CA1099744A

CA1099744A - Mannich base composition

Info

Publication number: CA1099744A
Application number: CA294,114A
Authority: CA
Inventors: Donovan R. Wilgus; John M. King
Original assignee: Chevron Research and Technology Co
Current assignee: Chevron USA Inc
Priority date: 1977-01-03
Filing date: 1977-12-29
Publication date: 1981-04-21
Also published as: AU513354B2; DE2759109A1; FR2376166A1; GB1590931A; BR7708772A; FR2376166B1; NL7800073A; AU3214278A; JPS5384927A

Abstract

ABSTRACT OF THE DISCLOSURE
New Mannich bases and the alkaline earth metal salts thereof, wherein the Mannich bases are prepared by condensing formaldehyde and a polyamine with (A) a phenolic mixture consisting of (a) from 95 to 30% phenol alkylated with a straight-chain alpha-olefin of from 16 to about 28 carbon atoms or alpha-olefin mixtures wherein the alpha-olefins are of from 16 to about 28 carbon atoms, or (B) a sulfur-containing phenolic mixture consisting of (1) from 5 to 40% of a sulfurized alkylphenol of the formula

Description

BAC~G~OllND OF THE INVENTION
This invention relates to novel Mannich bases and their uses as lubricating oil additives.
For a variety of reasons, higher sulfur content fuels are now being used, particularly ln marine engines. This high sulfur content leads to the formation in the presence of oxygen of corrosive sulfur acids, particularly sulfuric acid. To prevent damage to the engine from these sulfur acids, they must be neutralized with a basic material. This basic material is ordinarily an additive in the oil used to lubricate the engine. As higher sulfur con-tent fuels are used, a greater and greater reservo:ir or alkalinity must be included in the lubricating oil to neutralize the acids. However, using conventional additives, such as calcium phenates, an increase in the amount of additive leads to an increase in ash formation, which is detrimental to the engine.
It is an object of this invention to provide a lubricating additive which is effective in neutralizing sulfur acids. It is a further object of this invention to provide a lubricating oil additive which is also an effective dispersant. It is an additlonal object o this invention to pro-vide an additive which can neutralize large quantities of these acids with , lower resultant ash formation than for conventional additives.
- DESCRIPTION OF THE PRIOR ART
United States Patent 3,036,003 teaches the use in lubricating oils of a combination of a detergent amount of a basic alkaline earth metal petro-leum sulfonate and the condensation product of an alkyl-substituted phenol in which the alkyl group contains from 4 to 2Q carbon atoms, formaldehyde and an alkylene polyamine and the alkaline earth metal salts thereof. The

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. A
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molar ratio of the reactants of this condensation product are 0.5-2 mols of each of the phenol and formaldehyde for each nitrogen atom present in the polyamine. , United States Patent 3,649,229 teaches the use of high molecular weight ~annich reaction products as additives for hydrocarbon fuels. The condensation product is prepared by reacting a high molecular weight alkyl-hydroxyaromatic compound ha~ing a molecular weight of from about 600 to 3000 with an amine and an aldehyde. The molar ratio of the reactants is l:a.l-lo ~ :
to 0.1-10. A specific example teaches the preparation of a Mannich con-densation product from polypropylphenol o 90Q molecular weight with di-ethylene triamine and paraformaldehyde in the ratio 1:0.75-1.
S~M~ARY OF T}IE INVENTION
The Mannich bases and the alkali-ne earth metal salts- thereof of ' , this invention are prepared from formaldehyde, a polyamine and ~A) a phenolic mixture consisting of ~a~ from 95 to 30% phenol alkylated with a propylene ~,' tetramer and (b) from 5 to 70% phenol alkylated with a straight-chain alpha-olefin of from 16 to about 28 carbon atoms or alpha-olefin mi~tures wherein the alpha-olefins are of from 16 to about 28 carbon atoms or ~B) a sulfur-containing phenolic mixture consisti,ng of ~1) from 5 to 40% of' a sulfurized alkylphenol of the formula OH ~ O}l H t ~ ~ (S~n ~ ~

wherein ~ is C8-C36 alkyl, n is an integer from 1 to 8, and y is an integer from 1 to 9, and (2~ from 95 to 60% o:E a phenolic mixture consisting of (a) from 95 to 30% phenol alkylated with a propylene tetramer and (b) from 5 to 70% phenol alkylated with a straight-chain alpha-olefin of from 16 to about 28 carbon atoms or alpha-olefin mixtures wherein the oleFins contain from 16 to about 28 carbon atoms. These Mannich bases and their salts are useEul as lubricating oil additives.
DETAILED DESCRIPT~ON OF THE INVENTION
Component 1 of the sulfur-containing phenolic mixture is a sulfurized alkylphenol. These materials are well known for use in lubricating oils.
They usually contain from 4-20 weight percent sulfur and usually 8-18 weight percent sulfur. For the most part, they have the formula O~l OH
H ~ ~ - ~S)n -R R
_ _ Y' wherein R is C8-C36 alkyl, n is an integer from 1 to 8~ and y~is an integer ; 10 from 1 to 9. Various methods for preparing these sulfurized alkylphenols are dîsclosed in United States Patent 3,7~1,896.
Component a of the phenol~c mixture is prepared by alkylating phenol with propylene tetramer. It is also known in the art as tetrapropenyl phenol or dodecylphenol.
Component b of the phenolic mixture can be a phenol alkylated with a straight-chain alpha-olefin of 16 to about 28 carbon atoms, or a phenol which has been alkylated with a mixture of alpha-olefins of from 16 to about 28 carbon atoms in each olefin. It is important for the effectiveness oE the additive that at least one olefin alkylating group contains at least 16 carbon atoms. Thus~ a phenol alkylated with, for example, two groups containing 9 carbon atoms each would not, when used to prepare additives of this invention, provide adequate perfor~ance, especially from the standpoint of forming a product with a viscosity suitable for use in commercial operations.
Mixtures of alpha-olefins, available on a commercial basis, are suitable for alkylation of the phenols for use in this lnvention. These mix-tures normally contain predominantly C2Q to C28 olefins, but may contain a small proportion of olefins having less than 16 or more than 28 carbon atoms.

7 ~ r A representative olefin mixture is Dailen 208*, manufactured by Mitsubishi.
Preferred olefins are those ~hich are a mixture of about 60-80 mol percent C18-C28 alpha-olefins and about ~0 to 20 mol percent C24-C28 alpha-olefins.
The percent of each phenolic compounds a and b used in the phenolic mixture is based on the phenol equivalents (calculated from the measured hydroxyl number~ of each.
Formaldehyde, or a formaldehyde precursor, such as paraformaldehyde, is used to prepare the condensation product of this invention.
The polyamines used in preparing the novel compositions of this invention are the well-known ethylene amines, specifically ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentamine, and pentaethylene hexamine. These compounds are usually prepared by the reaction of an alkylene chloride with ammonia. This reaction yields a somewhat complex mixture of alkylene amines, includiIIg some cyclic condensation pro-duct. These mixtures are also included within the scope of the term "poly-amine". Also included within the scope of the term "polyamine" are those amines prepared by reaction of acr~lonitrile with an ethylene amine as des-cribed above, or with an am~ne of the formula H2N-(CH2) NH2, where x is 3-6, followed by reduction of the resultant intermediate. For example, the product prepared from ethylene diamine and acrylonitrile would be H2N-(CH2)3NH-(CH2)2NH-(CH2~3-NH2. Preferred polyamine, for use in this invention, is diethylene triamine.
The Mannich bases of this invention can be prepared by conventional methods as described in the art. It is preferred to prepare the Mannich bases by reacting 1 mol of the phenolic mixture with Q.5-0.85 mol formaldehyde and at least 0.3 mol of polyamine. The reaction is carried out at a temperature of 25-140C, prefera~ly 25-130C, and in the presence of a suitable solvent 3 such as benzene or toluene, which can be recovered from the reaction product.
If desired, the reaction may be carried out in a mineral lubricating oil and the the condensation produce is recovered as a lubricating oil concentrate.

*Trademark 5 ~,1 1~95~
.

Alkaline earth metal salts of the Mannich bases of this invention are particularly useful as lubricating oil additives. Preferred alkaline earth metal salts are calcium and magnesium.
The alkaline earth metal salts oE the Mannich bases are prepared using conventional methods, for example, by treating the Mannich base with an alkaline earth metal hydroxide, such as calcium hydroxide or magneslum meth-oxide, in the presence of a promoter, such as water, ethylene glycol, 193-propane diol, 1,4-butane diol, diethylene glycol, butyl cellosolve, propylene glycol~ 1,3-butylene glycol, methylcarbitol, diethanol amine, N-methyldi-ethanol amine, dimethyl formamide, N-methyl acetamide, or dimethyl acetamide.
Preferred promoters are water, ethylene glycol and dimethyl acetamide. ~lost preferred is ethylene glycol. The reaction is carried out at 100-175C. After the reaction is completed, the product is stripped at a higher temperature, such as 175-202C and at reduced pressure, for example, 20 mm Hg, to remove any unreacted low-molecular-weight polyamines, such as ethylene diamine and ~-~
diethylene triamine, and other volatile components.
The Mannich bases and the alkaline earth metal salts thereof of this invention provide a high alkalinity value. The alkaline earth metal salts provide a particularly high alkalinity value at a lower ash content than is present in conventional dispersants and acid neutralizers used in lubricating oil additives.
Alkalinity value is one method of specifying the degree of overbas-ing of the phenate portion of Mannich base. It is also a measure of the acid-neutralizing properties of the compound. The method for determining the alkalinity value of a composition is set forth in A5TM Method D-2896. Briefly, the alkalinity value is the total base number given as milligrams of potassium hydroxide per gram of sample. It is the quantity of perchloric acid expressed in terms of equivalent number o milligrams of potassium hydroxide that is required to neutrali7e all basic constituents present in one gram of sample.
For example, if a composition has the same acid-neutralizing capacity per gram as 10 mg of potassium hydroxide, the composition is given an alkalinity value of 10. The lower limit of alkalinity value is 0 Eor a neutral phenate.
Values of 200-260 are especially desirable for use in lubricants which are exposed to the decomposition products of sulfur-containing diesel -Euels.
Further, the high alkalinity value is achieved with a lower amount of ash ~ from the calcium salt for the products of this invention than would be pre-; sent if conventional metal phenate additives were used.
Most importantly, the Mannich bases of this invention have a suf-ficiently low viscosity to enable their preparation using conventional processing equipment. The products have a viscosity of from about 1000 to 3000 Saybolt Universal Seconds (SUS) at 99C.
The lubricant composition is prepared by admixing through conven-tional admixing techniques the appropriate amount of the Mannich base or the alkaline earth metal salt of the Mannich base with a lubricating oil. The selection of the particular base oil depends on the contemplated application of the lubricant and the presence of other additives. Generally, the amount of the Mannich base or the alkaline earth metal and salt thereof used in the luhricating oil will vary from 0.1 to ~0% ky weight, and preferably from 3 to 35% by weight.
The lubricating oil which may be used in this invention includes a wide variety of hydrocarbon oils, such as naphthenic bases, paraffin bases and mixed base oils. The lubricating oils may be used individually or in combination and generally haye a viscosity which ranges from 50 to 5000 SUS
and usually from 100 to 1500 SUS at 38C.
In many instances, it may be advantageous to form concentrates of the ~annich base or the alkaline earth metal salts thereof of this invention within a carrier liquid. These concentrates provide a convenient method of handling and transporting the additives of this invention before their sub-sequent dilution and use. The concentration of the Mannich base or the alkaline earth metal salt of the Mannich base within the concentrates may vary 7~

from 85 to 40% by weight, although it is preferred to maintain the concentra-tion between about 50 and 70% by weight.
; As desired, other additives may be included in the lubricating oil compositions of this invention. These additives include antioxidants or oxidation inhibitorsJ dispersants, rust inhibitors, anticorrosive agents, and so forth. Of particular interest are overbased sulfonates. Other types of lubricating oil additives which may be employed include antifoam agents, stabilizers, antistain agents, tackiness agents, antichatter agents, dropping point improvers, antisquawk agents, extreme pressure agents, odor control agents, and the like.
EXAMPLES
Example A
Into a reaction vessel are introduced 18,100 parts of phenol alkyl-ated with propylene tetramer, 750 parts of calcium oxide and 4620 parts of sulfur, the temperature of the mixture being maintained at 220F (10~C).
The temperature is then raised to 265-275F (130-136C) and 580 parts of ethylene glycol is charged. Hydrogen sulfide begins- to evolve and a low-rate nitrogen purge is begun oYer the top of the reactor. The temperature is slow-ly raised to 335-3~0F (169-171C~ and the temperature maintained for a period of 6 hours. The mixture is then cooled and the product isolated.
The following examples are presented to illustrate the practice of specific embodiments of this invention and should not be interpreted as limita-tions on the scope of the invention.
E.xample l Io a 3-liter flask is added 15a g diluent oil, 278 g ~0.6 mol) phenol alkylated with a mixture of 70% alpha-olefins of 18 to 28 carbon atoms and 30% alpha-olefins of 24 to 28 carbon atoms, 493 g (1.8 mol~ of phenol alkylated with propylene tetramer and 249 g (0.6 phenol equivalents calculat-ed from alkylphenol charged in the preparation as illustrated in Example A) of sulfuri~ed alkylphenol prepared by the method of Example A. The mixture is stirred Eor 5 minutes, and then 155 g ~1.5 mols) diethylene triamine is added. After stirring for 5 minutes, 70.5 g paraformalclehyde ~2.25 mols formaldehyde~ is added. The mixture is heated to 130QC over a period of 1 hour and held at 125-130C for an additional hour. 186 g (3 mols) ethylene glycol is added. After stirring the mixture at 112C for 10 minutes, 111 g (1.5 mols~ calcium hydroxide is added. The reaction mixture is heated to 175 C over a period of 1 hour and held for an additional hour at 175-178C.
The mixture is stripped to 202C ~ottoms at 20 mm Hg to yield 1338 g of crude product. 245 g diluent oil is added and the mixture filtered through diato-maceous earth to yield a product having an alkalinity value of 225. The pro-duct contains 3.96% calcium, 2~83% nitrogen and 1.02% sulEur and has a viscosity of 1565 SUS at 210F, Example 2 To a 3-liter flask is added 150 g diluent oil, 278 g ~0.6 mol) of phenol alkylated with a mixture of 70% alpha-olefins of 18 to 28 carbon atoms and 30% alpha-olefins of 24 to 28 carbon atoms, 509 g (1.8 mol) of phenol alkylated with propylene tetramer and 249 g ~9.6 phenol equivalents calculated from alkylphenol charged in the preparation as illustrated in Example A) of sulfuri~ed alkylphenol prepared according to the procedure of Example A.
After mixing there are added 155 g ~1.5 mols~ diethylene triamine and then 70.5 g paraformaldehyde ~2.25 mols formaldehyde). The mixture is heated to 130C over a period of 1 hour and held for l hour at 125-130C. 186 g ~3 mols~ ethylene glycol is added with s~irring for lO minutes at 112C and then 111 g ~1.5 mols) calcium hydroxide is added. The reaction mixture is heated ,~
to 175 C for 1 hour and held at 175-178C for an additional hour. The mix-ture is stripped to 175C bottoms at 20 mm Hg to yield 1380 g crude product.
260 g diluent oil is added and the mixture filtered through diatomaceous earth to yield a product having an alkalinity value of 224 and containing

3.83% calcium, 3.22% nitrogen and 1.07% sulfur. The product has a viscosity of 1373 SUS at 210F~

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Example 3 To a 3-liter flask is added 150 g diluent oil, 5~7 g (1.2 mols) phenol alkylated with a mixture of 70% alpha-olefîns oE 18 to 28 carbon atoms and 30% alpha-olefins of 24 to 28 carbon atoms, 329 g (1.2 mols) of phenol alkylated ~ith propylene tetramer, and 255 g (0.6 phenol equivalents calculat-ed from alkylphenol charged in the preparation as illustrated in Example A) of sulfurized alkylphenol prepared by ~he method Oe Example A. The mixture is heated to 80C and 155 g (1.5 mols) diethylene triamine and 71 paraformal-dehyde (2.25 mols formaldehyde~ are added. The mixture is heated to 125C
over a period of 1 hour and held at 125-130C for an additional hour. After cooling the reaction mixture to 110C, 186 g (3 mols) ethylene glycol and 111 g (1.5 mols~ calcium hydroxide are added. The react;on mixture is heated to 175C over a period of 1 hour and held for an additional hour at 175-177C.
The mixture is stripped to 202C bottoms at 20 mm Hg to yield 1470 g crude product. Diluent oil (113 g~ is added and the mixture is filtered through diatomaceous earth to yield a product having an alkalinity value of 240. The product contains 3.91% calcium, 3.04% nitrogen, and 1.17% sulfur and has a viscosity of 1638 SUS at 210F.
Example 4 To a 3-liter flask is added 15Q g diluent oil, 27~ g (0.6 mol) phenol alkylated with a mixture of 70% alpha-olefins of 18 to 28 carbon atoms and 30% alpha-olefins of 24 to 28 carbon atoms, 493 g (1.8 mols) phenol alkylated with propylene tetramer, and 255 g ~0.6 phenol equivalents calculat-ed from alkylphenol charged in the preparation as illustrated in Example A) of sulfurized alkylphenol prepared by the method of Example A. The mixture is heated to 80C and 155 g (1.5 mols) diethylene triamine and 71 g paraformal-dehyde ~2.25 mols formaldehyde) are added. The mixture is heated to 130C
; over a period of 1 hour and held at this temperature for an additional hour.
Ethylene glycol ~93 g, 1.5 mols) and calcium hydroxide (89 g, 1.2 mols) are added at 110C. The mixture is heated to 175 C over a period of 1 hour and - 10 ~

held at 175-180C for an additional hour. The mixture is stripped to 202C
at 20 mm Hg to yield 1311 g crude product. Diluent: oil (140 g) is added and the mixture filtered through diatomaceous earth to yield a pr~duct having an alkalinity value of 210. The product contains 3.45% calcium, 2.95% nitrogen and 1.2% sulfur and has a viscosity of 2919 SUS at 210F.
Example 5 To a 3-liter ~lask is added 150 g diluent oil, 274 g (0.6 mol) phenol alkylated with a mixture of 7Q% alpha-olefins of 18 to 28 carbon atoms and 30% alpha-olefins of 24 to 28 carbon atoms, 510 g (1.8 mols) phenol alkylated with propylene tetramer and 255 g (0.6 phenol equivalents calculated from alkylphenol charged in the preparation as illustrated in Example A) of sulfurized alkylphenol prepared by the method of Example A. ~t 80C, there is added 155 g (1.5 mols) ethylene glycol and 71 g paraformaldehyde (2.25 mols formaldehyde). The mixture is heated to 125C over a period of 1 hour and held at 125-130QC for an additional hour. Ethylene glycol (93 g, 1.5 mols~
and calcium hydroxide ~66.7 g, 0.9 mols) is added at 110C. The reaction mixture is heated to 175~C over a period of 1 hour and held at 175-178C for an additional hour. The mixture is stripped to 202C bottoms at 20 mm Hg to yield 1303 g crude product. Diluent oil (140 g~ is added and the mixture Eiltered through diatomaceous earth to yield a product having an alkalinity value of 180. The product contains 2.94% calcium, 1.14% nitrogen, 1.14% sul-fur and has a viscosity of 1741 SUS at 210F.
Example 6 To a 2-liter, 3-necked flask is added 283 g (0.62 mol) of phenol alkylated with a mixture of olefins comprising about 70% alpha-olefins contain-ing from 18 to 28 carbon atoms and about 30% alpha-oleEins containing from 24 to 28 carbon atoms, 91 g (0.32 mol~ of phenol alkylated with propylene tetra-mer, 52 g (9.5 mol~ diethylene triamine and 24 g paraEormaldehyde (0.75 mol formaldehyde~. The mixture is heated to 130C over a period of 1 hour and then held at 125-130C for an additional hour. To the mixt~re is added 62 g 7~

(1.0 mol) ethylene glycol. The mixture is stirred for 10 minutes and then 37 g (0.5 mol) calcium hydroxide is added. The mixture is heated to 175C
over a l-hour period and then held at this temperature for an additional hour.
The mixture is then stripped to 175C bottoms at 20 mm Hg to yield a product weighing 442 g. To this is added 24 g diluent oil. The mixtwre if filtered through diatomaceous earth to yield a procluct having an alkalinity value of 220 and containing 3.39% calcium and 3.11% nitrogen. The viscosity of the product at 210F is 1982 SUS.
Example 7 To a 3-liter flask is added 150 g dilllent oil, 550 g ~1.2 mol) phenol alkylated with a mixture of 70 mol percent alpha-olefins of 18 to 28 carbon atoms and about 30 mol percent alpha-olefins of 24 to 28 carbon atoms, 450 g (1.59 mols) phenol alkylated with propylene tetramer and 155 g (1.5 mols) diethylene triamine. The reaction mixture is stirred at 62C and 72 g para-formaldehyde (2.25 mols formaldehyde) is added. The mixture is heated to 130C over a period of 1 hour and then held for an additional hour at this temperature. Water is removed under vacuum and then 186 g ~3 mols) ethylene glycol is added. After stirring the mixture for 10 minutes, 111 g (1.5 mols) calcium hydroxide is added. The mixture is heated to 175C over a period of 1 hour and held for 1/2 hour at 178-180C. The mixture is then stripped to 176C bottoms at 20 mm Hg. To the crude product weighing 1341 g is added 150 g diluent oil to yield 1491 g of an 80% concentrate. This concentrate is filtered through diatomaceous earth to yield a product having an alkalinity value of 210. The product contains 3.32% calcium and 3.08% nitrogen and has a viscosity of 1019 SUS at 210F.
~xample 8 To a 3-liter flask is added 150 g diluent oil, 412 g (0.9 mol) of a phenol alkylated with a mixture of about 70 mol percent alpha olefins contain-ing froTn 18 to 28 carbon atoms and 30 mol percent olefins contailling 24 to 28 carbon atoms, and 525 g (1.86 mols) of phenol alkylated with propylene

4~

tetramer. The reaction mixture is stirred and 155 g ~1.5 mols) of diethylene triamine and 72 g paraformaldehyde (2.25 mols formaldehyde) are added. The mixture is heated to 125-130C over a period of 1 hour and then held for an additional 1 hour at this tempcrature. 186 g ethylene glycol is added with stirring at 122~C and then 111 g (1.5 mols~ of calcium hydroxide is aclded.
The mixture is heated to 175C over a l-hour periocl and held Eor an additional hour at 175-178C. The mixture is stripped to 175C bottoms at 20 mm Hg to yield 1282 g of product. 135 g diluent oil is added. The product is heated to 15QC and then flltered through diatomaceous earth to yield a product having an alkalinity value of 231. The product contains 3.53~ calcium and 3.36% nitrogen and has a viscosity of 3306 SUS at 210F.
Example 9 To a 3-liter flask is added 150 g diluent oil, 3~5 g (0.75 mol) phenol alkylated with a mixture oE 70% olefins having 18 to 28 carbon atoms and 30% alpha-olefins of 24 to 28 carbon atoms, and 6ao g (2.12 mols) phenol alkylated with propylene tetramer, 156 g ~1.5 mols) diethylene triamine and 72 g paraformaldehyde ~2.25 mols formaldhyde~. The reaction mixture is heated to 125C over a period of 1 hour and held for an additional h~ur at 125-132C.
Ethylene glycol (186 g, 3 mols~ is then added to the mixture at 100C. After stirring for 10 minutes, 111 g (1.5 mols) calcium hydroxide is added. The mixture is heated to 175C over a period of 1 hour and then held at 175-178C
for an additional hour. The mixture is stripped tc 175C hottoms at 20 mm ~Ig.
To the crude product, weighing 1292 g, is added 135 g diluent oil. The mix-ture is filtered through diatomaceous earth to yield a product having an alkalinity value of 230. The product contains 3.72% calcium, 3.35% nitrogen and has a viscosity at 2looF of 2738 S~S.
Example 10 To a 10-gallon reactor is added 1923 g diluent oil, 8~35 g (30.8 mols~ of phenol alkylated with propylene tetramer, 3563 g (7.75 mols) of phenol alkylated with a mixture of 70% alpha-ole~ins containing 18 to 28 ~, carbons atoms and 30% of a mixture of alpha-olefins containing 2~ to 28 car-bon atoms. To the mixture is added 20~0 g (:L9.~ mols~ dieth~lene triamine.
The reaction mixture is stirred, heated to 5~C and then 97~ g paraformal-dehyde (29.5 mols formaldehyde) is added. The mixture is heated over a period of 1 hour to 124-127C and then held for 1 hour at this temperature. 2385 g (38.5 mols~ ethylene glycol i5 added at 96-99C. After stirring to mix thoroughly~ 1423 g (19.2 mols~ calcium hydroxide is added. The reaction mix-ture is heated to 180-182~C over a period of l hour and held at this tempera-ture for an additional hour. The mixture is then stripped at this temperature lQ while applying Yacuum to 20 mm l-lg. The reaction mixture is then filtered through diatomaceous earth at 121-149C to yield 14,280 g product having an alkalinity value of 222. The product contains 3.68% calcium and 3.19% nitro-gen and has a viscosity of 1604 SUS at 210QF.
Example 11 To a 3-liter flask isi added 152 g diluent oil, 172 g (0.37 mol) phenol alky~lated with a mixture of 7~% alpha-olefins of 18 to 28 carbon atoms and 3Q% alpha-olefins of 24 to 28 car~on atoms, and 675 g (2.39 mols~ phenol alkylated with propylene tetramer and 156 g (1.5 mols~ diethylene triamine.
72 g paraformaldehyde (2.25 mols formaldehyde~ is added. The mixture is heated to 130C over a period of 1 hour and held for an additional hour at 125-130C. 186 g ~3 mols) ethylene glycol is added with stirring at 115C and then 111 g (1.5 ~ols) calcium hydroxide is added. The mixture is heated to 175C over a period of 1 hour and held at this temperature for an additional hour. The mixture is then stripped to 175C bottoms at 20 mm Hg to yield 1192 g of crude product. To this is added 250 g diluent oil. The mixture is heated to 15QC and fil-tered through diatomaceous earth to yield a product havlng an alkalinity value of 227. The product contains 3.6~% calcium 3.30% nitrogen~ and has a Yiscosity of 2029 SUS at 210F.
Example 12 The compounds of this invention are tested in lubr~cating oil - 1 'l -.

~f ~

compositions in the well-known l-G Caterpillar* test. In this test, a single-cylinder diesel engine having a 5-1/8" bore by 6-1/2" stroke is operated under the following conditions: timing, BTDC 8; brake mean effective pressure psi, 14l; brake horsepower, 42; BTU's per minute, 5850; speed 1800 rpm; air hoost 53" Hg absolute; air temperature in, 255~ (124C); water out, 190F ~88C); and sulfur in fuel, 0.4% by weight. At the end o~ each 12 hours of operation, sufficient oil is drained from the crankcase to allow addition of 1 quart o oil. In the test of the lubricating oil compositions of this invention, the l-G test is run for 60 hours. At the end of this period, the engine is dismantled and rated for cleanllness. The ring lands are rated on a scale of 0 to 8Q0, with 0 representing clean and 800 represent-ing black deposits. The ring grooves are rated on a scale of 0 to 100%
grooYe fill, with 0 representing clean. The underhead of the piston is rated !~
on a scale of 0 to 10, with 0 representing dirty and 10 representing clean.
The base Qil used in these tests is a Mi~dconti~nent ~ase stock SAE
30 oil containing the noted millimols of calcium from the product being tes-ted, as shown in Table L. T~e results of the testing of these lubricating oils are set forth in Table I.

TABLE I

Caterpillar l-G test Product ~mols of per Under Example kg Crooves Lands head 1 45 28-6.0-1.5 0.8 48a-50 55 8.2 2 43 45-14.1~1.8-1.1 47Q-125-55 8.Q
3 41 44-14.1-1.8-1.0 64Q-9Q-125 8.3 4 41 41-9.2-2.0-1.1 660-45-80 8.3 8 37 5Q-11.2-1.6-1.1 6~0-65-55 8.0 9 38 44-10.3--1.6-1.2 485-8Q-75 7.7 38 52-6.2-1.2-1.0 385-50-5Q 8.0 11 40 56-20.6-1.8-0.7 725-195-35 8.3 *Trademark

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A Mannich base condensation product and the alkaline earth metal salts thereof, said Mannich base being prepared by condensing formaldehyde and a polyamine with (A) a phenolic mixture consisting of (a) from 95 to 30% phenol alkylated with a propylene tetramer, and (b) from 5 to 70% phenol alkylated with an olefin of from 16 to about 28 carbon atoms or olefin mixtures wherein the olefins are of from 16 to about 28 carbon atoms, or (B) a sulfur-containing phenolic mixture consisting of (1) from 5 to 40% of a sulfurized alkylphenol of the formula wherein R is C8-C36 alkyl, n is an integer from 2 to 8, and y is an integer from 1 to 9, and (2) from 95 to 60% of a phenolic mixture consisting of (a) from 95 to 30% phenol alkylated with a propylene tetramer, and (b) from 5 to 70% phenol alkylated with an olefin of from 16 to about 28 carbon atoms or olefin mixtures wherein the olefins are of from 16 to about 28 carbon atoms.

2. The calcium salt of said condensation product of Claim 1 wherein said olefin is a mixture of olefins of 16 to about 28 carbon atoms.

3. The magnesium salt of said condensation product of Claim 1 wherein said olefin is a mixture of olefins of 16 to about 28 carbon atoms.

4. A lubricating oil composition comprising an oil of lubricating viscosity and from 0.1 to 40% by weight of the condensation product or an alkaline earth metal salt thereof of Claim 1.

5. A lubricating oil composition comprising an oil of lubricating viscosity and from 0.1 to 40% by weight of the calcium salt of Claim 2.

6. A lubricating oil composition comprising an oil of lubricating vis-cosity and from 9.1 to 40% by weight of the magnesium salt of Claim 3.

7. A lubricating oil concentrate comprising from 15 to 60% by weight of an oil of lubricating viscosity and from 85 to 40% by weight of the con-densation product or an alkaline earth metal salt thereof of Claim 1.

8. A process for preparing a Mannich base condensation product or an alkaline earth metal salt thereof which comprises condensing 0.5 to 0.85 mol formaldehyde, at least 0.3 mol of a polyamine, and 1.0 mol of a (A) phenolic mixture consisting of (1) from 95 to 30% phenol alkylated with propylene tetramer, and (2) from 5 to 70% phenol alkylated with an olefin of from 16 to about 28 carbon atoms or olefin mixtures wherein the olefins are of from 16 to about 28 carbon atoms, or (B) a sulfur-containing phenolic mixture consisting of (1) from 5 to 40% of a sulfurized alkylphenol of the formula wherein R is C8-C36 alkyl, n is an integer from 1 to 8, and y is an integer from 1 to 9, and (2) from 95 to 60% of a phenolic mixture consisting of (a) from 95 to 30% phenol alkylated with propylene tetramer, and (b) from 5 to 70% phenol alkylated with an olefin of from 16 to about 28 carbon atoms or olefin mixtures wherein the olefins are of from 16 to about 28 carbon atoms, and, optionally forming the alkaline earth metal salt thereof.

9. The product prepared according to the process of Claim 8.

10. The calcium salt of the product of Claim 9.