DE1070326B - lubricant - Google Patents

Description

C 1OM 169 / 00A32

Ιϊ £ 7Γ

GERMAN

PATENT OFFICE

ία. 23 c 1/01

INTERNAT. KL C 10 ΠΙ

N14045IVc / 23c

REGISTRATION DATE: AUGUST 26, 1957

NOTIFICATION OF THE REGISTRATION OND ISSUE OF THE EDITING LETTER:

DECEMBER 3, 1959

It is known per se that no ash-forming nitrogen-containing copolymers with nothing but polar Substituents in the main hydrocarbon chain as cleaning agents in mineral and synthetic Lubricating oils work. However, these additives prevent in practice the wear and tear of the metal parts of e.g. B. Engines inadequate, so that the usefulness of the lubricating oils modified in this way is limited. It has therefore already been proposed to also add certain oil-soluble lubricants to such polymer-containing lubricants Adding salts of polyvalent metals. Although a beneficial effect can be achieved in this way, it does occur the further difficulty of increased sludge formation.

A likewise already recommended addition of certain organophosphates to mixtures of one Lubricating oil and a nitrogen-containing copolymer which does not form ash makes the improvement possible the viscosity index and possibly a reduction in the corrosive attack on metals, however, these additives generally have no effect on wear and tear and freedom from sludge such lubricants.

According to the invention, this technical problem can now be solved by adding a synergistic mixture from

a) a smaller amount of an oil-soluble, neutral or basic, known per se as a lubricating oil additive Sulfonate, phenolate and / or carboxylic acid salt of a polyvalent metal and

b) a smaller amount of one also used as a lubricating oil additive known oil-soluble, saturated, non-aromatic amine having 6 to 36 carbon atoms Dissolve in the molecule to form a lubricating oil containing a copolymer.

The copolymers are preferably used in amounts between 0.5 and 10 percent by weight on the total mix.

The polymeric cleaning agents are derived from at least two different interpolymerizable ones Connections, namely

1. of a compound that is attached to the unsaturated molecule via an oxygen-containing radical Contains alkyl radical with at least 8 and preferably 12 to 20 carbon atoms bonded, and

2. from an unsaturated nitrogen-containing compound. Type 1 monomers include polymerizable esters

Ethers, acids and amides, for example esters of acrylic acid or alkyl acrylic acids with long-chain aliphatic Alcohols; Vinyl esters of long chain carboxylic acids; and esters of vinylenedicarboxylic acids and at least a long-chain alcohol.

Of the monomers of type 2, the basic nitrogen compounds are preferred, so that the polymer lubricant

Applicant:

N. V. DeBataafsche Petroleum Maatschappij, The hague

Representative: Dr. K. Schwarzhans, patent attorney, Munich 19, Romanplatz 9

Claimed priority: V. St. v. America August 28, 1956

Roland Frederick Bergstrom, Martinez, Calif., And Richard Charles Nelson, Contra Costa, Calif.

(V. St. Α.),
have been named as inventors

Cleaning agent contains basic nitrogen-containing substituents. Under "basic nitrogen compound" is a to understand primary, secondary or tertiary amine, amide or amino amide, which has a basic reaction and is in the form of the free base. Examples of suitable monomers are: amino-substituted olefins, Esters of amino alcohols with unsaturated carboxylic acids, unsaturated ethers of amino alcohols, unsaturated Amines; Amides of unsaturated carboxylic acids which have an N-containing substituent on the amide nitrogen atom wear; heterocyclic N-compounds with an unsaturated substituent, such as vinyl pyridines and vinyl alkyl pyridines, as well as lactams, e.g. B. N-vinyl lactams or C-vinyl lactams and in particular C-vinyl-N-alkyl lactams.

The vinyl butyrolactams, also called vinyl pyrrolidones, are preferred among the lactams.

The vinyl valerolactams, which can also be referred to as vinyl piperidones, are also very suitable. The copolymers used as cleaning agents may be from more than one monomer of type 1 and / or from more than one monomer of type 2 be derived. Furthermore, in the preparation of the polymers, in addition to the monomers of type 1 and 2 other monomers are also used, e.g. B.

Esters of unsaturated alcohols such as vinyl and allyl formate, acetate, propionate and butyrate; unsaturated hydrocarbons such as ethylene, propylene, isobutylene, Styrene, vinyl toluene, 1,3-butadiene, isoprene; unsaturated carboxylic acids and their derivatives, such as acrylic acid, methyl

909 687/385

3 4

methacrylate, acrylonitrile, methacrylamide; unsaturated had a molecular weight of over 250,000. The polymer

Ethers, such as ethyl vinyl ether, butyl vinyl ether. contained the monomeric units in the same ratio

The copolymers can be in any suitable form as the starting mixture.

Way to be made. .

The molecular weight of the same is preferably between 5. Example 5

1000 and 2500000 and in particular between 50,000 and A copolymer of lauryl methacrylate and

2500000. The molecular weight is determined according to the Me-N-vinylpyrrolidone was according to the procedure according to

method of light scattering, described in »Chemical Example 4 with the same ratio between the

Reviews ", Vol. 40 (1948), p. 319. Monomers produced, but 0.75 percent by weight

The ratio between the monomers of type 1 io α, α'-azodiisobutyronitrile used as a catalyst

and of type 2 in the copolymers can be internal. The molecular weight of the polymer was about

fluctuate halfway across boundaries, e.g. B. from 1:10 to 10: 1. 225,000.

Preferred ratios are between 7: 1 and 1: 1. Example 6

Particularly favorable polymers contain a ^p

larger proportion of type 1 monomers compared to 15 A copolymer of stearyl methacrylate / lauryl

the monomers of type 2. methacrylate / N-vinylpyrrolidone in a molar ratio of

The following examples explain the production of 2.8 / 5.6 / 1 using the procedure of Example 4

suitable polymers, but is prepared for the production, with α, α'-azodiisobutyronitrile as a catalyst

wise no protection was used per se in the context of the invention and the reaction time 48 hours

claimed. 20 was. The polymeric compound was oil soluble and had

Example 1 ^e * ⁿ molecular weight over 1,000,000.

A mixture of 2.5 moles of stearyl methacrylate, 5.3 moles of Example 7

Lauryl methacrylate, 1 mole of 2-methyl-5-vinylpyridine and an oil-soluble copolymer of stearyl meth-

0.2% α, α'-azodiisobutyronitrile, dissolved in 500 cm ^{3 of} acetone, 35 acrylate / N-vinylpiperidone, in which the reaction

was present in a reaction vessel for 45 hours with components in a molar ratio of 4: 1

65 ° C. with stirring in a nitrogen atmosphere using the procedure according to example 4

set. The polymer was then prepared dispersed in benzene.

and then with a mixture of acetone and Beis' el 8

Methanol precipitated. This treatment was repeated, 30 ^p

whereby a copolymer of stearyl methacrylate / 1020 parts of technical lauryl methacrylate, 100 parts Lauryl methacrylate / 2-methyl-5-vinylpyridine obtained methacrylanilide, 60 parts / S-diethylaminoethyl methwurden, that has a nitrogen content of 0.21 weight acrylate, 300 parts of mineral oil and 3.6 parts of α, α'-azodiiso percent and had a molecular weight over 800,000. The butyronitrile were polymerized under nitrogen at 60 ± 2 ° C contained the monomer units in the same 35 stirs. After 2 hours there was some thickening Ratio as in the starting mixture. of the starting mixture observed. During the next

16 hours became gradually as the progressed

Example 2 Polymerization 900 parts of mineral oil were added. Man

so received a somewhat stirrable oil solution one

A mixture of 1 mole of lauryl methacrylate, 1 mole of mixed polymer of the three polymerizable 2-methyl-5-vinylpyridine and 0.4 percent by weight of ben components, essentially in the ratio of the Auszoylperoxyd was in a reaction vessel during the initial mixture, ie 86.4 / 8 , 5 / 5.1. The technical lauryl atmosphere used in the above more than 2 hours at 80 to 85 ° C in a nitrogen-described procedure implemented. The unreacted compo methacrylate is the methacrylic acid ester of technical components were stripped at 185 ° C and 1 mm pressure. 45 lauryl alcohol, which has been obtained by reduction of the copolymer obtained was a rubber of the fatty acids from coconut oil, and a mixture of the like product which contained about 3 ° / ₀ nitrogen, a saturated, straight chain alcohols having 10 to 18 carbons-molecular weight over 150 000 and represented in hydrocarbon atoms. A typical example contains about substance oils that were soluble. 3 "/ ₀ C ₁₀ -, 61" / ₀ C ₁₂ -, 23% C ₁₄ -, 11 % C ₁₆ - and 2% C ₁₈ -

Example 3 ⁵ ° alcohols.

Following the procedure of Example 2, a ^p

Copolymer of lauryl methacrylate and 2-methyl A copolymer made from 90 parts of lauryl methacrylate 5-vinylpyridine, but the molar ratio and 10 parts of ß-diethylaminoethyl methacrylate of the reaction components was 4: 1. The nitrogen 55 prepared according to the procedure of Example 7. The content of the reaction product was about 2 ° / _0th The mole product was oil-soluble and possessed a good cleaning dead weight was over 75,000. The product had a sticky, shaft,
rubbery consistency, but was oil soluble. Example 10

Example 4 ^6o A copolymer of 90 parts of lauryl methacrylate

and 10 parts of N- (4-dimethylaminocyclohexyl) metha-

A mixture of 2 moles of lauryl methacrylate and 1 mole of crylamide was prepared according to the procedure of Example 8

N-vinylpyrrolidone and 0.5 weight percent benzoyl- produced. The product was oil soluble and possessed good

Peroxide became cleansing properties for 10 hours at 65 ° C.

Settlement brought. The polymer was then in benzene 65 One component of the synergistic additive

dispersed and then mixed with a mixture is an oil-soluble neutral or basic

Acetone and methanol precipitated. This treatment was suIf onate, phenate and / or carboxylic acid salt of a

repeated, resulting in a polyvalent metal copolymer. She is particularly in abundance

Lauryl methacrylate and N-vinylpyrrolidone obtained between 0.1 and 10 percent by weight, based on the

that has a nitrogen content of 2.20 percent by weight and 70 total mixture is used.

5 6

The sulfonates are preferably petroleum sulfonates of the suitable. Examples of organophosphates are Na, K,

Metals of Group II of the Periodic Table with Ca-, Ba-, Zn- and Al-methylcyclohexyl phosphate, -di

■ an atomic number from 12 to 56 (especially the methylcyclohexylditbiophosphate, -dihexylsäurethiophos-

Alkaline earth metals), such as. B. the neutral or basic phate, -laurylbenzylthiophosphate and -butyltrichloro-

Calcium, barium and magnesium salts of oil-soluble petroleum 5 methane phosphonate. A particularly preferred group sulfonic acids with a molecular weight of 350 to 550 and such compounds include the Zn and Ba salts of

preferably from 400 to 500. Alkyl dithiophosphate, Na, K and Ba salts of P ₂ S ₅ -PoIy-

The phenates are preferably salts of polybutene reaction products and / or P ₂ S ₅ terpene - (- pinene) -

phenols. Polyphenols are compounds that are reaction products. Such products are in the

which have a plurality of phenol residues, sold by the companies Lubri-Zol Corp.,

which are linked by hydrocarbon chains. Standard Oil Company of Indiana and Monsanto Chemical

Such compounds in which Company.

several simple phenolates in ortho- and / or para-Other suitable, optionally used additives position to the phenolic hydroxyl group by are metal dithiophosphate (Zn-dialkyldithiophosphate), alkylidene (z. B. methylene) residues are condensed. 15 metal thiocarbamates, such as zinc dibutyldithiocarbamate, such compounds can be obtained by improvers for the viscosity index and stick-condensing an alkylphenol (ζ. B. p-octylphenol) point-lowering, condensation products of chlorine with an aldehyde, such as formaldehyde, acetaldehyde or refined paraffin wax and naphthalene -Benzaldehyde. The preferred polyvalent metals in additives, such as oil-soluble polyhaloalkanephosphondene phenates, are the same as those above for 20 components, e.g. B. trichloromethanephosphonic acid, esters called sulfonates. Calcium and barium salts, amides or amine salts thereof, as well as organic condensation products of octylphenol-formaldehyde with sulfides and mixtures of such compounds.
Molecular weights from 500 to 1100 are particularly suitable. As a lubricating oil base, any natural or synthetic

The carboxylic acid salts include the neutral or table material that has lubricating properties of basic salts of a polyvalent metal and a 25. Thus, the base material can be an organic hydrocarbon carboxylic acid, e.g. B. be an aromatic carbon oil with a wide viscosity range, z. B. of bonsäure, such as highly basic alkaline earth salts (e.g. calcium, 2.92 ° E at 37.8 ⁰ C to 4.3 ° E at 98.9 ° C. The carbon, barium or magnesium salts) of alkylated benzoin, Hydrogen oils can be blended with fatty oils, salicylic, resorcylic, anthranilic or naphthoic acid, such as castor oil or lard oil, and / or with synthetic basic calcium salts of C 1 -C 4 -alkylbenzoic and lubricants such as polymerized olefins, mixed poly- C _lä -C ₁₈ -Alkylsalizylsäure. Other suitable basic salts of alkylene glycols and oxides, esters of polyvalent metals are the cycloaliphatic carbons (e.g. di-2-ethylhexyl sebacate, dioctyl phthalate, triacid salts, such as the basic calcium and barium octyl phosphate), polymeric tetrahydrofuranates, polyalkylnaphuranates. silicone polymers (e.g. dimethyl silicone polymer). Ge

The synthetic lubricants can, if desired, have the basicity of the mixtures according to the invention

Salts used can be between 2 and 1000 ° / ₀ and as the only lubricating base or in mixture with

preferably between 50 and 800%. The neutral fatty oils are used.

Salts from polyvalent metals and aromatic mineral oils, which are suitable for use in According to the customary methods, carboxylic acids are particularly desirable in the mixtures according to the invention and are readily available commercially. The 40 are are obtained from West Texas Ellenburger rough speakers Basic salts can be used according to any oils, East Texas crudes, Oklahoma crudes, or potash grade Method, e.g. B. according to the USA patents formic crude oils.

2 356043, 2 409687, 2 616 904, 2 616 905 and 2 616 910 _ν . · ". . ,, _α . , _Λ . . ,

• u χ η! a ^Em special, well usable refined oil such

getting produced. Origin has the following characteristics:

The other component in the synergistic addition- 45 0 t>

mixture is an oil-soluble, saturated, non-aromatic specific gravity, ⁰ API> 26.5

Amine with 6 to 36 carbon atoms in the molecule, e.g. B. Stockpunbt <- 12 ° C

a long-chain, primary, secondary or tertiary, flash point (COC)> 199 ⁰ C

saturated, aliphatic or cycloaliphatic mono-viscosity, ⁰ E at 37.8 ⁰ C 3.47 to 4.59

or polyamine. Aliphatic monoamines of this type are 50 viscosity index > 95

z. B. mono-, di- or trihexyl -, - octyl -, - decyl -, - dodecyl, ".

-tetradecyl-, -hexadecyl- or octadecylmonamine. At . Another such oil is with SAE 30 mineral oil

The secondary and tertiary amines can have the following properties:

remnants may be the same or different. The Aliphatic Specific Gravity, "API > 24.5

Polyamines include unsaturated alkylene, 55 Pour point <- 20.5 ⁰ C

as tetraethylenepentamine, or mono- or poly-C ₆ _i ₈ - Flash point (COC)> 213 ⁰ C

alkyl-substituted alkylene polyamines, in which the viscosity ⁰ E at 98.9 ° C 1.8 to 1.93

Alkyl substituent or the substituents at the same or viscosity index 50 to 60

different nitrogen atoms are bound in the molecule,

z. B. NC ₁₂ _ ₁₈ -Alkylpropylenediamine and N-Laurylpro- 60 ^The preferred composition of the invention

pylenediamine. The amines are preferably given in amounts according to lubricants as follows

between 0.01 and 1 percent by weight, based on the:

entire mixture, used. Non-ash-forming

The polymeric detergent lubricants of the present invention can also contain other additives ranging from 1 to 6 percent by weight

which organic compounds, which are the acid residues salt of a polyvalent

Inorganic phosphorus acids contain 0.5 to 5 percent by weight of metal

are particularly preferred, e.g. B. Amine reaction products 0.01 to 0.5 percent by weight

Olefins or terpenes with P ₂ O ₅ and P ₂ S ₅ . Also the additives of your choice 0.2 to 1 percent by weight

Salts of the above-mentioned reaction products are the remainder of the lubricating oil

The following examples further illustrate the invention

closer:.

Mixture A

Copolymer of lauryl methacrylate / diethylaminoethyl

methacrylate (90:10) 5 percent by weight

Basic calcium petroleum sulfonate .. 0.5 ⁰ Z ₀ sulfate residue

Octadecylamine 0.2 percent by weight

Zinc dialkyldithiophosphate 0.8 percent by weight

Mineral lubricating oil (SAE 10) rest

Mixture B

Copolymer of lauryl methacrylate / 2-methyl-5-vinylpyridine

Basic calcium petroleum sulfonate ..

Octadecylamine

Zinc dialkyldithiophosphate

Mineral lubricating oil

5 percent by weight 0.7% sulfate residue 0.2 percent by weight 0.8 percent by weight rest

Mixture C

Mixed polymer of lauryl methacrylate / stearyl methacrylate / 2-methyl-5-vinyl pyridine

Basic calcium petroleum sulfonate ..

Octadecylamine

Zinc dialkyldithiophosphate

Mineral lubricating oil

Mixture D

Mixed polymer of lauryl methacrylate / stearyl methacrylate / 2-methyl-5-vinyl pyridine

Neutral calcium petroleum sulfonate ..

5 percent by weight 0.7% sulfate residue 0.2 percent by weight 0.8 percent by weight rest

Mixture E.

■ Octadecylamine

Zinc dialkyldithiophosphate Mineral lubricating oil.

S Weight percent 0.7% sulphate residue

0.2 percent by weight 0.8 percent by weight remainder of the copolymer of lauryl methacrylate / diethylaminoethyl

methacrylate (90:10) 4 percent by weight

Calcium salt of octylphenol form

aldehyde condensation product 0.5% sulphate residue

Octadecylamine 0.2 percent by weight

ίο zinc dialkyldithiophosphate 0.8 percent by weight

Mineral oil remainder

Mixture F

Copolymer of lauryl methacrylate / diethylaminoethyl

methacrylate (90:10) 5 percent by weight

Basic calcium petroleum sulphonate .. 1% sulphate residue

Dimethyloctadecylamine 0.2 percent by weight

Zinc dialkyldithiophosphate 0.8 percent by weight

Mineral lubricating oil (SAE 30) rest

Mixture G

Copolymer of lauryl methacrylate / diethylaminoethyl

methacrylate (90:10) 5 percent by weight

Neutral calcium petroleum sulfonate .. 1% sulfate residue

Dimethyloctadecylamine 0.2 percent by weight

Zinc dialkyldithiophosphate 0.8 weight percent

Mineral lubricating oil (SAE 30) rest

The exceptionally favorable properties of the lubricants according to the invention when they are checked in a Caterpillar engine under L-I conditions and in a Chevrolet engine under EX-3 test conditions result from the table compiled Results.

Mixture Ll test
Rating *)

48.9 ^J C 71.1 ° C

EX-3 test "evaluation **)

Piston paint

Total deposit

Mud, overall

Final evaluation

Mixture A

Mixture F

Mixture C

Mixture U (Mixture F minus 0.2% dimethyloctadecylamine)

Mixture V (mineral oil SAE 10 -f copolymer of lauric methacrylate / diethylammoethyl methacrylate (90:10) 4-0.8% Zn dialkyldithiophosphate)

Mixture W (mineral oil SAE 10 + 0.5% SA ***) basic Ca petroleum sulfonate - <- 0.8% Zn dialkyldithiophosphate)

Mixture X (mineral oil SAE 10 + 0.5% SA ***) basic Ca petroleum sulfonate -j- 0.2% dimethyloctadecylamine)

93.7
92.7

92.6. 86.8

88.0 j 69.5

90.6 i 83.3

87.0 I 75.0

8.9
8.0

6.9

41.4
36.0

33.6

68.8 65.0

59.2

84.0 75.0

70.0

*) Piston purity; Rating: 100 = clean, 0 = dirty.
**) Piston paint; Rating: 10 = good, 0 = dirty; Total deposit; Rating: 50 = good, 0 = dirty;

Total sludge; Rating: 80 = - good, 0 - dirty; Final evaluation: 100 = good, 0 = dirty.
***) SA ^ Suliatruokstand.

The synergetic effect of the two components of the pillar engine with the mixtures H ₁ to H _{5 is} evident, the additional mixture which is incorporated into the copolymer. The results of this test are shown in the drawing, which is graphically illustrated. The individual mixtures had the following composition in a series of tests under LI conditions in the Cater-70:

Claims (1)

9 10 Mixture of H ₁ salt should have expected. The curve H ₁ Copolymer of lauryl meth- the results shown are surprising- Acrylate / Diethylaminoäthyl- wise far above the cumulative effect of the two methacrylate (90:10) 5 percent by weight types of additives addition. Basic calcium petroleum sulfonate .. 0.5% sulfate back 5 stand patent claims: Zinc dialkyldithiophosphate 0.8 weight percent Octadecylamine 0.2 percent by weight 1.Lubricant, consisting of a mine- Mineral oil rest rustle or synthetic oil and one . , " I ° small amount, preferably 0.5 to 10 weight mis ² percent, based on the total mixture, one Copolymer of Lauryhneth- or several oil-soluble and non-ash-forming ones acrylate / diethylaminoethyl copolymers from an unsaturated compound methacrylate (90:10) 5 percent by weight manure, which on the unsaturated part of the molecule Basic Calciumerdölsulfonat .. 0.5 ° / ₀ 15 Sulfatrück- an oxygen-containing radical with an alkyl radical stood at least 8 and preferably 12 to 20 carbon Zinc dialkyldithiophosphate contains 0.8 percent by weight of bonded atoms, and an unsaturated Mineral lubricating oil residues containing nitrogenous organic compounds, _. , -. characterized by the content of a synereistic Mixture H _{3 20 mmig from} Copolymer of lauryl meth- a) a smaller amount, preferably 0.1 to acrylate / diethylaminoethyl - 10 percent by weight, based on the total mixture, methacrylate (90:10) 5 percent by weight of an oil solvent known per se as a lubricating oil additive Zinc dialkyldithiophosphate 0.8 percent by weight borrowed neutral or basic sulfonate, phenolate Mineral lubricating oil residue 25 and / or carboxylic acid salt of a polyvalent . Metal and Mixture ^H * b) a smaller amount, preferably 0.01 to Copolymer of lauryl meth- 1 percent by weight, based on the total mixture, acrylate / diethylaminoethyl- one known per se as a lubricating oil additive, oil-soluble methacrylate (90:10) 5 percent by weight 30 borrowed, saturated, non-aromatic amine with Octadecylamine 0.2 percent by weight 6 to 36 carbon atoms in the molecule. Zinc dialkyldithiophosphate 0.8 weight percent 2. Lubricant according to claim 1, characterized in that Mineral oil residue indicates that the sulfonate, phenate or that carboxylic acid salt of an alkaline earth metal, especially Mixture H ₅ 35 special derived from calcium. Zinc dialkyldithiophosphate 0.8 percent by weight ? · Lubricant according to claims 1 and 2 thereby Mineral oil residue denotes that the oUoshche Amm is a pnmä- res, secondary or tertiary aliphatic amm, such as How the course of the curve H _{4 is} in comparison with that of octadecylamine or dimethyloctadecylamine. Curve H ₃ can be seen, an addition of 40 worsens Amine component alone the piston purity in the case of publications. application of the lubricating oils containing polymerizate French patent specifications no. 1101 147, 1111 338. substantial, so that one has more of an adverse effect with the simultaneous addition of an amine and an oil-dissolving agent. Older patents considered: borrowed metal sulfonate, phenolate and / or carboxylic acids 45 German patents 960 756, 1 003 897. 1 sheet of drawings © 90 »687ß85 11.59