US3923670A - Overbased phenates - Google Patents

Overbased phenates Download PDF

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US3923670A
US3923670A US444426A US44442674A US3923670A US 3923670 A US3923670 A US 3923670A US 444426 A US444426 A US 444426A US 44442674 A US44442674 A US 44442674A US 3923670 A US3923670 A US 3923670A
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alkylphenol
alkaline earth
sulfurized
earth metal
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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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • 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
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic 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
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • 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
    • C10N2010/02—Groups 1 or 11
    • 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
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • Ci 252/42.7 Overbased sulphurised alkyl p l Sulphur and a [51] CIOM U54; CIOM 3/48 CIOM 5/28; defined quantity of alkali metal hydroxide and heating CIOM 7/52 the reaction mixture simultaneously or subsequently [58] Field Of Search 252/427, 33.4, 33 i an alkaline earth metal base This is followed y carbonation and filtration. [56] References Cited UNITED STATES PATENTS 6 Claims N0 Drawings 2.680.097 H1965 Stewart 252/4247 The present invention relates to the production of overbased sulphurized alkaline earth phenates.
  • the process for the production of an overbased sulphurized alkyl phenate comprises heating together an alkyl phenol, sulphur, and between 0.2 and 1.3 moles of alkali metal hydroxide per mole of alkyl phenol and heating the reaction mixture with atleast 2 moles of alkaline earth metal base per mole of alkyl phenol followed by carbonation at elevated temperature, and filtration of the resulting product.
  • alkaline earthmetal base is meant throughout this specification a base containing one of the elements magnesium, calcium, strontium or barium.
  • alkaline earth metal bases examples include an oxide or hydroxide of magnesium, calcium, strontium or barium.
  • the alkyl phenol may be one having from 8 to 30 carbon atoms in the alkyl chain.
  • An example of a suitable alkyl phenol is the dodecyl phenol produced by the reaction of propylene tetramer and phenol.
  • the alkali metal hydroxide may be a hydroxide of any of the alkali metals e. g. LiOH, NaOH, KOH.
  • the quantity of alkali metal hydroxide used is from 0.2 to 1.3 moles, preferably at least 0.3 to 0.9 moles, per mole of alkyl phenol fed to the reaction, for example about 0.8 moles per mole of alkyl phenol.
  • the minimum quantity of alkali metal hydroxide must be above that required merely to catalyse the reaction of alkyl phenol and sulphur. It would normally require less than 0.1 mole of alkali metal hydroxide to catalyse the sulphurization of alkyl phenol.
  • the relative molar proportions of alkyl phenol and sulphur fed to the reaction are preferably in the range 1:1 to 1:2.
  • the heating of the reaction mixture with alkaline earth base may be carried out simultaneously with the reaction of the alkyl phenol, sulphur and alkali metal hydroxide .or. may be carried out after the first reaction is complete.
  • the quantity of alkaline earth metal base fed to the reaction is preferably not more than 5, preferably 2 to 3.5 mole per mole of alkyl phenol.
  • the reaction of the alkyl phenol, sulphur and alkali metal hydroxide are preferably carried out at temperatures in the range 140 to 200C, more preferably 150 to 170C.
  • the alkali metal hydroxide may beadded as a solid or as a solution in water.
  • a diol e.g. ethylene glycol is preferably added.
  • the reaction time may vary over a moderately wide range e.g. to 3 hours. A suitable reaction time is 1 hour.
  • the subsequent reaction with alkaline earth base can for example be carried out at temperatures in the range 110 to 190C, more preferably 140 to 180C.
  • suitable reaction times are those in the range 0.1 to 2 hours preferably about A: hour.
  • alkyl phenol It may be desirable to add a further quantity of alkyl phenol to the reaction with the alkaline earth metal base when this is carried out in a separate step from the reaction of the alkyl phenol, sulphur and alkali metal hydroxide. This quantity of alkyl phenol is to be taken into account in calculating the alkali metal hydroxidelalkyl phenol mole ratio.
  • glycol e.g. ethylene glycol and/or a high boiling alkanol e.g. tridecanol to be present.
  • the preferred temperatures are those preferred for the reaction with alkaline earth base in the two step reaction.
  • the alkaline earth base has been treated with the alkyl phenol/sulphur/alkali metal hydroxide reaction mixture.
  • water of reaction is preferably removed e.g. by heating under reduced pressure.
  • the resulting mixture is then carbonated by blowing in carbon dioxide while maintaining the mixture at elevated temperature e.g. to 190C preferably about 160C.
  • the carbonation may be carried out as a single step. Alternatively the carbonation may be carried out in two or more steps with treatment with alkaline earth base and glycol between the steps. 7
  • EXAMPLE 1 1 The following ingredients were mixed together and heated to 160C:
  • Carbon dioxide (88g) was then fed into the mixture, which was maintained at 160C.
  • the mixture was subject to sub-atmospheric pressure and heated to 200C to strip out any residual water and ethylene glycol and tridecanol.
  • the product was then cooled and filtered.
  • EXAMPLE 2 a A sulphurized alkyl phenol was prepared by reacting an alkyl phenol (10 mole) and sulphur (14 mole) in the presence of lithium hydroxide (2 mole) for 2 hours.
  • the alkyl phenol was a mixture of 60% by weight of C alkyl phenol and 40% by weight of C to C alkyl phenol.
  • the viscosity of the stripped product at 210F was greater than 1000 cS and the acid value was 320mg KOH/g.
  • EXAMPLE 3 Lithium hydroxide dihydrate (60g) and alkyl phenol of molecular weight (100g) were added to the sulphurized alkyl phenol (620g) prepared as in Example above. This weight of sulphurized alkyl phenol corresponded to 1.5 moles of alkyl phenol. The mixture was then reacted for 1 hour at 160C. Calcium hydroxide (240g) was then added to the mixture followed by ethylene glycol (100ml), diluent mineral oil (100ml) and tridecanol (100ml). The mixture was then heated at 150C under 400mmHg pressure for 1 hour after which time the pressure was raised to atmospheric pressure and carbon dioxide (90g) was bubbled through the mixture which was maintained at 150C.
  • the product was vacuum stripped while being heated to 205C.
  • the acid value of the product was 350.8 mgKOH/g and the viscosity was 850cS at a temperature of 210F.
  • EXAMPLE 4 This is an example of the process of the present invention in which the reaction of the alkali metal base, the alkyl phenol, and the sulphur takes place at the same time as the reaction with the alkali metal hydroxide.
  • Alkyl phenol (555g) in which the alkyl group contained C C carbon atoms (average molecular weight 340) was mixed with sulphur (72g), sodium hyd oxide (32g), calcium hydroxide (230g), diluent mineral o'il (150ml), and tridecanol (100ml), and heated together foxll hour.
  • the acid value of the final product was 299mg KOH/g and the viscosity at 210F was 527cS.
  • an overbased sulfurized alkaline earth metal alkylphenate wherein an alkylphenol having from 8 to 30 carbons in the alkyl group and sulfur are reacted in the presence of an alkali metal hydroxide to form a sulfurized alkylphenol and wherein the sulfurized alkylphenol is contacted with at least two molar parts of an alkaline earth metal base per molar part of alkylphenol in said sulfurized alkylphenol and in the presence of ethylene glycol to form a sulfurized alkaline earth alkylphenate which is thereafter carbonated to form said overbased sulfurized alkaline earth metal alkylphenate, the improvement comprises (l) reacting said alkylphenol and sulfur in the presence of 0.2l.3 molar parts of an alkali metal hydroxide per molar part of alkylphenol and (2) conducting said contacting and said carbonation steps in the presence of said alkali metal hydroxide.

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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)

Abstract

Overbased sulphurised alkyl phenol, sulphur and a defined quantity of alkali metal hydroxide and heating the reaction mixture simultaneously or subsequently with an alkaline earth metal base. This is followed by carbonation and filtration.

Description

United States Patent Crawford Dec. 2, 1975 ()VERBASED PHENATES 3.424.679 l/l969 Allphin 252/33 [76] inventor: John Crawford, Pemberley, l5 3437595 4/1969 Coup] md 5 l4 7 Ashcourt Drive, Hornsea, East Yorkshlre- England Primary Examiner-Delbert E. Gantz [22] Filed; 2 1974 Assistant Exuminerl. Vaughn Attorney, Agent, or Firm-G. F. Magdeburger; C. J. [21] Appl. No.: 444,426 Tonkm [30] Foreign Application Priority Data Feb. 22, 1973 United Kingdom 4. 8629/73 57 ABSTRACT [52] [1.8. Ci; 252/42.7 Overbased sulphurised alkyl p l Sulphur and a [51] CIOM U54; CIOM 3/48 CIOM 5/28; defined quantity of alkali metal hydroxide and heating CIOM 7/52 the reaction mixture simultaneously or subsequently [58] Field Of Search 252/427, 33.4, 33 i an alkaline earth metal base This is followed y carbonation and filtration. [56] References Cited UNITED STATES PATENTS 6 Claims N0 Drawings 2.680.097 H1965 Stewart 252/4247 The present invention relates to the production of overbased sulphurized alkaline earth phenates.
According to the present invention the process for the production of an overbased sulphurized alkyl phenate comprises heating together an alkyl phenol, sulphur, and between 0.2 and 1.3 moles of alkali metal hydroxide per mole of alkyl phenol and heating the reaction mixture with atleast 2 moles of alkaline earth metal base per mole of alkyl phenol followed by carbonation at elevated temperature, and filtration of the resulting product. I l
By alkaline earthmetal base is meant throughout this specification a base containing one of the elements magnesium, calcium, strontium or barium.
Examples of suitable alkaline earth metal bases are an oxide or hydroxide of magnesium, calcium, strontium or barium.
The alkyl phenol may be one having from 8 to 30 carbon atoms in the alkyl chain. An example of a suitable alkyl phenol is the dodecyl phenol produced by the reaction of propylene tetramer and phenol.
The alkali metal hydroxide may be a hydroxide of any of the alkali metals e. g. LiOH, NaOH, KOH.
The quantity of alkali metal hydroxide used is from 0.2 to 1.3 moles, preferably at least 0.3 to 0.9 moles, per mole of alkyl phenol fed to the reaction, for example about 0.8 moles per mole of alkyl phenol. The minimum quantity of alkali metal hydroxide must be above that required merely to catalyse the reaction of alkyl phenol and sulphur. Itwould normally require less than 0.1 mole of alkali metal hydroxide to catalyse the sulphurization of alkyl phenol.
The relative molar proportions of alkyl phenol and sulphur fed to the reaction are preferably in the range 1:1 to 1:2. The heating of the reaction mixture with alkaline earth base may be carried out simultaneously with the reaction of the alkyl phenol, sulphur and alkali metal hydroxide .or. may be carried out after the first reaction is complete. The quantity of alkaline earth metal base fed to the reaction is preferably not more than 5, preferably 2 to 3.5 mole per mole of alkyl phenol.
Where the reactions are carried out consecutively, the reaction of the alkyl phenol, sulphur and alkali metal hydroxide are preferably carried out at temperatures in the range 140 to 200C, more preferably 150 to 170C. The alkali metal hydroxide may beadded as a solid or as a solution in water. A diol e.g. ethylene glycol is preferably added. The reaction time may vary over a moderately wide range e.g. to 3 hours. A suitable reaction time is 1 hour.
The subsequent reaction with alkaline earth base can for example be carried out at temperatures in the range 110 to 190C, more preferably 140 to 180C. Examples of suitable reaction times are those in the range 0.1 to 2 hours preferably about A: hour.
It may be desirable to add a further quantity of alkyl phenol to the reaction with the alkaline earth metal base when this is carried out in a separate step from the reaction of the alkyl phenol, sulphur and alkali metal hydroxide. This quantity of alkyl phenol is to be taken into account in calculating the alkali metal hydroxidelalkyl phenol mole ratio.
It is desirable to carry out the reaction with alkaline earth metal base in the presence of a neutral calcium sulphonate to give better dispersal of the base. It is also desirable for the glycol e.g. ethylene glycol and/or a high boiling alkanol e.g. tridecanol to be present.
Where the reactions with alkali metal hydroxide and with alkaline earth base are carried out in a single step, the preferred temperatures are those preferred for the reaction with alkaline earth base in the two step reaction.
After the alkaline earth base has been treated with the alkyl phenol/sulphur/alkali metal hydroxide reaction mixture. water of reaction is preferably removed e.g. by heating under reduced pressure. The resulting mixture is then carbonated by blowing in carbon dioxide while maintaining the mixture at elevated temperature e.g. to 190C preferably about 160C. The carbonation may be carried out as a single step. Alternatively the carbonation may be carried out in two or more steps with treatment with alkaline earth base and glycol between the steps. 7
Water of reaction and any free glycol and high boiling alkanol are then removed. This may be done by heating under reduced pressure. The resulting product is then filtered, to give the lubricant additive.
The invention will now be further described by reference to the following example.
EXAMPLE 1 1 The following ingredients were mixed together and heated to 160C:
370g of C -C alkyl phenol (approx 1 mole) 54g of Sulphur 32g of NaOH 30g of a neutral calcium sulphonate The mixture was maintained at 160C for 1 hour and during the first ten minutes of this period 5 ml. of ethylene glycol were added dropwise. At the end of one hour the mixture was subjected to a sub-atmospheric pressure of 400 mm Hg, for half an hour to remove H 5] The following ingredients were then added to the mixture:
222g of Ca(OH) 100ml of tridecanol 166ml of ethylene glycol 300ml of lubricating oil The mixture was maintained at 160C under a subatmospheric pressure of 400 mmHg and water of reaction was removed over 30 minutes.
Carbon dioxide (88g) was then fed into the mixture, which was maintained at 160C. When the treatment with carbon dioxide was completed the mixture was subject to sub-atmospheric pressure and heated to 200C to strip out any residual water and ethylene glycol and tridecanol. The product was then cooled and filtered.
EXAMPLE 2 a. A sulphurized alkyl phenol was prepared by reacting an alkyl phenol (10 mole) and sulphur (14 mole) in the presence of lithium hydroxide (2 mole) for 2 hours. The alkyl phenol was a mixture of 60% by weight of C alkyl phenol and 40% by weight of C to C alkyl phenol.
b. Product (623g) made as in (a) above was mixed with calcium hydroxide (230g). The quantity of product used was equivalent to that obtained from 1.5 moles of alkyl phenol. Ethylene glycol (l 10ml), mineral oil (ml), and tridecanol (100ml) were then added and the mixture was heated to 150C at 400mmI-lg pressure for 1 hour to remove all the water of reaction. Carbon dioxide (80g) was then passed into the mixture for half an hour, the temperature of the mixture remaining at 150 to 160C. The resulting product was then heated to 200C in a vacuum stripping step to remove the glycol and the tridecanol.
The viscosity of the stripped product at 210F was greater than 1000 cS and the acid value was 320mg KOH/g.
EXAMPLE 3 Lithium hydroxide dihydrate (60g) and alkyl phenol of molecular weight (100g) were added to the sulphurized alkyl phenol (620g) prepared as in Example above. This weight of sulphurized alkyl phenol corresponded to 1.5 moles of alkyl phenol. The mixture was then reacted for 1 hour at 160C. Calcium hydroxide (240g) was then added to the mixture followed by ethylene glycol (100ml), diluent mineral oil (100ml) and tridecanol (100ml). The mixture was then heated at 150C under 400mmHg pressure for 1 hour after which time the pressure was raised to atmospheric pressure and carbon dioxide (90g) was bubbled through the mixture which was maintained at 150C.
The product was vacuum stripped while being heated to 205C.
The acid value of the product was 350.8 mgKOH/g and the viscosity was 850cS at a temperature of 210F.
EXAMPLE 4 This is an example of the process of the present invention in which the reaction of the alkali metal base, the alkyl phenol, and the sulphur takes place at the same time as the reaction with the alkali metal hydroxide.
Alkyl phenol (555g) in which the alkyl group contained C C carbon atoms (average molecular weight 340) was mixed with sulphur (72g), sodium hyd oxide (32g), calcium hydroxide (230g), diluent mineral o'il (150ml), and tridecanol (100ml), and heated together foxll hour.
Ethylene glyLTKTfUo nl) was slowly added and the reaction mixture heated f0? 1 hour to remove water of reaction. Carbon dioxide (80g) was then passed into the reaction mixture. The resulting product was then vacuum stripped while being heated to 200C, and was then filtered.
The acid value of the final product was 299mg KOH/g and the viscosity at 210F was 527cS.
I claim:
1. In a process for the production of an overbased sulfurized alkaline earth metal alkylphenate wherein an alkylphenol having from 8 to 30 carbons in the alkyl group and sulfur are reacted in the presence of an alkali metal hydroxide to form a sulfurized alkylphenol and wherein the sulfurized alkylphenol is contacted with at least two molar parts of an alkaline earth metal base per molar part of alkylphenol in said sulfurized alkylphenol and in the presence of ethylene glycol to form a sulfurized alkaline earth alkylphenate which is thereafter carbonated to form said overbased sulfurized alkaline earth metal alkylphenate, the improvement comprises (l) reacting said alkylphenol and sulfur in the presence of 0.2l.3 molar parts of an alkali metal hydroxide per molar part of alkylphenol and (2) conducting said contacting and said carbonation steps in the presence of said alkali metal hydroxide.
2. The process as defined in claim 1 wherein said alkali metal hydroxide is sodium hydroxide.
3. The process defined in claim 1 wherein said alkylphenol, sulfur and alkali metal hydroxide are heated at a temperature of 140-200C.
4. The process defined in claim 3 wherein said contacting of sulfurized alkylphenols and alkaline earth metal base is carried out at a temperature of 1 l0-190C.
5. In a process for the production of overbased sulfurized alkaline earth metal alkylphenates wherein an alkylphenol having from 8 to 30 carbons in the alkyl group and sulfur are reacted at a temperature of l40-200C in the presence of sodium hydroxide to form a sulfurized alkylphenol and wherein the sulfurized alkylphenol is then contacted at a temperature of 190F with at least 2 molar parts of an alkaline earth metal base per molar part of alkylphenol in said sulfurized alkylphenol in the presence of ethylene glycol to form a sulfurized alkaline earth metal alkylphenate which is thereafter carbonated with carbon dioxide to form said overbased sulfurized alkaline earth metal alkylphenate, the improvement comprises (1) reacting said alkylphenol and sulfur in the presence of 0.21 .3 molar parts of sodium hydroxide per molar part of alkylphenol and (2) conducting said contacting of said sulfurized alkylphenol and alkaline earth metal base and said carbonation steps in the presence of said sodium hydroxide.
6. The process described in claim 5 wherein said carbonation step is carried out at a temperature of l20-190C.

Claims (6)

1. IN A PROCESS FOR THE PRODUCTION OF AN OVERBASED SULFURIZED ALKALINE EARTH METAL ALKYLPHENATE WHEREIN AN ALKYLPHENOL HAVING FROM 8 TO 30 CARBONS IN THE ALKYL GROUP AND SULFUR ARE REACTED IN THE PRESENCE OF AN ALKALI METAL HYDROXIDE TO FORM A SULFURIZED ALKYLPHENOL AND WHEREIN THE SULFURIZED ALKYLPHENOL IS CONTACTED WITH AT LEAST TWO MOLAR PARTS OF AN ALKALINE EARTH METAL BASE PER MOLAR PART OF ALKYLPHENOL IN SAID SULFURIZED ALKYLPHENOL AND IN THE PRESENCE OF ETHYLENE GLYCOL TO FORM A SULFURIZED ALKALINE EARTH ALKYLPHENATE WHICH IS THEREOFTER CARBONATED TO FORM SAID OVERBASED SULFURIZED ALKALINE EARTH METAL ALKYLPHENATE, THE IMPROVEMENT COMPRISES (1) REACTING SAID ALKYLPHENOL AND SULFUR IN THE PRESENCE OF 0.2-1.3 MOLAR PARTS OF AN ALKALI METAL HYDROXIDE PER MOLAR PART OF ALKULPHENOL AND (2) CONDUCTING SAID CONTACTING AND SAID CARBONATION STEPS IN THE PRESENCE OF SAID ALKALI METAL HYDROXIDE.
2. The process as defined in claim 1 wherein said alkali metal hydroxide is sodium hydroxide.
3. The process defined in claim 1 wherein said alkylphenol, sulfur and alkali metal hydroxide are heated at a temperature of 140*-200*C.
4. The process defined in claim 3 wherein said contacting of sulfurized alkylphenols and alkaline earth metal base is carried out at a temperature of 110*- 190*C.
5. In a process for the production of overbased sulfurized alkaline earth metal alkylphenates wherein an alkylphenol having from 8 to 30 carbons in the alkyl group and sulfur are reacted at a temperature of 140*- 200*C in the presence of sodium hydroxide to form a sulfurized alkylphenol and wherein the sulfurized alkylphenol is then contacted at a temperature of 110*- 190*F with at least 2 molar parts of an alkaline earth metal base per molar part of alkylphenol in said sulfurized alkylphenol in the pResence of ethylene glycol to form a sulfurized alkaline earth metal alkylphenate which is thereafter carbonated with carbon dioxide to form said overbased sulfurized alkaline earth metal alkylphenate, the improvement comprises (1) reacting said alkylphenol and sulfur in the presence of 0.2-1.3 molar parts of sodium hydroxide per molar part of alkylphenol and (2) conducting said contacting of said sulfurized alkylphenol and alkaline earth metal base and said carbonation steps in the presence of said sodium hydroxide.
6. The process described in claim 5 wherein said carbonation step is carried out at a temperature of 120190C.
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2653717A1 (en) * 1975-12-15 1977-06-16 Karonite Chemical Co PROCESS FOR MANUFACTURING AN OVERBASED ADDITIVE TO LUBRICATING OILS
EP0006796A1 (en) * 1978-06-26 1980-01-09 Orogil Process for the preparation of overbased metalliferous detergent-dispersant agents for lubricating oils and product obtained
EP0007260A1 (en) * 1978-06-26 1980-01-23 Orogil Process for the preparation of metalliferous detergent-dispersant additives of high alkali content, especially for lubricating oils, and product obtained
EP0007257A1 (en) * 1978-06-26 1980-01-23 Orogil Process for the preparation of detergent-dispersant agents of high alkali content for lubricating oils and product obtained
US4664824A (en) * 1986-01-14 1987-05-12 Amoco Corporation Phenate product and process
EP0240327A2 (en) 1986-03-31 1987-10-07 Exxon Chemical Patents Inc. Cyclic phosphate additives and their use in oleaginous compositions
US4744921A (en) * 1986-10-21 1988-05-17 Chevron Research Company Methods for preparing, group II metal overbased sulfurized alkylphenols
EP0259974A3 (en) * 1986-08-08 1988-08-10 Chevron Research Company Overbased sulfurized alkyl-phenols as lubricating oil additives
US4865754A (en) * 1986-01-14 1989-09-12 Amoco Corporation Lubricant overbased phenate detergent with improved water tolerance
US4971710A (en) * 1986-10-21 1990-11-20 Chevron Research Company Methods for preparing, Group II metal overbased sulfurized alkylphenols
US4973411A (en) * 1989-09-15 1990-11-27 Texaco Inc. Process for the preparation of sulfurized overbased phenate detergents
US5024773A (en) * 1986-10-21 1991-06-18 Chevron Research Company Methods for preparing, group II metal overbased sulfurized alkylphenols
US5529705A (en) * 1995-03-17 1996-06-25 Chevron Chemical Company Methods for preparing normal and overbased phenates
US5677270A (en) * 1995-03-17 1997-10-14 Chevron Chemical Company Methods for preparing normal and overbased phenates
US20050026962A1 (en) * 1998-06-17 2005-02-03 Christoph Erdelen Agents for controlling plant pests

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US2680097A (en) * 1953-06-24 1954-06-01 California Research Corp Preparation of phenates
US3424679A (en) * 1966-08-15 1969-01-28 Chevron Res Nonvicinal glycols in overbased phenate preparation
US3437595A (en) * 1965-10-29 1969-04-08 Orobis Ltd Process for the production of overbased alkyl phenates suitable for use in lubricant additives

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2680097A (en) * 1953-06-24 1954-06-01 California Research Corp Preparation of phenates
US3437595A (en) * 1965-10-29 1969-04-08 Orobis Ltd Process for the production of overbased alkyl phenates suitable for use in lubricant additives
US3424679A (en) * 1966-08-15 1969-01-28 Chevron Res Nonvicinal glycols in overbased phenate preparation

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2653717A1 (en) * 1975-12-15 1977-06-16 Karonite Chemical Co PROCESS FOR MANUFACTURING AN OVERBASED ADDITIVE TO LUBRICATING OILS
EP0006796A1 (en) * 1978-06-26 1980-01-09 Orogil Process for the preparation of overbased metalliferous detergent-dispersant agents for lubricating oils and product obtained
EP0007260A1 (en) * 1978-06-26 1980-01-23 Orogil Process for the preparation of metalliferous detergent-dispersant additives of high alkali content, especially for lubricating oils, and product obtained
EP0007257A1 (en) * 1978-06-26 1980-01-23 Orogil Process for the preparation of detergent-dispersant agents of high alkali content for lubricating oils and product obtained
US4664824A (en) * 1986-01-14 1987-05-12 Amoco Corporation Phenate product and process
US4865754A (en) * 1986-01-14 1989-09-12 Amoco Corporation Lubricant overbased phenate detergent with improved water tolerance
EP0240327A2 (en) 1986-03-31 1987-10-07 Exxon Chemical Patents Inc. Cyclic phosphate additives and their use in oleaginous compositions
EP0259974A3 (en) * 1986-08-08 1988-08-10 Chevron Research Company Overbased sulfurized alkyl-phenols as lubricating oil additives
JPS63128099A (en) * 1986-10-21 1988-05-31 シエブロン　リサーチ　カンパニー Production of group-ii metal overbased phenol alkyl sulfate
US4744921A (en) * 1986-10-21 1988-05-17 Chevron Research Company Methods for preparing, group II metal overbased sulfurized alkylphenols
US4971710A (en) * 1986-10-21 1990-11-20 Chevron Research Company Methods for preparing, Group II metal overbased sulfurized alkylphenols
US5024773A (en) * 1986-10-21 1991-06-18 Chevron Research Company Methods for preparing, group II metal overbased sulfurized alkylphenols
JP2637117B2 (en) 1986-10-21 1997-08-06 シエブロン リサーチ カンパニー Method for producing Group II metal overbased sulfurized alkylphenol
US4973411A (en) * 1989-09-15 1990-11-27 Texaco Inc. Process for the preparation of sulfurized overbased phenate detergents
US5529705A (en) * 1995-03-17 1996-06-25 Chevron Chemical Company Methods for preparing normal and overbased phenates
US5677270A (en) * 1995-03-17 1997-10-14 Chevron Chemical Company Methods for preparing normal and overbased phenates
EP0808830A2 (en) * 1996-05-14 1997-11-26 Chevron Chemical Company Methods for preparing normal and overbased phenates
EP0808830A3 (en) * 1996-05-14 1998-04-22 Chevron Chemical Company Methods for preparing normal and overbased phenates
US20050026962A1 (en) * 1998-06-17 2005-02-03 Christoph Erdelen Agents for controlling plant pests

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