EP0690902B1 - Verfahren zu unterdrückung der nebelbildung von einzel verwendung schmieröl - Google Patents

Verfahren zu unterdrückung der nebelbildung von einzel verwendung schmieröl Download PDF

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Publication number
EP0690902B1
EP0690902B1 EP93907626A EP93907626A EP0690902B1 EP 0690902 B1 EP0690902 B1 EP 0690902B1 EP 93907626 A EP93907626 A EP 93907626A EP 93907626 A EP93907626 A EP 93907626A EP 0690902 B1 EP0690902 B1 EP 0690902B1
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Prior art keywords
copolymer
butene
monoolefin
mist
oil
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English (en)
French (fr)
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EP0690902A1 (de
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Harold Erich Bachman
Chung Kun Shih
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Priority claimed from US07/717,433 external-priority patent/US5227551A/en
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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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/08—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • 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
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, 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
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds 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
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • 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
    • 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
    • C10M2205/024—Propene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • 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
    • 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
    • C10M2207/287—Partial esters
    • C10M2207/288—Partial esters containing free carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/30—Anti-misting
    • 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
    • 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
    • C10N2040/38—Conveyors or chain belts

Definitions

  • This invention relates to a method of suppressing mist from single use lubricating oil, such as, for example, rock drill oils, agricultural spray oils, chain saw oils, ammonium nitrate fuel oil blasting agents, sheet metal drawing lubricants and the like. More particularly, this invention relates to the addition to single use lubricating oil, such as chain saw lubricating oil compositions, of a mist suppressing amount of a high molecular weight copolymer prepared from alpha-monoolefins having 3 to 20 carbon atoms.
  • Oil-containing compositions used as lubricants for chain saws generally comprise a lubricating oil component and a tackifier component which is intended to prevent the compositions from misting or spattering off the end of the chain during use.
  • Known chain saw lubricating compositions include such tackifying components as polyethylene glycol or polyacrylic amide, each having a molecular weight of 1 million or above, or colophonium-containing resins such as balsam resin obtained from terpentine balsam, root resin obtained by solvent extraction from root stocks, and tall resin obtained by fractional distillation of tall oil.
  • U.S. Patents 3,929,652 and 4,210,544 relate to dual purpose cutting oils which serve as heavy duty cutting oils and machine lubricants and which comprise a base oil, an extreme pressure agent, a copper corrosion inhibitor and, preferably, a copolymer of ethylene and propylene as an anti-mist additive.
  • Particularly preferred copolymer anti-mist additives are described as having a molecular weight ranging from 70,000 to 100,000 and a propylene content of from 35 to 50 percent.
  • British Patent 1,525,599 discloses a metal working lubricating oil composition which contains a major amount of an oil of lubricating viscosity, and a minor amount, sufficient to inhibit the composition from misting while in use, of at least one oil-soluble ethylene copolymer having a viscosity average molecular weight in the range from 130,000 to 250,000.
  • the ethylene copolymer is derived from the copolymerization of ethylene and a heavier olefin selected from terminally unsaturated straight chain monoolefins containing from 3 to 12 carbon atoms, alpha-phenyl-1-alkenes containing 9 or 10 carbon atoms, 2-norbornene, terminally unsaturated non-conjugated di-olefins containing from 5 to 8 carbon atoms, dicyclopentadiene, 5-methylene-2-norbornene, and mixtures thereof.
  • the heavier olefin is propylene and the mole ratio of ethylene to the heavier olefin in the copolymer is in the range of from 1:3 to 3:1.
  • U.S. Patent 3,919,098 relates to metal working compositions having improved low fog properties.
  • the disclosed compositions comprise a major amount of a hydrocarbon oil and a minor amount of an antifog additive selected from polyisobutylene, poly-n-butene and mixtures thereof.
  • the antifog additive is said to have a viscosity average molecular weight of from 0.3 to 10 million.
  • U.S. Patent 3,805,918 relates to mist oil lubricating systems which pneumatically distribute fine droplets of an oil composition to the areas of various machine elements to be lubricated.
  • the oil compositions described in this patent include a small amount of specified polyolefins to reduce the amount of stray mist during the lubrication process.
  • the polyolefins which are disclosed are C 2 C x copolymers of ethylene having a viscosity average molecular weight greater than 5,000.
  • the polyolefins contain 40-80 molar percent ethylene, and the units defined as C x are derived from a C 3 -C 12 monoolefin.
  • the preferred polyolefins are ethylene-propylene copolymers.
  • U.S. Patent 4,105,569 relates to yarn finishes, particularly of the coning oil type, which comprise a viscosity index improper such as a polymethacrylate, a polyalkylstyrene, an ethylene-propylene copolymer or a polyisobutylene.
  • the viscosity index improver provides better adherence of the finish to the yarn being treated, less propensity for dripping, and less finish "throw-off" during high speed winding of the treated yarn.
  • the yarn finish formulations also contain a polysiloxane which functions to reduce surface tension of the finish and to prevent mist formation during high speed winding.
  • U.S. Patent 4,400,281 relates to improving the adhesive and cohesive properties of a textile lubricating composition which contains mineral oil, fatty esters or natural oils and an emulsifying agent by adding to the textile lubricating composition 0.01-10 wt. % of a polymer having a molecular weight of 1-10 million and comprising either homopolymer of normal C 6 -C 4 alpha-monoolefins or copolymers of two or more normal C 4 -C 20 alpha-moolefins.
  • the addition of the polymer improves the adherency of the lubricating composition without reducing its lubricity and reduces the tendency for the composition to sling.
  • U.S. Patent 4,173,455 relates to aqueous diesel fuel emulsions which contain diesel fuel, a specified emulsifier, an antimisting agent, and water.
  • the antimisting agent is added to the fuel emulsion to prevent the emulsion from atomizing on impact when a fuel container is ruptured.
  • the antimist agent is supposed to cause the fuel emulsion to be expelled from the ruptured fuel container in "sheets" and "strings of beads” which do not provide sufficient surface area for explosive combustion.
  • the antimisting agents to be used in the diesel fuel emulsion are described as long-chain, high molecular weight polymers which were developed to improve flow of oil through pipelines.
  • U.S. Patents 4,384,089 and 4,527,581 relate to the reduction of friction loss normally occurring in hydrocarbon carrying conduits during the transportation of hydrocarbon liquids can be reduced by adding small amounts of certain copolymers to the hydrocarbon liquids.
  • the copolymers are described in U.S. Patent 4,384,089 as comprising copolymers of two or more alpha-monoolefins having 3 to 20 carbon atoms, and in U.S. Patent 4,527,581 as comprising copolymers of butene-1 and another alpha-monolefin having 5 to 20 carbon atoms. Neither of these patents suggests using the copolymers as anything other than hydrocarbon oil pipeline friction reducing agents.
  • Yet another object is to provide a lubricating oil composition which is suitable for single use applications, such as for lubricating chain saw bar and links, wherein the lubricating oil is inhibited from misting or spattering by the addition thereto of a mist suppressing amount of a copolymer prepared from at least two alpha-monoolefins containing from 3 to 20 carbon atoms and having a viscosity average molecular weight of from 500,000 to 10 million.
  • lubricating oil compositions with a major amount of a base oil component and a minor, mist suppressing amount of a copolymer component derived from at least one monoolefin selected from propylene and butene-1 and at one additional alpha-mono olefin having from 5 to 20 carbon atoms.
  • the mist suppressing copolymer is prepared by copolymerizing butene-1 with at least one other alpha-monoolefin having 5 to 20 carbon atoms.
  • the alpha-monoolefins copolymerized with the butene-1 are those having 6 to 14 carbon atoms, with hexene-1, octene-1, decene-1, dodecene-1 and tetradecene-1 being the most preferred comonomers.
  • the copolymer mist suppressing agent that is to be admixed with the base oil component desirably has a visccsity average molecular weight in excess of 100,000, for example, from 100,000 to 20 million, and generally will comprise 10 to 90 mole percent C 3 or C 4 hydrocarbon units and 90 to 100 mole percent of units derived from other C 5 -C 20 alpha-monoolefins.
  • the copolymer agent is added to the oil-containing functional fluid at a concentration which is effective to produce the desired mist suppression.
  • the copolymer mist suppressing agent contains 25 to 75 mole percent C 3 - or C 4 -derived hydrocarbon units, is added to the functional fluid composition at a concentration of from 0.0001 wt. percent (1 ppm) to 0.04 wt. percent (400 ppm), and has a viscosity average molecular weight in the range of from 500,000 to 10 million.
  • the more preferred copolymers for use in the invention are those prepared from butene-1 and one or more of hexene-1, octene-1, decene-1, dodecene-1 and tetradecene-1.
  • the chain saw lubricating fluid composition comprises a major amount of an oil of lubricating viscosity and a minor amount of a high molecular weight copolymer of propylene or butene-1 and at least one alpha-monolefin having from 5 to 20 carbon atoms.
  • the high molecular weight copolymer will be added to the chain saw lubricating fluid at a concentration of 0.005 to 0.04 wt. % to achieve the desired low levels of misting.
  • the copolymer additives are prepared from alpha-monoolefins having 4 to 16 carbon atoms.
  • Particularly useful alpha-monoolefins are hexene-1, octene-1, decene-1, dodecene-1 and tetradecene-1. These monomers are preferred for use in the process of the present invention since they are easily polymerized under liquid state polymerization techniques which are well known in the art.
  • Examples of two monomer component systems are propene-dodecene-1, butene-1-dodecene-1, butene-1-decene-1, hexene-1-dodecene-1, and octene-1-tetradecene-1, etc.
  • Examples of three component systems include butene-1-decene-1-dodecene-1, propene-hexene-1-dodecene-1, etc.
  • Preferred specific monomeric systems are propene-dodecene-1, butene-1-dodecene-1, butene-1-decene-1, and hexene-1-dodecene-1.
  • the method of copolymerization of the monomers is not a part of the invention.
  • any of the several well known methods for polymerizing alpha-monoolefins can be employed.
  • a particularly suitable method is the Ziegler process using catalyst systems comprising combinations of a compound of a metal of Groups IV-B, V-B, VI-B or VIII of the Periodic Chart of the Elements found on pages 392-393 of the Handbook of Chemistry and Physics, 37th Edition with an organometal compound of a rare earth or metal from Groups I-A, II-A, III-B of the Periodic Chart of the Elements.
  • Particularly suitable catalyst systems are those comprising titanium halides and organoaluminum compounds.
  • a typical polymerization procedure is to contact the monomeric mixture with the catalyst in a suitable inert hydrocarbon solvent for the monomers and the catalyst in a closed reaction vessel at reduced temperatures and autogenous pressure and in a nitrogen atmosphere. Further details of the Ziegler process are set forth in U.S. Patent Number 3,692,676.
  • the total C 3 or C 4 hydrocarbon concentration in the copolymers of the mist suppressing additives of the invention desirably varies from about 90 mole percent to about 10 mole percent.
  • the factor limiting the upper concentration of propylene or butene-1 in the copolymers of the invention is solubility. As the propylene or butene-1 concentration in the copolymers increases, the crystallinity increases and the solubility of the copolymers in hydrocarbons decreases. Decreasing solubility has an adverse effect on the lubricating composition.
  • the solubility limits of copolymers varies, of course, with different copolymer systems. In general, the practical upper propylene or butene-1 content limit for useful copolymers is about 90 mole percent.
  • Copolymer compositions having C 3 or C 4 concentrations exceeding about 90 mole percent have relatively poor mist suppressing properties.
  • the economic advantage of using the less expensive propylene or butene-1 in the preparation of the copolymer compositions is lost if the C 3 or C 4 hydrocarbon incorporation in the polymer drops below about 10 mole percent.
  • the total C 3 or C 4 hydrocarbon concentration in the copolymer additive is about 25 to 75 mole percent, and the total concentration of alpha-monoolefin having 5 to 20 carbon atoms is about 75 to 25 mole percent.
  • propylene or butene-1 may incorporate into the copolymer composition as homopolymer and that the above-stated C 3 or C 4 hydrocarbon concentrations refer to the total C 3 or C 4 hydrocarbon content of the copolymer compositions and includes propylene or butene-1 homopolymer and propylene or butene-1 present in copolymer form.
  • copolymers coming within the scope of the invention are those having 10 to 90 weight percent propylene or butene-1, and preferably 25 to 75 weight percent propylene or butene-1.
  • the optimum propylene or butene-1 concentrations will, of course, vary depending on which monomer or monomers are used as the other alpha-monoolefin component.
  • copolymers are used in the compositions of the invention.
  • the only practical limitation on molecular weight is that it must be high enough to produce effective mist suppression without being so high as to present handling difficulties.
  • copolymers of very high molecular weight are difficult to dissolve in the base oil of the lubricating oil compositions. They are also difficult to filter or to pour at low temperatures.
  • the use of very high molecular weight polymers also tends to result in lubricating oil formulations which are relatively unstable. Accordingly, the copolymers useful in this invention are generally limited to those having a viscosity average molecular weight of no more than about 10 million.
  • the viscosity average molecular weight of desirable copolymers is usually over 100,000, and typically is in the range of 100,000 to 10 million.
  • the average molecular weight of copolymers used in the invention preferably is in the range of 500,000 to 10 million, and most preferably is in the range of 1 to 8 million.
  • the effectiveness of the mist suppression increases as the molecular weight of the copolymer additive increases.
  • the molecular weight of polymers can be determined by any one of several methods, including light scattering and vapor phase osmometry, gel permeation chromatography (GPC), or the like. Some methods for determining molecular weight provide a weight average molecular weight, while others provide a number average molecular weight or viscosity average molecular weight. For the sake of uniformity the term "average molecular weight”, as used in this specification and appended claims, shall mean the viscosity average molecular weight. Typically, the viscosity average molecular weight can be determined by determined by gel permeation chromatography (GPC) conducted at 135°C.
  • GPC gel permeation chromatography
  • GPC uses the size of the polymer molecules, defined by the hydrodynamic radius, as a means for determining the molecular weight.
  • the technique involves passing a solution of the polymer through a bed of cross-linked polymer. Smaller molecules can diffuse into the pores of the cross-linked polymer bed such that their travel through the bed is delayed compared to larger molecules which pass by the pores and continue in the solvent phase.
  • the amount of copolymer additive required to be added to the chain saw lubricating oil compositions of this invention, to produce the desired mist suppressing result (expressed as weight percent, i.e. parts by weight of copolymer per 100 parts by weight of the fully formulated lubricating oil composition, including the copolymer) will vary depending on the physical properties and formulation of the lubricating oil composition. With some formulations, the desired result may be obtained by the addition of 0.0001 wt. % or less of the copolymer to the lubricating composition. On the other hand, some lubricating compositions may require as much as 1.0 wt. % or more of copolymer addition to produce the desired result.
  • the desired result typically is obtained by the addition from 0.005 to 0.5 wt. % of the copolymer to the chain saw lubricating composition.
  • the copolymer is added to the lubricating composition in amounts o from about 0.005 to about 0.04 wt. %.
  • the copolymer is a solid at the stated molecular weight it is usually preferred to dissolve it in a suitable solvent or suspend it in a suitable diluent prior to use since it is easier to add to the lubricating composition in the form of a solution or a slurry.
  • suitable solvents and diluents include kerosene, naphtha and other petroleum distillates and inert hydrocarbons such as hexane, heptane, octane or the like.
  • the lubricating base oil to which the mist suppressing copolymers are added to form the lubricating oil compositions of the present invention can be a mineral oil or a synthetic hydrocarbon oil of lubricating viscosity, typically having a viscosity of from 13.08 m 2 /s (70) to 69.6 m 2 /s (300 Saybolt Universal Seconds (SUS)) at 37.8°C (100°F). While the oil may be paraffinic, naphthenic, or mixed base, it is preferred that the base oil be substantially non-polar and that it be substantially inert. As used in the specification and appended claims, the term "substantially non-polar" is intended to mean that the base oil may contain no more than about 0.5 wt.
  • % of oxygen, nitrogen and/or sulfur is intended to mean that the material being described is inert to chemical or physical change under the conditions in which it is used so as not to materially interfere in an adverse manner with the preparation, storage, blending and/or functioning of the compositions, additives, compounds, etc., of this invention in the context of its intended use.
  • small amounts of base oil, or a solvent, diluent, etc. can undergo minimal reaction or degradation without preventing the making and using of the invention as described herein. In other words, such reaction or degradation, while technically discernible, would not be sufficient to deter the practical worker of ordinary skill in the art from making and using the invention for its intended purposes.
  • “Substantially non-polar” and “substantially inert” as used herein are, thus, readily understood and appreciated by those of ordinary skill in the art.
  • the base oils suitable for use in preparing compositions of the present invention include those conventionally employed in single use lubricating oil formulations.
  • liquids suitable for use as the base oil include mineral and synthetic oils, e.g., the solvent neutrals, white oils, naphthenic oils, etc., the linear and branched alkanes and haloalkanes of six to eighteen carbons, polyhalo- and perhaloalkanes of up to about six carbons, the cycloalkanes of five or more carbons, the corresponding alkyl-and/or halo-substituted cycloalkanes, the aryl hydrocarbons, the lower alkylaryl hydrocarbons, and the haloaryl hydrocarbons.
  • mineral and synthetic oils e.g., the solvent neutrals, white oils, naphthenic oils, etc.
  • the linear and branched alkanes and haloalkanes of six to eighteen carbons polyhalo- and perhaloalkanes of up to about six carbons
  • the cycloalkanes of five or more carbons the corresponding alkyl-
  • base oils are the low molecular weight, liquid polymers, generally classified as oligomers, which include the dimers, tetramers, pentamers, etc.
  • oligomers include the dimers, tetramers, pentamers, etc.
  • liquids as the propylene tetramers, isobutylene dimers, and the like.
  • Mineral oils are preferred. Suitable mineral lubricating oils vary widely as to their crude source, e.g., whether paraffinic, naphthenic, mixed paraffinic-naphthenic, and the like; as well as to their formation, e.g., distillation range, straight run or cracked, hydrofined, solvent extracted and the like.
  • the natural lubricating oil base stocks which can be used in the compositions of this invention may be liquid petroleum oils, straight mineral lubricating oil, solvent treated, acid treated or distillates derived from paraffinic, naphthenic, asphaltic, or mixed base crudes; or, if desired, various blended oils may be employed as well as residuals, particularly those from which asphaltic constituents have been removed. Oils of appropriate viscosity derived from coal or shale are also useful base oils.
  • Synthetic base oils include hydrocarbon oils, such as polymerized and interpolymerized olefins [e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, poly(1-hexenes), poly(1-octenes), poly(1-decenes)]; alkybenzenes [e.g., dodecylbenzenes, tetradecyl benzenes, dinonylbenzenes, di(2-ethlhexyl)benzenes]; polyphenyls [e.g., biphenyls, terphenyls, alkylated polyphenyls]; and the substantially non-polar derivatives, analogs and homologs thereof.
  • hydrocarbon oils such as polymerized and interpolymerized olefins [e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, poly
  • Unrefined, refined and rerefined oils can be used as the base oil according to the present invention.
  • Unrefined oils are those obtained directly from a mineral or synthetic source without further purification treatment.
  • a shale oil obtained directly retorting operations a petroleum oil obtained directly form distillation and used without further treatment would be an unrefined oil.
  • Syncrude obtained from tar sands is another example of unrefined oil.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, hydrotreating acid or base extraction, filtration and percolation are known to those skilled in the art.
  • Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
  • the preferred base oils include the linear and branched C 6 -C 18 alkanes, mineral oil and refined petroleum oils.
  • the chain saw lubricating oil compositions of the present invention may comprise only the base oil and the mist suppressing copolymer additive and may be formulated simply by blending together the base oil and the mist suppressing additive.
  • other additives may be combined with the base oil and mist suppressor copolymer additives to provide additional properties which enhance the desirability of the present compositions.
  • Other conventional additives which may be included in the chain saw compositions of this invention include, for example, rust inhibitors, anti-oxidants, pour point depressants, anti-wear additives, anti-foam additives and the like.
  • Rust inhibitors that may be added to the present chain saw lubricating compositions include, for example, basic nitrogen compounds such as dicarboxylic acid amides and fatty acid amides; imidazolines; and phosphoric acid derivatives, such as dialkyl- or diaryldithiophosphate salts.
  • Still other suitable rust inhibiting agents include alkyl phenols; sulfurized alkyl phenols; alkyl salicylates, alkenyl succinic anhydrides and other oil soluble mono- and dicarboxylic acids; mixtures derived from the reaction product of fatty acids (e.g., C 8 -C 22 ), boric acid and hydroxy amines, e.g., diethanolamine which contain borated fatty amides and borate hydroxy amine esters; borate esters of hydroxy alkyl amines such as diethanolamine ( See , U.S.
  • Patent 3,642,652 aryl sulfonamide carboxylic acids, their amine salts and mixtures of the same with borated esters of diethanolamine
  • aryl sulfonamide carboxylic acids, their amine salts and mixtures of the same with borated esters of diethanolamine See, U.S. Patent 4,297,236)
  • divalent metal or amine salts of sulfonic acid, polybasic acids (e.g., tall oil fatty acids) and alkanolamides See , U.S. Patent 4,395,286).
  • Oxidation inhibitors reduce the tendency of mineral oils to deteriorate in service which deterioration can be evidenced by the products of oxidation such as sludge and gum-like deposits on the chain saw links, bar or other metal surfaces being lubricated.
  • Such oxidation inhibitors include alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, e.g., calcium nonylphenol sulfide and barium octylphenyl sulfide; aromatic amines, e.g., dioctylphenylamine and phenylalpha-naphthylamine; phosphosulfurized or sulfurized hydrocarbons; and hindered phenols, such as butylated hydroxy toluene.
  • alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, e.g., calcium nonylphenol sulfide and barium octylphenyl sulfide
  • aromatic amines e.g., dioctylphenylamine and phenylalpha-naphthylamine
  • phosphosulfurized or sulfurized hydrocarbons and
  • pour point depressants otherwise known as lube oil flow improvers lower the temperature at which the fluid will flow or can be poured.
  • Such additives are well known.
  • those additives which usefully optimize the low temperature fluidity of a functional fluid are C 8 -C 18 dialkylfumarate vinyl acetate copolymers, polymethacrylates, alkylated polystyrene, and wax naphthalene.
  • Anti-wear additives which would be useful in certain applications to prevent scuffing of moving parts of the chain saw, include, for example, metal dithiocarbamates; molybdenum disulfide; chlorinated hydrocarbons; organic phosphates, such as tricresyl phosphate, and zinc salts of dialkyl- and diaryldithiophosphoric acids. Such zinc salts also function as an oxidation inhibitor and to prevent copper corrosion.
  • Friction modifiers serve to impart the proper friction characteristics to lubricating oil compositions such as chain saw oils.
  • Patent 3,852,205 which discloses S-carboxyalklene hydrocarbyl succinimide, S-carboxyalkylene hydrocarbyl succinamic acid and mixtures thereof;
  • U.S. Patent 3,879,306 which discloses N-(hydroxyalkylene)alkenylsuccinamic acids or succinimides;
  • U.S. Patent 3,932,290 which discloses reaction products of di-(lower alkyl) phosphites and epoxides;
  • U.S. Patent 4,028,258 which discloses the alkylene oxide adduct of phosphosulfurized N-(hydroxyalkyl) alkenyl succinimides.
  • the most preferred friction modifiers are succinate esters, or metal salts thereof, of hydrocarbyl substituted succinic acids or anhydrides and thiobis-alkanols such as described in U.S. Patent 4,344,853.
  • Foam control can be provided by an anti-foam additive of the polysiloxane type, e.g., silicone oil and polydimethyl siloxane.
  • an anti-foam additive of the polysiloxane type e.g., silicone oil and polydimethyl siloxane.
  • compositions when containing these conventional additives are typically blended into the base oil in amounts which are effective to provide their normal attendant function.
  • Representative effective amounts of the above classes of additives in the chain saw lubricating oil formulations of this invention are summarized below: Additive Type Broad Wt. % Preferred Copolymer mist suppressor 0.0001-1.0 0.005-0.04 Rust Inhibitor 0.03-3 0.05-0.5 Anti-oxidant 0.05-3 0.1-1.0 Pour point depressant 0.03-3 0.05-0.2 Anti-wear additive 0.03-3 0.05-0.4 Friction modifiers 0-3 0.05-0.2 Anti-foam 0.001-0.05 0.005-.01
  • the chain saw lubricating oil compositions may be prepared simply by blending together the various components. Typically all of the minor components will be added to the base oil; they may be added neat, or as concentrates in oil and/or solvent solutions, where the oil and/or solvent is compatible with the base oil. The components may all be blended simultaneously or, if desired, one or more of the components may be blended separately and the mixtures then further blended with the remaining components to form the final compositions.
  • a series of binary polymer/solvent mixtures (Formulations 1-7) were prepared by blending together a heptane carrier solvent and a mist suppressing butene-1-dodecene-1 copolymer (10% copolymer active ingredient dissolve in kerosene).
  • the butene-1-dodecene-1 copolymer was a commercial product available from Baker Performance Chemicals, Houston, Texas, under the tradename Flo R 1003 pipeline booster.
  • the copolymer is a white opaque viscous liquid having a flash point of 51.7°C (125°F), a boiling point of 176.7°C (350°F), and a specific gravity of 0.79.
  • the viscosity average molecular weight of the copolymer is approximately 4.4 million.
  • the composition of Formulations 1-7 is summarized in Table 1.
  • Example 1 The procedure of Example 1 was followed, except that the butene-1-dodecene-1 copolymer mist suppressor was replaced with a commercial polyisobutyene polymer mist suppressor.
  • the polyisobutylene polymer was a commercial product of Exxon Chemical Co., Houston Texas, and is available under the tradename VistanexTM MM L-140.
  • the polymer had a viscosity average molecular weight of 2.11 million and is believed to be the highest molecular weight grade polyisobutylene produced commercially in the United States.
  • the polymer was added neat to the heptane carrier solvent to form Formulations 8C-13C, the composition of which is summarized in Table 1.
  • Comparative Formulation 14C was prepared comprising only heptane with no mist suppressing additive.
  • composition of Formulations 1-7 and 8C-14C is summarized in Table 1 as follows:
  • the anti-mist properties imparted to a fluid by the addition thereto of a high molecular weight polymer can be observed by several techniques.
  • One simple technique, which provides a qualitative measure of the anti-mist properties is the Atomizer Spray Technique.
  • an atomizer spray bottle equipped with a pump to pressurize the contents of the bottle is employed.
  • One suitable bottle for use in this procedure, identified as the AirsprayTM spray bottle can be obtained from Consolidated Plastics Co., Twinsburg, Ohio.
  • Such atomizer spray bottles typically are equipped with a series of replaceable outlet tips or nozzles which control the pattern of the spray that is ejected therefrom.
  • the AirsprayTM spray bottle comes equipped with three standard nozzles which are designed to eject an unthickened material (such as water) from the bottle in a heavy mist pattern, a fine mist pattern, or a jet stream pattern, respectively.
  • an unthickened material such as water
  • a sample of Formulation 14C (heptane control sample) was charged to the sprayer which was equipped with the standard nozzle designed for expelling the contents of the bottle as a heavy mist.
  • the sprayer was then pumped to pressurize the heptane sample to a recorded level sufficient to eject the heptane sample from the bottle as a heavy mist.
  • Table 2 illustrates that butene-1-dodecene-1 copolymer was effective to suppress misting and to convert the fluid ejected from the spray bottle from a mist to a jet stream at a concentration level at least as low as 0.03 wt. %.
  • the commercially available polyisobutylene additive was not effective to suppress misting until it was added to the heptane carrier fluid at a concentration level of 0.23 wt. %.
  • the use of butene-1-dodecene-1 copolymer as the mist suppressing additive was more than 7 times as effective as the use of the polyisobutylene additive.
  • An alternative method for evaluating and predicting the anti-mist properties imparted by polymeric mist suppressor additives is to measure the extensional viscosity of a solution of the various additives.
  • extensional viscosity is difficult to measure because liquid cannot be grabbed and stretched at a constant velocity.
  • One method of measuring extensional viscosity of polymer solutions is outlined in Exxon Research And Engineering Company's Analytical Method Specification (AM-S) 89-006 (December 1990).
  • the specific tackiness (h/c) of the polymer in solution is suggestive of the anti-mist properties of the polymer, i.e., the greater the specific tackiness, the better are expected to be the anti-mist properties of the fluids in which the polymer is dissolved.
  • the vacuum used should be sufficient to maintain a substantially constant velocity of fluid flow through the needle. Generally, a vacuum of about -40 kPa will be employed. For more information, see K. K. K. Chao and M. C. Williams, J. Rheology, 27 (5) 451-474 (1983).
  • a series of sample formulations (Formulations 15-18, 19C and 20C) were prepared by dissolving varying concentrations of either butene-1-dodecene-1 copolymer (10 wt. % a.i. in kerosene) or high molecular weight polyisobutylene (5 wt. % a.i. in paraffinic oil) in NORPAR R 15 carrier oil.
  • Each of the samples was tested for its specific tackiness in accordance with Exxon Research And Engineering Company's Analytical Method Specification (AM-S) 89-006 (December 1990), as outlined above.
  • the composition and the specific tackiness of each formulation are summarized in Table 3.
  • Table 3 illustrates that butene-1-dodecene-1 copolymer is an effective tackifier agent for a mineral oil carrier, even at very low concentration levels.
  • the use of as little as 15.6 ppm of butene-1-dodecene-1 copolymer resulted in a polymer solution break height comparable to that observed when using 10,000 ppm of high molecular weight polyisobutylene as the tackifier resin.
  • a series of chain saw lubricating oil formulations (Formulations 21-26) was prepared by blending varying amounts of the butene-1-dodecene-1 copolymer mist suppressing agent of Example 1 with a lubricating oil basestock, an anti-oxidant additive and an anti-rust additive.
  • Several comparative formulations were prepared in which no mist suppressive resin was added (Formulation 27C), or in which the butene-1-dodecene-1 copolymer additive (10 wt. % a.i. in kerosene) was replaced either by the polyisobutylene polymer (5 wt. % a.i.
  • Example 2C in paraffin oil
  • Example 2C Formations 28C and 29C
  • a commercial polymeric tackifier solution which is believed to be an ethylene-propylene copolymer (5 wt. % a.i. in mineral oil basestock) having a viscosity average molecular weight of about 250,000 (Formulations 30C and 31C).
  • Comparative Formulation 32C was prepared comprising only the lubricating oil basestock with no mist suppressing additive, no anti-oxidant additive and no anti-rust additive.
  • the data in Tables 4-6 illustrates that chain saw lubricating oil formulations containing as little as 0.025 wt. % of butene-1-dodecene-1 copolymer mist suppressor additive are characterized by a measurable break height in the test procedure for determining a polymer solution's specific tackiness.
  • the data also illustrates that the measured break height when using butene-1-dodecene-1 copolymer as the mist suppressor is comparable to the break height recorded for formulations using five times as much polyisobutylene or ethylene-propylene copolymer in place of the butene-1-dodecene-1 copolymer.
  • the data also illustrates that formulations which contained no mist suppressor additive did not produce any measurable break height.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Treating Waste Gases (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Claims (10)

  1. Verfahren zur Unterdrückung einer Nebelbildung aus einem Schmieröl für den Einmalgebrauch, bei dem:
       0,0001 bis 0,04 Gew.-% eines Copolymers, das durch Copolymerisation von mindestens einem α-Monoolefin ausgewählt aus Propylen und Buten-1 mit mindestens einem zusätzlichen α-Monoolefin mit 5 bis 20 Kohlenstoffatomen hergestellt worden ist, wobei das Copolymer ein durchschnittliches viskositätsmäßiges Molekulargewicht von etwa 100 000 bis 20 Millionen aufweist, mit dem Einmalgebrauchschmieröl vermischt werden.
  2. Verfahren nach Anspruch 1, bei dem das Copolymer hergestellt worden ist, indem Buten-1 mit mindestens einem zusätzlichen α-Monoolefin mit 6 bis 14 Kohlenstoffatomen copolymerisiert worden ist.
  3. Verfahren nach Anspruch 2, bei dem das zusätzliche Monoolefin ausgewählt ist aus der Gruppe bestehend aus Hexen-1, Octen-1, Decen-1, Dodecen-1, Tetradecen-1 und Mischungen derselben.
  4. Verfahren nach Anspruch 3, bei dem das Copolymer mit den Fluiden in einer Konzentration von 0,005 bis 0,04 Gew.-% gemischt wird.
  5. Verfahren nach Anspruch 1, bei dem das Copolymer 10 bis 90 Mol.% sich von C3- bis C4-Monoolefin ableitende Einheiten und 90 bis 10 Mol.% von Einheiten umfaßt, die sich von C5- bis C20-Monoolefin ableiten.
  6. Verfahren nach Anspruch 5, bei dem das Copolymer 25 bis 75 Mol.% sich von C3- oder C4-Monoolefin ableitende Einheiten und von 75 bis 25 Mol.% von Einheiten umfaßt, die sich von C5- bis C20-Monoolefin ableiten.
  7. Verfahren nach Anspruch 1, bei dem das Copolymer 10 bis 90 Mol.% sich von Buten-1 ableitende Einheiten und 90 bis 10 Mol.% von Einheiten umfaßt, die sich von C6- bis C14-Monoolefin ableiten.
  8. Verfahren nach Anspruch 7, bei dem sich die von Buten-1 ableitenden Einheiten 25 bis 75 Mol.% des Copolymers ausmachen.
  9. Verfahren nach einem der Ansprüche 1 bis 8, bei dem das Copolymer ein durchschnittliches viskositätsmäßiges Molekulargewicht von 500 000 bis 10 Millionen aufweist.
  10. Verfahren nach einem der Ansprüche 1 bis 8, bei dem mit dem Einmalgebrauchschmieröl und dem Copolymer ferner eine wirksame Menge von mindestens einem zusätzlichen Additiv ausgewählt aus der Gruppe bestehend aus (i) Rostinhibitoren, (ii) Antioxidantien, (iii) Fließpunkterniedrigungsmitteln und (iv) Antiverschleißmitteln gemischt wird.
EP93907626A 1991-06-19 1993-03-22 Verfahren zu unterdrückung der nebelbildung von einzel verwendung schmieröl Expired - Lifetime EP0690902B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US07/717,433 US5227551A (en) 1989-11-19 1991-06-19 Method of suppressing mist formation from oil-containing functional fluids
PCT/US1993/002605 WO1994021760A1 (en) 1991-06-19 1993-03-22 Method of suppressing mist formation from oil-containing functional fluids
CN93104651A CN1033461C (zh) 1991-06-19 1993-03-30 消除含油功能流体形成油雾的方法
US08/061,899 US5329055A (en) 1991-06-19 1993-05-14 Method of suppressing mist formation from oil-containing functional fluids

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DE19530816A1 (de) 1995-08-23 1997-02-27 Cognis Bio Umwelt Verwendung von mutierter Subtilisin-Protease in kosmetischen Produkten
JP4761800B2 (ja) * 2005-03-23 2011-08-31 Ｊｘ日鉱日石エネルギー株式会社 エスカレータ用チェーンオイル
JP5170969B2 (ja) * 2006-03-17 2013-03-27 昭和シェル石油株式会社 潤滑油組成物
JP5138965B2 (ja) * 2007-03-30 2013-02-06 三井化学株式会社 潤滑油組成物、ミスト発生抑制剤
KR20130126608A (ko) * 2010-10-06 2013-11-20 더루우브리졸코오포레이션 연무 방지 첨가제를 함유하는 윤활유 조성물
CN106635309A (zh) * 2016-09-21 2017-05-10 广西大学 一种环境友好低速重载防锈抗盐雾开式齿轮齿条传动润滑剂组合物
CN109679756B (zh) * 2019-01-24 2022-01-11 苏州市神顺新晨科技有限公司 一种微乳切削液及其制备方法
CN110628493B (zh) * 2019-10-01 2021-09-21 中科孚迪科技发展有限公司 一种高抗氧化性微量润滑切削油及其制备方法和应用

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US3919098A (en) * 1973-11-05 1975-11-11 Chevron Res Cutting oil of reduced stray fog
CA1059111A (en) * 1974-12-20 1979-07-24 Dominic A. Apikos Metal working lubricant comprising ethylene copolymers
US4400281A (en) * 1981-08-19 1983-08-23 Atlantic Richfield Co. Yarn processing lubricants
US5227551A (en) * 1989-11-19 1993-07-13 Exxon Chemical Patents Inc. Method of suppressing mist formation from oil-containing functional fluids

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CA2156744A1 (en) 1994-09-29
CN1093106A (zh) 1994-10-05
ES2098731T3 (es) 1997-05-01
WO1994021760A1 (en) 1994-09-29
AU671625B2 (en) 1996-09-05
NO312910B1 (no) 2002-07-15
NO953727L (no) 1995-09-21
DE69307931D1 (de) 1997-03-13
CA2156744C (en) 2002-11-12
CN1033461C (zh) 1996-12-04
AU3816193A (en) 1994-10-11
JPH08512334A (ja) 1996-12-24
NO953727D0 (no) 1995-09-21
EP0690902A1 (de) 1996-01-10
DE69307931T2 (de) 1997-05-15
BR9307827A (pt) 1995-11-14

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