NL8601862A - EP ADDITIVES CONTAINING ADDITIVES FOR THE METAL WORKING INDUSTRY. - Google Patents

Description

*? NL / 33.640-Kp / f.

EP additives containing auxiliaries for the metalworking industry.

The invention relates to organic polysulphide-containing lubricating fluids which can be used for both metal cutting and chip-free cold-forming of metals, in particular for steel alloys.

As is known, the cooling lubricating fluids used in cutting, drilling and hollow-cold-forming cutting machines carried out on modern high-speed processing machines must simultaneously satisfy several stringent requirements.

10 In their application, nothing may be deposited or stored on the tool and cutting, they must not cause dirt deposits on the metal surfaces to be processed and they must also provide corrosion protection during the process.

Many cooling lubricants are known, including additive-free and additive-containing natural and synthetic oils and their aqueous emulsions, as well as other semisynthetic and synthetic substances.

The effectiveness of the various substances used differs depending on the cooling effect, the reduction of deposits and wear and the environmental effect, but none of the known substances offers a complete solution in all respects. Due to the aforementioned substance systems, the additives containing oils and their aqueous emulsions are the most important and the most widely used. The additives containing oils are oils of vegetable or mineral origin and combinations thereof, which as EP additives (extreme pressure) often contain chlorine, sulfur, nitrogen and phosphorus compounds or combinations thereof in addition to other solid additives, for example molybdenum sulfide or graphite. The EP additives are primarily required in the high speed machining operation, where in addition to the high pressure and v.a. the high surface temperature also the lubrication must be met.

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The object of the invention is the preparation of cooling lubricant products, which can be used in all areas of machining of carbide, such as during machining (cutting, turning, drilling, dragging, hollowing), as well as in chip-free cold processing (punching and deep drawing). are used.

The preparation of a multiply useful cooling lubricant fluid product family is based on the discovery that hitherto unused for this purpose, organic polysulfide EP additives prepared according to Hungarian patent application nos. 2268/85 and 2269/85, which also contain a contain active sulfur content.

These can be indicated by the general formula 1: / rI'VaVc 'Va 1 · where: 15 R1, r ^ ... rv have different and / or the same meaning and hydrogen atom or an open, straight and / or branched and / or represent cyclic saturated and / or unsaturated C 4-4 hydrocarbon residue and / or derivatives thereof, Ar is an aromatic hydrocarbon residue with one and / or more rings and / or derivatives thereof, b = 0-5, c = 2-10, d = 1-9, x = 1-6, which can be prepared by the reaction of halogen-containing alkyl aromatic compounds with sodium polysulfide and at least 1/3 of the mass consist of polysulfides, wherein in the general formula 1c at least 3 and d is at least 2 and further x is 2-6.

The sulfur content of a polyfulfide thus prepared is 30-50%, while the content of metallic sulfur reactive metallic sulfur which can be determined by the ASTM D-1662 method is at least 40% of the total sulfur content.

According to the literature, the sulfur-containing hydrocarbons suitable for the preparation of EP-containing hydrocarbons are prepared in a large quantity, for example by directly reacting unsaturated compounds with sulfur at high pressure and high temperature. The preparation of such compounds is described in U.S. Pat. Nos. 8601862-3 patents 4 119 650, 4 119 549, 3 221 056 and 3,419 614, as well as in German Pat. 2 838 981.

These known methods usually react with C18 olefin, especially isobutylene, diisobutylene, and triisobutylene with sulfur. The product thus prepared can be designated by the general formula 2: -CR1'111 2

X

wherein: R1, R11, R111 are different and / or the same and represent hydrogen, (usually less than C1), alkyl, alkenyl, aryl groups or derivatives thereof, x is substantially 1-3.

The weld load value of a ditertaire-butyl polysulfide sample with 38% sulfur content, which was prepared by reaction of isobutylene with sulfur according to German patent no. 2 838 981, is according to DIN 51350 at a concentration of 6, 5% in one

O

machine oil fraction with flash point 168 C 4000 N, 20 while at the same time the same base oil has the organic poly-sulfide formula 1 according to the invention at an equal concentration (6.5%) of a value of 6500 N and at a concentration of 3.5% a value of 4000N.

When choosing the polysulfide, it was found that the favorable EP action is not ensured by the absolute amount of built-in sulfur, but that here the structural construction of the organic groups, in particular sulfur-containing organic compound, is decisive.

The essence of the invention consists in that the mixture contains 2-8% organic polysulfide-EP-

IV

additive of general formula 1, in which R -R, Ar, b, c, d and x have the above-mentioned meanings, in addition to contain 3-12.5% detergent emulsifying additive and / or 0.5-15% viscosity, adhesion and lubrication changing additive and 0.5-1.5% corrosion inhibitor, 63-94% carrier hydrocarbon fraction or residual oil or chlorinated solvent and case by case as an additional component to the detriment of the carrier solvent 0.01-0.3 % oxidation inhibitor 8601862 * -4-hour and / or 0.01-0.5% of conventional bactericidal fungicidal additive and / or 0.01-0.1% organic dye and / or 0.2-0 , 4% odor-covering fragrance.

The preparations prepared in this composition provide versatile auxiliaries in metalworking, which can be used directly or as an emulsion diluted with 5-95% water for the machining or chip-free cold-forming of metals.

In addition to the selected organic polysulfide as a fatty and lubricating improving additive, the mixtures according to the invention can be used, inter alia, mono- and triglyceride, methyl ester as epoxy and ethoxylated ester of various natural fatty acids without vegetable fatty acids. Poly (methacrylic acid ester), polyisobutylene, solid and liquid chloroparaffin with low and high chlorine content, chlorinated and chloromethylated polyethylene or polypropylene can be used as viscosity-changing and adhesion-improving additives or the load-carrying additives. Detergent additives as well as emulsion formers as washing and rinsing agents may include the salts of alkyl benzene sulfonic acid, the fatty acid ester or ethylene oxide additions or fatty alcohol ethylene oxide additions of polyhydric alcohols, ethylene oxide additions of alkyl phenols, alkyl phenol-polyethylene glycol salts, modified organic acid glycol ether , oxyethylated fatty amide, butydiglycol are eligible. N-2-phenylnaphthylamine, dicyclohexylamine, triethanolamine oleate, N-acylsarcosine and fatty acid imidazole derivatives can be used as corrosion inhibitors.

The carrier hydrocarbon distillate does not need a particular oxidation inhibitor since it contains organic polysulfide active sulfur and also fulfills the role of the oxidation inhibitor, since during bifurcation at high temperature the divalent sulfur becomes tetravalent and hexavalent and as such acts oxygen acceptor.

In order to inhibit the esters of natural fatty acids used as lubricating additives, the phenolic compounds, such as 860 1 862 * -5-2,6-ter t-butyl-p-crescbl, alkylated dimethylamine-ter t-butylphenol, are best used. triethylene glycol bis-propionate and organic nitrogen compounds / for example the phenyl-2-naphthylamine are used. On a case-by-case basis, as additional components, bactericidal and fugicidal additives, for example, cetylpyridina chloride and bromide, and trimethoxy-netrometane, quaternary ammonium salts of alkyl amines, can become organic dye pigments such as odor-capping fragrances, for example, pine fragrance, turpentine oil and benzaldehide. used.

In addition to the lubricated polysulfide and the additional additives, the hydrocarbon-containing fraction or the chlorinated solvent or the aqueous emulsion appears to act mainly as a carrier medium and ensures the cooling-rinsing effect or the heat extraction. As carrier, the following hydrocarbon fractions are chosen: I. Aromatic light gas oil fractions:

Boiling point limit 200-280 ° C

20 Viscosity at 50 ° C 1.5-2.7 mm2 / s

Flash point (Marcusson) 80-100 ° C

aromatic content 15-35% II. Naphthene oil distillate: viscosity at 50 ° C 6-10 mm2 / s

Flash point (Marcusson) 140-180 ° C

freezing point below -40 ° C

number of C atoms present in the naphthene bond: at least 30% III. Spindle oil or Vaseline oil; 30 viscosity at 50 ° C 8-15 mm2 / s

flash point (Marcusson) min. 150 ° C

freezing point at most + 8 ° C.

IV. Machine oil fraction; viscosity at 50 ° C 15-50 mm2 <'fs

Flash point (Marcusson '150-200 ° C

freezing point at most -10 ° C

8601862 * -6- << V. Heavy oil fraction: viscosity at 50 ° C 50-120 mm2 / s

flash point (Marcusson) at least 200 ° C freezing point -15 - 25 ° C

VI. Residual oil; viscosity at 50 ° C at least 120 mm2 / s

flash point (Marcusson) above 240ÖC freezing point -8 - 18 ° C

Of the mineral oil derivatives, the 10 fractions with a viscosity above 8 mm 2 / s at 50 ° C can be used as a carrier independent of the group composition.

As the chlorinated solvent, the halogenated derivatives of C 15-15 hydrocarbons, for example, dichloretane, carbon tetrachloride, trichlorethylene, hexchlorobutadene or mixtures thereof, may be used.

The applicability of the mixtures according to the invention in a broad context indicates that the organic polysulfide sought in the said carrier solvent always has an excellent EP property. Moreover, according to the invention it has been found that this excellent EP property is due to the detergents used, in particular the ethylene oxide additions, of the fatty acid ester and fatty alcohol, as well as the lubricating additives, in particular the epoxidized and ethoxylated plant oil methyl ester was unexpectedly further improved. Synergy is demonstrated in the following model mixtures: 30 Aromatic light gas oil fraction 100%

four-ball weld strength 1200 N.

Aromatic light gas oil fraction 97% Organic polysulfide 3%

four-ball weld strength 4000 N.

25 Aromatic Light Gas Oil Fraction 90% Ethylene Oxide Additive of Fatty Alcohol 10% 8601862 * -7- £

four-ball welding strength 2000 N.

aromatic light gas oil fraction 87% organic polysulfide 3% ethylene oxide additive of fatty alcohol 10%

5 four-ball weld strength 8000 N.

The product family of the organic polysulfide-based metalworking auxiliaries is illustrated in more detail in the following examples:

Example A 10 organic polysulfide 5% fatty alcohol ethylene oxide adduct 8% fatty acid imidazole derivative 1% aromatic light gas oil fraction 84.99% organic dye of Monoazo type 0.01% 15 turpentine oil 1% viscosity at 50 ° C 4.2 mm2 / s flash point (Marcusson) 92 ° c

four-ball weld strength 8000 N.

corrosion at 100 ° C in three hours, steel negative 20 Example B.

organic polysulfide 6% fatty alcohol ethylene oxide adduct 6% mixed plant oil methyl ester 15% butyldiglycol 9% 25 acid imidazole derivative 1% aromatic light gas oil fraction 62.6% phtalocya 0.1% nine type organic dye

Benzaldehyde 0.2% 30 triethylene glycol bis propionate 0.1% viscosity at 50 ° C 4.8 mm2 / s

flash point (Marcusson) 107 ° C

four-ball weld strength 10,000 N

corrosion at 100 ° C in three hours, negative 35 steel 8601862 ψ -8-

Example C.

organic "polysulfide 6% fatty alcohol-ethylene oxide adduct 6% mixed plant oil-methyl ester 10% 5 fatty acid imidazole derivative 1% 1,1,1-trichlorethylene 77% viscosity at 50 ° C 3.4 mm2 / s

four-ball welding strength 3000 N.

corrosion at 100 ° C in three hours, steel negative 10 Example D ..

organic polysulfide 2% fatty alcohol-ethylene oxide adduct 3% chloroparaffin, 70%, liquid 10% fatty acid imidazole derivative 1% 15 dichloroethane-hexachlorobutadien 86% 1: 1 mixture

Viscosity at 50 ° C 8.4 mm2 / s

four-ball welding strength 6000 N.

corrosion at 100 ° C in three hours, steel negative 20 Example E.

organic polysulfide 3% alkylbenzene sulfonic acid sodium salt 5% epoxidized sunflower oil 12.5% N-acylsarcosine 0.5% 25 naphthenic oil distillate 79% viscosity at 50 ° C 6.3 mm2 / s

flash point (Marcusson) 153 ° C

four-ball weld strength 8000 N.

corrosion at 100 ° C in three hours, steel negative 30 Example F.

organic polysulfide 5% alkylphenol-polyethylene glycol ether 12.5% sunflower oil methyl ester 15% dicyclohexamine 0.5% 35 pivot oil 76.7% 2,6-tert-butyl-p-cre.sol 0.3% 8601862 -9-cetyl- pyridine chloride 0.5% viscosity, at 50 ° C 12 mm2 / s

flash point (Marcusson) 160 ° C

four-ball weld strength 5000 N.

5 corrosion at 100 ° C in three hours, steel negative 5% aqueous emulsion

four-ball welding strength 2000 N.

pH 8.0 corrosion, cast iron chip corrosion degree 1 10 Example G.

organic polysulfide 4% alkylphenol-polyethylene glycol ether 8.5% polycetyl methacrylate 8% triethyl amine oleate 1.5% 15 petrolatum oil 78% viscosity at 50 ° C 22 m2 / s

flash point (Marcusson) 155 ° C

four-ball welding strength 6000 N.

corrosion at 100 ° C in 3 hours, steel negative 20 Example H.

organic polysulfide 2% oxyethylated fatty amide 3% fatty acid sarcosine 1% machine oil fraction 94% 25 viscosity at 50 ° C 27 mm2 / s

flash point (Marcusson) 170 ° C

four-ball weld strength 4000 N.

corrosion at 100 ° C in 3 hours, steel negative

Example I.

30 organic polysulfide 3% fatty alcohol ethylene oxide adduct 5% chloroparaffin, 40% 8% polyisobutylene 3% dixyclohexylamine 1% 35 refined heavy oil 80% viscosity at 50% C 80 mm2 / s 8601862

a

-10-

flash point (Marcusson) 224 ° C

four-ball welding strength 7000 N.

corrosion at 100 ° C in three hours, steel negative

Example J.

5 organic polysulfide 7% alkylphenol-polyethylene glycol ether 7.25% chloroparaffin, 70% 7% rapeseed oil 15% N-2-phenyl-naphthylamine 0.5% 10 refined heavy oil 63% tert-butylphenol 0.15% trimethoxy-nitromethane 0, 1% viscosity at 50 ° C 96 mm2 / s

flash point (Marcusson) 226 ° C

15 four-ball weld strength 10,000 N

corrosion at 100 ° C in three hours, steel negative 10% aqueous emulsion

four-ball weld strength 5000 N.

pH 8.0 20 corrosion, cast iron chip corrosion degree 1 5% aqueous emulsion

four-ball welding strength 3500 N.

Example K.

organic polysulfide 6% 25 fatty alcohol ethylene oxide additive 12% stearin monoglycerin 10% triethyl amine oleate 1% refined residual oil 69% viscosity at 50 ° C 132 mm2 / s

Flash point (Marcusson) 265 ° C

four-ball weld strength over 11,000 N.

corrosion at 100 ° C in three hours, steel negative 5% aqueous emulsion

35 four-ball welding strength 5500 N.

corrosion, cast iron chip corrosion degree 1 860 t 8 62 -11-

Example L.

organic polysulfide 3% fatty alcohol-ethylene oxide additive 3% chlorinated polyethylene wax. 5.5% 5 fatty acid sarcosine 0.5% refined residual oil 88% viscosity at 50 ° C 122 mm2 / s

flash point (Marcusson) 155 ° C

four-ball welding strength over 8000 N.

10 corrosion at 100 ° C in three hours, steel negative

The wide field of application and the applicability of the mixtures according to the invention are summarized in the following tables:

Mixtures to be used for machining: 15 medium-hard stainless non-ferrous metal _ steel_ steel_ machining

run example A example A example B

example F example C 5% aqueous emulsion

drilling example A example A example A

example B example B example B

example C example C

example D

25 grinding example D example F example E

5% aqueous emulsion

example J

5% aqueous emulsion 8601862 t * -12- · «medium-hard · stainless non-ferrous metal steel processing

hollow out example A example A example A

example B example B example B

Mixtures suitable for chip-free deformation: 5 medium-hard stainless non-ferrous meta & l steel processing

wire drawing example E example G example F

rollers example E example I example E

example G example F

1 0 example G

punching example I example J example E

example F example G

deep drawing example K example K example I

15 example L example L

860 1 862

Claims (9)

1. An organic polysulphide-containing cooling lubricant mixture, which can be used in a similar manner to the chipping and chip-free deformation, characterized in that it contains 2-8% organic polysulphide of the general formula 1 / RI_V-Ar, / / S /, 1 bcxd wherein: R *, have different and / or the same meaning and represent hydrogen atom or an open, straight and / or branched and / or cyclic saturated and / or unsaturated ci_4q hydrocarbon radical and / or derivatives thereof, A is an aromatic hydrocarbon radical with one 1 and / or several rings and / or derivatives thereof, b = 0.5, c = 2-10, d = 1-9, x = 1-6. with the proviso that at least 1/3 of the mass of the organic polysulfide consists of polysulfide, in the general formula 1c at least 3 and 20d being at least 2, x = 2-6, while the active sulfur content is at least 40% of the entire sulfur content, the mixture additionally comprising: 3-12.5% detergent emulsifying agent and / or 0.5-15% lubrication-improving or viscosity-changing additive, 0.5-1, 5% corrosion inhibitor and 63-94% carrier mineral-oil derivative or chlorinated hydrocarbon based solvent and any disadvantages of the carrier solvent 0.1-0.3% oxidation inhibitor, 0.01-0.5% bioside additives, 0, 01-0.1% organic dye and 0.2-1.0% fragrance. 2. Mixture according to claim 1, characterized in that the mixture as carrier material is a mineral oil fraction with a flash point above 80-240 ° C and a viscosity or chlorinated at 50 ° C above 1.5-120 mm 2 / s. contains g-hydrocarbon as a solvent. 3. Mixture according to claim 1, characterized in that the mixture as emulsifier additive fatty alcohol-ethylene oxide additive or alkylphenol-sulfone-660186. -14 * * V contains acid Na salt or alkylphenol-polyethylene glycol ether or oxyethyl ethylated or oxyethylated fatty amide and / or butyl glycol. 4. Mixture according to claim 1, characterized in that the mixture is the lubricating improving and viscosity-changing additive of refined or epoxidized rapeseed or sunflower oil or rapeseed or sunflower oil methyl ester or a mixture thereof or chlorine paraffin with a chlorine content of 40- 70% or stearin monoglyceride or polycetyl methacrylate or polyisobutylene or chlorinated polyethylene wax. 5. Mixture according to claim 1, characterized in that the mixture contains as a corrosion inhibitor fatty acid imidazole derivative or N-acrylic sarcosine or fatty acid sarcosine or dicyclohexulamine or N-2-phenylnaphthalin or triethanolamine oleate. 6. Mixture according to claim 1, characterized in that the mixture contains oxidation inhibitor 2,6-tert-butyl-p-cresol or alkylated dimethylamine tert-butylphenol or triethylene glycol bis-propionate or phenol-2-naphthaline. 7. A mixture according to claim 1, characterized in that the mixture contains biocidal additive cetyl-pyridinium chloride or cetyl-pyridinium bromide or trimethoxy-nitrometane. 8. Mixture according to claim 1, characterized in that the mixture contains terpene oil or benzaldehyde as a fragrance. 9. Mixture according to claim 1, characterized in that the mixture contains, as an additional dye, fat and alcohol soluble dyes of monoazo or phthalocyanine type. 8601862