to 70 (:)/0 012 alkyl methacrylate, - from 12 to 35 (:)/0 014 alkyl methacrylate, - from 1 to 12 (:)/0 016 alkyl methacrylate, -from 0.1 to 15 %, preferably from 0.5 to 10 %, more preferably from 1 to 5 (:)/0 other methacrylates, by weight with regard to the total weight of the mixture.
[0021] In another embodiment of all aspects of the disclosure, the copolymer is substantially free of monomers other than monomer (A) and monomer (B), particularly free of methacrylates having a 01-05 alkyl group, including, for example, methyl methacrylate. Monomers such as methyl methacrylate decrease the solubility of the resulting copolymer in oil, and the presence of such monomers are limited or omitted in some embodiments.
[0022] In another embodiment of all aspects of the disclosure, the copolymer is free of methacrylates other than monomer (A) and monomer (B), particularly methacrylates having a C1-05 alkyl group, including, for example, methyl methacrylate.
[0023] Typically, copolymers according to the disclosure have an average Root Mean Square Radius of Gyration (Rg) as measured by Hydrodynamic Column Chromotography-Multi Angle Light Scattering (HCC-MALS) from about 100 to about 200 (nm) Rg, from about 120 to about 190 (nm), from about 130 to 180, or from about 140 to about 170 (nm) Rg.
[0024] In the second aspect, the copolymer is obtained by combining at least Monomers (B) and Monomers (A) in a mixture and co-polymerizing the monomers, wherein the monomers are present in a mass ratio of about 99:1 to about 10:90 Monomers (B) to Monomers (A).
[0025] The copolymer may be synthesized by conventional methods for vinyl addition polymerization known to those skilled in the art, such as, but not limited to, solution polymerization, precipitation polymerization, and dispersion polymerizations, including suspension polymerization and emulsion polymerization.
[0026] In some embodiments, the polymer is formed by suspension polymerization, wherein monomers that are insoluble in water or poorly soluble in water are suspended as droplets in water. The monomer droplet suspension is maintained by mechanical agitation and the addition of stabilizers. Surface active polymers such as cellulose ethers, poly(vinyl alcohol-co-vinyl acetate), poly(vinyl pyrrolidone) and alkali metal salts of (meth)acrylic acid containing polymers and colloidal (water insoluble) inorganic powders such as tricalcium phosphate, hydroxyapatite, barium sulfate, kaolin, and magnesium silicates can be used as stabilizers. In addition, small amounts of surfactants such as sodium dodecylbenzene sulfonate can be used together with the stabilizer(s).
Polymerization is initiated using an oil soluble initiator. Suitable initiators include peroxides such as benzoyl peroxide, peroxy esters such as tert-butylperoxy-2-ethylhexanoate, and azo compounds such as 2,2'-azobis(2-methylbutyronitrile).
At the completion of the polymerization, solid polymer product can be separated .. from the reaction medium by filtration and washed with water, acid, base, or solvent to remove unreacted monomer or free stabilizer.
[0027] In other embodiments the polymer is formed by emulsion polymerization, one or more monomers are dispersed in an aqueous phase and polymerization is initiated using a water soluble initiator. The monomers are io .. typically water insoluble or very poorly soluble in water, and a surfactant or soap is used to stabilize the monomer droplets in the aqueous phase. Polymerization occurs in the swollen micelles and latex particles. Other ingredients that might be present in an emulsion polymerization include chain transfer agents such as mercaptans (e.g. dodecyl mercaptan) to control molecular weight, electrolytes to control pH, and small amounts of organic solvent, preferably water soluble organic solvents, including but not limited to acetone, b-butanone, methanol, ethanol, and isopropanol, to adjust the polarity of the aqueous phase.
Suitable initiators include alkali metal or ammonium salts of persulfate such as ammonium persulfate, water-soluble azo compounds such as 2,2'-azobis(2-aminopropane)dihydrochloride, and redox systems such as Fe(II) and cumene hydroperoxide, and tert-butyl hydroperoxide-Fe(II)-sodium ascorbate. Suitable surfactants include anionic surfactants such as fatty acid soaps (e.g. sodium or potassium stearate), sulfates and sulfonates (e.g. sodium dodecyl 20 benzene sulfonate), sulfosuccinates (e.g. dioctyl sodium sulfosuccinate); non-ionic surfactants such as octylphenol ethoxylates and linear and branched alcohol ethoxylates; cationic surfactants such as cetyl trimethyl ammonium chloride;
and amphoteric surfactants. Anionic surfactants and combinations of anionic surfactants and non-ionic surfactants are most commonly used. Polymeric stabilizers such as poly(vinyl alcohol-co-vinyl acetate) can also be used as surfactants. The solid polymer product free of the aqueous medium can be obtained by a number of processes including destabilization/coagulation of the final emulsion followed by filtration, solvent precipitation of the polymer from latex, or spray drying of the latex.
[0028] The polymer can be isolated by conventional methods known to those skilled in the art, such as, but not limited to, solvent exchange, evaporation of solvent, spray drying and freeze-drying.
[0029] The characteristics of the copolymer obtained by combining at least Monomers (A) and Monomers (B) in a mixture and co-polymerizing can be manipulated by controlling the additional reagents added to the polymerization mixture. These reagents include, but are not limited to, initiator systems and surfactants.
[0030] The type and amount initiator system used in the polymerization mixture can influence the properties of the resulting copolymer. An initiator system can be a single initiator compound (e.g., a persulfate salt) or a mixture of two or more components (e.g., hydrogen peroxide and sodium ascorbate). In some examples, the initiator system can include an oxidant, reductant, and optionally a metal salt. The oxidant can be a persulfate, such as, for example, ammonium persulfate, or a peroxide, such as, for example, hydrogen peroxide (H202) or tert-butyl hydroperoxide (TBHP). A desirable copolymer may be obtained, for example, when the polymerization mixture includes tert-butyl hydroperoxide in about 0.01 to about 0.06 mass percent of all monomers in the mixture. In other examples, the mixture may include tert-butyl hydroperoxide in about 0.01 to about 0.03 mass percent of the monomers in the mixture. In some examples, the mixture further comprises tert-butyl hydroperoxide in about 0.013 mass percent of the monomers in the mixture. Useful initiators for the copolymers of the present disclosure include any conventional initiator, including any conventional redox initiator.
[0031] In some embodiments the reductant of the redox initiator system can be ascorbic acid or a salt thereof. For example, the polymerization mixture can include sodium ascorbate in about 0.04 to about 0.1 mass percent of the monomers in the mixture. In other examples, the sodium ascorbate may be present in about 0.08 to about 0.1 mass percent of the monomers in the mixture.
In some embodiments, the polymerization mixture includes sodium ascorbate in about 0.098 mass percent of the monomers in the mixture.
[0032] The initiator system may also include a metal salt. The metal may be any suitable transition metal, such as, for example, iron. In some embodiments, the metal salt of the initiator system can be ferrous sulfate (FeSO4). In some embodiments, the metal salt is present in the polymerization mixture in about 0.0005 to about 0.1 mass percent of the monomers in the mixture. In some examples, the metal salt is added to the polymerization mixture as a solution.
[0033] The copolymer may also be obtained for a polymerization mixture further including a surfactant. In some embodiments, the surfactant may contain a sulfonate group. For example, the surfactant may include a dialkyl sulfosuccinate, such as, for example, dioctyl sulfosuccinate sodium salt. In some examples, the surfactant may be Aerosol OT.
[0034] The copolymer can be a random copolymer, block copolymer, or mixture thereof. In some embodiments, the copolymer is a substantially random copolymer (e.g., greater than 90, 95, 98, or 99 mass percent). In other examples, the copolymer is a partially a random copolymer and partially a block copolymer. In these examples the weight percent ratio of random copolymer to block copolymer is generally 90:10, 80:20, 70: 30, 60:40, 50:50, 40:60, 30:70;
20:80 or 10:90. The copolymer may also be a substantially block copolymer (e.g., greater than 90, 95, 98, or 99 weight percent). In other examples, the copolymer can contain additional monomers in addition to Monomers (A) and Monomers (B) discussed. These additional monomers can be present in an amount less than 10 weight percent. In some embodiments, the additional monomers are present in an amount from about 0.5 to 10 weight percent, or about 1 to 10 weight percent or about 1 to 5 weight percent or about 5 to 10 weight percent. In other embodiments, the additional monomers are present in an amount less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or about 0.5 weight percent. The additional monomers can include, for example, cross-linking monomers, acrylate, styrene, C1-C3alkyl methacrylate and other similar monomers.
[0035] The copolymer may also be crosslinked. That is, the copolymer can contain monomeric units that connect one or more of the backbone chains of the polymer. In some examples, the copolymer contains crosslinked monomeric units present in up to about 5% by weight of the copolymer. In other .. embodiments, the copolymer is not crosslinked, or uncrosslinked, and is substantially free of monomers that function as a crosslinking agent. In other embodiments, the monomer mixture to make the copolymer is substantially free of crosslinking agents.
[0036] The crosslinked copolymer may be obtained when the polymerization mixture includes a crosslinking agent. In some embodiments, the crosslinking agent is a diacrylate or dimethacrylate crosslinking agent, such as, for example, 1,6-hexanediol dimethacrylate. In some examples, the mixture includes a crosslinking agent in up to about 0.005 mass percent of the monomers in the mixture.
[0037] Example copolymers are shown in Tables 1 and 2. For each example, Table 1 shows the ratio of Monomers (B) to Monomers (A) (e.g., 2-ethylhexyl methacrylate), and the amount of acetone, the components of the redox initiator system and surfactant used. Table 2 shows the molecular weight, Rg and viscosity of each example copolymer.
[0038] In a third aspect, a method of making a copolymer as described above is disclosed. The method includes the polymerization of Monomers (A) and a Monomers (B), wherein the mass ratio of Monomers (B) in the copolymer to Monomers (A) in the copolymer is about 99:1 to about 10:90 by weight (e.g.,
[0 0 1 0] We have also recognized that the method in which the copolymer is made can control the properties of the copolymer.
[0011] In a first aspect, the present disclosure provides a copolymer of alkyl methacrylate monomers wherein said alkyl methacrylate monomers comprise at least:
a. Monomers (A) selected from 06-010 alkyl methacrylate monomers, and b. Monomers (B) selected from 010-018 alkyl methacrylate monomers. The ratio of Monomers (B) in the copolymer to Monomers (A) in the copolymer is about 99:1 to about 10:90 by weight. In an embodiment, A is selected from 06-09 alkyl methacrylate monomers. In another embodiment, B is selected from 011-018 alkyl methacrylate monomers. In another embodiment, the ratio of Monomers (B) in the copolymer to Monomers (A) in the copolymer is about 99:1 to about 60:40 by weight.
[0012] In a second aspect, the present disclosure provides a copolymer obtained by combining at least Monomers (A) and Monomers (B) in a mixture and co-polymerizing the monomers, wherein the monomers are present in a mass ratio of about 99:1 to about 10:90, preferably about 99:1 to about 60:40, Monomers (B) to Monomers (A), and wherein Monomers (A) and Monomers (B) are distinct from one another.
[0013] In a third aspect, the present disclosure provides a method of making a copolymer as described above.
[0014] All publications referenced herein are incorporated by reference in their entirety to the extent they are not inconsistent with the teachings presented herein.
DETAILED DESCRIPTION
[0015] In the first aspect, the present disclosure provides a copolymer of alkyl methacrylate monomers wherein said alkyl methacrylate monomers comprise at least:
[0016] a. Monomers (A) selected from 06-010 alkyl methacrylate monomers, and b. Monomers (B) selected from 010-018 alkyl methacrylate monomers, wherein the mass ratio of Monomers (B) in the copolymer to Monomers (A) in the copolymer is about 99:1 to about 10:90, preferably 99:1 to 60:40, by weight.
[0017] The ratio of monomers in all aspects of the disclosure can be adjusted to manipulate the characteristics of the copolymer as desired. For example, the monomers can be present in ratios of Monomers (B) to Monomers (A) of 10:90, 15;85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, and 99:1. In one embodiment, the monomers are present in ratios of Monomers (B) to Monomers (A) of 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, and 99:1.
[0018] In some embodiments of all aspects of the disclosure, the Monomers (A) are linear or branched C8alkyl. In some embodiments, Monomers (A) are 2-ethylhexyl methacrylate.
[0019] In some embodiments of all aspects of the disclosure, the copolymer used in the lubricant composition according to the invention is prepared from a mixture of monomers that comprises at least two monomers: one monomer (A) and one monomer (B), distinct from one another. The monomers are preferably chosen from monomers which, when polymerized, form a copolymer that is soluble in liquid, preferably in oil, more preferably in marine diesel engine oil lubricants.
[0020] In another embodiment of all aspects of the disclosure, the copolymer is a copolymer of a mixture of monomers comprising at least: a 08 alkyl methacrylate, a 012 alkyl methacrylate, a 014 alkyl methacrylate, and a 016 alkyl methacrylate, and they are present in the mixture in weight ratio of:
- from 5 to 30 (:)/0 08 alkyl methacrylate, - from 40 to 70 (:)/0 012 alkyl methacrylate, - from 12 to 35 (:)/0 014 alkyl methacrylate, - from 1 to 12 (:)/0 016 alkyl methacrylate, -from 0.1 to 15 %, preferably from 0.5 to 10 %, more preferably from 1 to 5 (:)/0 other methacrylates, by weight with regard to the total weight of the mixture.
[0021] In another embodiment of all aspects of the disclosure, the copolymer is substantially free of monomers other than monomer (A) and monomer (B), particularly free of methacrylates having a 01-05 alkyl group, including, for example, methyl methacrylate. Monomers such as methyl methacrylate decrease the solubility of the resulting copolymer in oil, and the presence of such monomers are limited or omitted in some embodiments.
[0022] In another embodiment of all aspects of the disclosure, the copolymer is free of methacrylates other than monomer (A) and monomer (B), particularly methacrylates having a C1-05 alkyl group, including, for example, methyl methacrylate.
[0023] Typically, copolymers according to the disclosure have an average Root Mean Square Radius of Gyration (Rg) as measured by Hydrodynamic Column Chromotography-Multi Angle Light Scattering (HCC-MALS) from about 100 to about 200 (nm) Rg, from about 120 to about 190 (nm), from about 130 to 180, or from about 140 to about 170 (nm) Rg.
[0024] In the second aspect, the copolymer is obtained by combining at least Monomers (B) and Monomers (A) in a mixture and co-polymerizing the monomers, wherein the monomers are present in a mass ratio of about 99:1 to about 10:90 Monomers (B) to Monomers (A).
[0025] The copolymer may be synthesized by conventional methods for vinyl addition polymerization known to those skilled in the art, such as, but not limited to, solution polymerization, precipitation polymerization, and dispersion polymerizations, including suspension polymerization and emulsion polymerization.
[0026] In some embodiments, the polymer is formed by suspension polymerization, wherein monomers that are insoluble in water or poorly soluble in water are suspended as droplets in water. The monomer droplet suspension is maintained by mechanical agitation and the addition of stabilizers. Surface active polymers such as cellulose ethers, poly(vinyl alcohol-co-vinyl acetate), poly(vinyl pyrrolidone) and alkali metal salts of (meth)acrylic acid containing polymers and colloidal (water insoluble) inorganic powders such as tricalcium phosphate, hydroxyapatite, barium sulfate, kaolin, and magnesium silicates can be used as stabilizers. In addition, small amounts of surfactants such as sodium dodecylbenzene sulfonate can be used together with the stabilizer(s).
Polymerization is initiated using an oil soluble initiator. Suitable initiators include peroxides such as benzoyl peroxide, peroxy esters such as tert-butylperoxy-2-ethylhexanoate, and azo compounds such as 2,2'-azobis(2-methylbutyronitrile).
At the completion of the polymerization, solid polymer product can be separated .. from the reaction medium by filtration and washed with water, acid, base, or solvent to remove unreacted monomer or free stabilizer.
[0027] In other embodiments the polymer is formed by emulsion polymerization, one or more monomers are dispersed in an aqueous phase and polymerization is initiated using a water soluble initiator. The monomers are io .. typically water insoluble or very poorly soluble in water, and a surfactant or soap is used to stabilize the monomer droplets in the aqueous phase. Polymerization occurs in the swollen micelles and latex particles. Other ingredients that might be present in an emulsion polymerization include chain transfer agents such as mercaptans (e.g. dodecyl mercaptan) to control molecular weight, electrolytes to control pH, and small amounts of organic solvent, preferably water soluble organic solvents, including but not limited to acetone, b-butanone, methanol, ethanol, and isopropanol, to adjust the polarity of the aqueous phase.
Suitable initiators include alkali metal or ammonium salts of persulfate such as ammonium persulfate, water-soluble azo compounds such as 2,2'-azobis(2-aminopropane)dihydrochloride, and redox systems such as Fe(II) and cumene hydroperoxide, and tert-butyl hydroperoxide-Fe(II)-sodium ascorbate. Suitable surfactants include anionic surfactants such as fatty acid soaps (e.g. sodium or potassium stearate), sulfates and sulfonates (e.g. sodium dodecyl 20 benzene sulfonate), sulfosuccinates (e.g. dioctyl sodium sulfosuccinate); non-ionic surfactants such as octylphenol ethoxylates and linear and branched alcohol ethoxylates; cationic surfactants such as cetyl trimethyl ammonium chloride;
and amphoteric surfactants. Anionic surfactants and combinations of anionic surfactants and non-ionic surfactants are most commonly used. Polymeric stabilizers such as poly(vinyl alcohol-co-vinyl acetate) can also be used as surfactants. The solid polymer product free of the aqueous medium can be obtained by a number of processes including destabilization/coagulation of the final emulsion followed by filtration, solvent precipitation of the polymer from latex, or spray drying of the latex.
[0028] The polymer can be isolated by conventional methods known to those skilled in the art, such as, but not limited to, solvent exchange, evaporation of solvent, spray drying and freeze-drying.
[0029] The characteristics of the copolymer obtained by combining at least Monomers (A) and Monomers (B) in a mixture and co-polymerizing can be manipulated by controlling the additional reagents added to the polymerization mixture. These reagents include, but are not limited to, initiator systems and surfactants.
[0030] The type and amount initiator system used in the polymerization mixture can influence the properties of the resulting copolymer. An initiator system can be a single initiator compound (e.g., a persulfate salt) or a mixture of two or more components (e.g., hydrogen peroxide and sodium ascorbate). In some examples, the initiator system can include an oxidant, reductant, and optionally a metal salt. The oxidant can be a persulfate, such as, for example, ammonium persulfate, or a peroxide, such as, for example, hydrogen peroxide (H202) or tert-butyl hydroperoxide (TBHP). A desirable copolymer may be obtained, for example, when the polymerization mixture includes tert-butyl hydroperoxide in about 0.01 to about 0.06 mass percent of all monomers in the mixture. In other examples, the mixture may include tert-butyl hydroperoxide in about 0.01 to about 0.03 mass percent of the monomers in the mixture. In some examples, the mixture further comprises tert-butyl hydroperoxide in about 0.013 mass percent of the monomers in the mixture. Useful initiators for the copolymers of the present disclosure include any conventional initiator, including any conventional redox initiator.
[0031] In some embodiments the reductant of the redox initiator system can be ascorbic acid or a salt thereof. For example, the polymerization mixture can include sodium ascorbate in about 0.04 to about 0.1 mass percent of the monomers in the mixture. In other examples, the sodium ascorbate may be present in about 0.08 to about 0.1 mass percent of the monomers in the mixture.
In some embodiments, the polymerization mixture includes sodium ascorbate in about 0.098 mass percent of the monomers in the mixture.
[0032] The initiator system may also include a metal salt. The metal may be any suitable transition metal, such as, for example, iron. In some embodiments, the metal salt of the initiator system can be ferrous sulfate (FeSO4). In some embodiments, the metal salt is present in the polymerization mixture in about 0.0005 to about 0.1 mass percent of the monomers in the mixture. In some examples, the metal salt is added to the polymerization mixture as a solution.
[0033] The copolymer may also be obtained for a polymerization mixture further including a surfactant. In some embodiments, the surfactant may contain a sulfonate group. For example, the surfactant may include a dialkyl sulfosuccinate, such as, for example, dioctyl sulfosuccinate sodium salt. In some examples, the surfactant may be Aerosol OT.
[0034] The copolymer can be a random copolymer, block copolymer, or mixture thereof. In some embodiments, the copolymer is a substantially random copolymer (e.g., greater than 90, 95, 98, or 99 mass percent). In other examples, the copolymer is a partially a random copolymer and partially a block copolymer. In these examples the weight percent ratio of random copolymer to block copolymer is generally 90:10, 80:20, 70: 30, 60:40, 50:50, 40:60, 30:70;
20:80 or 10:90. The copolymer may also be a substantially block copolymer (e.g., greater than 90, 95, 98, or 99 weight percent). In other examples, the copolymer can contain additional monomers in addition to Monomers (A) and Monomers (B) discussed. These additional monomers can be present in an amount less than 10 weight percent. In some embodiments, the additional monomers are present in an amount from about 0.5 to 10 weight percent, or about 1 to 10 weight percent or about 1 to 5 weight percent or about 5 to 10 weight percent. In other embodiments, the additional monomers are present in an amount less than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or about 0.5 weight percent. The additional monomers can include, for example, cross-linking monomers, acrylate, styrene, C1-C3alkyl methacrylate and other similar monomers.
[0035] The copolymer may also be crosslinked. That is, the copolymer can contain monomeric units that connect one or more of the backbone chains of the polymer. In some examples, the copolymer contains crosslinked monomeric units present in up to about 5% by weight of the copolymer. In other .. embodiments, the copolymer is not crosslinked, or uncrosslinked, and is substantially free of monomers that function as a crosslinking agent. In other embodiments, the monomer mixture to make the copolymer is substantially free of crosslinking agents.
[0036] The crosslinked copolymer may be obtained when the polymerization mixture includes a crosslinking agent. In some embodiments, the crosslinking agent is a diacrylate or dimethacrylate crosslinking agent, such as, for example, 1,6-hexanediol dimethacrylate. In some examples, the mixture includes a crosslinking agent in up to about 0.005 mass percent of the monomers in the mixture.
[0037] Example copolymers are shown in Tables 1 and 2. For each example, Table 1 shows the ratio of Monomers (B) to Monomers (A) (e.g., 2-ethylhexyl methacrylate), and the amount of acetone, the components of the redox initiator system and surfactant used. Table 2 shows the molecular weight, Rg and viscosity of each example copolymer.
[0038] In a third aspect, a method of making a copolymer as described above is disclosed. The method includes the polymerization of Monomers (A) and a Monomers (B), wherein the mass ratio of Monomers (B) in the copolymer to Monomers (A) in the copolymer is about 99:1 to about 10:90 by weight (e.g.,
10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, 99:1).
[0039] In some embodiments, the method includes: combining Monomers (B) and Monomers (A) in a ratio of about 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, 99:1 and initiating the polymerization of the monomers to provide a copolymer.
[0040] In some embodiments, the ratio of monomers and the initiator, or initiator system, can be selected as described above. The method may include further components to provide a copolymer with desirable properties. For example, the method may include a surfactant, such as, for example, Aerosol OT, or a crosslinker, such as, for example, 1,6-hexanediol dimethacrylate.
[0041] Polymerization can occur in an aqueous mixture or a mixture that comprises both aqueous and organic solvents. For example, the polymerization mixture can include a mixture of water and acetone. In some embodiments the polymerization mixture may require an organic solvent. Often it will be desirable to include an organic solvent when lauryl methacrylate is in the polymerization mixture. Organic solvents for use in such polymerization reactions are known io and routinely selectable by those of ordinary skill in the field of polymer synthesis. Suitable organic solvents include, for example and without limitation, acetone, 2-butanone, methanol, ethanol, and isopropanol.
[0042] The copolymer of the first or second aspect can be present in the oil in an amount from about 0.5% to about 25% by weight. Depending on the oil used the, the copolymer may be present in the oil in an amount from about 1`)/0 to about 25.
[0043] The oil may be selected from those known in the art, and may be a mineral oil, i.e., those obtained from the processing of crude oil, or a synthetic oil, i.e., an artificially made oil typically containing polyglycols or esters, or a semi-synthetic oil, i.e., a blend of mineral and synthetic oils. In some embodiments, the oil is a mineral base oil, i.e., a complex mixture of paraffins, naphthenes, and aromatics. In some examples, the oil may be a paraffinic base oil, such as 150 Neutral Solvent, 600 Solvent Neutral or a bright stock. The oil composition may include further components, particularly those used in marine diesel engine oil lubricants.
[0044] A test measuring the enhanced lubrication properties and usability of oil containing a copolymer of the first or second aspect was undertaken under the following conditions. The oil/polymer compositions were examined for performance/suitability as a lubricant by a finger pull test, which is performed by pipetting a droplet of sample fluid (about 65p1) onto the thumb of a gloved hand.
The thumb and forefinger are gently squeezed together to ensure contact of the droplet with both fingers, and then the fingers are pulled apart vertically for about 1 second over a distance of about 7.5 cm., while observing the amount of time the composition provides a fluid connection between the thumb and forefinger once the fingers are moved apart. All finger pull tests were performed at ambient temperature, about 21 C. The performance of the sample was characterized as "very short," "short," "medium," "long," or "very long"
depending upon the duration that the sample provided a fluid connection between thumb and forefinger remain . Compositions with "very short" performance in the finger pull test being less than 1 second, "short" ranging from 1-4 seconds, "medium"
ranging from 4-7 seconds, "long" ranging from 7-60 seconds, and "very long"
describing the situation where the composition remains connected to both fingers indefinitely . Compositions with "very short" and "very long" textures do not exhibit enhanced suitability or performance as a lubricant. Compositions with "short," "medium," or "long" textures exhibit improved suitability as a lubricant to varying degrees because, for example, their ability to effectively .. spread on the cylinder wall of the engine being lubricated is enhanced.
Compositions with "long" texture have particularly good suitability as a lubricant.
The results of the finger pull test are shown in Table 2.
[0045] One advantage of the copolymers disclosed herein is that they can be used to enhance the performance of an oil as a lubricant, while at the same .. time maintaining the ability to handle the oil in a manner necessary for use in the field. For example, many lubricants are pumped via a fluid pump, and therefore the lubricant should have an appropriate viscosity to allow it to be pumped without creating mechanical complications or damage to the pumping equipment. A lubricant with improper viscosity (particularly a viscosity that is .. too high) can prevent the lubricant from being pumped properly, or otherwise require the exertion of much higher power to pump the lubricant. The polymers disclosed herein maintain the balance between enhancing lubricant oil performance while at the same time maintaining the viscosity at a sufficient level to allow for efficient handling in the field. It has been unexpectedly discovered that the combination of Monomer B homopolymer with oil also provides enhanced lubricant performance at a viscosity that allows for efficient handling. The combination of oil with a copolymer having a 5:95 Monomer B to
[0039] In some embodiments, the method includes: combining Monomers (B) and Monomers (A) in a ratio of about 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10, 95:5, 99:1 and initiating the polymerization of the monomers to provide a copolymer.
[0040] In some embodiments, the ratio of monomers and the initiator, or initiator system, can be selected as described above. The method may include further components to provide a copolymer with desirable properties. For example, the method may include a surfactant, such as, for example, Aerosol OT, or a crosslinker, such as, for example, 1,6-hexanediol dimethacrylate.
[0041] Polymerization can occur in an aqueous mixture or a mixture that comprises both aqueous and organic solvents. For example, the polymerization mixture can include a mixture of water and acetone. In some embodiments the polymerization mixture may require an organic solvent. Often it will be desirable to include an organic solvent when lauryl methacrylate is in the polymerization mixture. Organic solvents for use in such polymerization reactions are known io and routinely selectable by those of ordinary skill in the field of polymer synthesis. Suitable organic solvents include, for example and without limitation, acetone, 2-butanone, methanol, ethanol, and isopropanol.
[0042] The copolymer of the first or second aspect can be present in the oil in an amount from about 0.5% to about 25% by weight. Depending on the oil used the, the copolymer may be present in the oil in an amount from about 1`)/0 to about 25.
[0043] The oil may be selected from those known in the art, and may be a mineral oil, i.e., those obtained from the processing of crude oil, or a synthetic oil, i.e., an artificially made oil typically containing polyglycols or esters, or a semi-synthetic oil, i.e., a blend of mineral and synthetic oils. In some embodiments, the oil is a mineral base oil, i.e., a complex mixture of paraffins, naphthenes, and aromatics. In some examples, the oil may be a paraffinic base oil, such as 150 Neutral Solvent, 600 Solvent Neutral or a bright stock. The oil composition may include further components, particularly those used in marine diesel engine oil lubricants.
[0044] A test measuring the enhanced lubrication properties and usability of oil containing a copolymer of the first or second aspect was undertaken under the following conditions. The oil/polymer compositions were examined for performance/suitability as a lubricant by a finger pull test, which is performed by pipetting a droplet of sample fluid (about 65p1) onto the thumb of a gloved hand.
The thumb and forefinger are gently squeezed together to ensure contact of the droplet with both fingers, and then the fingers are pulled apart vertically for about 1 second over a distance of about 7.5 cm., while observing the amount of time the composition provides a fluid connection between the thumb and forefinger once the fingers are moved apart. All finger pull tests were performed at ambient temperature, about 21 C. The performance of the sample was characterized as "very short," "short," "medium," "long," or "very long"
depending upon the duration that the sample provided a fluid connection between thumb and forefinger remain . Compositions with "very short" performance in the finger pull test being less than 1 second, "short" ranging from 1-4 seconds, "medium"
ranging from 4-7 seconds, "long" ranging from 7-60 seconds, and "very long"
describing the situation where the composition remains connected to both fingers indefinitely . Compositions with "very short" and "very long" textures do not exhibit enhanced suitability or performance as a lubricant. Compositions with "short," "medium," or "long" textures exhibit improved suitability as a lubricant to varying degrees because, for example, their ability to effectively .. spread on the cylinder wall of the engine being lubricated is enhanced.
Compositions with "long" texture have particularly good suitability as a lubricant.
The results of the finger pull test are shown in Table 2.
[0045] One advantage of the copolymers disclosed herein is that they can be used to enhance the performance of an oil as a lubricant, while at the same .. time maintaining the ability to handle the oil in a manner necessary for use in the field. For example, many lubricants are pumped via a fluid pump, and therefore the lubricant should have an appropriate viscosity to allow it to be pumped without creating mechanical complications or damage to the pumping equipment. A lubricant with improper viscosity (particularly a viscosity that is .. too high) can prevent the lubricant from being pumped properly, or otherwise require the exertion of much higher power to pump the lubricant. The polymers disclosed herein maintain the balance between enhancing lubricant oil performance while at the same time maintaining the viscosity at a sufficient level to allow for efficient handling in the field. It has been unexpectedly discovered that the combination of Monomer B homopolymer with oil also provides enhanced lubricant performance at a viscosity that allows for efficient handling. The combination of oil with a copolymer having a 5:95 Monomer B to
11 Monomer A ratio results in a substance having a viscosity and other physical handling properties that prevent this composition from being efficiently handled in the field.
[0046] In an embodiment the polymers have a molecular weight >20000 D.
[0047] In an embodiment the polymers have a bimodal molecular weight distribution.
[0048] Copolymers having a molecular weight (Mw), average root mean square radius of gyration (Rg) and viscosity correlation in a certain range are particularly suitable as an oil additive to enhance the performance of oil as a lo lubricant while maintaining the ability to handle and pump the oil. A
preferred correlation of a bimodal Mw, Rg and viscosity values for one embodiment of the copolymers disclosed herein is represented by the following formula:
Performance X = 1139.69418+(2.54756* Peak 1 Mw)-(0.91396* Peak 1 Rg)-(66.18535* Peak 2 Mw)-(0.23020* Viscosity+1.18947E-003* Peak 1 Rg) *(Viscosity), where the units for Mw is 106 g/mol, Rg is nm, and Viscosity is mPa.s, as set forth in Table 2. A performance X value between 500 and 900, more preferably between 550 and 800, and most preferably between 600 and 750 is indicative of a copolymer having properties that are particularly suitable to enhance the performance of oil as a lubricant.
Definitions [0049] As used herein, lauryl methacrylate is dodecyl methacrylate (012;
CAS 142-90-5) or a mixture of 014-16alkyl methacrylates including dodecyl methacrylate. That is, lauryl methacrylate may include a mixture of which dodecyl methacrylate is a component, but which also includes one or more other C14_16alkyl methacrylates such as tetradecyl methacrylate (014; CAS 2549-53-3) and hexdecyl methacrylate (016; CAS 2495-27-4). For example, the lauryl methacrylate could be a mixture of about 40-70 weight percent dodecyl methacrylate, 15-40 weight percent tetradecyl methacrylate, and 4-10 weight
[0046] In an embodiment the polymers have a molecular weight >20000 D.
[0047] In an embodiment the polymers have a bimodal molecular weight distribution.
[0048] Copolymers having a molecular weight (Mw), average root mean square radius of gyration (Rg) and viscosity correlation in a certain range are particularly suitable as an oil additive to enhance the performance of oil as a lo lubricant while maintaining the ability to handle and pump the oil. A
preferred correlation of a bimodal Mw, Rg and viscosity values for one embodiment of the copolymers disclosed herein is represented by the following formula:
Performance X = 1139.69418+(2.54756* Peak 1 Mw)-(0.91396* Peak 1 Rg)-(66.18535* Peak 2 Mw)-(0.23020* Viscosity+1.18947E-003* Peak 1 Rg) *(Viscosity), where the units for Mw is 106 g/mol, Rg is nm, and Viscosity is mPa.s, as set forth in Table 2. A performance X value between 500 and 900, more preferably between 550 and 800, and most preferably between 600 and 750 is indicative of a copolymer having properties that are particularly suitable to enhance the performance of oil as a lubricant.
Definitions [0049] As used herein, lauryl methacrylate is dodecyl methacrylate (012;
CAS 142-90-5) or a mixture of 014-16alkyl methacrylates including dodecyl methacrylate. That is, lauryl methacrylate may include a mixture of which dodecyl methacrylate is a component, but which also includes one or more other C14_16alkyl methacrylates such as tetradecyl methacrylate (014; CAS 2549-53-3) and hexdecyl methacrylate (016; CAS 2495-27-4). For example, the lauryl methacrylate could be a mixture of about 40-70 weight percent dodecyl methacrylate, 15-40 weight percent tetradecyl methacrylate, and 4-10 weight
12 percent hexdecyl methacrylate, such as commercially available methacrylic ester 13.0 (Evonik trade name: VISIOMERO Terra 013,0-MA).
[0050] As used herein, the term "about" refers to the given value 10 (:)/0 of the value.
[0051] As used herein, the term "08a1ky1" refers to a group comprised of eight saturated carbon atoms connected in a linear or branched configuration.
Examples of linear 08a1ky1 groups include n-octyl. Examples of branched 08a1ky1 groups include, but are not limited, to 2-ethylhexyl.
[0052] As used herein, the term "alkyl methacrylate" refers to compounds io wherein a methacrylol radical is bonded to a linear or branched, saturated or unsaturated alkyl group.
[0053] As used herein, the term "substantially free of monomers" means that there is no more than 3.0 (:)/0 by weight of the copolymer, preferably no more than 1.0% by weight, and more preferably no more than 0.5% by weight of the monomer present in the copolymer.
[0054] As used herein, the term "substantially free of crosslinking agents"
means that there is no more than 1.0 (:)/0 by weight of the copolymer, preferably no more than 0.5% by weight, of monomeric units that connect two or more of the backbone chains of the polymer.
[0055] It is noted that any embodiment disclosed herein can be combined with any other embodiment with the result being subject matter in accordance with the invention.
[0056] It is noted that, unless use differently, " /0" means percent by weight.
Examples [0057] Lauryl methacrylate as used in Examples 1-8 was provided as methacrylic ester 13.0, which is commercially available as VISIOMER Terra 013,0-MA from Evonik Industries.
[0050] As used herein, the term "about" refers to the given value 10 (:)/0 of the value.
[0051] As used herein, the term "08a1ky1" refers to a group comprised of eight saturated carbon atoms connected in a linear or branched configuration.
Examples of linear 08a1ky1 groups include n-octyl. Examples of branched 08a1ky1 groups include, but are not limited, to 2-ethylhexyl.
[0052] As used herein, the term "alkyl methacrylate" refers to compounds io wherein a methacrylol radical is bonded to a linear or branched, saturated or unsaturated alkyl group.
[0053] As used herein, the term "substantially free of monomers" means that there is no more than 3.0 (:)/0 by weight of the copolymer, preferably no more than 1.0% by weight, and more preferably no more than 0.5% by weight of the monomer present in the copolymer.
[0054] As used herein, the term "substantially free of crosslinking agents"
means that there is no more than 1.0 (:)/0 by weight of the copolymer, preferably no more than 0.5% by weight, of monomeric units that connect two or more of the backbone chains of the polymer.
[0055] It is noted that any embodiment disclosed herein can be combined with any other embodiment with the result being subject matter in accordance with the invention.
[0056] It is noted that, unless use differently, " /0" means percent by weight.
Examples [0057] Lauryl methacrylate as used in Examples 1-8 was provided as methacrylic ester 13.0, which is commercially available as VISIOMER Terra 013,0-MA from Evonik Industries.
13 Example 1 [0058] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and the subsurface nitrogen purge was started. To the reaction was then added container 270.0 g of lauryl methacrylate, 30.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone. The reaction was heated up to 43 C by using a temperature controlled water batch set at 45 C. Once the reaction reached io 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held an additional 5 hours, cooled to room temperature and isolated.
Example 2 [0059] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and the subsurface nitrogen purge was started. To the reaction was then added container 240.0 g of lauryl methacrylate, 60.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone. The reaction was heated up to 43 C by using a temperature controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held an additional 5 hours, cooled to room temperature and isolated.
Example 3 [0060] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and
Example 2 [0059] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and the subsurface nitrogen purge was started. To the reaction was then added container 240.0 g of lauryl methacrylate, 60.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone. The reaction was heated up to 43 C by using a temperature controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held an additional 5 hours, cooled to room temperature and isolated.
Example 3 [0060] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and
14 the subsurface nitrogen purge was started. To the reaction was then added container 210.0 g of lauryl methacrylate, 90.0 g of 2-ethylhexyl methacrylate and 129.9 g of acetone. The reaction was heated up to 43 C by using a temperature controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held an additional 5 hours, cooled to room temperature and isolated.
Example 4 [0061] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and the subsurface nitrogen purge was started. To the reaction was then added container 180.0 g of lauryl methacrylate, 120.0 g of 2-Ethylhexyl Methacrylate and 129.9 g of acetone. The reaction was heated up to 43 C by using a temperature controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held an additional 5 hours, cooled to room temperature and isolated.
Example 5 [0062] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and the subsurface nitrogen purge was started. To the reaction was then added container 120.0 g of lauryl methacrylate, 180.0 g of 2-Ethylhexyl Methacrylate and 129.9 g of acetone. The reaction was heated up to 43 C by using a temperature controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held an additional 5 hours, cooled to room temperature and isolated.
Example 6 [0063] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and io the subsurface nitrogen purge was started. To the reaction was then added container 60.0 g of lauryl methacrylate, 240.0 g of 2-Ethylhexyl Methacrylate and 129.9 g of acetone. The reaction was heated up to 43 C by using a temperature controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held an additional 5 hours, cooled to room temperature and isolated.
Example 7 [0064] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and the subsurface nitrogen purge was started. To the reaction was then added 30.0 g of lauryl methacrylate, 270.0 g of 2-Ethylhexyl Methacrylate and 129.9 g of acetone. The reaction was heated up to 43 C by using a temperature controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held an additional 5 hours, cooled to room temperature and isolated.
Example 8 [0065] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and the subsurface nitrogen purge was started. To the reaction was then added
Example 4 [0061] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and the subsurface nitrogen purge was started. To the reaction was then added container 180.0 g of lauryl methacrylate, 120.0 g of 2-Ethylhexyl Methacrylate and 129.9 g of acetone. The reaction was heated up to 43 C by using a temperature controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held an additional 5 hours, cooled to room temperature and isolated.
Example 5 [0062] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and the subsurface nitrogen purge was started. To the reaction was then added container 120.0 g of lauryl methacrylate, 180.0 g of 2-Ethylhexyl Methacrylate and 129.9 g of acetone. The reaction was heated up to 43 C by using a temperature controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held an additional 5 hours, cooled to room temperature and isolated.
Example 6 [0063] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and io the subsurface nitrogen purge was started. To the reaction was then added container 60.0 g of lauryl methacrylate, 240.0 g of 2-Ethylhexyl Methacrylate and 129.9 g of acetone. The reaction was heated up to 43 C by using a temperature controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held an additional 5 hours, cooled to room temperature and isolated.
Example 7 [0064] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and the subsurface nitrogen purge was started. To the reaction was then added 30.0 g of lauryl methacrylate, 270.0 g of 2-Ethylhexyl Methacrylate and 129.9 g of acetone. The reaction was heated up to 43 C by using a temperature controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held an additional 5 hours, cooled to room temperature and isolated.
Example 8 [0065] To a 4-neck 2000 mL flask equipped with an overhead stirrer, a condenser, a thermocouple and a subsurface nitrogen purge was added 645.5 g of water and 8.7 g of Aerosol OT. The stirring was turned up to 200 rpm and the subsurface nitrogen purge was started. To the reaction was then added
15.0 g of lauryl methacrylate, 285.0 g of 2-Ethylhexyl Methacrylate and 129.9 g of acetone. The reaction was heated up to 43 C by using a temperature controlled water batch set at 45 C. Once the reaction reached 43 C, 0.04 g of t-butyl hydroperoxide in 7.5g of water was added. After 5 minutes, 0.29 g of sodium ascorbate dissolved in 7.5 g of water and 0.60 g of a 0.25% solution of iron sulfate hexahydrate was added. The nitrogen purge was then changed to a nitrogen blanket. The reaction was held an additional 5 hours, cooled to room temperature and isolated.
Preparation of 5% Solids Solution of Copolymer in Oil [0066] To a 4-neck 1000mL flask equipped with an overhead stirrer, a Barrett distillation trap with a condenser and a thermocouple was added an amount of the emulsion of any of Examples 1-8 to give 20.0 g of polymer.
Neutral Solvent 600 was then added to bring the total up to 400.0 g, followed by 150.0 g of toluene. The stirring was turned up to 200 rpm and the mixture was brought up to reflux. As water condensed in the Barrett trap it was drained off.
Once the water stopped overflowing, the contents of the reactor were brought up to 130 C to distill of a majority of the toluene. The remaining material was transferred to a 1000mL single neck round bottom and concentrated at vacuum with a bath at 60 C until the material reached a constant weight.
Method for Determining Molecular Weight and Radius of Gyration [0067] The Molecular Weight and Radius of Gyration of the polymer samples, supplied at 5% solids in base oil, was determined by the procedure outlined below:
[0068] Eluant: HPLC Grade Tetrahydrofuran stabilized with 0.01`)/0 Butylated Hydroxytoluene [0069] Column: Phenogel Column 100A 10um 300mm x 7.8mm.
[0070] Flow Rate: 0.50 ml/min.
[0071] Detectors: Wyatt Dawn Heleos-II MultiAngle Light Scattering (MALS) at 663nm and room temperature and Wyatt Optilab T-rEX Refractive Index Detector at 658nm and 40 C
[0072] Pump/Autosampler: Agilent 1100 Isocratic HPLC Pump and Autosampler [0073] Column Compartment: 40 C.
[0074] Standards: There were no standards directly correlated with the analysis, but the Heleos-II MALS calibration constant was established with lo Toluene and the Optilab T-rEX calibration constant was established with NaCI
in water. The 17 angles on the Heleos-II were normalized with a narrow range polystyrene standard at 28,500 Molecular Weight and the detector delay volume was adjusted with the same standard.
[0075] Sample Preparation: The samples were prepared by gravimetrically diluting about 8.0 mg of sample with about 5.0 g of tetrahyrofuran. The actual concentration of polymer in mg/ml was calculated based on the density of tetrahydrofuran (0.889 g/m1) and the percentage solids in the sample solutions (5.0 A) by weight).
[0076] Injection: 50 pl.
[0077] Run time: 20 minutes.
[0078] Software: Wyatt Astra Version 6.1.4.25.
[0079] Calculations: The Astra software provides several choices of formalisms and exponent order to fit the data. All samples were fit with a 2nd order Berry. The angles used were adjusted to give the best fit, using a minimum of 13 angles and up to the maximum of 17. The dn/dc was calculated from the refractive index data assuming 100% recovery. The software reported the average Molecular Weight as Mw and the average Root Mean Square Radius of Gyration as Rg. The results are shown in Table 2.
Method for Determining Viscosity The shear viscosity of the polymer samples, supplied at 5% solids in base oil, was determined by stress-controlled rheometer MCR 302, manufactured by Anton Paar GmbH, located at Anton Paar Strasse 20, 8054, Graz, Austria. The Double Gap System of Measurement was used for good accuracy (Instruction Manual, MCR Series, Modular Compact Rheometer MCR 52/102/302/502, page 50, Anton Parr, Graz, Austria, 2011). The temperature was set at 22 C
with the accuracy of 0.1 C. The shear rate was gradually increased from 1/sec to 100/sec with 10 points of viscosity reading per decade. At each of these points, 10 second equilibrium time was given before the reading, which lasted seconds. The viscosity at 10/sec shear rate is shown in Table 2. Software for instrument control and data acquisition is RheoCompassTM, version 1.13.445.
io Table 1 FeSO4 Exampl LMA 2- Acetone TBHP Ascorbate Aeroso e 1 EHMA1 2 2 2 (0.25% I 0T2 ) 1 90 10 43.3 0.013 0.098 0.20 2.90 2 80 20 43.3 0.013 0.098 0.20 2.90 3 70 30 43.3 0.013 0.098 0.20 2.90 4 60 40 43.3 0.013 0.098 0.20 2.90 5 40 60 43.3 0.013 0.098 0.20 2.90 6 20 80 43.3 0.013 0.098 0.20 2.90 7 10 90 43.3 0.013 0.098 0.20 2.90 8 5 95 43.3 0.013 0.098 0.20 2.90 Base Oil 1 Percentage of monomer as a mass percent of the total amount of monomer 2 Weight percent based on the total amount of monomer LMA = lauryl methacrylate; 2-EHMA = 2-ethylhexyl methacrylate.
Table 2, Hydrodynamic Chromatography/MALS
Mw Rg Mw Peak 5%S
Peak Rg Peak 2 1 NS600 Finger Example LMA1 2- 1 2 Peak 1 EHMA' (106 (nm) viscosityPull Test (106 (nm) g/mol) [mPa=s]
g/mol) 1 90 10 133 6.4 140 108 3610 I
I
2 80 20 133 7.0 104 135 2152 3 70 30 146 7.0 132 106 2572 m 4 60 40 169 9.7 135 119 2294 m 40 60 129 8.1 133 111 4865 I
6 20 80 132/131 8.1/7.6 152/152 122/1204089 I
7A3 10 90 92 5.3 166 101 8213 I
7B 10 90 136/149 6.4/7.2 176/176 112/11810600 I
8 5 95 36 5.4 192 112 41083 vi NS600 -- vs Base Oil -1 Percentage of monomer as a mass percent of the total amount of monomer LMA = lauryl methacrylate; 2-EHMA = 2-ethylhexyl methacrylate;
5 VS = very short, s = short, m = medium, I = long, vi = very long 3 Two duplicate samples for Example 7 were created using the Example 7 preparation method described lo
Preparation of 5% Solids Solution of Copolymer in Oil [0066] To a 4-neck 1000mL flask equipped with an overhead stirrer, a Barrett distillation trap with a condenser and a thermocouple was added an amount of the emulsion of any of Examples 1-8 to give 20.0 g of polymer.
Neutral Solvent 600 was then added to bring the total up to 400.0 g, followed by 150.0 g of toluene. The stirring was turned up to 200 rpm and the mixture was brought up to reflux. As water condensed in the Barrett trap it was drained off.
Once the water stopped overflowing, the contents of the reactor were brought up to 130 C to distill of a majority of the toluene. The remaining material was transferred to a 1000mL single neck round bottom and concentrated at vacuum with a bath at 60 C until the material reached a constant weight.
Method for Determining Molecular Weight and Radius of Gyration [0067] The Molecular Weight and Radius of Gyration of the polymer samples, supplied at 5% solids in base oil, was determined by the procedure outlined below:
[0068] Eluant: HPLC Grade Tetrahydrofuran stabilized with 0.01`)/0 Butylated Hydroxytoluene [0069] Column: Phenogel Column 100A 10um 300mm x 7.8mm.
[0070] Flow Rate: 0.50 ml/min.
[0071] Detectors: Wyatt Dawn Heleos-II MultiAngle Light Scattering (MALS) at 663nm and room temperature and Wyatt Optilab T-rEX Refractive Index Detector at 658nm and 40 C
[0072] Pump/Autosampler: Agilent 1100 Isocratic HPLC Pump and Autosampler [0073] Column Compartment: 40 C.
[0074] Standards: There were no standards directly correlated with the analysis, but the Heleos-II MALS calibration constant was established with lo Toluene and the Optilab T-rEX calibration constant was established with NaCI
in water. The 17 angles on the Heleos-II were normalized with a narrow range polystyrene standard at 28,500 Molecular Weight and the detector delay volume was adjusted with the same standard.
[0075] Sample Preparation: The samples were prepared by gravimetrically diluting about 8.0 mg of sample with about 5.0 g of tetrahyrofuran. The actual concentration of polymer in mg/ml was calculated based on the density of tetrahydrofuran (0.889 g/m1) and the percentage solids in the sample solutions (5.0 A) by weight).
[0076] Injection: 50 pl.
[0077] Run time: 20 minutes.
[0078] Software: Wyatt Astra Version 6.1.4.25.
[0079] Calculations: The Astra software provides several choices of formalisms and exponent order to fit the data. All samples were fit with a 2nd order Berry. The angles used were adjusted to give the best fit, using a minimum of 13 angles and up to the maximum of 17. The dn/dc was calculated from the refractive index data assuming 100% recovery. The software reported the average Molecular Weight as Mw and the average Root Mean Square Radius of Gyration as Rg. The results are shown in Table 2.
Method for Determining Viscosity The shear viscosity of the polymer samples, supplied at 5% solids in base oil, was determined by stress-controlled rheometer MCR 302, manufactured by Anton Paar GmbH, located at Anton Paar Strasse 20, 8054, Graz, Austria. The Double Gap System of Measurement was used for good accuracy (Instruction Manual, MCR Series, Modular Compact Rheometer MCR 52/102/302/502, page 50, Anton Parr, Graz, Austria, 2011). The temperature was set at 22 C
with the accuracy of 0.1 C. The shear rate was gradually increased from 1/sec to 100/sec with 10 points of viscosity reading per decade. At each of these points, 10 second equilibrium time was given before the reading, which lasted seconds. The viscosity at 10/sec shear rate is shown in Table 2. Software for instrument control and data acquisition is RheoCompassTM, version 1.13.445.
io Table 1 FeSO4 Exampl LMA 2- Acetone TBHP Ascorbate Aeroso e 1 EHMA1 2 2 2 (0.25% I 0T2 ) 1 90 10 43.3 0.013 0.098 0.20 2.90 2 80 20 43.3 0.013 0.098 0.20 2.90 3 70 30 43.3 0.013 0.098 0.20 2.90 4 60 40 43.3 0.013 0.098 0.20 2.90 5 40 60 43.3 0.013 0.098 0.20 2.90 6 20 80 43.3 0.013 0.098 0.20 2.90 7 10 90 43.3 0.013 0.098 0.20 2.90 8 5 95 43.3 0.013 0.098 0.20 2.90 Base Oil 1 Percentage of monomer as a mass percent of the total amount of monomer 2 Weight percent based on the total amount of monomer LMA = lauryl methacrylate; 2-EHMA = 2-ethylhexyl methacrylate.
Table 2, Hydrodynamic Chromatography/MALS
Mw Rg Mw Peak 5%S
Peak Rg Peak 2 1 NS600 Finger Example LMA1 2- 1 2 Peak 1 EHMA' (106 (nm) viscosityPull Test (106 (nm) g/mol) [mPa=s]
g/mol) 1 90 10 133 6.4 140 108 3610 I
I
2 80 20 133 7.0 104 135 2152 3 70 30 146 7.0 132 106 2572 m 4 60 40 169 9.7 135 119 2294 m 40 60 129 8.1 133 111 4865 I
6 20 80 132/131 8.1/7.6 152/152 122/1204089 I
7A3 10 90 92 5.3 166 101 8213 I
7B 10 90 136/149 6.4/7.2 176/176 112/11810600 I
8 5 95 36 5.4 192 112 41083 vi NS600 -- vs Base Oil -1 Percentage of monomer as a mass percent of the total amount of monomer LMA = lauryl methacrylate; 2-EHMA = 2-ethylhexyl methacrylate;
5 VS = very short, s = short, m = medium, I = long, vi = very long 3 Two duplicate samples for Example 7 were created using the Example 7 preparation method described lo
Claims (28)
1. An uncrosslinked copolymer of alkyl methacrylate monomers wherein said alkyl methacrylate monomers comprise:
a. Monomers (A) selected from C6-C10 alkyl methacrylate monomers, and b. Monomers (B) selected from C10-C18 alkyl methacrylate monomers, wherein the mass ratio of Monomers (B) in the copolymer to Monomers (A) in the copolymer is 99:1 to 60:40 by weight, wherein Monomers (A) and Monomers (B) are distinct from one another, wherein the copolymer contains not more than 3.0% by weight of methyl methacrylate, and wherein the copolymer has an average root mean square radius of gyration from 100 nm to 200 nm as measured by hydrodynamic column chromatography-multi angle light scattering where tetrahydrofuran is used as a solvent.
a. Monomers (A) selected from C6-C10 alkyl methacrylate monomers, and b. Monomers (B) selected from C10-C18 alkyl methacrylate monomers, wherein the mass ratio of Monomers (B) in the copolymer to Monomers (A) in the copolymer is 99:1 to 60:40 by weight, wherein Monomers (A) and Monomers (B) are distinct from one another, wherein the copolymer contains not more than 3.0% by weight of methyl methacrylate, and wherein the copolymer has an average root mean square radius of gyration from 100 nm to 200 nm as measured by hydrodynamic column chromatography-multi angle light scattering where tetrahydrofuran is used as a solvent.
2. The copolymer of claim 1, wherein the copolymer contains not more than 1.0% by weight of methyl methacrylate.
3. The copolymer of claim 1 or 2, wherein the copolymer contains not more than 0.5% by weight of methyl methacrylate.
4. An uncrosslinked copolymer obtained by combining at least:
a. Monomers (A) selected from C6-C10 alkyl methacrylate monomers, and b. Monomers (B) selected from C10-C18 alkyl methacrylate monomers, in a mixture and co-polymerizing the monomers, wherein the monomers are present in a mass ratio of 99:1 to 60:40 Monomers (B) to Monomers (A), wherein Monomers (A) and Monomers (B) are distinct from one another, wherein the copolymer contains not more than 3.0% by weight of methyl methacrylate, and wherein the copolymer has an average root mean square radius of gyration from 100 nm to 200 nm as measured by Date Recue/Date Received 2023-08-11 hydrodynamic column chromatography-multi angle light scattering where tetrahydrofuran is used as a solvent.
a. Monomers (A) selected from C6-C10 alkyl methacrylate monomers, and b. Monomers (B) selected from C10-C18 alkyl methacrylate monomers, in a mixture and co-polymerizing the monomers, wherein the monomers are present in a mass ratio of 99:1 to 60:40 Monomers (B) to Monomers (A), wherein Monomers (A) and Monomers (B) are distinct from one another, wherein the copolymer contains not more than 3.0% by weight of methyl methacrylate, and wherein the copolymer has an average root mean square radius of gyration from 100 nm to 200 nm as measured by Date Recue/Date Received 2023-08-11 hydrodynamic column chromatography-multi angle light scattering where tetrahydrofuran is used as a solvent.
5. The copolymer of claim 4, wherein the copolymer contains not more than 1.0% by weight of methyl methacrylate.
6. The copolymer of claim 4 or 5, wherein the copolymer contains not more than 0.5% by weight of methyl methacrylate.
7. The copolymer of any one of claims 1 to 6 wherein the mass ratio of the monomers is about 80:20 Monomers (B) to Monomers (A).
8. The copolymer of any one of claims 1 to 6 wherein the mass ratio of the monomers is about 90:10 Monomers (B) to Monomers (A).
9. The copolymer of any one of claims 1-8 wherein Monomers (B) are lauryl methacrylate.
10. The copolymer of any one of claims 1-9 wherein Monomers (A) are C8alkyl methacrylate.
11. The copolymer of claim 10 wherein the C8alkyl methacrylate is 2-ethyl hexyl methacrylate.
12. The copolymer of any one of claims 1-11 wherein the copolymer is a substantially random copolymer.
13. The copolymer of any one of claims 1-12 wherein the copolymer is a partially random copolymer and partially a block copolymer.
Date Recue/Date Received 2023-08-11
Date Recue/Date Received 2023-08-11
14. The copolymer of any one of claims 1-13 wherein monomers (A) and monomers (B) represent at least 75% by weight of the total weight of monomers used to prepare the copolymer.
15. The copolymer of any one of claims 1-14 wherein monomers (A) and monomers (B) represent at least 90% by weight of the total weight of monomers used to prepare the copolymer.
16. The copolymer of any one of claims 1-15 wherein monomers (A) and monomers (B) represent at least 95% by weight of the total weight of monomers used to prepare the copolymer.
17. The copolymer of any one of claims 1-16 wherein monomers (A) and monomers (B) represent at least 99% by weight of the total weight of monomers used to prepare the copolymer.
18. The copolymer of any one of claims 1-17 wherein the copolymer is a mixture of C12 alkyl methacrylate, C14 alkyl methacrylate, C16 alkyl methacrylate, and C18 alkyl methacrylate, and a C8 alkyl methacrylate.
19. The copolymer of any one of claims 1-18 wherein the copolymer has a molecular weight of from 5,300,000 to 169,000,000 g/mol.
20. The copolymer of any one of claims 1-19 wherein the copolymer has a molecular weight of from 6,400,000 to 169,000,000 g/mol.
21. An uncrosslinked copolymer of C8 alkyl methacrylate and lauryl methacrylate, wherein the mass ratio of lauryl methacrylate monomers in the copolymer to C8 alkyl methacrylate monomers in the copolymer is 99:1 to 60:40 by weight, and wherein the copolymer has an average root mean square radius of gyration from 100 nm to 200 nm as measured by Date Recue/Date Received 2023-08-11 hydrodynamic column chromatography-multi angle light scattering where tetrahydrofuran is used as a solvent.
22. The copolymer of claim 21 wherein the copolymer has a molecular weight of from 5,300,000 to 169,000,000 g/mol.
23. The copolymer of claim 1 wherein Monomers (B) are lauryl methacrylate and wherein Monomers (A) are 2-ethyl hexyl methacrylate and wherein the copolymer has a weight average molecular weight of from 5,300,000 to 92,000,000 g/mol.
24. The copolymer of claim 1 wherein Monomers (B) are lauryl methacrylate and wherein Monomers (A) are 2-ethyl hexyl methacrylate and wherein the copolymer has a weight average molecular weight of from 6,400,000 to 149,000,000 g/mol.
25. The copolymer of claim 1 wherein Monomers (B) are lauryl methacrylate and wherein Monomers (A) are 2-ethyl hexyl methacrylate and wherein the copolymer has a weight average molecular weight of from 7,600,000 to 132,000,000 g/mol.
26. The copolymer of claim 1 wherein Monomers (B) are lauryl methacrylate and wherein Monomers (A) are 2-ethyl hexyl methacrylate and wherein the copolymer has a weight average molecular weight of from 8,100,000 to 129,000,000 g/mol.
27. The copolymer of claim 1 wherein Monomers (B) are lauryl methacrylate and wherein Monomers (A) are 2-ethyl hexyl methacrylate and wherein the copolymer has a weight average molecular weight of from 6,400,000 to 146,000,000 g/mol.
28. The copolymer of claim 1 wherein Monomers (B) are lauryl methacrylate and wherein Monomers (A) are 2-ethyl hexyl methacrylate and wherein Date Recue/Date Received 2023-08-11 the copolymer has a weight average molecular weight of from 9,700,000 to 169,000,000 g/mol.
Date Recue/Date Received 2023-08-11
Date Recue/Date Received 2023-08-11
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US5763374A (en) * | 1994-08-10 | 1998-06-09 | Sanyo Chemical Industries, Ltd. | Lubricating oil compositions of reduced high-temperature high-shear viscosity |
US6124249A (en) * | 1998-12-22 | 2000-09-26 | The Lubrizol Corporation | Viscosity improvers for lubricating oil compositions |
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- 2017-06-16 TW TW106120156A patent/TW201819436A/en unknown
- 2017-06-16 CN CN201780035850.7A patent/CN109312251A/en active Pending
- 2017-06-16 SG SG11201810714QA patent/SG11201810714QA/en unknown
- 2017-06-16 WO PCT/EP2017/064756 patent/WO2017216332A1/en active Search and Examination
- 2017-06-16 KR KR1020187037264A patent/KR102059973B1/en active IP Right Grant
Also Published As
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SG11201810714QA (en) | 2018-12-28 |
CN109312251A (en) | 2019-02-05 |
TW201819436A (en) | 2018-06-01 |
CA3026812A1 (en) | 2017-12-21 |
WO2017216332A1 (en) | 2017-12-21 |
KR20190007501A (en) | 2019-01-22 |
KR102059973B1 (en) | 2019-12-27 |
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