CN105247023A - Vibration resistant industrial gear oils - Google Patents
Vibration resistant industrial gear oils Download PDFInfo
- Publication number
- CN105247023A CN105247023A CN201480030110.0A CN201480030110A CN105247023A CN 105247023 A CN105247023 A CN 105247023A CN 201480030110 A CN201480030110 A CN 201480030110A CN 105247023 A CN105247023 A CN 105247023A
- Authority
- CN
- China
- Prior art keywords
- industrial gear
- oil composition
- gear oil
- ester
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000010722 industrial gear oil Substances 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 claims abstract description 157
- 239000000654 additive Substances 0.000 claims abstract description 45
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- 150000001875 compounds Chemical class 0.000 claims description 51
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- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 150000002148 esters Chemical class 0.000 claims description 21
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- 238000000034 method Methods 0.000 claims description 20
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- 230000015572 biosynthetic process Effects 0.000 claims description 8
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- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N methyl heptene Natural products CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N n-hexene Natural products CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- TYQTYRXEMJXFJG-UHFFFAOYSA-N phosphorothious acid Chemical class OP(O)S TYQTYRXEMJXFJG-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1 JZALLXAUNPOCEU-UHFFFAOYSA-N 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
-
- 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/08—Ammonium or amine 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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
-
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
-
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
-
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/043—Ammonium or amine 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/049—Phosphite
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/76—Reduction of noise, shudder, or vibrations
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
Abstract
The invention relates to industrial gear oil compositions that have been specially designed to be vibration resistant. That is the industrial gear oil compositions of the invention provide good performance and/or protection even when the equipment in which the composition is used is subjected to external vibration, including but not limited to vibration during transportation of the equipment. The industrial gear oil compositions include a combination of additives that provide surprisingly good protection against damage caused by vibration.
Description
The present invention relates to the Industrial gear oil composition being specifically designed as anti-vibration.That is, Industrial gear oil composition of the present invention provides good performance and/or protection, even if the equipment that composition is used for wherein stands external vibration, includes but not limited to vibrate during equipment conveying.Industrial gear oil composition comprises provides surprising good protection in case by the additive combination vibrating the infringement caused.
background of invention
The industrial gearbox operated in grinding machine or device usually stands vibratory stress or is derived from vibration that is nearest or surrounding devices.The source of this vibration can be wheel casing, motor, pump etc. near other.In addition, industrial gearbox during transportation can meet with vibratory stress.Backlash also can be the vibration source of industrial gearbox.
Many industrial gearboxes are not used in mobile equipment, but are a part for stationary installation.This kind of device, comprises the industrial gearbox be present in device and is not usually designed for reactivity, is also not used in the power standing to occur along with movement, the ability of involving vibrations.But this equipment nearly all and/or its assembly must at some points being transported to device assembles and/or operation from its manufacturing site location.
Can for long and during this haulage stage relating to railway and/or transport by road, equipment, comprising industrial gearbox stands much power and stress, involving vibrations.It should be pointed out that this vibration is not itself caused by the operation of industrial gearbox, but the external vibration usually stood when it be industrial gearbox itself is non-operating state.Namely the internals of industrial gearbox itself do not move, or at least its each normal running, are not mobile.
Similarly, even after industrial gearbox is installed, it usually by the miscellaneous equipment that usually operates around, even if the inoperation of industrial gearbox own.This surrounding devices can produce the various power and stress that can act on industrial gearbox, involving vibrations, as the above-mentioned power during transportation experienced.
Therefore produce unique environment, wherein industrial gearbox is through stressed and stress, comprises external vibration described in this, and wherein the Industrial gear oil composition of non-specialized designs industrial gearbox and industrial gearbox inside is used for it.That is, the Industrial gear oil composition of industrial gearbox and their inside is usually with the industrial gearbox of operation and imagination, operate by this power and stress design that cause, and provides good protection and performance between this working life.The condition that industrial gearbox experiences during the no-operation stage and stress, comprise In transit and may to experience and/or vibration from neighbouring operating equipment is left in the basket usually.
Find that this vibration may cause noticeable wear in industrial gearbox and premature fatigue and/or fault; even if regular industrial gear oil composition is present in industrial gearbox, and the wearing and tearing that cause of this vibration and premature fatigue can reduce the work-ing life of equipment and produce higher cost of equipment maintenance and stop time.
Still need to develop Industrial gear oil composition, described composition not only can provide acceptable performance and protection between the working life of industrial gearbox, and stands external force and stress at industrial gearbox, provides protection during comprising the no-operation of external vibration.
summary of the invention
The invention provides to be designed for and stand external force and stress at industrial gearbox, the Industrial gear oil composition of protection was provided during the no-operation stage comprising external vibration.These Industrial gear oil composition also can provide acceptable performance and protection between the working life of industrial gearbox using them.Disclosed technology providing package is containing the Industrial gear oil composition with the oil of lubricant viscosity, P contained compound and sulfurized fatty ester.
In some embodiments, P contained compound does not contain substantially, or not phosphate ester-containing and/or its amine salt even completely.
The invention provides described Industrial gear oil composition, the oil wherein with lubricant viscosity comprises mineral and/or natural base oil.In some embodiments, the oil base with lubricant viscosity does not originally contain, or even completely not containing synthesis base oil.
The invention provides described Industrial gear oil composition, the oil wherein with lubricant viscosity comprises synthesis base oil.In some embodiments, the oil base with lubricant viscosity does not originally contain, or even completely not containing mineral and/or natural base oil.
The invention provides described Industrial gear oil composition, wherein P contained compound comprises alkyl phosphite (phosphite), phosphoric acid ester, the amine salt of phosphoric acid ester or its some combinations.
The present invention further provides described Industrial gear oil composition, wherein P contained compound comprises alkyl phosphite or its ester.
The invention provides described Industrial gear oil composition, wherein sulfurized fatty ester comprises sulfurized natural oils.
The invention provides described Industrial gear oil composition, wherein sulfurized fatty ester comprises sulfurized rapeseed oil.
The invention provides described Industrial gear oil composition, wherein sulfurized fatty ester comprises one or more other additives further.These other additives for olefine sulfide (being different from sulfurized fatty ester), phosphoric acid ester, thiophosphate, thiophosphatephosphorothioate and/or its amine salt, thiadiazoles and/or can replace thiadiazoles, tolyl-triazole and/or substituted triazole, polyethers, alkenyl amine and/or polyolefin amide alkene amine, ester copolymer, carboxylicesters, dispersion agent, hydrocarbon polymer, or its any combination, comprises more than a kind of other additive any.
In some embodiments, these other additives are not containing antioxidant.In some embodiments, the not fatty amine of these other additives.In some embodiments, these other additives are not containing high total basicnumber overbased detergent.In some embodiments, these other additives are not containing zinc dithiophosphate.
The present invention further provides described Industrial gear oil composition, wherein in Industrial gear oil composition, the weight ratio of P contained compound and sulfurized fatty ester is 1:10-10:1.In other embodiments, weight ratio is 1:1-1:10, or 1:5-5:1, or 1:1-1:5, or 1:1-1:3, or even about 1:2.
The present invention further provides described Industrial gear oil composition, wherein P contained compound exists with the 0.1-10 of total Industrial gear oil composition % by weight, and sulfurized fatty ester exists with the 0.1-20 of total Industrial gear oil composition % by weight.
The present invention further provides the method preparing Industrial gear oil composition, described method comprises step: (a) is had the mixing of the oil of lubricant viscosity, (b) P contained compound and (c) sulfurized fatty ester by (1), produces Industrial gear oil composition.The method can be used for preparing any Industrial gear oil composition as herein described.
The present invention further provides the method for the vibration resistance improving Industrial gear oil composition, described method comprises step: (1) adds (b) P contained compound and (c) sulfurized fatty ester to comprising (a) and having in the Industrial gear oil composition of the oil of lubricant viscosity, produces the Industrial gear oil composition with the vibration resistance of improvement.The method can use any Industrial gear oil composition as herein described.
The present invention further provides the purposes that additive-package improves the vibration resistance of Industrial gear oil composition, wherein Industrial gear oil composition comprises the oil that (a) has lubricant viscosity, and wherein additive-package comprises (b) P contained compound and (c) sulfurized fatty ester.This purposes can use any Industrial gear oil composition as herein described.
detailed Description Of The Invention
Set forth below by indefiniteness and describe each preferred feature and embodiment.
The invention provides Industrial gear oil composition, it comprises the oil that (a) has lubricant viscosity; (b) P contained compound; (c) sulfurized fatty ester.
there is the oil of lubricant viscosity
The present composition comprises the oil with lubricant viscosity.
The oil with lubricant viscosity with regard to lubricant compositions, with primary amount, or for enriched material and/or compositions of additives, can exist with concentrate forming amount.Industrial gear oil composition of the present invention can be lubricant compositions or enriched material and/or compositions of additives.
Suitable oil comprises natural and ucon oil and composition thereof.Preparing in lubricant completely, the oil with lubricant viscosity exists with primary amount (being namely greater than the amount of 50 % by weight) usually.Usually, have the 75-98 % by weight of oil with total composition of lubricant viscosity, the amount being usually greater than 80 % by weight exists.
The oil with lubricant viscosity can comprise natural and synthetic oil, derived from hydrocracking, hydrogenation and hydrorefined oil, non-refining, refining and refining oil or its mixture again.Non-refining oil is usually without (or seldom) purification processes further, directly obtained by natural or synthesis source those.Refining oil is similar to non-refining oil, unlike they being processed to improve one or more performances further in one or more purification step.Purification techniques is as known in the art, comprises solvent extraction, second distillation, acid or alkali extraction, filtration, diafiltration and similar approach.Refining oil is also referred to as regeneration or reprocessed oils again, and is obtained by the method be similar to for obtaining refining oil.Usually by refining oil again by being intended to the technology processing removing useless additive and oil decomposition product.
Natural oil as the oil with lubricant viscosity comprises animal oil and vegetables oil (such as Viscotrol C, lard), mineral lubricating oils as the solvent treatment of liquid petroleum or paraffinic hydrocarbons, naphthenic hydrocarbon or combination chain alkane naphthenic type or acid-treated mineral lubricating oils, with the oil derived from coal or shale, or its mixture.
The synthetic oil with lubricant viscosity comprises hydrocarbon ils, such as polymerization and copolyolefine (such as polybutene, polypropylene, propylene isobutylene copolymers); Poly-(1-hexene), poly-(1-octene), poly-(1-decene) and composition thereof; Alkylbenzene (such as dodecylbenzene, Tetradecylbenzene, dinonyl benzene, two-(2-ethylhexyl) benzene); Polyphenyl (such as biphenyl, terphenyl, alkylated polyphenyls); Alkylated dipheny ethers and alkylated diphenyl sulfides and derivative, analogue and homologue or its mixture.In some embodiments, for the oil with lubricant viscosity in the present invention for comprising the synthetic oil of polymerization polyisobutene, in some embodiments, for the oil with lubricant viscosity in the present invention for comprising the synthetic oil of polymerization polyisobutene and polyalphaolefin.
Another synthetic oil with lubricant viscosity comprise be different from alkyl end-blocking polyalkylene polyol as described herein polyol ester, dicarboxylic ester, phosphoric acid liquid ester (such as the diethyl ester of Tritolyl Phosphate, trioctyl phosphate and decane phosphonic acids), or polytetrahydrofuran.The conventional synthetic oil with lubricant viscosity also comprises those that prepared by fischer-tropsch reaction, can be F-T synthesis hydrocarbon or the wax of hydroisomerizing usually.In one embodiment, the oil with lubricant viscosity by Fischer-Tropsch gas to the preparation of liquid (gastoliquid) synthesis program and other gas to liquid oil.
The oil with lubricant viscosity can define further as described in AmericanPetroleumInstitute (API) BaseOilInterchangeabilityGuidelines.Five groups of base oils are as follows: I group (sulphur content >0.03 % by weight, and/or <90 % by weight saturates, viscosity index 80-120); II group (sulphur content≤0.03 % by weight, and >=90 % by weight saturatess, viscosity index 80-120); III group (sulphur content≤0.03 % by weight, and >=90 % by weight saturatess, viscosity index >=120); IV group (all polyalphaolefins or PAO, such as PAO-2, PAO-4, PAO-5, PAO-6, PAO-7 or PAO-8); With V group (comprise " all other ").The oil with lubricant viscosity comprises APII group, II group, III group, IV group, V group oil or its mixture.In one embodiment, the oil with lubricant viscosity is APII group, II group, III group, IV group oil or its mixture.As selection, the oil with lubricant viscosity is generally APIII group, III group or IV group oil or its mixture.
In some embodiments, lubricating oil component of the present invention comprises II group or III group base oil or its combination.Oil also can derived from wax, the hydroisomerization of such as slack wax or Fischer Tropsch waxes.This kind of " gas is to liquid " oil is characterized by III group usually.
The present composition can comprise the I group base oil of a tittle, and even IV group and V group base oil.But in some embodiments, lubricating oil component of the present invention comprises no more than 20,10,5 or even 1 % by weight I group base oil.These limit are also applicable to IV group and V group base oil.In other embodiments, the lubricating oil be present in the present composition is at least 60,70,80,90 or even 98 % by weight II group and/or III group base oils.In some embodiments, the lubricating oil be present in the present composition is only II group and/or III group base oil substantially, wherein can there is the base oil of other type a small amount of, but not be the attribute of remarkably influenced total composition or the amount of performance.
In some embodiments, the present composition comprises I group and/or the II group base oil of a tittle.In other embodiments, the present composition is oil mainly I group and/or the II group base oil wherein with lubricant viscosity, or is I group and/or II group base oil even substantially, or the lubricating composition of even only I group and/or II group base oil.
In some embodiments, the invention provides II group composition, the oil namely with lubricant viscosity comprises II group oil, and if not only, and can even mainly II group be oily.
The oil described in various with lubricant viscosity can use alone or in combination.The oil with lubricant viscosity can with about 40 % by weight to about 99.6 % by weight, or the minimum value to 99.6 of 49.8,70,85,93,93.5 or even 97,98.8,98.3 or even 96.8 % by weight maximum value be used in described industrial gear lubricant composition.In other embodiments, have lubricant viscosity oil can with 40,65,73,73.5 or even 81 minimum value to 99.6,99.5, the maximum value of 98.6,94.1,88.3 or even 80.8 % by weight uses.
p contained compound
The present composition comprises P contained compound.
P contained compound can comprise the amine salt of alkyl phosphite, phosphoric acid ester, phosphoric acid ester, or its any combination.In some embodiments, P contained compound comprises alkyl phosphite (ester) (phosphite), its ester or its combination.In some embodiments, P contained compound comprises alkyl phosphite.
In some embodiments, alkyl phosphite is alkyl phosphite.Alkyl means the alkyl only comprising carbon and hydrogen atom, but expects saturated or unsaturated alkyl, or even its mixture.In some embodiments, P contained compound comprises the alkyl phosphite with complete saturated alkyl.In some embodiments, P contained compound comprises and has that some are unsaturated, such as the alkyl phosphite of the alkyl of a double bond between carbon atom.This kind of unsaturated alkyl also can be described as thiazolinyl, but unless otherwise noted, is included in term as used herein " alkyl ".
In some embodiments, P contained compound comprises alkyl phosphite, phosphoric acid ester, the amine salt of phosphoric acid ester or its any combination.In some embodiments, P contained compound comprises alkyl phosphite, its ester or its combination.In some embodiments, P contained compound comprises alkyl phosphite.
In some embodiments, P contained compound comprises the amine salt of thiazolinyl phosphite, phosphoric acid ester, phosphoric acid ester, or its any combination.In some embodiments, P contained compound comprises thiazolinyl phosphite, its ester or its combination.In some embodiments, P contained compound comprises thiazolinyl phosphite.
In some embodiments, P contained compound comprises dialkyl group phosphorous acid hydrogen salt.
In some embodiments, P contained compound does not contain substantially, or not phosphate ester-containing and/or its amine salt even completely.
In some embodiments, P contained compound can be described as fatty phosphites.Suitable phosphite comprises and has at least one and have 4 or more, or 8 or more, or those of the alkyl of 12 or more carbon atoms.On alkyl, carbonatoms object typical range comprises 8-30, or 10-24, or 12-22, or 14-20, or 16-18.Phosphite can be phosphite, the phosphite of dialkyl replacement or the phosphite of trialkyl replacement that single alkyl replaces.In one embodiment, phosphite is not sulfur-bearing, and namely phosphite is not thiophosphorous acid salt.
There is at least one phosphite with the alkyl of 4 or more carbon atoms can be expressed from the next:
Wherein R
5, R
6and R
7in at least one can for comprising the alkyl of at least 4 carbon atoms, and another can be hydrogen or alkyl.In one embodiment, R
5, R
6and R
7it is all alkyl.Alkyl can be alkyl, cycloalkyl, aryl, acyclic or its mixture.There are all 3 radicals R
5, R
6and R
7formula in, compound can be three-alkyl replace phosphite, i.e. R
5, R
6and R
7being all alkyl, in some embodiments, can be alkyl.
Alkyl can be linear or branching, usually linearly, and saturated or unsaturated, usually saturated.R
5, R
6and R
7the example of alkyl comprise octyl group, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, vaccenic acid base, nonadecyl, eicosyl or its mixture.
In some embodiments, fatty phosphites component of the present invention and/or total composition do not contain substantially, or not phosphate ester-containing and/or its amine salt even completely.
In some embodiments, fatty phosphites comprises thiazolinyl phosphite or its ester, such as the ester of dimethyl phosphorous acid hydrogen salt.Dimethyl phosphorous acid hydrogen salt can for esterification, in some embodiments, by with alcohol as oleyl alcohol reacts and transesterify.
Fatty phosphites can with 0.3-10 % by weight, or in other embodiments, 0.3,0.7 or even 1.2 minimum content to 10,5,2.5, the maximum level of 2.0,1.7,1.5 or even 1.2 % by weight is present in total industrial gear lubricant composition.
sulfurized fatty ester
The present composition comprises sulfurized fatty ester.
These sulfurized fatty esters can comprise the mixture of sulfurized fatty ester and olefine sulfide and/or polysulphide.Olefine sulfide and polysulphide can derived from iso-butylene, butylene, propylene, ethene or its some combinations.In some instances, sulfurized fatty ester is the olefine sulfide derived from any above-mentioned natural oil or synthetic oil or even its some combinations.Such as, sulfurized fatty ester can derived from vegetables oil.
The example of suitable sulfurized fatty ester comprises sulfuration animal or plant fat and/or oily, such as tallow, lard, fish oil, rape seed oil or soybean oil.Other example comprises sulfuration unsaturated fatty acid ester, and wherein ester is reacted by unsaturated fatty acids and one or more various alcohol and obtained.Described sulfurized fatty ester can based on the example of useful unsaturated fatty acids comprise oleic acid, linolic acid, and the lipid acid extracted by above-mentioned animal or plant fat and oil.The specific examples of useful sulfurized fatty ester comprises sulfuration Witconol 2301, the misery ester of sulfuration rice bran fats, sulfurized rapeseed oil and composition thereof.
In some embodiments, sulfurized fatty ester comprises sulfurized natural oils.In some embodiments, sulfurized fatty ester comprises sulfuration animal and/or vegetables oil.In some embodiments, sulfurized fatty ester comprises vulcanized vegetable oil.In some embodiments, sulfurized fatty ester comprises sulfuration unsaturated oil.In some embodiments, sulfurized fatty ester comprises the unsaturated natural oil of sulfuration.In some embodiments, sulfurized fatty ester comprises sulfuration polyunsaturated vegetable oil.
In some embodiments, above-mentioned sulfurized fatty ester comprises one or more olefine sulfides and/or polysulphide further.
In some embodiments, sulfurized fatty ester comprises sulfurized rapeseed oil.
other additive
The present composition can comprise one or more other additives further, and such as the present composition can comprise industrial gear additive-package.In other words, the present composition is designed to industrial gear lubricant or the additive-package for the preparation of it.The present invention does not relate to automobile gear lubricant or other lubricating composition.
Any combination of the conventional additives bag being designed for industrial gear application can be used.The present invention imagines this kind of additive-package inherently substantially not containing above-mentioned P contained compound and sulfurized fatty ester, or does not at least comprise P contained compound and the sulfurized fatty ester of the type of being specified by particular of the present invention.
Other additive that can be present in Industrial gear oil composition of the present invention comprises: demulsifying compound, pour point reducer, antioxidant, dispersion agent, metal passivator (such as copper passivator), anti-wear agent, extreme pressure agent, viscosity modifier or its some mixtures.In some embodiments, additive can separately with 50,75,100 or even 150ppm to 5,4,3,2 or even 1.5 % by weight, or 75ppm to 0.5 % by weight, 100ppm to 0.4 % by weight, or 150ppm to 0.3 % by weight exists, and wherein % by weight value is about total lubricating oil composition.But, should be understood that some additives that can be used as and select to be considered to a part for basic fluid, comprise viscosity modified polymkeric substance and with higher amount, can comprise and reach 30,40 or even 50 % by weight existence when thinking and separating with basic fluid.Other additive described can use separately or as its mixture separately.
Defoamer also referred to as froth suppressor is as known in the art, and includes but not limited to organopolysiloxane and non-silicon froth suppressor.The example of organopolysiloxane comprises dimethyl polysiloxane and polysiloxane.The example of non-silicon froth suppressor includes but not limited to the multipolymer of polyethers, polyacrylic ester and composition thereof and ethyl propenoate, 2-EHA and optional vinyl-acetic ester.In some embodiments, defoamer is polyacrylic ester.Defoamer can with 0.001-0.012 or 0.004pbw or even 0.001 to 0.003pbw be present in composition.
Demulsifying compound is as known in the art, includes but not limited to the derivative of propylene oxide, ethylene oxide, polyoxygenated enol, sequentially with ethylene oxide or replace the alkylamine of ethylene oxide or its mixture reaction, amino alcohol, diamines or polyamines.The example of demulsifying compound comprises polyoxyethylene glycol, polyoxyethylene, polyoxytrimethylene, (ethylene oxide-propylene oxide) polymkeric substance and composition thereof.In some embodiments, demulsifying compound is polyethers.Demulsifying compound can be present in composition with 0.002-0.2pbw.
Pour point reducer is as known in the art, includes but not limited to the ester of maleic anhydride-styrene copolymers; Polymethacrylate; Polyacrylic ester; Polyacrylamide; The condensation product of halogenated paraffins and aromatic substance; Carboxylic acid vinyl ester polymer; With the terpolymer of dialkyl fumarate, vinyl fatty ester, vinyl-vinyl acetate copolymer, alkyl phenol formaldehyde condensation resins, alkyl vinyl ether and composition thereof.
The present composition also can comprise the rust-preventive agent being different from more above-mentioned additives.Suitable rust-preventive agent comprises the alkyl amine salt of dialkyl dithiophosphoric acid, the alkyl amine salt of alkyl arene-sulfonic acids, aliphatic carboxylic acid or its ester, ester, ammonium sulphonate, tetrahydroglyoxaline, single thiophosphate salt or ester containing nitronic acid, or its any combination; Or its mixture.The example of dialkyl dithiophosphoric acid alkyl amine salt of the present invention include but not limited to above-mentioned those, and diheptyl or dioctyl or dinonyl phosphorodithioic acid and quadrol, morpholine or Primene
tMthe reaction product of 81R or its mixture.Be expressed from the next for the suitable alkyl arene-sulfonic acids alkyl amine salt in rust-preventive agent bag of the present invention:
Wherein Cy is benzene or naphthalene nucleus.R
1for having about 4 to about 30, preferably about 6 to about 25, the more preferably from about alkyl of 8 to about 20 carbon atoms.Z independently 1,2,3 or 4, most preferably z is 1 or 2.R
2, R
3and R
4same as described above.The example of alkyl arene-sulfonic acids alkyl amine salt of the present invention includes but not limited to the ethylenediamine salt of dinonylnaphthalene sulfonic acid.The example of suitable fat carboxylic acid or its ester comprises glyceryl monooleate and oleic acid.The example of the suitable ester containing nitronic acid comprises oil base sarkosine.Rust-preventive agent can exist with 0.02-0.2,0.03-0.15,0.04-0.12 or 0.05-0.1 of lubricating oil composition % by weight.Rust-preventive agent of the present invention can use separately or with its mixture.
Lubricating composition of the present invention also can comprise metal passivator.The katalysis be oxidized in lubricating oil with metal promoted during metal passivator is used for.Suitable metal passivator includes but not limited to triazole, tolyl-triazole, thiadiazoles or its combination and derivative thereof.Example comprises and is different from those benzotriazole derivatives, benzoglyoxaline, 2-alkyl dithio benzoglyoxaline, 2-alkyl dithio benzothiazole, 2-(N above-mentioned, N '-dialkyl dithio-carbamyl) benzothiazole, 2, two (alkyl-dithio)-1 of 5-, 3,4-thiadiazoles, 2,5-two (N, N '-dialkyl dithio-carbamyl)-1,3,4-thiadiazoles, 2-alkyl dithio-5-dimercaptothiodiazole or its mixture.These additives can with 0.01-0.25 % by weight in total composition.In some embodiments, metal passivator is alkyl substituted benzene benzotriazole compound.The benzotriazole cpd with hydrocarbyl substituent comprises at least one in following ring position 1-or 2-or 4-or 5-or 6-or 7-benzotriazole.Alkyl containing having an appointment 1 to about 30, preferably about 1 to about 15, more preferably from about 1 to about 7 carbon atom, most preferred metal passivator is 5-Methylbenzotriazole that is independent or that use with its mixture.Metal passivator can exist with 0.001-0.5,0.01-0.04 or 0.015-0.03pbw of lubricating oil composition.Metal passivator also can be present in composition with 0.002 or 0.004 to 0.02pbw.Metal passivator can use separately or with its mixture.
Also can there is antioxidant, comprise (i) alkylated diphenylamine and (ii) substituted hydrocarbon radical monosulphide.In some embodiments, alkylated diphenylamine of the present invention is two-nonylated diphenylamine and two-octylated diphenylamine.In some embodiments, substituted hydrocarbon radical monosulphide comprises dodecyl-2-hydroxyethyl thioether, 1-(tertiary dodecylthio)-2-propyl alcohol or its combination.In some embodiments, substituted hydrocarbon radical monosulphide is 1-(tertiary dodecylthio)-2-propyl alcohol.Antioxidant bag also can comprise sterically hindered phenol.The example of the suitable alkyl of sterically hindered phenol includes but not limited to 2-ethylhexyl or n-butyl, dodecyl or its mixture.The example of methylene-bridged sterically hindered phenol includes but not limited to 4,4 '-methylene radical-bis-(6-butyl o-cresol), 4,4 '-methylene radical-bis-(2-tert-pentyl-ortho-cresol), 2,2 '-methylene radical-bis-(4-methyl-6-tert butyl phenol), 4,4 '-methylene radical-bis-(2,6-, bis--tert-butyl phenol) or its mixture.
In some embodiments, other additive of existence comprises nitrogenous dispersion agent, and such as alkyl replaces nitrogenous additive.Suitable alkyl replaces nitrogenous additive and comprises ashless dispersant and polymeric dispersant.Ashless dispersant appellation like this is because they do not comprise metal when providing, and does not therefore contribute vitriol ash when adding in lubricant.But, certainly, when they being added in the lubricant comprising containing metal species, they may with the metal interaction of surrounding.The feature of ashless dispersant is connected to the polar group on higher molecular weight hydrocarbon chain.The example of this kind of material comprises succinimide dispersants, Mannich dispersant and berated derivatives thereof.
In some embodiments, other additive of existence comprises the sulfocompound being different from above-mentioned sulfurized fatty ester.This kind of sulfocompound can comprise olefine sulfide and polysulphide.Olefine sulfide or polysulphide can derived from iso-butylene, butylene, propylene, ethene or its some combinations.
In some embodiments, other additive existed comprises one or more phosphamidon salt (being different from above-mentioned P contained compound), but be a certain amount of, gained industrial gear lubricant composition is made to comprise no more than 1.0 % by weight, or not even more than 0.75 or 0.6 % by weight this kind of material, in other embodiments, gained industrial gear lubricant composition does not substantially contain or does not contain this kind of phosphamidon salt even completely.
In some embodiments, other binder component comprises one or more wear preventive additives and/or extreme pressure agent, one or more rust and/or corrosion inhibitor, one or more froth suppressor, one or more demulsifying compounds or its any combinations.In other embodiments, other additive and/or gained industrial gear lubricant composition substantially not containing or even completely not phosphorous amine salt, dispersion agent or the two.
In some embodiments, other additive and/or gained industrial gear lubricant composition comprise demulsifying compound, corrosion inhibitor, friction improver, or its two or more combination.In some embodiments, corrosion inhibitor comprises tolyl-triazole.In other embodiment again, other binder component and/or gained industrial gear lubricant composition comprise one or more olefine sulfides or polysulphide; One or more phosphamidon salt; One or more thiophosphatephosphorothioates, one or more thiadiazoles, tolyl-triazole, polyethers and/or alkenyl amine; One or more ester copolymers; One or more carboxylicesterss; One or more succinimide dispersants or its any combination.
In some embodiments, the present composition comprises (d) one or more other additives further, other additive described can comprise one or more olefine sulfides, phosphoric acid ester, thiophosphate, thiophosphatephosphorothioate and/or its amine salt, thiadiazoles and/or replace thiadiazoles, tolyl-triazole and/or substituted triazole, polyethers, alkyl and/or alkenyl amine and/or polyolefin amide alkene amine, ester copolymer, carboxylicesters, dispersion agent, hydrocarbon polymer, or its any combination.
The dispersion agent be applicable in the present composition is unduly limited, and can comprise borated dispersants, non-borated dispersants, succinimide dispersants (comprising boration and non-boration succinimide dispersants), Mannich dispersant etc.
In some embodiments, the present composition is not containing antioxidant.In some embodiments, the not fatty amine of the present composition.In some embodiments, the present composition is containing high TBN overbased detergent (wherein high TBN can mean to have the TBN of >100, >50, >20 or even >10).In some embodiments, the present composition is not containing zinc dithiophosphate.
industrial application
As mentioned above, the present invention includes industrial gear lubricant composition and the industrial gear additive concentrate compositions that can be used for preparing industrial gear lubricant composition.
In industrial gear lubricant of the present invention: component (a) has the oil of lubricant viscosity can with 49.8-99.6, or 70-99.6, or 85-99.6, or 93-99.6, or 93-98.8, or 93.5-98.3 or even with about 96.8 % by weight exist; Component (b) P contained compound can with 0.3-10, or 0.3-5, or 0.3-2, or 0.7-2, or 0.7-1.5, or even exists with about 1.2 % by weight; And component (c) sulfurized fatty ester can with 0.1-20, or 0.1-10, or 0.1-5, or 0.5-5, or 1-5, or 1-4, or 1-3, or even about 2 % by weight exist.
In other embodiments of the present invention, when there are one or more other additives, component (a) has the oil of lubricant viscosity can with 40-99.6, or 40-99.5, or 65-99.5, or 73-98.6, or 73-94.1, or 73-94.1, or 73.5-88.3, or even exist with about 80.8 % by weight; Component (b) P contained compound can with 0.3-10, or 0.3-5, or 0.3-2, or 0.7-2, or 0.7-1.5, or even exists with about 1.2 % by weight; Component (c) sulfurized fatty ester can with 0.1-20, or 0.1-10, or 0.1-5, or 0.5-5, or 1-5, or 1-4, or 1-3, or even about 2 % by weight exist; And one or more other additives of component (d) can with 0 or 0.1 to 50, or 0 or 0.1 to 30, or 0.1-20, or 1-20, or 5-20, or 10-20, or even about 16 % by weight exist.
About each scope of said components by keeping component (b) when existing, (c) compare with identical between (d), the amount of adjustment (a) simultaneously and be applicable to concentrate composition (namely the amount of (a) is much lower compared with lubricant compositions in concentrate composition).In this kind of embodiment, when it is present, % by weight value about component (b), (c) and (d) can be used as weight part (pbw) and treats, wherein oil forms the surplus of concentrate composition, comprise 0 or 0.1 or 0.5 or even 1pbw to 10,20,30 or even 40 or 50pbw in any number.
In some embodiments, in the compositions of the present invention, can be usefully specified ingredients (b) P contained compound relative to the weight ratio of component (c) sulfurized fatty ester.In some embodiments, component (b) is 1:10-10:1 with the weight ratio of component (c), or 1:1-1:10, or 1:5-5:1, or 1:1-5:1, or 1:1-1:3, or 1:1-1:2, or even about 3:5.These are than being applicable to industrial gear lubricant composition of the present invention and/or industrial gear additive concentrate compositions of the present invention.
The present invention includes the method for the above-mentioned industrial gear lubricant composition of preparation and/or industrial gear additive concentrate compositions.These class methods comprise and described component being mixed.Think the particular order of adding or method is not obvious affects result.
The present invention also comprises the method improving industrial gearbox and/or the vibration resistance for the industrial gear oil's lubricant compositions in this industrial gearbox.The method comprising the steps of: (1) adds following component to comprising (a) and having in the Industrial gear oil composition of the oil of lubricant viscosity: (b) P contained compound; (c) sulfurized fatty ester; Produce the Industrial gear oil composition with the vibration resistance of improvement.
The method also can relate to and adds in industrial gearbox by industrial gear lubricant described herein for one; wheel casing is wherein then made to stand external vibration; producing relative to standing the same industry wheel casing of same external vibration and industrial gearbox comprises not containing the industrial gear lubricant of given combination of above-mentioned additive, there is the protection of improvement and/or resistance in case the industrial gearbox of any infringement of being caused by this external vibration and/or wearing and tearing.
Unless otherwise indicated, the amount of described each chemical composition is expressed as to eliminate and usually can be present in any solvent in commercial materials or thinning oil, namely based on active chemical.But unless otherwise indicated, each chemical mentioned herein or composition should be understood to the commercial grade material that can comprise isomer, by product, derivative and usually be to be understood that other this kind of material be present in commercial grade.
As used herein, term " hydrocarbyl substituent " or " alkyl " use with its conventional meaning well known to those skilled in the art.Specifically, it refers to have the carbon atom that is connected directly between on molecule rest part and mainly has the group of hydrocarbon character.The example of alkyl comprises:
-hydrocarbon substituent, i.e. aliphatic series (such as alkyl or alkenyl), alicyclic (such as cycloalkyl, cycloalkenyl group) substituting group, with aromatics-, aliphatic series-and the aromatic substituent of alicyclic replacement, and wherein ring completes the cyclic substituents of (such as two substituting groups form ring together) by another part of this molecule;
The hydrocarbon substituent of-replacement, namely contains the substituting group of the non-hydrocarbon (such as halogen (especially chlorine and fluorine), hydroxyl, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group and sulfinyl (sulphoxy)) not changing substituent main hydrocarbon character in the context of the present invention;
-assorted substituting group, namely in the context of the present invention, while there is main hydrocarbon character in the ring be made up of carbon atom or chain containing the substituting group being different from carbon, comprise substituting group as pyridyl, furyl, thienyl and imidazolyl.Heteroatoms comprises sulphur, oxygen and nitrogen.Generally speaking, for every 10 carbon atoms, in alkyl, have no more than 2, or no more than 1 substituents; As selection, in alkyl, substituents can not be there is.
More known above-mentioned materialss may interact in final preparaton, make the component of final preparaton may be different from those originally adding.Such as, metal ion (such as purification agent) can migrate to other acid or anionic site of other molecule.The product formed thus, comprising the product formed through using the present composition with its intended use may not describe.But all this kind of improvement and reaction product include within the scope of the invention; The present invention includes by the composition of preparation by said components mixing.
The present invention is understood better with reference to following nonlimiting examples.
Embodiment
Prepare and test one group of embodiment to prove advantage of the present invention.
comparative example 1. reference example is by being mixed into 1.75 % by weight industrial gear oil additive bags (additive-package A) in I group ISO220 base oil and preparing.Additive-package A comprises extreme pressure agent, anti-wear agent combination, rust-preventive agent, metal passivator, defoamer, demulsifying compound, copper passivator and some thinning oils, and wherein extreme pressure agent comprises phosphoric acid ester and/or amine salt.
comparative example 2. baseline embodiment is by being mixed into 2.0 % by weight industrial gear oil additive bags (additive-package B) in II group ISO220 base oil and preparing.Additive-package B and additive-package category-A seemingly, do not contain unlike it the phosphoric acid ester and/or the agent of amine salt extreme pressure that exist in additive-package A.
comparative example 3. comparative example by taking a part for comparative example 2 and adding 4 % by weight sulfurized fatty esters, sulfurized rapeseed oil and preparing in this embodiment.
comparative example 4. comparative example by taking a part for comparative example 2 and adding 2 % by weight alkyl phosphites, transesterify dimethyl phosphorous acid hydrogen salt and preparing in this embodiment.
the embodiment of the present invention 5. the embodiment of the present invention is by taking a part for comparative example 2 and adding 2 % by weight sulfurized fatty ester, in this embodiment sulfurized rapeseed oil, and 1 % by weight alkyl phosphite, in this embodiment transesterify dimethyl phosphorous acid hydrogen salt and preparing.
The preparaton of these embodiments is summarized in following table:
table 1: embodiment preparaton
| Embodiment | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | The embodiment of the present invention 5 |
| I group ISO 220 | 98.3 | ||||
| II group ISO 220 | 98.0 | 94.0 | 97.0 | 95.0 | |
| Additive-package A | 1.5 | ||||
| Additive-package B | 1.8 | 1.5 | 1.8 | 1.8 | |
| Alkyl phosphite | 0.2 | 0.2 | 0.2 | 1.2 | 1.2 |
| Sulfurized fatty ester | 4.0 | 2.0 |
These preparatons are tested to simulate the oscillatory type that in this area, industrial gear can experience at laboratory test machine.Wheel casing for testing uses little primary speed-down bevel gear set, and it uses new one group of gear and wheel casing to run separately.For each test, make wheel casing stand constant high capacity and the constant low speed fixing time length, wherein the first test journey does not have vibration, and then the second test journey has vibration.Vibrating and be connected to vibrator on the axle of wheel casing apply by using, being placed on vibration transducer on wheel casing for monitoring the vibration of transmission.For each test, adjustment vibrator is with the gear mesh frequency harmonic wave with test parts.For test, use temperature does not control.After each test, measure shape error (formerror) on each tooth (namely on tooth between set point and calculating device skeletal lines with the distance that micron represents) and the wearing and tearing of prototype gear by using PECOND-300 profilograph.6 times are carried out for each pinion(gear) flank of tooth measure, wherein 3 traces (" up and down " trace) on contour direction, and 3 traces (" right-left " trace) on hand of helix.For each test, measure all 17 wheel teeth, obtain each pinion(gear) and measure for 102 times.
In above-mentioned trier, test comparison example 1 is to prove that trier distinguishes the ability of preparaton performance relative to the existence of vibration.There is provided gathering of the shape error measuring of this test below, wherein lower shape error value represents less wearing and tearing.Spiral-line average value measured is that all spiral-linees are measured, and is included in the population mean of all three traces that each wheel tooth obtains.Profile measurement mean value is all profile measurements, is included in the population mean of all three traces that each wheel tooth obtains.
table 2: the result of comparative example 1 gathers
Result shows, and testing sequence display vibration is on the spiral-line of testing gears and the impact of profile.Test-results display when applying vibration, especially for spiral-line measurement, higher shape error value and so higher wearing and tearing.Test method shown in the display of these results is the useful instruction of industrial gear oil's performance when standing external force as vibrated.
With the value of the testing method set up, also use said procedure test comparison example 2,3 and 4 and the embodiment of the present invention 5.Hereafter provide the gathering of shape error measuring (μm to represent) from this test, wherein lower shape error value represents less wearing and tearing.Spiral-line average value measured is that all spiral-linees are measured, and is included in the population mean of all three traces that each wheel tooth obtains.Helical trajectory 1 mean value is the mean value that all spiral-linees obtained in trace 1 are measured, and wherein trace 1 is closest to Gear Root (therefore seeing higher stress).Helical trajectory 2 mean value is the mean value that all spiral-linees obtained in trace 2 are measured, wherein trace 2 be second closest to Gear Root or middle trace.Helical trajectory 3 mean value is the mean value that all spiral-linees obtained in trace 3 are measured, and wherein trace 3 apart from Gear Root farthest (so should see minimum stress level).
table 3: result gathers
| Comparative example 2 | Comparative example 3 | Comparative example 4 | The embodiment of the present invention 5 | |
| Spiral-line average value measured | 4.45 | 4.88 | 4.95 | 3.72 |
| Helical trajectory 1 mean value | 6.62 | 7.18 | 6.79 | 4.06 |
| Helical trajectory 2 mean value | 3.82 | 3.75 | 3.91 | 3.36 |
| Helical trajectory 3 mean value | 2.92 | 3.99 | 4.21 | 3.74 |
Result shows, and the embodiment of the present invention provides the polishing machine higher than comparative example and therefore better vibration resistance.Comparative example 2 is industrial gear oil, but does not comprise the additive of the synergistic combination providing the present invention to pay close attention to.Comparative example 3 comprises sulfurized fatty ester, but does not comprise phosphorus compound of the present invention.Comparative example 4 comprises phosphorus compound, but does not comprise sulfurized fatty ester.Only the embodiment of the present invention 5 comprises the combination of described phosphorus compound and sulfurized fatty ester, and to be offered the best in test polishing machine and so best vibration resistance by this additive combination.Should be understood that phosphorus compound used and sulfurized fatty ester in the embodiment of the present invention 5 with 3 % by weight total amount exist, be less than 4 % by weight sulfurized fatty esters used in comparative example 3, demonstrating the effect realized by the present invention is not only due to higher processing rate, but due to the synergy between additive.
At this by above-mentioned each file, any previous application (no matter whether clearly listing hereinbefore) comprising claimed right of priority is incorporated to the present invention by reference.Mentioning of any file is not the accreditation this file being obtained to prior art qualification, or is formed the general knowledge of technician with any authority.Except in embodiment, or outside clearly stating in addition, all quantity describing the amount of material, reaction conditions, molecular weight, carbonatoms etc. are in this manual to be understood that is modified by wording " about ".Be to be understood that the upper and lower bound of amount described herein, scope and ratio can combine independently.Similarly, the scope of each element of the present invention can use with the scope of other element any or together with measuring with amount.
As used herein, with " comprising ", " containing " or " feature is ... " the transitional term of synonym " comprise " be comprising property or opening and do not get rid of other element do not described or method steps.But, in each description " comprised " in this article, be intended to as alternative, this term also comprise phrase " substantially by ... composition " and " by ... form ", wherein " by ... composition " does not comprise any element or step that not do not describe, and " substantially by ... composition " allows other non-descriptive element or step of the fundamental sum new features comprising composition that not substantial effect considers or method.
Although show some representative embodiment and details to set forth the present invention, those skilled in the art learn and can not depart from scope of the present invention and make various changes and improvements herein.On this point, scope of the present invention only limits by following claims.
Claims (15)
1. Industrial gear oil composition, it comprises:
A () has the oil of lubricant viscosity;
(b) P contained compound; With
(c) sulfurized fatty ester.
2. Industrial gear oil composition according to claim 1, the oil wherein with lubricant viscosity comprises mineral base oil.
3. Industrial gear oil composition according to claim 1, the oil wherein with lubricant viscosity comprises synthesis base oil.
4. Industrial gear oil composition as claimed in one of claims 1-3, wherein P contained compound comprises alkyl phosphite, phosphoric acid ester, the amine salt of phosphoric acid ester or its some combinations
5. Industrial gear oil composition as claimed in one of claims 1-4, wherein P contained compound comprises alkyl phosphite or its ester.
6. Industrial gear oil composition as claimed in one of claims 1-5, wherein sulfurized fatty ester comprises sulfurized natural oils.
7. Industrial gear oil composition as claimed in one of claims 1-6, wherein sulfurized fatty ester comprises sulfurized rapeseed oil.
8. Industrial gear oil composition as claimed in one of claims 1-7, wherein composition comprises (d) one or more other additives further;
Wherein component (d) comprises one or more olefine sulfides, phosphoric acid ester, thiophosphate, thiophosphatephosphorothioate and/or its amine salt, thiadiazoles and/or replaces thiadiazoles, tolyl-triazole and/or substituted triazole, polyethers, alkenyl amine and/or polyolefin amide alkene amine, ester copolymer, carboxylicesters, dispersion agent, defoamer, hydrocarbon polymer, sulfurized fatty ester and or its any combination.
9. Industrial gear oil composition as claimed in one of claims 1-8, wherein in Industrial gear oil composition, component (b) is 1:10-10:1 with the weight ratio of component (c).
10. Industrial gear oil composition as claimed in one of claims 1-9, wherein component (b) exists with the 0.1-10 of total Industrial gear oil composition % by weight; And
Wherein component (c) exists with the 0.1-20 of total Industrial gear oil composition % by weight.
11. methods preparing Industrial gear oil composition, it comprises step: following component mixes by (1):
A () has the oil of lubricant viscosity;
(b) P contained compound; With
(c) sulfurized fatty ester;
Produce Industrial gear oil composition.
12. methods according to claim 11, the oil wherein with lubricant viscosity comprises mineral base oil, synthesis base oil or its combination;
Wherein P contained compound comprises alkyl phosphite, phosphoric acid ester, the amine salt of phosphoric acid ester or its some combinations;
Wherein sulfurized fatty ester comprises sulfurized natural oils; And
Wherein (d) one or more other additives are mixed in Industrial gear oil composition optional comprising further by step (1);
Wherein component (d) comprises one or more olefine sulfides, phosphoric acid ester, thiophosphate, thiophosphatephosphorothioate and/or its amine salt, thiadiazoles and/or replaces thiadiazoles, tolyl-triazole and/or substituted triazole, polyethers, alkenyl amine and/or polyolefin amide alkene amine, ester copolymer, carboxylicesters, dispersion agent, defoamer, hydrocarbon polymer, sulfurized fatty ester and or its any combination.
13. methods of vibration resistance improving Industrial gear oil composition, it comprises step: (1) adds following component to comprising (a) and having in the Industrial gear oil composition of the oil of lubricant viscosity:
(b) P contained compound; With
(c) sulfurized fatty ester;
Produce the Industrial gear oil composition with the vibration resistance of improvement.
14. methods according to claim 13, the oil wherein with lubricant viscosity comprises mineral base oil, synthesis base oil or its combination;
Wherein P contained compound comprises alkyl phosphite, phosphoric acid ester, the amine salt of phosphoric acid ester or its some combinations;
Wherein sulfurized fatty ester comprises sulfurized natural oils; And
Wherein (d) one or more other additives are mixed in Industrial gear oil composition optional comprising further by step (1);
Wherein component (d) comprises one or more olefine sulfides, phosphoric acid ester, thiophosphate, thiophosphatephosphorothioate and/or its amine salt, thiadiazoles and/or replaces thiadiazoles, tolyl-triazole and/or substituted triazole, polyethers, alkenyl amine and/or polyolefin amide alkene amine, ester copolymer, carboxylicesters, dispersion agent, defoamer, hydrocarbon polymer, sulfurized fatty ester and/or its any combination.
15. additive-package improve the purposes of the vibration resistance of Industrial gear oil composition;
Wherein Industrial gear oil composition comprises the oil that (a) has lubricant viscosity; And
Wherein additive-package comprises (b) P contained compound and (c) sulfurized fatty ester.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361828717P | 2013-05-30 | 2013-05-30 | |
| US61/828,717 | 2013-05-30 | ||
| PCT/US2014/039496 WO2014193782A2 (en) | 2013-05-30 | 2014-05-27 | Vibration resistant industrial gear oils |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105247023A true CN105247023A (en) | 2016-01-13 |
Family
ID=51023094
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480030110.0A Pending CN105247023A (en) | 2013-05-30 | 2014-05-27 | Vibration resistant industrial gear oils |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20160122678A1 (en) |
| EP (1) | EP3004296B1 (en) |
| CN (1) | CN105247023A (en) |
| CA (1) | CA2913173A1 (en) |
| TW (1) | TWI649417B (en) |
| WO (1) | WO2014193782A2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6678647B2 (en) * | 2014-08-06 | 2020-04-08 | ザ ルブリゾル コーポレイションＴｈｅ Ｌｕｂｒｉｚｏｌ Ｃｏｒｐｏｒａｔｉｏｎ | Additive package for industrial gear lubricants with biodegradable sulfur components |
| US20160168504A1 (en) * | 2014-12-10 | 2016-06-16 | Hyundai Motor Company | Low viscosity gear oil composition providing enhanced fuel efficiency |
| CN106479635A (en) * | 2016-09-21 | 2017-03-08 | 广西大学 | A kind of environmental friendliness width temperature water-resistant antirust rail top lubricant composition |
| US10253275B2 (en) | 2017-07-19 | 2019-04-09 | American Chemical Technologies, Inc. | High viscosity lubricants with polyether |
| US10788633B2 (en) | 2018-04-30 | 2020-09-29 | Hewlett Packard Enterprise Development Lp | Complementary reverse order filters |
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- 2014-05-27 EP EP14733830.5A patent/EP3004296B1/en active Active
- 2014-05-27 CA CA2913173A patent/CA2913173A1/en not_active Abandoned
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2014193782A2 (en) | 2014-12-04 |
| CA2913173A1 (en) | 2014-12-04 |
| EP3004296A2 (en) | 2016-04-13 |
| TWI649417B (en) | 2019-02-01 |
| WO2014193782A3 (en) | 2015-01-22 |
| US20160122678A1 (en) | 2016-05-05 |
| TW201512391A (en) | 2015-04-01 |
| EP3004296B1 (en) | 2023-04-19 |
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