JPS5925343A - Manufacture of lubricating oil additive - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing alkaline earth metal alkylphenols or sulfurized alkaline earth metal alkylphenates. In particular, the present invention provides overbased
The present invention relates to the production of alkyl phenates of sed) and to rib oil compositions containing them.

In internal combustion engines, byproducts from the combustion chamber often blow by the piston and mix with its lubricating oil. Many of these by-products form acidic substances within the lubricating oil. This is particularly true in diesel engines that operate with high-sulfur, low-grade fuels that produce corrosive acids upon combustion. As a result, the acids mixed in the lubricating oil include IIItlJ&, which is produced by the oxidation of sulfur, and halogenated lead scavengers (Halogenleadθcavengθr) in the fuel.
Bitrobaric acid (Hydro
halic acids), and nitrates produced by the oxidation of the air within the combustion chamber.

Such acids cause sludge build-up and corrosion of bearings and engine parts, leading to rapid wear and premature failure of the engine.

One type of compound commonly used to neutralize this acidic material in lubricating oils and disperse sludge is metal alkyl phenates, where the metal is an alkaline earth metal such as calcium, magnesium or barium. and myelinating metal alkyl phenates. [Standard] (nor
Both alkaline earth metal phenates (mal) and [overbased] alkaline earth metal phenates have been used. The word [overbase] is
When referring to alkaline earth metal alkyl phenates in which the ratio of the number of equivalents of the alkaline earth metal moiety to the number of equivalents of the phenolic moiety is greater than 1, and usually greater than 1.2, and may also be 4, 5 or more. use In contrast, the ratio of the alkaline earth metal moiety to the phenol moiety in the [standard] alkaline earth metal alkyl phenate is 1. Thus, [overbased] substances have the corresponding [
An alkaline earth metal in excess of 20% or more than that present in a standard substance. Therefore, [overbased] alkaline earth metal alkyl phenates have a greater ability to neutralize acidic substances than the corresponding [standard] alkaline earth metal alkyl phenates. The present invention includes the production of both 1-substance and 1-substance materials.

The prior art teaches many methods of making both standard and overbased metal alkyl phenates. One such method for producing [overbased] alkyl phenates is to combine an alkylphenol with a hydroxyl compound and an excess of an alkaline earth metal hydroxide (to neutralize the alkylphenol) in the presence or absence of sulfur. (in excess of the theoretical proportion required for
aarbonation), heading
Single lime additi
This is a method called "on process". The production of the intermediate product is accompanied by a significant increase in viscosity, but the subsequent carponation reduces its viscosity to a relatively low level. This increase in viscosity associated with the formation of intermediate products is undesirable because it makes stirring the reaction mixture difficult and impairs subsequent reactions. This viscosity increase can also be brought to an acceptable level by incorporating less h(alkaline earth metal hydroxide) in the reaction, but the overbased alkylphenote product is Its neutralization capacity decreases.In order to obtain a product with high neutralization capacity and at the same time control the viscosity of the intermediate product within an acceptable range,
The alkaline earth metal hydroxide is added in two stages [general K, double lime addition method].
n, processes)) or in three separate reaction steps, followed by a carbonation step.

However, this method requires a relatively long batch time (batch
timθ) is required. Alternatively, a viscosity reducing agent such as tridecanol (VieCOθity eLθpre
Bθants) in the production of its intermediate products, but such an approach increases the cost of raw materials for the process. A commonly used hydroxyl solvent is ethylene dalicol, but this one! 1ifi
%, producing a large amount of undesirable hydrogen sulfide.

Other solvents are also used in this step. For example, English 1. ! ! Il, i/l' No. 1.391,847
吋 [Continental Oil Company (0ontine+, ta
l Oll Oompany)
(a) (113 to 80% by weight of formula% formula% (1) (where Ar represents an aromatic residue and R represents 4 to 3 carbon atoms)
Saturation or unsatisfaction of a straight button or branch button with 0 pieces 41
1 aliphatic hydrocarbon group, where n is an integer with a value of 1 to 2, il, L, l (all carbon atoms in n, atomic scissors shall be 8 to 40) ) or 1) sulfurized alkylphenols produced from the alkylphenols of IJ, (Ill 0.10
~95 heavy supernatant with a boiling point of 20,000 or more
Bath additive (Ill O, 5-25 C1 parts by weight), 15,000
A volatile process solvent with a boiling point of
1v) forming a mixture of 0.2 to 14 Jt parts of water (kl) and adding magnesium, calcium or barium to the mixture of step (a) while its temperature is in the range of 20 to 55°C; An overbasing anoun of a glycol ether solution is added, wherein the glycol ether has the formula % (wherein R is an alkyl group from C to C6), or the formula % It is represented by the formula % (wherein R is a C-C4 alkyl group).

(0) Maintaining the temperature of the mixture above the step temperature and adding to it a neutralizing amount of glycol solution of magnesium, calcium or barium within the range of 55-100°C; ,(1)
The cation is the same as in step (bl K), and (11) the glycol ether is the one obtained in step (b), and (dl the volatiles are removed by heating). describes and claims a process for the preparation of highly basic magnesium, calcium or barium salts of alkylphenols or sulfurized alkylphenols consisting of: (1) glycol ethers of magnesium, calcium or barium; The overbased 1-Iil is 0.1 to 5 equivalents h1 per month of alkyl phenol or flA-alkyl phenol; The total h1 is 0.4 ~ in the case of magnesium.
M 41i'Jll , and 0.4 to 50 double fluorescence for calcium or barium, and (Ii
il engineering % (al (The amount of water in lvl is
It is further characterized as being of sufficient quality to amount to 1.0 to 2.5 moles of dispersed magnesium, calcium or barium.

It is also known to use solvents other than ethylene glycol in combination with promoters. For example, U.S. Patent No. 341
No. 0798 [Luprizol Co., Ltd.
In this method, (A) phenol, (B) (a yellow and (Cl) alkaline earth metals are combined with about 5 to 20 mol of carboxylic acid or the like based on the amount of component (Al) at a temperature of 150° C. or higher. A promoter consisting of an alkali metal, alkaline earth metal, zinc or lead salt and (El solvent) 2R(ORI)XOH1 (wherein R is hydrogen or an alkyl group and 1.RY is an alkylene group, and X is an integer of at least 2 when R is hydrogen, or an integer of at least 1 when R is an alkyl group), wherein said component E is 150"0 or more, the ratio of equivalents of component B to component A is between about 1:1 and 221, and the ratio of equivalents of component C to component A is at least about 2.
:1, and then removing all volatile components from the reaction product,
A method for producing an oil-soluble, basic sulfurized alkaline earth metal phenate is described and claimed.

The purpose of the methods described in the aforementioned US Pat. No. 3,410,798 and British Patent No. 1,391,847 is to.

11t of alkaline earth metal in the alkyl phate product produced. The inventors have determined that a high degree of overbasing (ovθ
I discovered that rbaaing)) can be achieved. This combination has other undesirable advantages, such as easier absorption of carbon dioxide in the subsequent carbonation reaction, which further improves overspeed.

Therefore, the present invention provides, in the presence or absence of sulfur,
As a solvent, the formula, R(OR") is an integer in the range from 1 to 6)° (: any of the indicated alkylene glycol alkyl ethers or polyalkylene glycol alkyl ethers, and enriched with alkyl phenols and alkaline earth metal bases in the presence of an inorganic halide as a catalyst. The present invention provides a method for producing either alkaline earth metal amylphenol or sulfurized alkaline earth metal amylphenol, which is characterized in that the reaction is carried out at a temperature of 1.

Alkylphenols suitable for use in the process of the present invention have the general formula % ( ) where Ar is an aromatic residue and R' is at least 4, preferably from 4 to 50, more preferably from 8 to 25 a straight-chain or branched alkyl group having 5 carbon atoms, and n is 0 or an integer from 1 to 6). Typical alkylphenols that may be used include, for example, phenol, phthylphenol, amylphenol, octylphenol, dioctylphenol, nonylphenol, dinonylphenol, dodecylphenol, cetylphenol and the alkyl group R4.
However, olefin polymers such as polyzolopyrene, polybutylene, and mixtures thereof may also be interfered with quaternary alkylphenols. Particularly good] I! I
The i-alkylphenol is a C12-alkylphenol obtained by alkylating phenol with zoropyrene tetramer.

The alkaline earth metal base may suitably be an alkaline earth metal oxide or hydroxide. Among the alkaline earth smoked apple oxides or hydroxides, hydroxides are preferred. Preferably, the alkaline earth metal may be calcium, magnesium or barium. Calcium hydroxide may be added, for example in the form of slaked lime. The alkaline earth metal base is added in an amount substantially equal to the theoretical m required to neutralize the alkylphenol, in which case a [standard] product would result, or in excess. It can be added preferably in excess of 20% by weight or more over the theoretical amount, in which case an [overbased] product is obtained.

Generally, the amount of alkaline earth metal base added can be up to the maximum amount that maintains acceptable solubility in the base oil. The alkaline earth metal base may be added entirely to the first reactants, or a portion may be added to the first reactants and the remainder may be added in portions or portions at intermediate stages of the process. good.

As a bath agent, the formula: R(ORI)XOR2 (wherein R, R1, R2 and is butylene, R2 is hydrogen or an O-C4 alkyl group, and X is 1-C4;
(which is an integer of 4) is used. Suitable solvents include the monomethyl or dimethyl ether of ethylene glycol, diethylene glycol, triethylene glycol or tetraethylene glycol. A particularly suitable solvent is methylzogol (OH300H,l;)1200H20H20H)
It is. In the mixture with ether solvents, vicinal glycols such as ethylene glycol or globylene glycol can be suitably used in amounts up to 60% by weight of the bath agent mixture. The total amount of solvent present is suitably from 90.1 to 2 mol, preferably from 0.5 to 1 mol per mole of alkaline earth metal base.
Within the molar range.

As the SCu medium, an inorganic halide such as a hydrogen halide, an ammonium halide or a metal halide is preferably used. Suitably the metal portion of the metal halide is zinc, aluminum or an alkaline earth metal, preferably calcium. Among the halides, chloride is preferred. Suitable catalysts include hydrogen chloride,
Calcium chloride, ammonium chloride, aluminum chloride and zinc chloride are used. The amount of catalyst used is preferably up to 2.0% w/w, for example 0.4-0.9% w/w.
/w, although higher concentrations may be used if desired.

In one embodiment of the invention, sulfur is excluded from the reactants to produce the alkaline earth metal alkyl 7-enate.

In other embodiments, sulfurized alkaline earth metal alkyl phenates are prepared by adding sulfur to the reactants. The amount of sulfur added is preferably 1 in the sulfurized alkaline earth metal alkyl phenate.
The amount is sufficient to achieve ~1[], preferably 2.5 to 5 times. Generally, this amount will be in the range of 4 to about 15% by weight, based on the weight of the reaction mixture.

Whether the desired product is an alkyl phenate or a blunted alkyl phenate, it is preferred to carbonate it at some stage in the process. The addition of carbon dioxide may occur at one or more intermediate points during the reaction, or at the final product, or both. The carbon dioxide can be added as a gas, solid or liquid, and is preferably added as a gas, preferably by blowing carbon dioxide gas into the reaction mixture. The amount of carbon dioxide added is suitably within the range of 10 to 300 molar, preferably 10 to 150 molar, of the used °f alkylphenol. When using solvents with low boiling points, it is desirable to add additional bath agent to compensate for bath agent losses.

□Additional diluents may be added to facilitate handling of the reaction products before, during, or at the completion of the process.
It is preferable to add In theory, any inert, water-soluble organic medium that does not react with or interfere with the reactants can be used as the supplemental diluent, or it is preferred to use a lubricating oil. By using lubricating oils in this manner, the desired product oil worm thickening is obtained. Suitable lubricants include a wide range of petroleum lubricants such as naphthenic thread based, paraffin based and mixed pace lubricants. Alternatively, synthetic lubricating oils such as alkylene polymers, alkylene oxide polymers and carboxylic acid esters can also be used. Preferably, the lubricating oil is a solvent neutral oil.
il). The amount of supplementary diluent used suitably ranges from 10 to 60% of the reaction mixture, preferably from 25 to 4%.
It is 5% w/w.

Optionally, dispersant additives such as sulfonated dispersants may be used.

It is preferred to use an acid, preferably up to 2% w/w of Tojo. This acid can be either a mineral acid or an organic acid. Suitable acids include, for example, formic acid, stearic acid, sulfonic acid, etc. Acids include acetic acid, propionic acid, glycolic acid and dodecylsulfonic acid.

Important properties of alkylphenols, especially in marine lubricants (
In marine utility applications, their ability to minimize the formation of emulsions in water. From this point of view, it has been found that the addition of stearic acid or sulfonic acid to the reactants promotes this property.

The increased 1M degree is preferably 160-200,
It is preferably within the range of 145 to 1746C, and the pressure is preferably atmospheric pressure, overpressure (5upper atmospheric pressure)
spheric pleasure), or reduced pressure (
Subatmoepherio), preferably at or near atmospheric pressure.

This method is either [single lime addition] or [two-stage lime 61\
It can be done as an addition method. Preferably, the method of the present invention is described, for example, in British Patent No. 900,059;
It may be carried out by the method described in Zenki Meikashi Ikkichi of No. 121437 and No. 1144084. A preferred method for carrying out the present invention is to combine, in the first step, an initial mixture of an alkylphenol, optionally a flIy yellow, and a theoretical excess of an alkaline earth metal base with an ethereal solvent and a catalyst. react at an elevated temperature to form an intermediate product, and
Thereafter, in the second step, the intermediate product is reacted with carbon dioxide.

The reaction temperature used in the first step is preferably 160
-200°C, preferably 145-175°C, and the pressure is atmospheric, superatmospheric or subatmospheric, preferably about atmospheric. The addition of the ether bath agent is preferably carried out when the temperature of the reaction mixture is within the range mentioned above. More preferably, the bath agent is added gradually over a period of 0.5 to 6 hours while the temperature is gradually increased.

In the non-method second step, carbon dioxide is reacted with the intermediate product. The carbon dioxide is preferably introduced as a gas, preferably by blowing it into the reaction mixture. The reaction between this intermediate product and carbon dioxide is preferably carried out for 1
It is carried out at a temperature in the range from 65 to 200 °C and at elevated pressure, reduced pressure or atmospheric pressure, but preferably 14
It is carried out at 1 m degree within the range of 5-175°C and at or near atmospheric pressure.

The method can be performed in a patch or continuous manner. Preferably, the process is carried out continuously with continuous recirculation of the recovered ether bath.

Typically, this batch process involves, in a first step, an initial mixture of mineral lubricating oil, alkaline earth metal hydroxide, catalyst, carboxylic acid, and alkylphenol;
A stirred reactor with overhead distillation and condensation equipment is charged and heated at or near atmospheric pressure to a temperature K of 165-200°C, preferably 145-175°C, and the temperature is within the ranges mentioned above. 1. During 5-6 hours, an ether solvent is added to the filtrate, the water formed during the reaction is removed as a head, and the intermediate product is and in a second step react the intermediate product from the first step with carbon dioxide at 165-200°C, preferably 145-175°C, at or near atmospheric pressure.

In a further preferred embodiment of the invention &1, ore 91
1 rA The initial mixture consisting of lubricating oil, alkyl phenol, alkaline earth gold maple hydrochloride, catalyst, carboxylic acid and ether bath agent is heated to 165-200, preferably 145-200
feed in batches to a first stirred reactor maintained at a temperature in the range of 175°C and a pressure at or near atmospheric pressure to remove o/f-head water and form an intermediate product. , this is 165-200. Preferably 145-175
°C and atmospheric pressure or l'T are placed in a second stirred reactor maintained at atmospheric pressure where the intermediate product is reacted with carbon dioxide to form the carbonated product and the final step , +: r+, separating the ether solvent at
The first method is to recirculate the reactor to the k reactors.

Either method results in a product mixed with an ether solvent and perhaps also a lubricating oil diluent. Therefore, this mixture is fed to a distillation column operated at reduced pressure and a temperature such that the ether solvent can be removed as an overhead fraction, and the residual base product is then filtered to remove insoluble material. preferable. The distillation column is preferably operated at a temperature of up to 200" O and a pressure of 50 mbar. The residual base product is heated, for example, at a temperature of about 120" C. and a pressure of about 90 mbar.
Can be filtered at a pressure of In a continuous process, it is preferred to recycle the removed ether solvent to the first reactor.

Alternatively, the process of the invention can be carried out by reacting an alkylphenol with a stoichiometric amount of alkaline earth metal hydroxide at elevated temperature in the presence of an ether solvent and a catalyst. The addition may be carried out by two or more separate additions, and the carbon dioxide may be introduced into the reaction mixture either before and/or after each gram of alkali metal hydrate addition.

Another method of the invention provides a finished lubricating oil composition comprising a II8!1 lubricating viscosity oil and the product obtained by the process described in MiJ.

The concentration of the product in the finished lubricating oil composition will vary depending on the degree of overbasing of the product, the particular properties desired and the type of lubricating oil selected. However, generally the concentration of the product will be within the range of 0.5 to 80 tons.

Oils of lubricating viscosity that may be used in the formulation of the finished lubricating oil compositions of this invention can be selected from a wide range of natural and synthetic oils, such as naphthenic, paraffinic and mixed base lubricating oils. The oil preferably has a temperature of 35 to 5,000 EIUS at 100'F' or 21 o'off.
ond)).

The lubricating oil compositions may additionally contain other additives well known in the trade, such as Vl improvers, antioxidants, rust inhibitors, antiwear agents, pour point depressants, and the like.

The invention will be further described with reference to the following examples.

Example 1 200 g methyl digol, 27.0.9 sulfur, 90
．． 0,! i' lime, 4. OS acetic acid and 6.0I
A slurry consisting of calcium chloride (h1) was heated to 145 °C/700 mm Hg. 200 g of dodecylphenol was added within 15 minutes while the temperature rose to 165 °C/700 mm Hg. (
80% para isomer) was added and IH1 was maintained at 3'y4.

351/ml of carbon dioxide at 165° C./1 bar were added. The temperature was increased to 200'c/10 HI while 140.9 flVI lubricant was added and unreacted methyl digol was collected for recycle. ``equipment''
Almost 95% of methylzogol was recovered; filtration was rapid and 9.6%-Oa, 6.5%
The product contains 8.5.3% w/w of CO2 and has a base number of 271 mQ KOH/7.

Comparative test 1 200,? of dodecylphenol (80% heteroisomer 1
4-), 43.1. ? A slurry consisting of persubstituted calcium sulfide alkyl phenylene 1., Roro, 6 & Nashi Huang, 90.0 & lime and 158.4.9 4 & 1 Bin No. Then, it was heated to 145℃/700 Q11g.That m1 degree or 165℃/7 D D y
Im 45 within 15 minutes during Hg stop and J +, -
．． 1/2 inch of ethylene glycol was added and held for 6 hours. Then 40 at 165°O/1 bar
& carbon dioxide and 200'c/1
Unreacted ethylene glycol was removed at 0 mrnHg.

Almost 50% of the ethylene glycol contained in the shell was recovered,
It was used for recirculation. The PA product is 9.311 μg of O
a, 3.6% w/w of 81 and 4.42% w/w of 0
I had a 02. This product has a temperature of 25% at 100°C.
Viscosity of Q cst and Alkalinity Value of 250 m9 KOVg
(AM).

Comparative test 2 200 & dodecylphenol (80% para isomer),
ia, og overbased calcium sulfide alkyl phenate, 55.6 g sulfur, 89.051 lime and 15
A slurry consisting of 8.6 g of lubricating oil was stirred and heated to 145°C/700 HI. The temperature was increased to 165° O/700° Hg during which time 116I methylzogol was added within 60 minutes and held for 37 hours. Then 40.9 ml of carbon dioxide at 1656 C/1 bar is added and the unreacted methylcigol is
Removed at 00°C/10vm Hg. More than 95% of the methyldigol charge was recovered for recirculation. The filtered product was 4.06% w/w Oa, 4.6
It contained 7% w/w of 8 and 1.72% w/w of CO2. This product has a temperature of 31 ast at 100°C.
and an AV of 118 da KOH/j9.

Comparative Test 6 The method of Comparative Test 2 was followed except that 4.0 ml of glacial acetic acid was added to the initial slurry. The filtered product is 8.3
%w/w ca, 4.8%w/w 6 and 6.8%w
/w of 002. The viscosity of this product is 100
567 set at °C and 247 m9
It was an AV with KOH power.

Comparative Test 4 The method of Comparative Test 6 was followed except that the bright yellow, groove base purification power, lucium alkyl phenate, and lubricating oil were omitted in the initial slurry charge. Methyl digol loading 5B, 6'
Reduced to &. The filtered product was 6.1% w/w O
a, 0.02% ψ of 8 and 4.2% w/w C0
Contained 2. This product is 69 at 100°C.
Viscosity of cst and AV of 1611119KOH/9
Met.

Comparative Tests 1-4 are not methods of the invention and are presented for comparison purposes only.

Example 2 A slurry consisting of 200g of methylzogol, 275' of sulfur, 90y of lime, 8g of glacial acetic acid and 1y of zinc chloride is heated to 165°O/700h& and 200y of dodecyl in 10 minutes. Phenol (80% para isomer) was added. Maintain that temperature for 6y4 hours,
Then 50g of 002 at 165°C/1 bar
was added. After addition of 140I lubricating oil, unnecessary solvent was removed at 200'C/10mlLH,9. The filtered product was 10.4% w/w Oa, 3.4% w
81/w and 0% of 6.4% W tide. This product is 100° CIc O'C549cst (
') Viscous W O, i: H287 mg' ””y4/
It was an AV.

Example 6 The method of Example 2 was repeated except that zinc chloride was replaced with calcium chloride (1,9)K. The filtration product is 9.7
1 w/w Oa, 3.4% w/w S, and 7.6
%w/w of CO2. This product is 100°
Viscosity of 16708t in C and 272m9KO
H/, jil's AV, 6.

Example The method of Example 2 was carried out except that ammonium chloride (3, &l: IWm) was used to convert lead to chloride.The filtration product was
, 0% W, , 4 Ca, 3.1%''/' 8, and 4
．． Contained 6% w/w CO2. This product is 10
Viscosity of 201 cElt at 0°C and 286 m
t;) It was AV of KOk% force.

Example 5 The method of Example 2 was repeated except that zinc chloride was replaced with aluminum chloride (6y). The filtered product was 9.8%-7'Oa, 3.6%゜81 and 5% Oa.
．． Contained 5%φ of Co2y. This product is 100°
389 cst depletion and 274 mg KO in C.
It was AV of H/9.

Example 6 200 I of dodecylphenol was added to the slurry and 200.9 of methyldigol was added to 165°C/near 00 via H,! Example 3 except that it was added at i'
I did it using this method. The filtration products are 1o, 1yw, i
of Oa, 6.6% w/w S and 5.8% w/w C
Contains O2.

Example 7 The method of Example 6 was repeated except that the acid monomer was replaced with glycolic acid (4 g). The filtered product contained 8.81φ Oa, 3.4% w/w 81 and 6.4% w/w 002. This product has a viscosity of 152 cSt at 100'O and 2531ψKOH/,9
It was an AV.

Example 8 The method of Example 2 was repeated except that acetic acid was replaced with formic acid (4 g). The filtration product is 10.6% ψ Oa, 3
．． 6% W, A of Sl and 7.2% w/w CO2
Contained. The product is 296 cS at 100°C
The viscosity was 295 mg KOH/, 9 AV.

Example The procedure of Example 6 was repeated except that acetic acid was replaced with zolopionic acid (4I). The filtered product was 9.8% W/w
of Cia, 3.5% W/W S, and 5.2% W/W CO2. This product has a viscosity of 312 cst at 100'C and a viscosity of 277 In9KOH/
It was AV of 9.

Example 10 A slurry containing a mixture of 150& of dodecylphenol (80% 0% rose≦L), 27g of fvlj yellow, 90.9g of lime, 4g of ammonium chloride, 4y of glacial acetic acid was heated to 165°0/ Added up to 700 dragons and 14. 20
Add 0I methylcigor for 20 minutes, and set the sono temperature to 165°O/700y+mH,! 7 KHolded for 6 hours. Then, 35. ? of C02 was added at 165° C./1 bar and then 140 g of lubricating oil were added at 65°C. Next, methyl digol wo 200'0/10 tomo H,
? It was removed in The filtration product was 11.4%w
/w Ca, 3.8%w/w 8 and 7.2%φC
Contains O2. This product has a viscosity of 669C8t and a viscosity of 620°C at i o o'c.

The AV was m9KOH/i.

1 liter of 11 120 g of dodecylphenol, 15 g of sulfur and 9
The method of Example 10 was repeated except that 5.9 lime was used. The filtered product was 12.7% W/'W Oa
, 2.7% ”/' S and 8,8% w/
It contained w of CO2. This product has a viscosity of 438 cst at 100°C and a viscosity of 352 l9KOH
The AV was /g.

Example 12 Example 110 except that 1 t of sulfur addition was reduced to 109
The method was repeated. The filtered product was 12.6% w/w
oa, 2.1% w/h S and 8.9% W/W
Noao2wo? v, (i l-ta. cono product c, 10
0'C ni "C3520131; 17) Sticky reaction,
J: U 357 mq KOH/, 9 AV.

As previously mentioned herein, a desirable property of alkyl phenate lubricating oil solutions is the ability to minimize emulsion formation with water. This is particularly relevant to marine oil formulations, which meet ASTM D 140
This method can be conveniently measured by method 4.
Determine the amount of water separated from the emulsified mixture of the 4DC1n3 oil sample in 0cTL3 water as i1+11.

Example 16 Dodecylphenol at 200@ (80% para isomer)
, 271 sulfur, 90g lime, 4g ice Q'1Eat
and 6y chloride, and 165°C/700, H,p
Heated to K. 200° of methylzogol was added during 20 minutes and the reaction was maintained at 165°C/700 Hg for 6 hours.

adding 35 g of C02 at 165°C/1 bar;
Subsequently, 140 g of monolubricated oil was added. Methyl digol was removed at 20 °C/1 [J Ryu H, Sl.

The filtration product is 10.1%AzW Ca, 6.6
Contains %W/AN of S and 5.8 cmv7w of CO2. This generation 1 course takes 4520s at 100'C.
Viscosity of t and AV-'C of 290 m9KOHl&:
C: Water content P+I# according to ASTM D 14Q1
is 8cIn3 Tea Tsuta.

) I: Lateral 14 The method of Example 13 was repeated except that 1.0.9 of stearic acid was added in the slurry charge 9. The filtered product had an Oa of 10.3% w/'W, 3. (5%W/'
It contained 8 of W and 5.7% w/w of 002. The product had a viscosity of 51 [1 cat and an AV of 2 s 6 = Kon, z, y at 100°C. Water separation according to ASTM D 1401 is 26cn
It was L3.

Example 15 After the carbonation step, 130 g of lubricating oil and 1
Example 1 except that a mixture of 0 & sulfonic acids was added.
Step 6 was repeated. The filtered product is 9.6%
W/W Ca, 3.5% w/w 8 and 6.1% W/
Contained 002 of AIi. This product has a viscosity of 335 cSt at 100°C and 262 mg KOH
It was an AV of //l. Water separation by ASTM D 14Ql was 33 cx''.

Example 16 165°C/7,00 mm H,! The method of Example 16 was repeated except that the reaction time in Example 7 was reduced from 6 hours to 1 hour. The filtered product contained 9.9% w/w Oa, 3.6% w/w 8 and 5.9% φ CO2. This product is 386 cs at 100°C
t and an AV of 267 m9 KOH/g.

Water content according to ASTM D1401 1911 is 20 cm
It was 3.

JM1+Li 17 The reaction time at 165°O/700 shochu HP was reduced from 6 hours to 5 minutes. The filtered product was 9.9% VW Oa, 6.7% w
8/w and 5.6% w/w of 002. This product has 61 of 39 Q cSt at 100°C.
AM at 1 degree and 231 mg KOH strength.

Water separation according to ASTM D 140'l is 25 cm
``There was a time.

Example 18 The method of Example 16 was repeated except that the glacial acetic acid was omitted and replaced with 4y ethylene glycol. The filtration product contained 9.8% W/ca, 3.6%''/'S and 5
．． Contained 6% W/W CO2. This product is 10
Viscosity of 38Q cE]t and 277 I at 0°C
The AV was n9xou/,y. ASTM D14
Separation of water by []1 was 25cIrL3.

Continuation of page 1 Priority claim July 22, 1982 ■ United Kingdom (GB
) ■ 8221268 0 Inventor Anthony Ghana - United Kingdom Etstu - 88 Nissef Full Holderness Lord Marsay Street 1 Procedural Amendment (Voluntary) February 8, 1933 / ζ Date, Mr. Commissioner of the Patent Office ■, Minor Case Indication Show (n58 Patent Application No. 90562 2, Title of Invention 1 Buto Lubricating Oil Additive Manufacturing Method 3, Supplement 11 Relationship with Person f'r Patent Applicant 4, Agent IM ( fu year month [''6, number of inventions increased by supplementary IF7, subject specification of 1liilmi

Claims (1)

[Claims] (1) In the presence or absence of sulfur, as a solvent, the formula: % formula %) (wherein R is an alkyl group from C to C6, B1 is an alkylene group, and R2 is hydrogen or 0, ~c6 alkyl group, and X is an integer ranging from 1 to 6)
in the presence of an inorganic halide as a catalyst, and in the presence of an inorganic halide as a catalyst,
A process for the production of either alkaline earth metal alkylphenols or sulfurized alkaline earth metal alkylphenols, characterized in that the alkylphenols and alkaline earth metal bases are reacted at elevated temperatures. (2) so(7) y /l, potassium earth metal base,
The method according to item 1, wherein the alkylphenol is added in an excess amount of 20 weight or more over the theoretical amount required to neutralize the alkylphenol. (3) In the formula R(ORI)XOR2, R is C□~C
4 alkyl group, B1 is ethylene ipropylene or ethylene, R2 is hydrogen or an alkyl group of 0□ to c4, and X is an Ii number in the range of 1 to 4. The method described in any of Section 2. (4) Any one of the above items 1 to 6, wherein the solvent of formula R(ORI)XOR2 is monomethyl or dimethyl ether of ethylene glycol, diethylene glycol, triethylene glycol, or tetraethylene glycol.
The method described in section. (57 The method according to item 4 above, wherein the solvent is methyldigol. (6) 60% by weight of the solvent of formula R(ORI)XOR2.
The method according to any one of paragraphs 6 to 5 above, wherein wJ is mixed with ethylene or zolopylene glycol up to (Force) The catalyst is hydrogen halide, ammonium halide, alkaline earth metal halide, zinc halide or aluminum halide
6. The method according to any one of items 6 to 6. (8) The catalyst is hydrogen chloride, ammonium chloride,
8. The method according to item 7, wherein the chloride is aluminum chloride, calcium chloride or zinc chloride. (9) adding carbon dioxide either at one or more intermediate points during the reaction, or to the final product K, or both during the reaction and to the final product; A method according to any one of Sections. 00) The method according to any one of the above items 1 to 9, wherein an acid is added to the reaction mixture. αJ) The method according to item 10, wherein the acid is formic acid, acetic acid, propionic acid, stearic acid, glycolic acid, sulfonic acid or dodecylsulfonic acid. α2) The above-mentioned 1 to 1 adding a supplementary diluent which is a lubricating oil
The method according to any one of paragraphs 1 to 1. 03) Oil of lubricating viscosity and alkaline earth metal alkyl phenate or sulfurized alkaline earth metal alkyl phenate obtained by the method described in items 1 to 12 above.
．． Completed dQl characterized by containing 5 to 80%
? it oil composition.