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GB1569730A - 0,0-diiso-propyl-s-(2-carboethoxyethyl)-phosphorodithioate and lubricating oil compositions containing it - Google Patents

0,0-diiso-propyl-s-(2-carboethoxyethyl)-phosphorodithioate and lubricating oil compositions containing it Download PDF

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Publication number
GB1569730A
GB1569730A GB24607/78A GB2460778A GB1569730A GB 1569730 A GB1569730 A GB 1569730A GB 24607/78 A GB24607/78 A GB 24607/78A GB 2460778 A GB2460778 A GB 2460778A GB 1569730 A GB1569730 A GB 1569730A
Authority
GB
United Kingdom
Prior art keywords
compound
formula
lubricating oil
carboethoxyethyl
phosphorodithioate
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
GB24607/78A
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.)
Novartis AG
Original Assignee
Ciba Geigy AG
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
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Priority to GB24607/78A priority Critical patent/GB1569730A/en
Priority to NL7904137A priority patent/NL7904137A/en
Priority to DE19792921620 priority patent/DE2921620A1/en
Priority to IT23111/79A priority patent/IT1121528B/en
Priority to FR7913610A priority patent/FR2427338A2/en
Priority to BE0/195444A priority patent/BE876605A/en
Publication of GB1569730A publication Critical patent/GB1569730A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • C10M137/10Thio derivatives
    • C10M137/105Thio derivatives not containing metal
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/06Phosphorus compounds without P—C bonds
    • C07F9/16Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165Esters of thiophosphoric acids
    • C07F9/1651Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/047Thioderivatives not containing metallic elements
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/02Bearings
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/08Hydraulic fluids, e.g. brake-fluids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10Form in which the lubricant is applied to the material being lubricated semi-solid; greasy

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)

Description

(54) O ;O-DIISOPROPYL-S-(CARBOETHOXYETHYL)PHOSPHORODITHIOATE AND LUBRICATING OIL COMPOSITIONS CONTAINING IT (71) We CIBA-GEIGY AG, a Swiss Body Corporate, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: In the British Patent Application No. 4296/70, which was published on August 31, 1972, as Patent Specification No. 1 287 331, a class of phosphorodithioates was claimed having the general formula I XiCO-CH(R)-CH2-S-P(S) (OR1) (OR2) Z I wherein R is hydrogen or an alkyl radical containing from 1 to 3 carbon atoms, R1 and R2 are the same or different and are hydrocarbyl radicals, containing from 1 to 20 carbon atoms unsubstituted or substituted by one or more halogen atoms or alkoxy groups, Z is an integer from 1 to 6, and X is an alkoxy radical derived from an aliphatic alcohol having from 2 to 20 carbon atoms and containing from 1 to 6 hydroxyl groups. This patent specification was amended under Section 29 of the Patent Act 1949 and subsequently reprinted on 19th April 1973. The patent now claims a compound having the above formula I where R is hydrogen or an alkyl radical containing from 1 to 3 carbon atoms, R1 and R2 are the same or different and are hydrocarbyl radicals containing from 1 to 20 carbon atoms unsubstituted or substituted by one or more halogen atoms or alkoxy groups, Z is an integer from 2 to 6, and X is an alkoxy radical derived from an aliphatic alcohol having from 2 to 20 carbon atoms and containing from 2 to 6 hydroxyl groups. The compounds are claimed to be useful as antioxidants and extreme pressure additives for lubricants.
It has now been found that one particular compound of formula I wherein Z is 1, shows interesting properties as an oil additive, this compound being 0,0-diisopropyl-S-(2-carbo ethoxyethyl -phosphorodithioate.
Therefore the instant invention relates to the compound of the formula II (iso-C3H7O)2P(S)-S-CH2CH2COOC2Hs II as well as to compositions comprising a lubricating oil and the compound of formula II in an amount of 0.1 to 5% by weight based on the weight of the lubricating oil.
The compound of formula II is a new chemical compound which may be prepared by the addition of ethyl acrylate to 0,0-diisopropyl phosphorodithioic acid.
The lubricating oil may be a mineral oil or a synthetic oil or a mixture of both types of oil.
It may further contain other additives which are conventionally used to improve the oil properties, such as metal passivators, rust inhibitors, viscosity index improvers, pour point depressants, or other antioxidants and extreme pressure additives. Preferably, the compound of formula II is present in an amount of 0.1 to 3% by weight based on the weight of the lubricating oil.
The lubricating oil compositions containing the compound of formula II show excellent friction modifying characteristics and outstanding anticorrosive properties in contact with iron, silver, brass, copper or similar metals. Therefore such lubricating oil compositions are highly useful as industrial gear oils, hydraulic oils, slideway lubricants, metal working oils, or engine oils and for the manufacture of lubricating greases.
The following Examples further illustrate the invention.
Example 1 621.6 g of phosphorus pentasulfide and 1392 g of toluene are charged to a 4 1-vessel and heated to 800C with agitation. 672 g of isopropanol are added dropwise within 90 minutes at this temperature. The evolved hydrogen sulfide is absorbed in a wash bottle filled with NaOH solution. The reaction is continued at 80"C until all P255 has reacted and a clear solution is obtained which contains 0,0-diisopropyl-phosphorodithioic acid. 504 g of ethyl acrylate is then added dropwise at 80"C within 90 minutes and heating is continued for 3 hours. The reaction mixture is cooled to room temperature and filtered. The filtrate is washed with aqueous sodium carbonate solution and afterwards with water to neutrality.
The washed toluene solution is dried over Na2SO4 and after filtration the solvent is removed in a rotating vacuum evaporator.
The residue (1554 g) is an amber oil showing an analytical content of 9,9% phosphorus and 20,5% sulfur. The theoretical values for 0,0-diisopropyl-S-(2-carboethoxyethyl)phosphoro-dithioate are 9,87% P and 20,38% S.
The yield is 98% based on the used ethyl acrylate.
Example 2 To show the extreme pressure properties and anti-wear properties the compound of formula II was tested in a 4-Ball Lubricant Testing Apparatus using 500-Solvent neutral (a mineral oil) as oil base. The tests were carried out according to IP 239 or DIN 51 530 by measuring the Initial Seizure Load (ISL), the Weld Load (WL) and the Wear Scar Diameter (WSD) when a load of either 70 Kg or 40 Kg has been applied for 1 hour.
ISL WL WSD Oil with additive 60 kg 160 kg 70 kg 40 kg 2.4 mm 0.85 mm Oil with 1% by weight of compound of formula 100 kg 240 kg 0.8 mm 0.35 mm Example 3 According to DIN 51 354 the extreme pressure characteristics for gear oils were tested in a FZG-apparatus using 150-Solvent neutral (mineral oil) by measuring the failure load stage (Schadens-Kraftstufe): Without additive failure load stage 6 0.5% b.w. compound of formula II ,, > 12 0.25% b.w. compound of formula II " 12 Example 4 On an IAE Gear Machine the extreme pressure characteristics were measured according to IP 166, test condition B (pinion speed 4000 revolutions per minute, test oil temperature 70"C, test oil flow 1 pint per minute) using 500-Solvent neutral (a mineral oil). The failure loads were as follows: Without additive 50 lb failure load 0.25% b.w. compound 125 lb failure load of formula II From Examples 2, 3 and 4 it is clear that the compound of formula II significantly enhances the load carrying ability (extreme pressure activity) of the mineral oil.

Claims (6)

WHAT WE CLAIM IS:
1. A compound having the formula II (iso-C3H7O)2 P(S)-S-CH2-CH2-COOC2Hs II
2. A process of preparing a compound having the formula II which comprises adding ethyl acrylate to 0,0-diisopropyl phosphorodithioic acid.
3. A process as claimed in claim 2 substantially as described in Example 1. 1.
4. A compound having the formula II whenever prepared by a process according to claim 2 or claim 3.
5. A composition comprising a lubricating oil and the compound of formula II in an amount of 0.1 to 5% by weight based on the weight of the lubricating oil.
6. A composition as claimed in claim 5 substantially as described in any of Examples 2 to 4.
GB24607/78A 1978-05-30 1978-05-30 0,0-diiso-propyl-s-(2-carboethoxyethyl)-phosphorodithioate and lubricating oil compositions containing it Expired GB1569730A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
GB24607/78A GB1569730A (en) 1978-05-30 1978-05-30 0,0-diiso-propyl-s-(2-carboethoxyethyl)-phosphorodithioate and lubricating oil compositions containing it
NL7904137A NL7904137A (en) 1978-05-30 1979-05-25 A DITHIOPHOSPHORIC ACID EESTER AND ITS USE AS AN ADDITIVE FOR LUBRICATING OIL.
DE19792921620 DE2921620A1 (en) 1978-05-30 1979-05-28 A NEW DITHIOPHOSPHORIC ACID ESTER AND ITS USE AS A LUBRICANT ADDITIVE
IT23111/79A IT1121528B (en) 1978-05-30 1979-05-29 DI-THIO-PHOSPHORIC ACID ESTER AND ITS USE AS AN ADDITIVE FOR LUBRICANT OILS
FR7913610A FR2427338A2 (en) 1978-05-30 1979-05-29 NEW PHOSPHORODITHIOATE AND ITS USE AS AN ADDITIVE FOR LUBRICANTS
BE0/195444A BE876605A (en) 1978-05-30 1979-05-29 NEW PHOSPHORODITHIOATE AND ITS USE AS AN ADDITIVE FOR LUBRICANTS

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB24607/78A GB1569730A (en) 1978-05-30 1978-05-30 0,0-diiso-propyl-s-(2-carboethoxyethyl)-phosphorodithioate and lubricating oil compositions containing it

Publications (1)

Publication Number Publication Date
GB1569730A true GB1569730A (en) 1980-06-18

Family

ID=10214329

Family Applications (1)

Application Number Title Priority Date Filing Date
GB24607/78A Expired GB1569730A (en) 1978-05-30 1978-05-30 0,0-diiso-propyl-s-(2-carboethoxyethyl)-phosphorodithioate and lubricating oil compositions containing it

Country Status (6)

Country Link
BE (1) BE876605A (en)
DE (1) DE2921620A1 (en)
FR (1) FR2427338A2 (en)
GB (1) GB1569730A (en)
IT (1) IT1121528B (en)
NL (1) NL7904137A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4734210A (en) * 1985-07-30 1988-03-29 Ciba-Geigy Corporation Additives for lubricant compositions
US4808324A (en) * 1986-04-04 1989-02-28 Lonza Ltd. Lubricant system for sheet and section rolling mills
US4965005A (en) * 1987-09-17 1990-10-23 Ciba-Geigy Corporation Aminomethyl derivatives of monothiocarbamates and dithiocarbamates as additives for lubricants
US5346635A (en) * 1993-06-03 1994-09-13 Material Innovation, Inc. Low and light ash oils
WO1995010584A1 (en) * 1993-10-12 1995-04-20 Behrooz Khorramian Low and light ash lubricating oils
US6627584B2 (en) 2002-01-28 2003-09-30 Ethyl Corporation Automatic transmission fluid additive comprising reaction product of hydrocarbyl acrylates and dihydrocarbyldithiophosphoric acids
US6660695B2 (en) * 2002-03-15 2003-12-09 Infineum International Ltd. Power transmission fluids of improved anti-shudder properties
EP1871861B1 (en) 2005-04-08 2020-01-15 The Lubrizol Corporation Additive system for lubricants
EP4438699A1 (en) * 2023-03-31 2024-10-02 Afton Chemical Corporation Antiwear system for improved copper corrosion
EP4438701A1 (en) * 2023-03-31 2024-10-02 Afton Chemical Corporation Antiwear system for improved copper corrosion
CN119060089A (en) * 2024-09-06 2024-12-03 青岛市资源化学与新材料研究中心 A dialkyl dithiophosphate compound and its preparation method and application as grease additive

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4772405A (en) * 1985-08-26 1988-09-20 Ciba-Geigy Corporation Lubricant compositions which contain sulfur-containing phenol derivatives, and novel sulfur-containing phenol derivatives
CH668265A5 (en) * 1985-09-09 1988-12-15 Lonza Ag METHOD FOR THE PRODUCTION OF LUBRICANTS IN POWDERED TO PASTOESE FORM.
US5271854A (en) * 1986-09-23 1993-12-21 Lonza Ltd. High temperature lubricant containing carboxylated styrene-butadiene latex
CH674096A5 (en) * 1988-01-19 1990-04-30 Lonza Ag
CH674477A5 (en) * 1988-03-30 1990-06-15 Lonza Ag
US5099667A (en) * 1989-06-16 1992-03-31 Lonza Ltd. System for suspending and applying solid lubricants to tools or work pieces
FR2789084B1 (en) * 1999-01-28 2001-03-09 Lorraine Laminage OIL-IN-WATER EMULSION COMPRISING AT LEAST ONE LUBRICATION ADDITIVE

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2645657A (en) * 1949-03-30 1953-07-14 Standard Oil Dev Co Thiophosphate esters

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4734210A (en) * 1985-07-30 1988-03-29 Ciba-Geigy Corporation Additives for lubricant compositions
US4808324A (en) * 1986-04-04 1989-02-28 Lonza Ltd. Lubricant system for sheet and section rolling mills
US4965005A (en) * 1987-09-17 1990-10-23 Ciba-Geigy Corporation Aminomethyl derivatives of monothiocarbamates and dithiocarbamates as additives for lubricants
US5346635A (en) * 1993-06-03 1994-09-13 Material Innovation, Inc. Low and light ash oils
US5439605A (en) * 1993-06-03 1995-08-08 Khorramian; Behrooz A. Phosphorus and phosphours-free low and light ash lubricating oils
WO1995010584A1 (en) * 1993-10-12 1995-04-20 Behrooz Khorramian Low and light ash lubricating oils
US6627584B2 (en) 2002-01-28 2003-09-30 Ethyl Corporation Automatic transmission fluid additive comprising reaction product of hydrocarbyl acrylates and dihydrocarbyldithiophosphoric acids
US6660695B2 (en) * 2002-03-15 2003-12-09 Infineum International Ltd. Power transmission fluids of improved anti-shudder properties
EP1871861B1 (en) 2005-04-08 2020-01-15 The Lubrizol Corporation Additive system for lubricants
EP4438699A1 (en) * 2023-03-31 2024-10-02 Afton Chemical Corporation Antiwear system for improved copper corrosion
EP4438701A1 (en) * 2023-03-31 2024-10-02 Afton Chemical Corporation Antiwear system for improved copper corrosion
JP2024146889A (en) * 2023-03-31 2024-10-15 アフトン・ケミカル・コーポレーション Anti-wear systems for improved copper corrosion
CN119060089A (en) * 2024-09-06 2024-12-03 青岛市资源化学与新材料研究中心 A dialkyl dithiophosphate compound and its preparation method and application as grease additive

Also Published As

Publication number Publication date
FR2427338A2 (en) 1979-12-28
DE2921620A1 (en) 1979-12-13
BE876605A (en) 1979-11-29
IT7923111A0 (en) 1979-05-29
IT1121528B (en) 1986-04-02
FR2427338B2 (en) 1982-05-28
NL7904137A (en) 1979-12-04

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Legal Events

Date Code Title Description
PS Patent sealed [section 19, patents act 1949]
PCNP Patent ceased through non-payment of renewal fee