Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/02—Sulfurised compounds
  • C10M135/04—Hydrocarbons
• • 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
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
  • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
• • 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
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more 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
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/22—Acids obtained from polymerised unsaturated acids
• • 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
  • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
  • C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen 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
  • 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
• • 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
  • C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
• • 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
• • 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
  • C10M2223/042—Metal 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
• • 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
  • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
  • C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
• • 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
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12

Definitions

• Sulfurized olefins are well-known additives in lubricating oil, cutting oil and the like.
• U.S. Patent Specification No. 2,249,312 describes such a product.
• U.S. Patent Specification No. 2,708,199 describes a similar product in which a sulfur halide is reacted with an olefin using a lower alkanol promoter to obtain an intermediate which is reacted with an alkali or alkaline earth metal polysulfide.
• 3,471,404 describes a product in which sulfur monochloride is reacted with olefin to obtain an intermediate which is reacted with sulfur and alkali metal sulfide at a critical ratio of 1.8 to 2.2 gram moles of metal fulfide per gram mole of sulfur. This material is then typically refluxed for 1 to 24 hours with aqueous alkali metal hydroxide (in general terms, "reacted with an inorganic base").
• an improved sulfurized olefin additive for lubricating oil may be obtained by reacting sulfur monochloride with an aliphatic monoolefin to form an adduct which is then reacted with sulfur and sodium sulfide, using from 0.1 to 0.4 gram atom sulfur per gram mole of sodium sulfide, and then recovered by conventional methods without the need for further treatment with aqueous inorganic base (caustic).
• the invention provides a sulfurized lubricating oil additive for imparting extreme pressure properties to lubricating oil which has been made by a process comprising (a) reacting sulfur mono.chloride with a lower aliphatic monoolefin to produce an adduct, (b) reacting the adduct produced in (a) with sulfur and sodium sulfide in an aqueous alkanol medium using-from 0.1 to 0.4 gram atom of sulfur per gram mole of sodium sulfide, and (c) recovering the additive resulting from (b) without heating with aqueous caustic.
• a preferred embodiment of this invention is a sulfurized lubricating oil additive which imparts improved extreme pressure properties made by the process consisting essentially of (a) reacting S C 1 2 with a C 3-6 aliphatic monoolefin at about 30 to 100°C. to produce an adduct, (b) reacting said adduct with sulfur and Na 2 S in an aqueous alkanol medium at a temperature of about 50°C. up to reflux using about 0.1 to 0.4 gram atom of sulfur per gram mole of Na 2 S and then (c) recovering said additive without"treatment with an inorganic base".
• Useful olefins are the monoethylenically unsaturated aliphatic hydrocarbons referred to as aliphatic monoolefins containing 3 to about 6 carbon atoms. These include 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-l-butene, 2-methyl-2-butene, 1- hexene, 2-hexene, 3-hexene, 2-methyl-1-nentene, 2-methyl-2-pentene, 2-ethyl-2-butene and the like,including mixtures thereof.
• the olefins are branched-chain olefins such as isobutene, 2-methyl-I-butene, 2-methyl-2-butene, 2-me.thyl-2-pentene and the like. More preferably the ethylenic double bond adjoins a tertiary carbon atom such as isobutylene, the most preferred olefin.
• the first stage reaction is preferably conducted by adding the olefin to the sulfur monochloride.
• the olefin can be added as a gas or liquid. Preferably it is added beneath the surface of the sulfur monochloride as a liquid.
• olefin is added until the reaction with the sulfur monochloride stops as indicated by loss of exotherm.
• An amount of about 0.75 to 2.0 gram moles of olefin for each 0.3 to 0.75 gram mole of sulfur monochloride usually suffices,
• a preferred amount is about 1,8 to 2,2 gram moles of olefin per gram mole of sulfur monochloride,
• an alkanol promoter In the reaction between sulfur monochloride and the olefin, the use of an alkanol promoter is preferred. In the present process use of such a promoter can give products having significantly better EP (extreme pressure) properties.
• the lower alkanol promoter used in the first stage contains from about 1 to about 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, isobutanol, tert-butanol and the like.
• the most nreferred promoter is methanol.
• the lower alkanol promoter can be added to the sulfur monochloride initially, added to the reaction mixture continuously or periodically during the course of the olefin addition or the alkanol can be mixed with the olefin and added together with the olefin.
• the preferred modes of addition are to either add the entire amount initially and then add the olefin or to concurrently add both alkanol and olefin.
• the amount of alkanol promoter is preferably about 0.001 to about 0.3 gram moles for each 0.3 to 0.75. gram mole of sulfur monochloride.
• the first stage reaction can be conducted at any temperature high enough to cause the reaction to proceed, but not so high as to cause decomposition of the reactants or products.
• a useful range is about 30 to 100° C.
• a more preferred range is about 40 to 75° C. and a most preferred range is about 50 to 60° C.
• the first stage reaction should be conducted for a time sufficient to complete the reaction between sulfur monochloride and olefin. This is usually limited by heat removal. Olefin feed rate is preferably controlled to hold the temperature within the desired range. When the sulfur monochloride has been consumed the temperature will drop. External heat may be added to continue the reaction for a further time, but this does not appear to be necessary.
• the overall time required to complete the reaction depends upon the scale of the process and can vary from a few minutes up to 12 or more hours. The time is not critical.
• HCl gas . is evolved so means should be provided to scrub the vent gas from the reactor to remove HC1 prior to releasing it to the atomsphere.
• adduct from the first stage is reacted with sodium sulfide and sulfur in an aqueous alkanol reaction medium.
• the second stage is preferably carried out by charging aqueous sodium sulfide, water, alkanol and'elemental sulfur flowers to a reactor and then adding the adduct to this at reaction temperature.
• the sodium sulfide may be obtained from any of a number of sources. For example, it can be made by mixing approximately equal mole amounts of sodium hydrosulfide and sodium hydroxide. If hydrogen sulfide is available, it can be adsorbed in aqueous NaOH to form a solution of sodium sulfide and/or sodium hydrosulfide depending upon the amount of hydrogen sulfide adsorbed. Whatever the source, the resulting solution should be adjusted with either NaOH, NaSH or H 2 S so that the resulting solution consists mainly of sodium sulfide with little or no free sodium hydroxide.
• the amount of sodium sulfide can vary somewhat. For- example, from about 0.45 to 0.7 gram mole for each 0.3 to 0.75 gram mole of sulfur monochloride used in the first reaction stage.
• the amount of sodium sulfide is about 0.7 to 2 gram mole per mole of sulfur monochloride and most preferably about 0.8 to 1 gram mole per gram mole of sulfur monochloride. What is essential is that from 0.1 to 0.4 gram atom sulfur be used per gram mole of sodium sulfide.
• the amount of water can vary widely without detrimental effect. Good results can be obtained using about 10 to 20 gram moles of water per gram mole of sodium sulfide. This includes water added as such, water in aqueous reactants and water which might be formed by reaction of hydrogen sulfide or sodium hydrosulfide with sodium hydroxide in forming _sodium sulfide solution.
• Alcohol is required in the second stage reaction.
• these are lower alkanols containing 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, n-butanol, isobutanol, tert-butanol and the like, including mixtures thereof.
• the preferred alkanol is isopropanol either alone or mixed with other alkanols such as tert-butanol.
• the amount of alkanol can likewise vary over a wide range.
• a useful range is about 0.1 to 0.5 parts by weight per each part by weight of water.
• a more preferred range is about 0.2 to 0.4 parts by weight alkanol per each part by weight water.
• Preferred amounts of sulfur and sodium sulfide in the second reaction are 0.05 to 0.18 gram atom of sulfur and 0.45 to 0,7 gram mole of sodium sulfide, It is also preferred that about 0,1 to 0.25 gram atom of sulfur be used per gram mole of sodium sulfide.
• the mixture of sodium sulfide, sulfur and aqueous alkanol is stirred and heated to reaction temperature and then the adduct is added to it.
• the reaction can be carried out in other ways such as by adding the sodium sulfide, sulfur and aqueous alkanol mixture to the adduct or by mixing everything together and heating the mixture.
• the preferred second stage reaction temperature is about 50°C. up to reflux temperature. A more preferred reaction temperature is about 60 to 80°C.
• the mixture is preferably heated to reflux for about 2 to 8 hours to assure completion of the reaction.
• An essential feature of the new sulfurized product is that when made according to the foregoing disclosure there is no need for further caustic treatment in order to obtain a useful EP additive. Accordingly, the present invention does not contemplate a product which is subsequently heated with aqueous inorganic base (caustic) solution such as is disclosed in U.S. Patent Specification No. 3,471,404.
• aqueous inorganic base (caustic) solution such as is disclosed in U.S. Patent Specification No. 3,471,404.
• the product may be recovered by conventional methods such as removing alkanol, water washing and filtering.
• Example illustrates the manner of making the present sulfurized olefin additive.
• the present sulfurized olefin additives are especially useful in lubricating oil formulations used in gear applications.
• the base oil may be a mineral oil or a synthetic oil.
• Useful synthetic oils include olefin oligomers such as decene trimer, tetramer and pentamer made by oligomerizing 1-decene using a BF 3 catalyst.
• Useful olefin oligomers can be made using other catalysts such as the aluminum alkyl Ziegler catalyst.
• other olefins can be used such as C 6 - 14 1-olefins.
• Synthetic alkylbenzenes can also be used such as di-dodecylbenzene and the like.
• Synthetic ester lubricating oil can also be employed such as the alkyl esters of dicarboxylic acid (e.g., di-2-ethyl-hexylsebacate), fatty acid esters of polyols (e.g., trimethylolpropane, tripelargonate) or complex esters of alkanols, alkane, polyols and carboxylic or polycarboxylic acid.
• dicarboxylic acid e.g., di-2-ethyl-hexylsebacate
• fatty acid esters of polyols e.g., trimethylolpropane, tripelargonate
• complex esters of alkanols, alkane, polyols and carboxylic or polycarboxylic acid e.g., trimethylolpropane, tripelargonate
• the sulfurized olefin is added in an amount sufficient to improve the E p property of the lubricant.
• An amount of 0.1 to 10.0 weight percent is usually sufficient.
• Fully formulated gear lubricants include other conventional additives which perform various functions.
• other additives are corrosion inhibitors for ferrous and non-ferrous metals such as tetrapropenyl succinic acid and bis-(2,5-alkyldithia)-1,3,4-thiadiazoles, and antiwear additives such as alkyl or aryl phosphonates, phosphite, thiophosphates, dithiophosphates, and phosphoric acids.
• antiwear additives such as alkyl or aryl phosphonates, phosphite, thiophosphates, dithiophosphates, and phosphoric acids.
• zinc dialkyl or diaryl dithiophosphate chlorinated hydrocarbons, sulfurized fatty esters and amines.
• the invention includes a lubricating oil composition comprising lubricating oil and an extreme pressure improving amount of an additive of the invention.
• the invention further provides lubricating oil additive package comprising an additive of the'invention and one or more further additives selected from corrosion inhibitors for ferrous or non-ferrous metals, antiwear additives, zinc dialkyl or diaryl dithiophosphates, chlorinated hydrocarbons and sulfurized fatty esters and amines.
• the tests were conducted in SAE 90 mineral oil. The first was a 4-ball weld test (ASTM D2783) in which a steel ball is rotated in loaded contact with three fixed balls. The maximum load without weld is recorded as the pass load.

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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)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Cited By (5)

Citations (4)

• 1980
  • 1980-01-15 EP EP80300128A patent/EP0032281B1/fr not_active Expired
  • 1980-01-15 DE DE8080300128T patent/DE3067302D1/de not_active Expired

Patent Citations (4)

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