CN1668727A - 缓释润滑添加剂凝胶 - Google Patents
缓释润滑添加剂凝胶 Download PDFInfo
- Publication number
- CN1668727A CN1668727A CNA038168030A CN03816803A CN1668727A CN 1668727 A CN1668727 A CN 1668727A CN A038168030 A CNA038168030 A CN A038168030A CN 03816803 A CN03816803 A CN 03816803A CN 1668727 A CN1668727 A CN 1668727A
- Authority
- CN
- China
- Prior art keywords
- lubricant additive
- gel
- oil
- dispersion agent
- lubricant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003879 lubricant additive Substances 0.000 title claims abstract description 76
- 239000000654 additive Substances 0.000 claims abstract description 59
- 230000000996 additive effect Effects 0.000 claims abstract description 41
- 239000003921 oil Substances 0.000 claims description 84
- 239000003795 chemical substances by application Substances 0.000 claims description 63
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 33
- 239000002270 dispersing agent Substances 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 29
- 238000000746 purification Methods 0.000 claims description 28
- 229960002317 succinimide Drugs 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 21
- -1 phenates Chemical compound 0.000 claims description 20
- 239000003599 detergent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 230000035322 succinylation Effects 0.000 claims description 7
- 238000010613 succinylation reaction Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000010687 lubricating oil Substances 0.000 claims description 5
- 238000005461 lubrication Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 230000001131 transforming effect Effects 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 3
- 229960001860 salicylate Drugs 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 239000013618 particulate matter Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract 3
- 239000000499 gel Substances 0.000 description 74
- 238000012360 testing method Methods 0.000 description 27
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 12
- 229910052791 calcium Inorganic materials 0.000 description 12
- 239000011575 calcium Substances 0.000 description 12
- 230000001050 lubricating effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000005987 sulfurization reaction Methods 0.000 description 8
- 229920002367 Polyisobutene Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000010721 machine oil Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000013268 sustained release Methods 0.000 description 3
- 239000012730 sustained-release form Substances 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
- HJRYTDKISXDCLR-UHFFFAOYSA-N C(CCCCCC)C1=C(C=CC=C1)O.[Ba] Chemical compound C(CCCCCC)C1=C(C=CC=C1)O.[Ba] HJRYTDKISXDCLR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 230000003534 oscillatory effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- NSOAQRMLVFRWIT-UHFFFAOYSA-N 1-ethenoxydecane Chemical class CCCCCCCCCCOC=C NSOAQRMLVFRWIT-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- FHRLECAMEQJXGP-UHFFFAOYSA-N C1(CCCCC1)[Zn]C1CCCCC1.P(O)(O)(=S)S Chemical compound C1(CCCCC1)[Zn]C1CCCCC1.P(O)(O)(=S)S FHRLECAMEQJXGP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical group CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HYJODZUSLXOFNC-UHFFFAOYSA-N [S].[Cl] Chemical compound [S].[Cl] HYJODZUSLXOFNC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- GCFAUZGWPDYAJN-UHFFFAOYSA-N cyclohexyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OC1CCCCC1 GCFAUZGWPDYAJN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYJZNXAVZMEXDH-UHFFFAOYSA-N octadecan-8-yl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCC(OC(=O)C(C)=C)CCCCCCC LYJZNXAVZMEXDH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000333 poly(propyleneimine) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GAJQCIFYLSXSEZ-UHFFFAOYSA-L tridecyl phosphate Chemical compound CCCCCCCCCCCCCOP([O-])([O-])=O GAJQCIFYLSXSEZ-UHFFFAOYSA-L 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010698 whale oil Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M165/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- 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
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0091—Treatment of oils in a continuous lubricating circuit (e.g. motor oil system)
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
-
- 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
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Abstract
本发明提供了一种通过使两种或更多种润滑添加剂凝胶化而制得润滑添加剂凝胶用以缓慢地释放所述添加剂组分至液体中。当与所述液体例如油接触时，所述润滑添加剂凝胶可以缓慢地释放成其组成润滑添加剂，从而起到润滑液例如润滑油的作用。
Description
发明领域
本发明涉及一种凝胶形式的可以缓慢释放到液体中的润滑添加剂。此外，本发明涉及一种发动机润滑添加剂凝胶，其可缓慢地释放到被过滤的油中，即其可以缓慢地释放使得该添加剂在所述油的整个使用寿命的相当大的一部分期间内持续释放。
发明背景
油滤清器中的缓释润滑添加剂是已知的。某些这类滤清器中的添加剂可以混入缓慢溶解到被处理油中的热塑性聚合物内。例如，参见美国专利4,075,098。另外，所述添加剂可以混入在升高的发动机温度下可渗透油的聚合物中。例如，参见美国专利4,066,559。另外，所述添加剂可以混入不可溶于油但可被油润湿的颗粒中。例如，参见美国专利5,478,463。在另一方案中，在油滤清器内部提供可用作为粘度改性剂的油溶性固体聚合物，其中该聚合物中可以混入附加添加剂或者不混入附加添加剂。例如，参见美国专利4,014,794。
虽然这些体系可以将润滑添加剂供入被过滤的油中，但是它们通常需要惰性载体用于将所述添加剂缓慢释放到所述油中。另外，需要复杂的机械系统来实现缓慢释放，所述系统例如囊腔、穿孔片、隔板、专门设计的注射器和/或附加部分。例如，参见美国专利5,718,258。
因此，希望提供不需要惰性载体或复杂的机械系统就可将其缓释计量加入液体例如油内的缓释润滑添加剂。
发明概述
根据本发明，已经发现润滑添加剂凝胶可以缓慢地为液体例如油提供润滑添加剂。特别地，已经发现油溶性润滑添加剂凝胶当与流经油滤清器的油接触时会缓慢地分解为其组成润滑添加剂部分。由于这些凝胶的分解速率如此缓慢并且由于这些凝胶会分解为其组成润滑添加剂部分，因此它们可以有效地将这些添加剂缓慢释放到被过滤的油中。因此，它们可以以原样使用而不需要惰性载体或非润滑添加剂的基质，例如用于实现缓慢释放润滑添加剂的早期系统中所需的复杂机械系统或聚合物骨架。
因此，本发明提供了一种通过将所述油与以润滑添加剂凝胶形式的润滑油添加剂接触而将一种或多种润滑添加剂缓慢供给所述油的新方法。
此外，本发明提供了一种新型物质组合物-润滑添加剂组合体，其包含通过过碱性清净剂与琥珀酰亚胺分散剂混合而成的润滑添加剂。
此外，本发明提供了一种用于商业和/或工业系统(例如内燃机)中的新型油滤清器。该滤清器包括壳体、用于从通过该滤清器的油中除去颗粒物质的过滤器以及位于所述壳体内用以缓慢释放到所述油中的油溶性润滑添加剂，其中至少一些油溶性润滑添加剂为润滑添加剂凝胶的形式。
本发明的润滑添加剂凝胶可以用在任何液体调节装置中，这些装置包括但不限于内燃机、固定发动机、润滑机械系统、液压系统等。
附图简述
参照附图可以更容易地理解本发明，其中：
图1是根据本发明制造的一种油滤清器的示意图；和
图2是根据本发明制造的另一种油滤清器的示意图。
发明详述
根据本发明，为液体调节装置提供润滑添加剂凝胶形式的缓释润滑添加剂组合体。所述润滑添加剂凝胶可以用于润滑机械系统以缓慢释放为满足所述系统的性能要求而特别配制的胶化润滑剂组分。此外，所述胶化润滑添加剂组分的缓慢释放可以调节所述液体。所述润滑机械系统包括但不限于内燃(SI和CI)机、天然气发动机、固定发动机、金属加工冷却系统、中速和高速船用柴油发动机、润滑机械系统、工业润滑系统、油滤清器、液压系统、传送系统等中的那些。
滤清器结构
图1中示意性地说明了本发明的油滤清器，该图显示了以10表示的油滤清器，其通常由壳体12、用于从所述油中除去颗粒污染物的过滤介质部件14和端板16组成。端板16限定了入口18和出口20，其设置方式使得油分别沿着一般以箭头A、B和C所示的方向进入滤清器10、经由过滤部件14、然后排出滤清器10。
将润滑油添加剂凝胶22装在壳体12内使得它可以在该滤清器中与油密切接触的方式。在所示的具体实施方案中，通过Teflon网筛26和多孔板28将润滑添加剂凝胶22装在壳体12下部的储料器24中。网筛26和板28中的孔隙允许油沿着箭头D和E的方向移动，从而与润滑添加剂凝胶22接触。根据本发明，润滑添加剂凝胶22是通过混合两种或更多种可形成润滑添加剂凝胶22的油溶性润滑添加剂而制得的凝胶。已经发现当在滤清器10中与所述油接触时这种润滑添加剂凝胶会缓慢分解为其组成润滑添加剂，从而产生这些添加剂以加入油中。通过适当地控制所述润滑添加剂凝胶22的化学性质，可以容易地控制润滑添加剂凝胶22分解为其组成润滑剂部分的速率。
图2中说明了本发明的油滤清器的另一实施方案，其中相同标号表示与图1的油滤清器相同的部件。该滤清器的结构类似于图1滤清器的结构，不同之处在于储料器124设置在端板116附近，以使得进入该滤清器内的所有油或大体上所有油与润滑添加剂凝胶122接触。在图1的滤清器中，一些油会绕过储料器24，如箭头F所示。因此应当认识到可以通过适当地选择储料器24/124的设计和位置而进一步控制进入所述滤清器中与凝胶22/122接触的油的比例，因而控制该凝胶溶解为其组成润滑剂部分的速率。
例如，虽然以上描述表明润滑添加剂凝胶22被放置在油滤清器底部的储料器中，但是可以采用使得所述油与润滑添加剂凝胶密切接触的任何形状、结构和/或布置。例如，如果需要，所述润滑添加剂凝胶可以放置在过滤部件14上。作为选择，也可以使用例如以下文献中所述的任何其他机械系统和装置：上文提到的美国专利4,014,794；美国专利4,061,572；美国专利4,066,559；美国专利4,075,097；美国专利4,075,098；美国专利4,144,166；美国专利4,144,169；美国专利4,751,901；美国专利5,327,861；美国专利5,552,040和美国专利5,718,258中。应该认识到以下方面不是关键所在，并且通常可以是任何已知的用于缓释剂或缓释装置的那些：所述凝胶在例如滤清器的装置中的位置，或者在滤清器外可以使得所述凝胶缓慢释放到所述液体中的任何位置；如果存在的话，用于容纳凝胶的装置；所述装置的结构，例如滤清器或凝胶容器；或者设计。
还应该认识到以上结构仅用于说明油滤清器，并且由于润滑添加剂凝胶可用任何润滑机械系统中，因此油滤清器可以具有任何可以使被过滤的油与润滑添加剂凝胶接触的结构。
润滑添加剂凝胶
现代机油通常通过将预制润滑添加剂组合体与精制或合成的基础油料混合而制得。反过来，所述润滑添加剂组合体通常是通过将多种不同的润滑添加剂一起混合从而形成该组合体的方式制得的。由于润滑添加剂呈液体形式时更容易处理和测试，因此在添加至其他成分以前，一般将那些通常呈固态的添加剂溶解在少量的作为载体的基础油料中。此外，成品润滑组合体中通常包含附加量的基础油，例如40wt％，这样还是为了使得处理和测试更容易。
大多数润滑油含有许多不同的润滑添加剂。工业上已发现当制备包含润滑添加剂混合物的润滑添加剂组合体时，偶尔会在所述添加剂组合体中不可控地形成不希望的凝胶。已发现，在某些情况下，视所用添加剂的类型和/或用量而定，当混合时会在两种或更多种润滑添加剂之间出现凝胶化作用。例如参见美国专利6,140,279。这种凝胶会对其中存在所述凝胶的成品液体(例如成品油)的流变性质造成不利影响，因此实践中总是避免这种凝胶。本发明通过供入油滤清器和其他机械润滑系统中的方式控制润滑添加剂凝胶的形成及其应用。润滑添加剂凝胶的受控形成可以起到缓释剂的作用以将制备所述缓释剂的润滑添加剂供给成品液体。
凝胶是包含两种或更多种物质的混合物的材料，并且以半固态的形式存在，相对于液体而言其更类似于固体。参见Parker，Dictionary ofScientific and Technical Terms，第5版，McGraw Hill，1994。也可参见Larson，“The Structure and Rheology of Complex Fliuds”，第5章，OxfordUniversity Press，New York，1999，并通过引用将其内容并入本文。可以通过小幅振荡剪切测试来测量凝胶的流变性质。这种方法可以测量凝胶的结构特征，并得到储能模量项(表示弹性能的储存)和损耗模量(表示弹性能的粘度损耗)项。损耗模量/储能模量的比被称为损耗角正切或“tanδ”，并且对于类似液态的材料来说该比值＞1，对于类似固态的材料来说该比值＜1。
根据本发明，由两种或更多种油溶性润滑添加剂组合形成的任何凝胶可用来制备润滑添加剂凝胶22。该润滑添加剂凝胶包括但不限于那些由分散剂混合形成的凝胶、由分散剂和酸混合形成的凝胶、由分散剂和碱混合形成的凝胶、由分散剂和过碱性清净剂混合形成的凝胶，随后将在说明书对其进行说明。在一个实施方案中所述凝胶的tanδ值为约≤1，在一个实施方案中所述凝胶的tanδ值为约≤0.75，在一个实施方案中所述凝胶的tanδ值为约≤0.5，或者在一个实施方案中所述凝胶的tanδ值为约≤0.3。
根据本发明特别使用的一类凝胶是其中通过混合过碱性清净剂和琥珀酰亚胺无灰分散剂而产生凝胶化作用的那些。在该实施方案中，所述清净剂与分散剂的比值通常为约10∶1～1∶10，更特别地为约5∶1～1∶5、约4∶1～1∶1，并且甚至为约4∶1～2∶1。此外，所述过碱性清净剂的TBN通常至少为100，更通常至少为300，或者甚至为350，或者甚至为400。在使用过碱性清净剂混合物的情况下，至少一种清净剂的TBN值应该处于这些范围内。但是，这些混合物的平均TBN也可以对应于这些值。
在一个实施方案中，所述凝胶中优选的无灰分散剂是聚异丁烯琥珀酰亚胺。聚异丁烯琥珀酰亚胺无灰分散剂是可商购的产品，其通常通过以下方式制备：将数均分子量(“Mn”)为约300～10,000的聚异丁烯与马来酸酐一起反应以形成聚异丁烯琥珀酸酐(“PIBSA”)，然后将由此得到的产物与通常含有以每分子计1～10个乙二胺基团的多聚胺反应。由此得到的分散剂通常由不同化合物的混合物形成，并且可以用多种不同的变量来表征，所述变量包括胺取代程度(即氨基与羰基的当量比，或者N∶CO)、马来酸酐转化程度(即马来酸酐与PIB的摩尔比，如美国专利4,234,435中定义的，通过引用将其内容并入本文)、PIB基的Mn和该分散剂的制备方式(热辅助的琥珀酰化或Cl2辅助的琥珀酰化)。也可以使用由其他多聚胺(例如聚丙烯胺)和其他烯基片段(例如聚丙烯)制得的类似化合物。这种类型的无灰分散剂例如在美国专利4,234,435中作了描述，通过引用将其内容并入本文。
通常，这些聚异丁烯琥珀酰亚胺无灰分散剂的N∶CO比可以为约0.6～1.6，更典型地为约0.7～1.4，或者甚至为0.7～1.2。此外或者作为选择地，这些聚异丁烯琥珀酰亚胺无灰分散剂的马来酸酐转化程度通常可以为约1.3，更典型地为至少约1.5，或者甚至为1.6或更大。此外或者作为选择地，这些聚异丁烯琥珀酰亚胺无灰分散剂的聚异丁烯片段的Mn通常≥约350，更典型地为至少约1200，至少约1500，或者甚至为1800或更高。此外或者作为选择地，也可以采用Cl2辅助的琥珀酰化而不是热辅助的琥珀酰化制得这些聚异丁烯琥珀酰亚胺无灰分散剂，因为这种方法可以制得的PIBSA的转化率高于热方式制备的PIBSA的转化率(后者被称作DA或者直接加成PIBSA的转化率)。
所用的润滑添加剂凝胶包含溶解或分散于其中的多种附加成分。此外，这种凝胶通常可以含有相对少量的精制或合成的基础油料，这是因为如上文所述，如果将其溶解于这种基础料中，那么可以非常容易地提供、储存和处理所述多种添加剂。然而，本发明的润滑添加剂凝胶通常可以包含至少约30wt％、更典型地约50wt％、甚至60wt％、甚至70wt％或甚至80wt％的凝胶，并且余量为本文进一步描述的其他成分。当然，如果需要，本发明的凝胶可以由100％的凝胶组成。
可以将许多不同类型的油溶性润滑添加剂混入目前可得到的润滑油中。实例包括清净剂、分散剂、极压剂、减磨剂、抗氧化剂、粘度指数改进剂、防沫剂及其混合物等。
油溶性清净剂是本领域已知的，其包括但不限于过碱性磺酸盐、酚盐、水杨酸盐、羧酸盐等。这种清净剂例如在美国专利5,484,542以及在该专利中提到的许多其他专利和出版物中作了描述。通过引用将所有这些专利和出版物的公开内容并入本文。可以使用所述清净剂的组合。所述清净剂存在于成品液态混合物中的量以该组合物的重量计为约0.1～25重量％，优选为约1～20重量％，更优选为约3～15重量％。
所述清净剂包括但不限于过碱性磺酸钙清净剂。这些可商购的制品通常通过将二氧化碳与烷基苯磺酸盐和石灰(氢氧化钙)的混合物反应以生成含有碳酸钙的胶束而制成。使用更多当量的石灰和二氧化碳使得所述清净剂制品变成碱性。方便地以总碱值(“TBN”)来描述这种材料，该值是衡量所述制品的碱性的一个标准。通常使用TBN为10～400的过碱性清净剂作为润滑油清净剂。含有不同于钙的金属(例如Mg、Ba、Sr、Na和K)的过碱性清净剂也可以包含于其中。
许多油溶性分散剂也是已知的。所述分散剂可以组合使用。所述分散剂存在于成品液态混合物中的量以该组合物的重量计为约0.1～25重量％，优选为约1～20重量％，更优选为约3～15重量％。油溶性分散剂包括但不限于无灰型分散剂和聚合物分散剂。无灰型分散剂的特征在于连接至分子量相对较高的烃链上的极性基团。典型的无灰分散剂包括N-取代的长链烯基琥珀酰亚胺，其具有多种化学结构，典型地包括：
其中R1分别独立地为烷基，通常是分子量为500～5000的聚异丁基；R2为烯基，通常是乙烯基(C2H4)。在美国专利4,234,435中对琥珀酰亚胺分散剂作了更全面的描述，通过引用将其公开内容并入本文。该专利中所述的分散剂对于制备本发明的凝胶特别有效。
另一类无灰分散剂是高分子量的酯。在美国专利3,381,022中对这种材料作了更详细的描述。
另一类无灰分散剂是曼尼希型分散剂。这些化合物是其中烷基包含至少约30个碳原子的烷基酚与醛(特别是甲醛)和胺(特别是聚亚烷基多胺)的反应产物。美国专利3,036,003和美国专利3,980,569中所述的材料可以用作说明。具有以下一般结构(包括多种不同的异构体等)的曼尼希碱是特别引起关注的。
这种材料在美国专利3,634,515中作了更详细的描述。
另一类分散剂是羧酸分散剂。这些“羧酸分散剂”的实例在英国专利1,306,529和许多美国专利包括US 3,219,666、US 4,234,435和Re.26,433中作了描述。
胺分散剂是分子量相对较高的脂族卤化物和胺类、优选聚亚烷基多胺的反应产物。其实例在美国专利3,275,554和美国专利3,565,804中作了描述。
聚合物分散剂是油溶性单体(例如甲基丙烯酸癸酯、乙烯基癸基醚和高分子量烯烃)与含有极性取代基的单体(例如丙烯酸氨烷基酯或丙烯酰胺和聚-(氧化乙烯)取代的丙烯酸酯)的共聚物。在以下美国专利3,329,658和3,702,300中公开了聚合物分散剂的实例。
也可以通过与多种试剂中的任一种反应对分散剂进行后处理。这些试剂中有脲、硫脲、二巯基噻二唑、二硫化碳、醛、酮、羧酸、烃取代的琥珀酸酐、腈、环氧化物、硼化合物和磷化合物。美国专利4,654,403中列出了详述描述这种处理的参考文献。
油溶性极压抗磨添加剂包括但不限于硫或氯硫EP剂、氯化烃EP剂、或含磷EP剂或者它们的混合物。这种EP剂的实例是氯化蜡、有机硫化物和多硫化物，例如二苄化二硫、二氯苄化二硫、二丁四硫、硫化鲸油、油酸的硫化甲酯、硫化烷基酚、硫化二戊烯、硫化萜烯和硫化Diels-Alder加合物；磷硫化烃，例如硫化磷与松节油或油酸甲酯的反应产物；含磷酯类，例如磷酸二烃基酯和磷酸三烃基酯，即磷酸二丁酯、磷酸二庚酯、磷酸二环己基酯、磷酸戊基苯基酯、磷酸二戊基苯基酯、磷酸三癸酯、磷酸二硬脂基酯和聚丙烯取代酚的磷酸酯；金属硫代氨基甲酸盐，例如二(辛基二硫代氨基甲酸)锌和二酸式庚基苯酚钡(barium heptylphenol diacid)，例如可以使用二环己基二硫代磷酸锌和二硫代磷酸的锌盐的组合。油溶性EP剂存在的量以成品液态混合物的重量计为约0～10重量％，优选为约0.25～5重量％，更优选为约0.5～2.5重量％。
油溶性抗氧化剂包括但不限于烷基取代的酚类，例如2，6-二叔丁基-4-甲基酚、硫化酚盐(phenate sulfides)、磷硫化萜烯、硫化酯、芳胺和受阻酚。抗氧化剂的另一个实例是酯取代的受阻酚，其可以通过在碱催化条件(例如KOH水溶液)下加热2，6-二烷基酚和丙烯酸酯而制备。可以使用它们的组合。抗氧化剂存在的量以成品液态混合物的重量计通常为约0～12重量％，优选为约0.1～6重量％，更优选为约0.25～3重量％。
已知的防沫剂包括但不限于有机硅氧烷，例如二甲基硅氧烷等。可以使用它们的组合。防沫剂的用量以成品液态混合物的重量计通常为约0～1重量％，优选为约0.02～0.5重量％，更优选为约0.05～0.2重量％。
粘度改进剂也是已知的并可以商购获得。可以使用粘度改进剂的组合。粘度改进剂存在的量以成品液态混合物计为约0～20％，优选为约5～15％，更优选为约7～10％。VI改进剂可以同时提供粘度改进特性和分散特性。分散剂-粘度改进剂的实例包括但不限于乙烯基吡啶、N-乙烯基吡咯烷酮和N，N’-二甲基氨基乙基异丁烯酸酯是含氮单体的实例。由一种或多种烷基丙烯酸酯的聚合或共聚得到的聚丙烯酸酯也可用作粘度改进剂。
官能化聚合物也可以用作粘度指数改进剂。这种聚合物的常见类型有烯烃共聚物和丙烯酸酯或甲基丙烯酸酯的共聚物。官能化烯烃共聚物例如可以是用活性单体例如马来酸酐接枝和然后用醇或胺衍生的乙烯和丙烯的共聚物，如美国专利4,089,794中所述的。另外的这种共聚物是与氮化合物反应或用氮化合物接枝的乙烯和丙烯的共聚物，如美国专利4,068,056中所述的。聚丙烯酸酯的衍生物是公知的分散剂-粘度指数改进剂添加剂。分散剂丙烯酸酯或聚甲基丙烯酸酯粘度改进剂是特别有用的，例如RohMax的AcryloidTM 985或ViscoplexTM 6-054。固态油溶性聚合物也可用作粘度指数改进剂，例如美国专利4,014,794中所述的PIB、甲基丙烯酸酯、聚烷基苯乙烯、乙烯/丙烯和乙烯/丙烯/1，4-己二烯聚合物。
附加成分
如上所述，本发明的特殊优点在于润滑添加剂凝胶22可以以原样使用，即不存在附加成分，这是因为不需要早期体系中所用类型的惰性载体来支持或计量其润滑添加剂。当然，如果需要，可以使用这种惰性载体。此外，润滑添加剂凝胶22也可以包含其他活性成分，即为过滤的油提供有益功能的成分。例如，如果需要，也可以包含不参与凝胶形成反应的附加的油溶性润滑添加剂。此外，也可以包含固态颗粒添加剂，例如美国专利6,045,692中所示的PTFE、MoS2和石墨。另外通过引用将该专利的公开内容并入本文。此外，也可以包含上文背景部分提到的专利中所述的固态油溶性和油可润湿性颗粒。
实际上，根据本发明，基本不含惰性载体但是包含大量的一种或多种附加添加剂的润滑添加剂凝胶特别引人关注。因而，根据本发明，包含5、10、15、20、25、30、35或甚至40％或更多的所述附加润滑添加剂并且存在或不存在惰性载体的润滑添加剂凝胶特别引人关注。可以使用包含抗氧化剂、粘度指数改进剂、减磨剂、防沫剂和/或附加油溶性润滑添加剂作为附加的非凝胶化成分的润滑添加剂凝胶。
实施例
为了更透彻地说明本发明，提供了下面的实施例。在这些实施例中，测试了两种不同的润滑剂配方。各配方均包含N∶CO比为0.83和马来酸酐转化率为1.6的PIB-琥珀酰亚胺分散剂，其通过对Mn为2000的PIB聚合物进行Cl2辅助的琥珀酰化而制得。各配方均还包含总碱值为300或400的过碱性烷基磺酸钙清净剂。各配方还包含作为抗氧化剂的壬基化二苯胺。这两种不同配方的组成列于下表中：
表1
| 组分 | 配方A(wt％) | 配方B(wt％) |
| 300TBN钙-清净剂 | 15 | 5 |
| 400TBN钙-清净剂 | - | 10 |
| PIB-琥珀酰亚胺分散剂 | 5 | 5 |
| 抗氧化剂 | 5 | 5 |
| 总计 | 25 | 25 |
以上配方是通过将以上列出的成分按上文给出的顺序混合在一起而制得的。然后，将由此得到的混合物在室温下放置1周，或者加热至60～100℃约1小时。然后用小幅振荡剪切测试法确定各配方的凝胶性质，如用损耗角正切tanδ来衡量，并且发现配方A没有形成凝胶(tanδ值＞＞1.0)，而配方B形成tanδ值约为0.3的凝胶。
驾驶测试
本发明的凝胶化润滑添加剂缓慢释放到过滤油中的能力是通过驾驶测试来确定的，在每次测试中驾驶1989 Honda Accord行进达366英里，其中近似一半行程是在高速公路上，另一半在停止和行驶的交通中。在每次测试开始时，向该Accord的4夸脱机油箱中装入新供料Valvoline AllClimate 10w-40机油，并周期地取出正被过滤的机油样品以确定其清净剂浓度。以两种不同的方式来测定清净剂的浓度，其中通过ICP确定油中钙的百分率，通过ASTM D4739确定总碱值。
进行3次独立的测试，分别使用图2中所示具有一般结构的FRAMPH3593A油滤清器。在第一次测试中，对照样1，滤清器中不包括润滑添加剂。在第二次测试中，对比实施例A，将约25gms非胶凝化配方A置于滤清器“较脏”侧的减压阀的上面，如图中122处所示。在第三次测试中，实施例1，滤清器中包括约25gms的本发明的胶凝化配方B。
所得结果列在下表2中。
表2
驾驶测试
清净剂浓度
| 钙％ | TBN | |||||
| 英里 | 对照样1 | 对比实施例A | 实施例1 | 对照样1 | 对比实施例A | 实施例1 |
| 0 | 0.1841 | 0.1925 | 0.1928 | 5.7 | 5.9 | 6 |
| 9 | 0.2251 | 0.2102 | 6.6 | 6.9 | ||
| 16 | 0.1916 | 5.7 | ||||
| 48 | 0.1937 | 5.6 | ||||
| 67 | 0.2319 | 6.6 | ||||
| 116 | 0.2013 | 5.2 | ||||
| 117 | 0.2322 | 6.7 | ||||
| 137 | 0.2299 | 6.3 | ||||
| 210 | 0.1977 | 5.5 | ||||
| 260 | 0.1998 | 5.2 | ||||
| 366 | 0.2441 | 6.8 | ||||
从表2中可以看出，被对照滤清器过滤的油中钙浓度在测试过程中基本保持恒定，表明清净剂浓度恒定(仅有钙源)。相比较而言，在使用非胶凝化配方A的对比实施例A中，清净剂浓度立即上升至相对高的水平，并在测试过程中保持在该水平。这表明非胶凝化混合物中存在的润滑添加剂不是缓慢地释放到油中的，而是当一旦使用滤清器时就几乎完全释放。但是，在根据本发明的实施例1中，钙浓度在测试过程中缓慢上升，并且直至测试终点仍在上升。这表明该滤清器中的胶凝化润滑添加剂缓慢地释放到被过滤的油中，从而证实了所述胶凝化润滑添加剂的缓释能力。
固定发动机测试
重复以上测试，不同之处在于使用在最大输出为6500瓦的发电机上的固定式Honda ES6500型内燃机(最大马力12.2，排量359cc)。该发动机具有以2.25gpm速率过滤的1.5夸机油箱。该发动机在平均油温为93℃下连续运行(即功率恒定)，并要求以6盎司/天的补充速率来补充油。
进行4次不同的测试，一个是使用不添加润滑油的对照样，一个是使用配方A的对比实施例，另2个是使用配方B的本发明实施例。实施例3不同于所有其他实施例的地方在于当充入配方B之后但在使用之前，将滤清器的外部加热约至100～200℃约5分钟。该实施例的目的是确定热是否会对滤清器的性能造成不利影响。
所得结果列在下表3中：
表3
固定发动机测试
清净剂浓度
| 钙％ | TBN | |||||||
| 小时 | 对照样2 | 对比实施例B | 实施例2 | 实施例3 | 对照样2 | 对比实施例B | 实施例2 | 实施例3 |
| 0 | 0.1925 | 0.1925 | 0.1925 | 0.1925 | 5.9 | 5.9 | 5.9 | 5.9 |
| 24 | 0.1968 | 0.3135 | 0.2069 | 0.2650 | 5.2 | 7.9 | 5.3 | 5.8 |
| 48 | 0.1996 | 0.3036 | 0.2278 | 0.2131 | 4.7 | 7.3 | 5.5 | 5.9 |
| 72 | 0.2024 | 0.2184 | 0.2246 | 4.8 | 8.2 | 5.5 | 4.9 | |
| 96 | 0.1939 | 0.3384 | 0.2198 | 0.2253 | 5.0 | 8.1 | 5.2 | 5.0 |
| 120 | 0.2073 | 0.3268 | 0.2241 | 0.2300 | 4.4 | 7.7 | 5.0 | 5.2 |
类似前面的测试，这些测试也表明当使用非胶凝化配方A时，钙浓度在过滤开始后立即上升至相对高的稳定值。对照而言，当使用根据本发明的胶凝化配方B时，钙浓度的上升缓慢得多。这再次证实了本发明凝胶的缓释能力。实施例3还表明商业涂饰操作不会对本发明凝胶的性能不利影响。
固定发动机测试-袋装添加剂
重复以上固定式发动机测试，不同之处在于在放入滤清器之前，将润滑添加剂配方置于LLDPE(线型低密度聚乙烯)袋中。这样做是为了有助于对添加剂配方进行处理，因为这些袋是由在操作温度下与油接触时可以溶解或熔化的材料制成的，从而释放出添加剂凝胶配方用于与被过滤的油接触。
进行3次测试，一个是无添加剂组合体的对照样，一个是使用配方A的对比实施例，另一个是使用配方B的本发明实施例。所得结果列在下表4中：
表4固定式发动机测试
清净剂浓度
| 钙％ | TBN | |||||
| 小时 | 对照样3 | 对比实施例C | 实施例4 | 对照样3 | 对比实施例C | 实施例2 |
| 0 | 0.1925 | 0.1925 | 0.1925 | 5.9 | 5.9 | 5.9 |
| 24 | 0.1892 | 0.2056 | 4.6 | 5.5 | ||
| 48 | 0.1871 | 0.2017 | 4.5 | 8.3 | 5.2 | |
| 72 | 0.1955 | 0.3020 | 0.2058 | 3.5 | 8.4 | 5.2 |
| 96 | 油泄漏 | 0.3015 | 0.2211 | 油泄漏 | 8.2 | 4.1 |
| 120 | 0.2638 | 0.2194 | 7.1 | 4.2 | ||
类似前面的固定式发动机测试，这些测试也表明凝胶形式的润滑添加剂组合体可以以缓慢释放的方式将润滑添加剂供给被过滤的油，而包含基本相同的非胶凝化形式添加剂组合体的基本相同的滤清器不能达到该效果。
虽然上文仅描述了本发明的一些实施方案，但是应该认识到可以在不偏离本发明的精神和范围下进行多种变换。所有这样的变换均包括在本发明的范围内，本发明的范围仅由下面的权利要求来限定。
Claims (17)
1.一种润滑添加剂组合体，其包含一种或多种以可以缓慢地将所述润滑添加剂组分释放到液体中的润滑添加剂凝胶形式的润滑添加剂。
2.根据权利要求1所述的润滑添加剂组合体，其中所述润滑添加剂凝胶通过使至少两种选自清净剂、分散剂、酸、碱、过碱性清净剂和其组合的润滑添加剂凝胶化而制成。
3.根据权利要求1所述的润滑添加剂组合体，其中所述润滑添加剂凝胶由清净剂和分散剂制得。
4.根据权利要求2所述的润滑添加剂组合体，其中所述分散剂是无灰分散剂或聚合物分散剂。
5.根据权利要求2所述的润滑添加剂组合体，其中所述清净剂是磺酸盐、酚盐、水杨酸盐、羧酸盐或其混合物。
6.根据权利要求2所述的润滑添加剂组合体，其中所述分散剂选自N取代的长链烯基琥珀酰亚胺、聚异丁烯琥珀酰亚胺、高分子量酯、曼尼希碱、胺分散剂、聚合物分散剂或其混合物。
7.根据权利要求2所述的润滑添加剂组合体，其中所述润滑添加剂凝胶包含至少一种不参与凝胶形成的附加润滑添加剂，所述附加润滑添加剂选自抗氧化剂、防沫剂、减磨剂、粘度改进剂、极压剂或其混合物。
8.根据权利要求1所述的润滑添加剂组合体，其中所述润滑添加剂凝胶的tanδ值≤1。
9.根据权利要求1所述的润滑添加剂组合体，其中所述组合体的至少30wt％由通过混合TBN至少为300的过碱性清净剂和具有至少一种下述性质的聚异丁烯琥珀酰亚胺分散剂而形成的凝胶组成：
(a)所述聚异丁烯琥珀酰亚胺的N∶CO比为0.6～1.6，
(b)所述聚异丁烯琥珀酰亚胺的马来酸酐转化程度为至少约1.3，
(c)所述聚异丁烯琥珀酰亚胺的聚异丁烯基片段的Mn为至少约1200，和
(d)所述聚异丁烯琥珀酰亚胺通过Cl2辅助的琥珀酰化制得，和其中所述润滑添加剂组合体的tanδ值≤1。
10.一种为液体提供一种或多种润滑油添加剂的方法，其包括将所述液体与润滑添加剂凝胶接触。
11.根据权利要求10所述的方法，其中所述润滑添加剂凝胶通过使至少两种选自清净剂、分散剂、酸、碱、过碱性清净剂和其组合的润滑添加剂凝胶化而制得。
12.根据权利要求10所述的方法，其中所述润滑添加剂凝胶由清净剂和分散剂制得，并且其tanδ值≤1。
13.根据权利要求12所述的方法，其中所述分散剂选自N取代的长链烯基琥珀酰亚胺、聚异丁烯琥珀酰亚胺、高分子量酯、曼尼希碱、胺分散剂、聚合物分散剂或其混合物，所述清净剂选自磺酸盐、酚盐、水杨酸盐、羧酸盐或其混合物。
14.一种用于润滑系统的油滤清器，其包括壳体、用于从通过滤清器的油中除去颗粒物质的过滤器和用于缓慢释放到所述油中的润滑添加剂，其中所述润滑添加剂为润滑添加剂凝胶的形式。
15.根据权利要求14所述的油滤清器，其中所述润滑添加剂凝胶通过使至少两种选自清净剂、分散剂、酸、碱、过碱性清净剂和其组合的润滑添加剂凝胶化而制得。
16.根据权利要求14所述的油滤清器，其中所述润滑添加剂凝胶由清净剂和分散剂制得，并且其tanδ值≤1。
17.根据权利要求15所述的油滤清器，其中所述清净剂是TBN至少为300的过碱性清净剂，并且另外所述分散剂是具有至少一种下述性质的聚异丁烯琥珀酰亚胺：
(a)所述聚异丁烯琥珀酰亚胺的N∶CO比为0.6～1.6，
(b)所述聚异丁烯琥珀酰亚胺的马来酸酐转化程度为至少约1.3，
(c)所述聚异丁烯琥珀酰亚胺的聚异丁烯基片段的Mn为至少约1200，和
(d)所述聚异丁烯琥珀酰亚胺通过Cl2辅助的琥珀酰化制得。
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-
2002
- 2002-07-16 US US10/196,441 patent/US6843916B2/en not_active Expired - Lifetime
-
2003
- 2003-07-10 CN CNB038168030A patent/CN1304541C/zh not_active Expired - Fee Related
- 2003-07-10 MX MXPA05000600A patent/MXPA05000600A/es active IP Right Grant
- 2003-07-10 EP EP10011055A patent/EP2284248A3/en not_active Withdrawn
- 2003-07-10 BR BRPI0312711-7A patent/BR0312711B1/pt not_active IP Right Cessation
- 2003-07-10 CA CA002492293A patent/CA2492293A1/en not_active Abandoned
- 2003-07-10 KR KR1020057000768A patent/KR101046837B1/ko not_active IP Right Cessation
- 2003-07-10 JP JP2004521945A patent/JP4478017B2/ja not_active Expired - Fee Related
- 2003-07-10 WO PCT/US2003/022331 patent/WO2004007653A2/en active Application Filing
- 2003-07-10 AU AU2003253966A patent/AU2003253966B2/en not_active Ceased
- 2003-07-10 EP EP03764779.9A patent/EP1622996B1/en not_active Expired - Lifetime
-
2004
- 2004-10-13 US US10/964,435 patent/US7417012B2/en not_active Expired - Fee Related
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2008
- 2008-05-28 US US12/128,042 patent/US7799745B2/en not_active Expired - Fee Related
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2010
- 2010-08-23 US US12/861,148 patent/US8076273B2/en not_active Expired - Fee Related
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102388120A (zh) * | 2009-02-09 | 2012-03-21 | 卢布里佐尔公司 | 改进官能流体性能的方法 |
| CN102575187A (zh) * | 2009-08-04 | 2012-07-11 | 卢布里佐尔公司 | 具有速释和缓释组分的组合物 |
| CN104302747A (zh) * | 2012-05-15 | 2015-01-21 | 巴斯夫欧洲公司 | 新的低粘度功能性流体组合物 |
| CN104302747B (zh) * | 2012-05-15 | 2016-12-28 | 巴斯夫欧洲公司 | 新的低粘度功能性流体组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| BR0312711A (pt) | 2005-04-26 |
| US7417012B2 (en) | 2008-08-26 |
| US20120067798A1 (en) | 2012-03-22 |
| JP4478017B2 (ja) | 2010-06-09 |
| US20100317553A1 (en) | 2010-12-16 |
| US20050085399A1 (en) | 2005-04-21 |
| JP2005533155A (ja) | 2005-11-04 |
| KR101046837B1 (ko) | 2011-07-06 |
| AU2003253966B2 (en) | 2009-01-22 |
| EP2284248A3 (en) | 2012-07-04 |
| US7799745B2 (en) | 2010-09-21 |
| EP1622996A1 (en) | 2006-02-08 |
| US20040014614A1 (en) | 2004-01-22 |
| KR20050028031A (ko) | 2005-03-21 |
| MXPA05000600A (es) | 2005-04-19 |
| BR0312711B1 (pt) | 2014-10-07 |
| US6843916B2 (en) | 2005-01-18 |
| CA2492293A1 (en) | 2004-01-22 |
| US8076273B2 (en) | 2011-12-13 |
| US8299000B2 (en) | 2012-10-30 |
| WO2004007653A9 (en) | 2004-06-10 |
| AU2003253966A1 (en) | 2004-02-02 |
| WO2004007653A2 (en) | 2004-01-22 |
| EP2284248A2 (en) | 2011-02-16 |
| CN1304541C (zh) | 2007-03-14 |
| EP1622996B1 (en) | 2014-07-02 |
| US20080257803A1 (en) | 2008-10-23 |
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