EP0228489B1 - Procédé pour la sulfuration d'oléfines et leurs produits, et compositions contenant ces oléfines et leur production - Google Patents

Procédé pour la sulfuration d'oléfines et leurs produits, et compositions contenant ces oléfines et leur production Download PDF

Info

Publication number
EP0228489B1
EP0228489B1 EP85309479A EP85309479A EP0228489B1 EP 0228489 B1 EP0228489 B1 EP 0228489B1 EP 85309479 A EP85309479 A EP 85309479A EP 85309479 A EP85309479 A EP 85309479A EP 0228489 B1 EP0228489 B1 EP 0228489B1
Authority
EP
European Patent Office
Prior art keywords
sulfur
sulfurized olefin
olefin
adduct
lubricating 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.)
Expired
Application number
EP85309479A
Other languages
German (de)
English (en)
Other versions
EP0228489A1 (fr
Inventor
Paul G. Griffin
William Yuk-Lun Lam
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Afton Chemical Corp
Original Assignee
Afton Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to US06/556,968 priority Critical patent/US4563302A/en
Application filed by Afton Chemical Corp filed Critical Afton Chemical Corp
Priority to DE8585309479T priority patent/DE3571048D1/de
Priority to AT85309479T priority patent/ATE44043T1/de
Priority to EP85309479A priority patent/EP0228489B1/fr
Publication of EP0228489A1 publication Critical patent/EP0228489A1/fr
Application granted granted Critical
Publication of EP0228489B1 publication Critical patent/EP0228489B1/fr
Expired legal-status Critical Current

Links

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
    • 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

Definitions

  • No 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 1.8-2.2 gram moles of metal sulfide per gram mole of sulfur. This material is then refluxed for 1-24 hours with aqueous alkali metal hydroxide.
  • an effective sulfurized olefin is made by reacting sulfur monochloride with an olefin in the presence of a lower alkanol promoter to obtain an adduct which is reacted with sodium sulfide and sulfur in aqueous alkanol.
  • U.S. 4 188 297 discloses a method for making a lubricating additive in which an olefinically unsaturated hydrocarbon is reacted with elemental sulfur and a mercaptan.
  • a sulfurized olefin having improved solubility especially in alpha-olefin oligomer lubricating oil is made by a process comprising:
  • the olefins used are the monoethylenically unsaturated aliphatic hydrocarbons referred to as aliphatic monoolefins containing 3 to 6 carbon atoms.
  • Useful olefins are the monoethylenically unsaturated aliphatic hydrocarbons referred to as aliphatic monoolefins containing 3 to 6 carbon atoms. These include 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 2-methyl-2-pentene, 2-ethyl-2-butene and the like including mixtures thereof.
  • the olefins are branched-chain olefin such as isobutene, 2-methyl-1-butene, 2-methyl-2-butene, 2-methyl-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 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 0.75-3.0 gram moles of olefin for each 0.3-0.75 gram mole of sulfur monochloride usually suffices.
  • a preferred amount is 1.5-2.0 gram moles of olefin per gram mole of sulfur monochloride.
  • the reaction between sulfur monochloride and olefin will proceed without adding an alcohol promoter, and since alcohol will tend to cause corrosion of metal equipment, it is not a highly preferred method of conducting the first stage.
  • the use of an alcohol promoter is included in one embodiment of the invention.
  • Lower alcohol promoters which can be used in the first stage contains from 1 to 4 carbon atoms. Typical examples are methanol, ethanol, n-propanol, isopropanol, isobutanol, tert-butanol and the like.
  • a preferred promoter is methanol.
  • the amount of alcohol promoter is preferably 0.001 to 0.3 gram moles for each 0.3-0.75 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 30 ° -100 ° C.
  • a more preferred range is 40 ° -75 ° C and a most preferred range is 50 ° -60 ° C.
  • the first stage reaction should be conducted for a time sufficient to complete the reaction between the sulfur chloride and olefin. This time is controlled by the rate at which heat can be removed. Olefin feed rate is preferably controlled to hold the temperature within the desired range. When the sulfur chloride 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.
  • HCI gas is evolved so means should be provided to scrub the vent gas from the reactor to remove HCI prior to releasing it to the atmosphere.
  • adduct from the first stage is reacted with sodium sulfide, sulfur, alkyl mercaptan and optionally sodium hydrosulfide in an aqueous alcohol reaction medium.
  • the second stage is preferably carried out by charging aqueous sodium hydrosulfide, sodium hydroxide, water, alcohol and elemental sulfur flowers or powdered sulfur to a reactor and then adding the adduct and alkyl mercaptan to this at reaction temperature.
  • the NaSH and NaOH react to form sodium sulfide. Excess NaSH remains.
  • 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 absorbed. 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 and optionally sodium hydrosulfide with little or no free sodium hydroxide.
  • the amount of sodium sulfide can vary from 0.5-2.0 gram mole for each gram mole of sulfur chloride used in the first reaction stage.
  • the amount of sodium sulfide is 0.5-1.0 gram mole per mole of sulfur chloride and most preferably 0.6-1.0 gram mole per gram mole sulfur chloride.
  • Presence of NaSH is optional. Use of up to 0.5 gram moles of NaSH per mole of S 2 CI 2 has given satisfactory results. A preferred amount is 0.1-0.3 gram moles and most preferably 0.25 moles per mole of S 2 CI 2 .
  • Alcohol is required in the second stage reaction.
  • these are lower alcohols containing 1-4 carbon atoms such as methanol, ethanol, n-propanol, n-butanol, isobutanol, tert-butanol and the like, including mixtures thereof.
  • the preferred alcohol is isopropanol either alone or mixed with other alkanols such as tert-butanol.
  • the amount of alcohol can likewise vary over a wide range.
  • a useful range is 0.25-0.75 parts by weight per each part by weight of water.
  • a more preferred range is 0.4-0.6 parts by weight alcohol per each part by weight water.
  • the alkyl mercaptan can be added separately to the aqueous alcohol reaction medium or it can be mixed with the first stage adduct and the mixture added to the aqueous alcohol containing the sodium sulfide and sulfur. When added separately it is preferred that it be added concurrently with the first stage adduct to the aqueous alcohol containing the sodium sulfide and sulfur. Sequential addition can be used but it is not preferred.
  • the alkyl mercaptans used are those in which the alkyl group contains 1 to 12 carbon atoms. Representative example of these are methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, i-propyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, sec-butyl mercaptan, tert-butyl mercaptan, n-pentyl mercaptan, isopentyl mercaptan, tert-pentyl mercaptan, 2-ethyl hexyl mercaptan, n-octyl mercaptan, 1-methyl-heptyl mercaptan, 1-ethyl-decyl mercaptan and the like including mixtures thereof.
  • mercaptans are the tert-alkyl mercaptans. Of these the more preferred are the tert-alkyl mercaptans containing 4-8 carbon atoms. The most preferred alkyl mercaptan is tert-butyl mercaptan.
  • the amount of alkyl mercaptan can vary over a wide range.
  • a useful range in which to test is 0.05 to 0.8 moles for each mole of sulfur monochloride used in the first stage.
  • a preferred range is 0.08 to 0.5 moles of alkyl mercaptan per mole of sulfur monochloride and a more preferred range is 0.1 to 0.4 moles per mole of sulfur monochloride.
  • the most preferred amount of alkyl mercaptan is 0.25 to 0.35 moles per mole of sulfur monochloride.
  • the preferred amount of sulfur added is 0-0.3 gram atom for each gram mole of S 2 CI 2 . More preferably, 0.05-0.15 gram atom of sulfur and most preferably 0.0-0.15 gram atom are used per gram mole of S P OI 2 .
  • the mixture of sodium sulfide, sulfur and aqueous alkanol is stirred and heated to reaction temperature and then the adduct and alkyl mercaptan are added to it.
  • the reaction can be carried out in other ways such as by adding the sodium sulfide, sulfur, alkyl mercaptan and aqueous alkanol mixture to the adduct or by mixing everything together and heating the mixture.
  • Preferred second stage reaction temperature is 50 ° C up to reflux temperature.
  • a more preferred 10 reaction temperature is 75-85°C.
  • the mixture is preferably heated to reflux just below for 2-8 hours to assure completion of the reaction.
  • a very convenient way in which to make an effective sulfurized isobutylene is to base the amount of Na 2 S and NaSH (or NaOH plus NaSH or NaOH plus H 2 S), sulfur and tert-butyl mercaptan on the weight of S 2 CI 2 - isobutylene adduct.
  • the Kg of Na 2 S, NaSH, sulfur and tert-butyl mercaptan per each 100 Kg of sulfurized isobutylene is preferably 15-45:0-12:0-7.5:3-20:100, more preferably 20-35:2-10:1-6:4-18:100 and most preferably 25-30:4-8:2-5:5-15:100.
  • a sulfurized isobutylene adduct was made by adding isobutylene to sulfur monochloride at 50-65°C until reaction stopped.
  • aqueous alcohol (64.7 wt% isopropanol, 13.8 wt% tert-butanol, 20.3 wt% water), 23.4g water, 240.4g 29.09% aqueous NaSH solution (0.9 moles), 76.2g 81.6g 50% aqueous NaOH solution (0.95 moles) and 12.3g (0.38 moles) sulfur.
  • aqueous alcohol (same as in Example 1), 23.3g water 246.0g 29.09 wt% aqueous NaSH (1.27 moles), 78.0g 50% aqueous NaOH (0.98 moles) and 6.1g sulfur (0.44 moles).
  • This mixture was stirred and heated to 75 ° C and then 270.0g of the sulfurized isobutylene adduct described in Example 1 was fed to the reaction mixture together with 33.9g tert-butyl mercaptan over a two hour period at 75 ° to reflux. Reflux was continued for three hours and then solvent was distilled out up to liquid temperature of 90 ° C. Vacuum was applied and heating stopped.
  • Example 3 Another product was made following the same procedure as Example 3 except using 98.27g 34.3 wt% aqueous NaSH, 36.48g 50wt% aqueous NaOH, 2.95g sulfur, 42.70g water, 84.66g of same aqueous isopropanol tert-butanol solution 16.33g tert-butyl mercaptan and 130.64g S 2 CI 2 - isobutylene adduct. The product analyzed 46.4 weight percent sulfur.
  • Example 3 followed the same procedure as Example 3 except using 94.85g 35.04 wt% aqueous NaSH, 35.96g 50 wt% aqueous NaOH, 6.22g sulfur, 29.77g water, 99.83g 56.39 wt% isopropanol - 13.85 wt% tert-butanol - water solution, 16.21g tert-butyl mercaptan and 129.70g S 2 CI 2 - isobutylene adduct. The product analyzed 48 weight percent sulfur.
  • the sulfurized olefins 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 BFa catalyst.
  • Useful olefin oligomers can be made using other catalysts such as the aluminum alkyl Ziegler catalyst.
  • other olefins can be used such as Cs- 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-ethylhexylsebacate), 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-ethylhexylsebacate
  • fatty acid esters of polyols e.g. trimethylolpropane, tripelargonate
  • complex esters of alkanols, alkane, polyols and carboxylic or polycarboxylic acid e.g. di-2-ethylhexylsebacate
  • the sulfurized olefin is added in an amount sufficient to improve the EP property of the lubricant.
  • An amount of 0.1 to 10.0 wt % 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.
  • Antiwear additives such as alkyl or aryl phosphonates, phosphite, thiophosphates, dithiophosphates, and phosphoric acids. Also zinc dialkyl or diaryl dithiophosphate, chlorinated hydrocarbons, 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.
  • test additive was blended in the base oil at a concentration which imparted 1.0 weight percent sulfur to the oil. Results obtained were as follows:
  • the present additive was used as a component in a formulated gear oil.
  • the test was an L-42 High Speed Axle Test. Using the additives of Example 1 or 2 gave a gear oil which passed the test.
  • the mercaptan-capped sulfurized olefins of this invention have been found to be much more soluble in hydrogen-treated mineral oil and alpha-olefin oligomer synthetic lubricating oil compared to the same sulfurized olefin made without mercaptans.
  • first comparison blends are made at 4.0 weight percent sulfurized olefin in a hydrotreated base oil, a hydrocracked base oil an alpha-decene oligomer.
  • the blends were rated as clear or cloudy. The results were as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (9)

1. Procédé de production d'une oléfine sulfurée de solubilité renforcée dans une huile lubrifiante, procédé caractérisé en ce qu'il consiste:
(A) à faire réagir un halogénure de soufre choisi entre S2CI2 et SCI2 avec une mono-oléfine aliphatique contenant 3 à 6 atomes de carbone pour former un produit d'addition,
(B) à faire réagir ledit produit d'addition avec du soufre, Na2S, en une quantité de 0,5 à 2,0 molécules- grammes par mole de chlorure de soufre, un alkyl-mercaptan contenant 1 à 12 atomes de carbone et 0 à 0,5 molécule-gramme de NaSH par mole d'halogénures de soufre dans un milieu alcoolique aqueux à une température allant de 50°C à la température de reflux pour former ladite oléfine sulfurée,
(C) à séparer cette oléfine sulfurée du milieu alcoolique aqueux.
2. Procédé suivant la revendication 1, dans lequel ledit halogénure de soufre est 820)2.
3. Procédé suivant la revendication 2, dans lequel ladite mono-oléfine est une mono-oléfine à chaîne ramifiée ayant 4 à 6 atomes de carbone.
4. Procédé suivant la revendication 3, dans lequel ladite mono-oléfine est l'isobutylène.
5. Oléfine sulfurée pouvant être utilisée comme additif d'extrême-pression dans une huile lubrifiante ayant une solubilité renforcée, ladite oléfine sulfurée étant le produit préparé par un procédé qui consiste:
(A) à faire réagir un halogénure de soufre choisi entre S2CI2 et SC12 avec une mono-oléfine aliphatique contenant 3 à 6 atomes de carbone pour former un produit d'addition,
(B) à faire réagir ledit produit d'addition avec du soufre, Na2S, en une quantité de 0,5 à 2,0 molécules- grammes par mole de chlorure de soufre, un alkyl-mercaptan contenant 1 à 12 atomes de carbone et 0 à 0,5 molécule-gramme de NaSH par mole d'halogénure de soufre dans un milieu alcoolique aqueux à une température allant de 50°C à la température de reflux pour former ladite oléfine sulfurée,
(C) à séparer cette oléfine sulfurée du milieu alcoolique aqueux.
6. Oléfine sulfurée suivant la revendication 5, définie en outre par les particularités de l'une quelconque ou plusieurs des revendications 2 à 4.
7. Composition d'huile lubrifiante comprenant une quantité dominante d'une huile de viscosité propre à la lubrification, contenant une quantité secondaire améliorant les propriétés d'extrême-pression d'une oléfine sulfurée suivant la revendication 5 ou la revendication 6.
8. Composition d'huile lubrifiante suivant la revendication 7, dans laquelle ladite oléfine est l'isobutylè- ne, ledit halogénure de soufre est S2S12 et ledit alkyl-mercaptan est le tertio-butyl-mercaptan.
9. Procédé de production d'une composition, qui consiste à incorporer par mélange dans une huile de base ou dans un liquide hydrocarboné une oléfine sulfurée suivant la revendication 5 ou la revendication 6 de manière à produire ou bien une composition suivant la revendication 7 ou bien un additif conditionné ou un concentré d'additif dans lequel la quantité de ladite oléfine dépasse ladite quantité secondaire améliorant l'extrême-pression, après quoi ledit additif conditionné convient pour une dilution ultérieure avec une huile lubrifiante de manière à produire une composition d'huile lubrifiante douée de propriétés de résistance à la pression.
EP85309479A 1983-12-01 1985-12-24 Procédé pour la sulfuration d'oléfines et leurs produits, et compositions contenant ces oléfines et leur production Expired EP0228489B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US06/556,968 US4563302A (en) 1983-12-01 1983-12-01 Sulfurized olefin process
DE8585309479T DE3571048D1 (en) 1985-12-24 1985-12-24 Sulfurized olefin process and products thereof, and compositions containing such olefins and their production
AT85309479T ATE44043T1 (de) 1985-12-24 1985-12-24 Verfahren zur herstellung von sulfurierten olefinen und produkte davon und diese olefine enthaltende zusammensetzungen und deren herstellung.
EP85309479A EP0228489B1 (fr) 1985-12-24 1985-12-24 Procédé pour la sulfuration d'oléfines et leurs produits, et compositions contenant ces oléfines et leur production

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP85309479A EP0228489B1 (fr) 1985-12-24 1985-12-24 Procédé pour la sulfuration d'oléfines et leurs produits, et compositions contenant ces oléfines et leur production

Publications (2)

Publication Number Publication Date
EP0228489A1 EP0228489A1 (fr) 1987-07-15
EP0228489B1 true EP0228489B1 (fr) 1989-06-14

Family

ID=8194488

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85309479A Expired EP0228489B1 (fr) 1983-12-01 1985-12-24 Procédé pour la sulfuration d'oléfines et leurs produits, et compositions contenant ces oléfines et leur production

Country Status (3)

Country Link
EP (1) EP0228489B1 (fr)
AT (1) ATE44043T1 (fr)
DE (1) DE3571048D1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2007144A1 (fr) * 1989-01-31 1990-07-31 David J. Degonia Olefines sulfures, solubles dans des huiles traitees a l'hydrogene; leur preparation
US5428714A (en) * 1990-11-16 1995-06-27 Seiko Epson Corporation Status and command function extension for industry standard printer interfaces
CN108409619A (zh) * 2018-03-16 2018-08-17 山东豪迈化工技术有限公司 硫氯化异丁烯的合成方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1599288A (en) * 1977-07-22 1981-09-30 Cooper & Co Ltd Edwin Sulphurized olefins and their use as lubricant additives
US4204969A (en) * 1978-10-10 1980-05-27 Edwin Cooper, Inc. Lubricant composition containing sulfurized olefin extreme pressure additive

Also Published As

Publication number Publication date
ATE44043T1 (de) 1989-06-15
EP0228489A1 (fr) 1987-07-15
DE3571048D1 (en) 1989-07-20

Similar Documents

Publication Publication Date Title
US4204969A (en) Lubricant composition containing sulfurized olefin extreme pressure additive
US4954274A (en) Sulfurized olefin extreme pressure additives
US2760933A (en) Lubricants
US4563302A (en) Sulfurized olefin process
US4966720A (en) Oil soluble sulfurized olefins and two temperature zone process for their preparation
EP0211066B1 (fr) Compositions contenant du soufre et additifs concentres et huiles lubrifiantes les contenant
JPS62500590A (ja) 硫化された組成物および潤滑剤
JPH0651876B2 (ja) ホウ素−硫黄含有組成物，および該ホウ素−硫黄含有組成物を含有する添加濃縮物および潤滑オイル
EP0201197B1 (fr) Oléfines sulfurées
US4175043A (en) Metal salts of sulfurized olefin adducts of phosphorodithioic acids and organic compositions containing same
US5410088A (en) Process for sulfurized olefinic product
JPH0446319B2 (fr)
US4152275A (en) Sulfurized olefin adducts of phosphorodithioic acids and organic compositions containing same
US4212753A (en) Reaction products of sulfurized olefin adducts of phosphorodithioic acids and organic compositions containing same
EP0228489B1 (fr) Procédé pour la sulfuration d'oléfines et leurs produits, et compositions contenant ces oléfines et leur production
US5403960A (en) Process for sulfurized olefinic product
EP0032281B1 (fr) Procédé de préparation d'additif pour huile de lubrification à pression extrême
JPS63110289A (ja) 多硫化オレフィン組成物の製造方法
CA1260460A (fr) Preparation d'olefine sulfure
EP0208513B1 (fr) Compositions lubrifiantes
US4814097A (en) Reaction products of dialkyl phosphites with elemental sulfur, alkylene oxide compositions containing same, and their use in lubricant compositions
US5133889A (en) Polysulfurized olefin compositions, their preparation and use as additives in lubricants
EP0526214B1 (fr) Procédé pour la préparation d'un produit polyalcylène polysulfuré
EP0381350B1 (fr) Oléfines sulfurées hydroraffinées solubles dans l'huile et leur préparation
CA1122594A (fr) Lubrifiant avec additif l'olefine soufree pour pressions extremes

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19861112

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19871111

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

REF Corresponds to:

Ref document number: 44043

Country of ref document: AT

Date of ref document: 19890615

Kind code of ref document: T

ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

REF Corresponds to:

Ref document number: 3571048

Country of ref document: DE

Date of ref document: 19890720

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19921116

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19921117

Year of fee payment: 8

Ref country code: AT

Payment date: 19921117

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19921119

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19921120

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19921123

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19921127

Year of fee payment: 8

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19921231

Year of fee payment: 8

EPTA Lu: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19931224

Ref country code: GB

Effective date: 19931224

Ref country code: AT

Effective date: 19931224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19931225

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19931231

Ref country code: CH

Effective date: 19931231

Ref country code: BE

Effective date: 19931231

BERE Be: lapsed

Owner name: ETHYL PETROLEUM ADDITIVES INC.

Effective date: 19931231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19940701

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19931224

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19940901

EUG Se: european patent has lapsed

Ref document number: 85309479.5

Effective date: 19940710

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19951114

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19970829

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST