JP2017133004A - Metal detergents - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of making sulfurized calcium phenate detergents with a reduced content of alkylphenols.SOLUTION: Sulfurized calcium phenate detergents having a reduced content of unsulfurized alkyl-substituted phenol are made by: (A) preparing a sulfurized calcium phenate detergent, made from an unsulfurized alkyl-substituted phenol, that optionally may have been further reacted with carbon dioxide; (B) adding to the detergent 1 to 100 mass%, based on the mass of the detergent, of an organic solvent that has a boiling point of above 100°C and below the boiling point of the unsulfurized alkyl-substituted phenol; and (C) removing the organic solvent from the detergent thereby to reduce the content of the unsulfurized alkyl-substituted phenol.SELECTED DRAWING: None

Description

  The present invention relates to a process for producing a sulfurized calcium phenate detergent having a reduced alkylphenol content.

Sulfurized calcium alkyl phenate detergents are well known additive components for lubricating oil compositions (or lubricants) for internal combustion engines. Unreacted alkylphenol used in its manufacture can be present in the detergent. Such alkylphenols have undesirable properties such as the occurrence of corrosion, and certain alkylphenols (eg, nonylphenol and tetrapropenylphenol) are classified as reproductive toxins.
The art describes a method to overcome this problem, a recent example is US 8,772,209 B2 ('209), which protonates a phenate detergent with an acidic compound followed by unreacted alkylphenol and protonated It describes that the unsulfurized salt is removed, for example, by distillation. One problem associated with this approach is that the acid salt that is formed (e.g., Ca stearate) is neutralized to release organic acids into the lubricant, which acid is the above internal combustion engine. Harmful to you.
WO 2015/153160 A1 ('160) describes the production of overbased and sulfurized alkaline earth metal alkyl phenate compositions in oil. The composition is heated and subjected to steam stripping and then filtered. The resulting product is stated to exhibit improved filtration rate and filtration efficiency, but without further illustration, the product was prepared by conventional means without the steam stripping step. It also states that it may contain reduced levels of free monomeric alkyl phenates or alkyl phenols (eg, tetrapropenyl phenol (TPP)) rather than materials. WO 2015/153160 A1 does not mention any solvent addition to this product obtained prior to carrying out the stripping step.

  US 2014 / 0142015A describes a method for producing a salt of a sulfurized alkyl-substituted hydroxyaromatic composition having a reduced content of the non-sulfided alkyl-substituted hydroxyaromatic compound and its non-sulfided metal salt. It is described. This method involves the addition of an immiscible solvent such as a low molecular weight alcohol (eg, methanol and ethanol) followed by extraction with a separatory funnel. The solvent is immiscible with the sulfurized, alkyl-substituted hydroxyaromatic composition and consequently needs to form separate layers. One disadvantage of this method is that extra equipment is required in the production plant (ie, equipment not previously used in the phenate production plant) to perform the separation. Similarly, solvents not previously used in the manufacturing process must also be usable and need to be stored in a separate storage tank. Moreover, methanol and ethanol as used in certain examples in US 2014/0142015 are toxic solvents.

  The present invention provides a specified ratio of a solvent having a boiling point lower than that of the alkylphenol as an auxiliary for distilling the alkylphenol from the cleaning agent without generating harmful species to the internal combustion engine. The above problems are overcome by adding to the detergent.

That is, in a first aspect, the present invention provides a method for producing a sulfurized calcium phenate detergent with a reduced content of non-sulfided alkyl-substituted phenol, the method comprising: Process of:
(A) providing a sulfided calcium phenate detergent, prepared from a non-sulfided alkyl-substituted phenol, optionally further reacted with carbon dioxide;
(B) 1-100 mass%, preferably 5-40 mass%, more preferably 5-30 mass%, higher than 100 ° C. and unsulfided alkyl, based on the mass of the detergent. Adding an organic solvent having a boiling point lower than that of the substituted phenol; and
(C) distilling the solvent from the detergent, thereby reducing the content of the non-sulfided alkyl-substituted phenol.
In a second aspect, the present invention provides a cleaning agent obtained or obtainable by the method according to the first aspect.
In a third aspect, the present invention provides a lubricating oil composition comprising a large amount of oil having a lubricating viscosity and a small amount of the cleaning agent according to the second aspect of the present invention.
The organic solvent is preferably miscible with the sulfurized calcium phenate detergent so that no excessive mixing is required.
One advantage of our invention is that distillation is commonly used in phenate detergent production plants so that the equipment is readily available. Another advantage of the present invention is that solvents already used in the preparation of sulfurized calcium phenate detergents, such as isodecanol, can be used as organic solvents having a boiling point of about 100 ° C.
The following examples of the present invention demonstrate their surprising advantages.

Definition:
As used herein, the following terms and expressions, if used and, if used, have the following accepted meanings:
“Active ingredients” or “(ai)” refers to an additive material that is not a diluent or solvent;
The word “comprising” or any synonymous terms specifies the presence of the stated feature, step, or integer or component, but one or more other features, steps, integers, components or It does not exclude the presence or addition of the group; the expression “consists of” or “consists essentially of” or the word of the same origin includes the word “contains” or of the same origin. Wherein “consisting essentially of” makes it possible to include the material without substantially affecting the characteristics of the composition to which the material is applied;
“Major amount” means 50% or more, preferably 60% or more, more preferably 70% or more, and most preferably 80% by weight of a composition. Or means exceeding this;
“Minor amount” means less than 50%, preferably less than 40%, more preferably less than 30%, and most preferably less than 20% by weight of a composition;
“TBN” means total base number as measured by ASTM D2896.

Furthermore, if used herein, and if used,
“Calcium content” is as measured by ASTM D4951;
“Phosphorus content” is as measured by ASTM D5185;
“Sulfate ash content” is as measured by ASTM D874;
“Sulfur content” is as measured by ASTM D2622;
“KV100” means kinematic viscosity at 100 ° C. as measured by ASTM D445.
Similarly, various ingredients that are essential as well as optional and customary may react under the conditions of formulation, storage or use, and the present invention may be the result of any such reaction as well. It will be understood that it also provides a product that can be obtained or is obtained.
Further, it is understood that any upper and lower limits in the amounts, ranges and ratios set forth herein can be combined independently.

From now on, features of the present invention related to one or more aspects of the present invention will be discussed in more detail below, where appropriate.
Process (A)
Examples of the phenate additive include those having a TBN in the range of 50-400. The alkyl group may have 9 to 100, preferably 9 to 70, most preferably 9 to 50 carbon atoms.
Examples of alkylphenol starting materials can include those prepared via alkylation of phenol with propylene-based alkenes, which can be characterized by branched-chain p-alkyl substitution, where the chain The bond to the benzene ring is through the C-2 or C-3 carbon atom. A notable example is tetrapropenylphenol (“TPP”).
The art describes the preparation of phenate detergents from alkylphenols. The phenate of the present invention may optionally be carbonated by reaction with carbon dioxide to give an overbased phenate. Specific examples are given in the examples section of this specification.

Process (B)
Examples of organic solvents that can be used include alkanols and aromatic hydrocarbons. Isodecanol is preferred and has a boiling point of 220 ° C (as opposed to 313 ° C for TPP). It should be noted that the Ca phenate starting material may contain a small amount of organic solvent, the amount given herein is that added as in step (B).
Process (C)
All or most of the organic solvent is removed in step (C). Preferably, after step (B) and before step (C), a base oil is added, which will reduce the phenate before distillation rather than after distillation and will result in a viscosity benefit. .
Steps (B) and (C) can be carried out by a series of repeated steps, or can be carried out as individual steps (one step (B) involves one step (C) and thus a step (B and C are each performed only once).
If further reduction of the alkylphenol content is required, the phenolic functional group in the product according to step (C) is, for example, ethylene as described in EP-A-2682451. Oxyalkylation can be achieved by reaction with carbonate, propylene carbonate or butylene carbonate.

As indicated on the lubricating oil composition , this is an aspect of the present invention.
An oil having a lubricating viscosity (often referred to as a base oil or lubricating oil) provides any major proportion of the composition and can be any oil suitable for lubricating internal combustion engines.
This can range from light fraction mineral oil to heavy lubricating oil in terms of viscosity. Generally, the viscosity of the oil is in the range of 2-40 mm ² / sec as measured at 100 ° C.
Natural oils include animal and vegetable oils (eg, castor oil, lard oil); liquid petroleum oils and paraffinic, naphthenic and mixed paraffin-naphthenic hydrorefined, solvent-treated or acid-treated mineral oils. Including. Oils with a lubricating viscosity derived from coal or shale also serve as useful base oils.
Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and copolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, poly (1-hexene), poly (1-octene). ), Poly (1-decene)); alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene); polyphenyl (eg, biphenyl, terphenyl, alkylated polyphenols) And alkylated diphenyl ethers; and alkylated diphenyl sulfides and their derivatives, analogs and homologues.

Alkylene oxide polymers and copolymers and their derivatives whose terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another group of known synthetic lubricating oils. These include polyoxyalkylene polymers made by polymerization of ethylene oxide or propylene oxide, and alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-poly-isopropylene glycol ether having a molecular weight of 1,000 or a molecular weight of 1,000 to 1,500. And the mono- and polycarboxylic acid esters thereof, such as their acetates, mixed C3-C8 fatty acid esters and C13 oxo acid diesters of tetraethylene glycol.
Another suitable group of synthetic lubricants are dicarboxylic acids (e.g. phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid. Esters of acid dimers, malonic acid, alkylmalonic acid, alkenylmalonic acid) with various alcohols (for example, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol) including. Specific examples of such esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, Diaicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and a complex ester formed by reacting 1 mol of sebacic acid with 2 mol of tetraethylene glycol and 2 mol of 2-ethylhexanoic acid Including.

Esters useful as synthetic oils also include esters made from C5 to C12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
Silicon-based oils, such as polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils constitute another useful group of synthetic lubricants Such oils include tetraethyl silicate, tetraisopropyl silicate, tetra- (2-ethylhexyl) silicate, tetra- (4-methyl-2-ethylhexyl) silicate, tetra- (p-tert-butylphenyl) silicate, hexa Includes-(4-methyl-2-ethylhexyl) disiloxane, poly (methyl) siloxane and poly (methylphenyl) siloxane. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofuran.
Unrefined, refined and rerefined oils can be used in the lubricating oils of the present invention. Unrefined oils are those obtained directly from natural or synthetic sources without further purification. For example, shale oil obtained directly from retorting operations; petroleum oil obtained directly by distillation; or ester oil obtained directly by esterification and used without further treatment is an unrefined oil . Refined oils are similar to unrefined oils, except that the oil has been further processed in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art. Rerefined oil is obtained by a method similar to that used to provide refined oil, but starts with oil already used in operation. Similarly, such rerefined oils are also known as reclaimed or reprocessed oils and are often subjected to additional processing, using techniques for removing spent additives and oil breakdown products. .

Publications of the American Petroleum Institute (API): “Engine Oil Licensing and Certification System”, Industry Services Department, 14th edition, December 1996 , Addendum 1, December 1998, classifies the base stock group. Examples of oils with lubricating viscosity that can be used in the lubricating oil composition of the present invention include 90% saturates, and 50% by weight or more containing less than or equal to 0.03% sulfur. An oil or a mixture thereof containing more than a base stock. Preferably this comprises 60% by weight or more of the base stock or mixtures thereof, for example 70, 80 or 90% by weight or more. The oil having the lubricating viscosity may consist of or consist essentially of the base stock or a mixture thereof.
Oils with a lubricating viscosity may constitute 50% by weight or more of the composition. Preferably this provides 60% or more, eg 70, 80 or 90% or more by weight of the composition.
In addition to the detergent additive of the present invention, the composition comprises one or more ashless dispersants, detergents, corrosion inhibitors, antioxidants, pour point depressants different from the additive of the present invention. One or more additive components selected from agents, antiwear agents, friction modifiers, demulsifiers, defoamers and viscosity modifiers can be included.
Engine The above detergent additive of the present invention may be used in lubricants for a range of internal combustion engines (spark ignition or compression ignition), such as automotive engines and marine engines. In connection with the latter, mention may be made of 2-stroke marine diesel cross-head engines and marine trunk piston engines.

The present invention is illustrated by the following examples, but the present invention is not limited to these examples.
Example 1
(A) Ca phenate detergents From each tetrapropenylphenol ("TPP"), two detergents were prepared, one as a low TBN variant and one as a high TBN variant. The following procedure was used:
Tetrapropenyl phenol, isodecanol (reaction solvent), ethylene glycol and antifoam were charged to the reactor and heated to 50 ° C.
-The mixture was heated to 90 ° C during which elemental sulfur and calcium oxide were charged to the mixture.
• Once at 90 ° C, additional ethylene glycol and base oil were charged as needed and the temperature was increased to 115 ° C.
CO ₂ addition was started at 115 ° C. and added over 6-8 hours while increasing the temperature to 190-215 ° C.
Once the carbonation was complete, the reaction mixture was heated to 210-215 ° C. or maintained at that temperature and evacuated to remove the reaction solvent and water.
(B) High TBN Ca phenate (500 g) and isodecanol (IDA; 210.9 g) were added to the reactor flask.
(C) The product was subjected to the following heat treatment method:

Next, vacuum stripping was performed at less than about 3 kPa (30 mbar) for 40 minutes, cooling with compressed air for 15 minutes, and cooling to ambient temperature overnight.
Reference example
Without the addition of IDA, high TBN Ca phenate (200 g) was subjected to an extensive series of heat treatments and vacuum distillations. Samples were taken after the first, second and third distillation treatments.
Result :

These results show that Example 1 (of the present invention) reduced the% TPP of the Ca phenate starting material and produced a product with a significantly lower viscosity than the above reference examples. The viscosity measurement for the reference example is too high to be usable.
Example 2
(A) The high TBN Ca phenate of Example 1 was used.
(B) and (C) IDA (10 wt%) was charged to the Ca phenate and the mixture was subjected to the vacuum distillation process described in Example 1. The% TPP of this product was measured. The treatment process was repeated twice more, in each case 10% IDA addition, vacuum distillation and% TPP measurement. In this way,% TPP measurements were obtained for 0, 10, 20 and 30% IDA-charged products, as listed below. These measurements are the content of C10, C11, C12 + alkylphenol in mass% as measured by reverse phase high performance liquid chromatography (HPLC) using a UV detector.

  These results show the results of solvent addition and subsequent removal by distillation over a number of steps.

Claims (14)

A process for producing a sulfurized calcium phenate detergent having a reduced content of non-sulfided alkyl-substituted phenol, the process comprising the following steps:
(A) providing a sulfided calcium phenate detergent made from an unsulfurized alkyl-substituted phenol, optionally further reacted with carbon dioxide;
(B) 1-100 mass%, preferably 5-40 mass%, more preferably 5-30 mass%, higher than 100 ° C. and not sulfided, based on the mass of the detergent. Adding an organic solvent having a boiling point lower than that of the alkyl-substituted phenol; and
(C) distilling the solvent from the detergent, thereby reducing the content of the unsulfided alkyl-substituted phenol;
Said method.   The method of claim 1, wherein the organic solvent is miscible with the sulfurized calcium phenate detergent.   The method of claim 1 or 2, wherein the organic solvent is an alkanol or an aromatic solvent.   The method of claim 1, wherein the organic solvent is isodecanol.   The method of claim 1, wherein the alkylphenol is tetrapropenylphenol.   The method of claim 1, wherein the base oil is added after step (B) and prior to step (C).   The method of claim 1, wherein steps (B) and (C) are performed in a series of repeated steps.   The method of claim 1, wherein steps (B) and (C) are each performed separately.   The method of claim 1, wherein the phenolic functional group in the product according to step (C) is oxyalkylated.   The process of claim 9, wherein the oxyalkylation is carried out by reaction with ethylene carbonate, propylene carbonate or butylene carbonate.   A sulfurized calcium phenate detergent obtained by the method of claim 1.   A lubricating oil composition comprising a large amount of oil having a lubricating viscosity and the detergent according to claim 11 or produced by mixing them.   The method of claim 1, wherein in step (B), the organic solvent is added to the cleaning agent in an amount of 5 to 40% by weight, based on the weight of the cleaning agent.   14. The method of claim 13, wherein the organic solvent is added to the cleaning agent in an amount of 5-30% by weight based on the weight of the cleaning agent.