US3888704A

US3888704A - Methods of treating hardening oil before use by adding a mixture of ethoxylated acyclic compounds and film-forming acyclic compounds

Info

Publication number: US3888704A
Application number: US444223A
Authority: US
Inventors: Per Olof Lindstedt
Original assignee: Olof Lindstedt & Co AB
Current assignee: Olof Lindstedt & Co AB
Priority date: 1974-02-20
Filing date: 1974-02-20
Publication date: 1975-06-10
Anticipated expiration: 1992-06-10

Abstract

A mixture consisting of ethoxylated acyclic compounds as emulsifiers, acyclic compounds as film-forming agents and possibly antioxidants and corrosion inhibitors, is added to a mineral-oil based hardening oil.

Description

United States Patent Lindstedt 1 June 10, 1975 METHODS OF TREATING HARDENING OIL [56] References Cited BEFORE USE BY ADDING A MIXTURE OF UNITED STATES PATENTS ETHOXYLATED ACYCLIC COMPOUNDS 3,192,165 6/1965 Fields et a1, 252/79 AND FILM-FORMING ACYCLIC 3,224,910 12/1965 McEwen 148/143 COMPOUNDS 3,281,288 10/1966 Carver et a1..... 148/20.6 3,340,193 9/1967 Fields et al. 252/79 [75] Inventor: Per Olof Lindstedt, Molndal,

Sweden Primary ExaminerWalter R. Satterfield [73] Assignee: Olof Lindstedt & Co. AB, Molndal,

Sweden [57] ABSTRACT [22] Filed: Feb 20, 1974 A mixture consisting of etl oxylated acyclic compounds as emulsifiers, acyclic compounds as film- [21] App]. No.: 444,223 forming agents and possibly antioxidants and corrosion inhibitors, is added to a mineral-oil based harden- 52 US. Cl. 148/29; 252/73; 252/77; mg

252/79 5 Claims, N0 Drawings [51] Int. Cl B23k 35/24 [58] Field of Search 148/29, 28, 27, 143, 20,6,

METHODS OF TREATING HARDENING OIL BEFORE USE BY ADDING A MIXTURE OF ETHOXYLATED ACYCLIC COMPOUNDS AND FILM-FORMING ACYCLIC COMPOUNDS The use of liquids for the hardening of metals is well known. For example, metallic objects can be cooled rapidly by immersing them in water or oil. Immersion in oil often produces a milder and a more even effect since the occurrence of stress within the material is avoided.

The oils used must be stable at the temperatures in question and often paraffinor naphthene-based mineral oils or mixtures thereof are used, if desired with additives included.

After the immersion the oil should be removed from the metal surface. This can be done by alkaline washing or by treatment with solvents, such as chlorinated hydrocarbons. Another possibility is to add an emulsifier to the hardening oil. In that case the oil after hardening is removed from the material by flushing with water.

The emulsifiers used in the latter case must possess a high emulsifying capacity and be thermostable so that no decomposition products are created which could have an injurious effect on the surface of the metal. The emulsifiers must also be relatively insensitive to the hardness and pH of the water, so that immersion or spraying with water does not result in precipitations which could be harmful to the metal surface.

From the point of view of environmental preservation it is important that the emulsifiers chosen can be decomposed biologically, so that they are incapable of causing any damage.

It has been found that certain ethoxylated acyclic compounds, viz. ester, alkyl ether, fatty acid amide and alkylamine-ethylene oxide adducts, satisfy the abovementioned requirements. Such acyclic compounds contain 8-20 C-atoms in straight or branched alkyl chains which can be saturated or unsaturated, or mixtures thereof, and at least one active H-atom. The fol lowing are suitable compounds:

a. Fatty acids containing 10-20 C-atoms.

b. Alkanols, primary or secondary, such as cetyl alcohol, oleyl/cetyl alcohol, tridecyl alcohol, C -C alkanols, C -C alkanols, etc.

0. Carboxylic acid amides, such as palmitic acidmono or diethanolamide, oleic acidlauric acidmonoor diethanol-amide, etc.

d. Primary, secondary or tertiary alkyl amines and alkyl polyamines,'such as lauryl amine, lauryl oleyl amine, tallow amine, tallow propylene diamine, etc.

After the building up of ethylene oxide these products contain 2-15, preferably 2-8, ethylene oxide units in the hydrophilic part.

It is of the utmost importance that a thin film be left on the surface of the metal after the removal of the hardening oil. In order to achieve this a compound which is, in itself, neither soluble in nor dispersible by water, is added to the oil, in addition to the emulsifier. In order to make this film adhere well to the metal surface it should contain one or more OH, -CONI-l or NH -groups. This oil film protects the surface against corrosion.

An addition of this type to the hardening oil acts also as solubilizer for the ethoxylated emulsifier, thereby ensuring a better distribution of the latter in the mineral oil.

Suitable film-forming additives are acyclic compounds or mixtures thereof with straight or branched, saturated or partially saturated alkyl chains containing 10-26 C-atoms and at least one polar group, such as Ol-l, CONH or NH -groups.

Suitable compounds are: fatty acid esters, cetyl oleyl alcohol, tridecyl alcohol, stearyl alcohol, alkanols with 10-16 C-atoms, lauric acid mono-ethanolamide, lauryl amine, tallow amine, tallow diamine, etc.

It is advisable to mix the emulsifier with the filmforming additive before adding it to the mineral oil. In this case suitable mixing proportions are: 60-95 percent ethoxylated acyclic compounds and 40-5 percent film-forming additives. This mixture is added to the oil in an amount of 1-10 percent, preferably 2-5 percent, by weight of the oil. I

Also other additions may prove appropriate. Thus, the addition of an antioxidant, such as dibutyl phenol or dibutylmethyl phenol, may be considered. The addition ratio is approximately 0.5-] percent by weight of the oil.

In certain cases the addition ofa corrosion inhibitor may also be required. An acyclic amine compound containing 10-20 C-atoms, such as cetylamine or lauryl diamine, can be used for this purpose, the addition ratio being 0.5-1 .5 percent by weight of the oil.

The invention will be illustrated by the following Examples in which two mineral oils were used, i.e. one paraffin-based oil with 2.1 E/50C viscosity and one naphthene-based oil with 7.5 E/50C viscosity.

The mineral oils were mixed with an emulsifier or an emulsifier mixture in the proportion 97:3 percent by weight. The mineral oil containing the emulsifier or emulsifier mixture was then mixed with water in the proportion 5 parts by weight of mineral oil emulsifier to parts by weight of water.

In certain cases, the mineral oil emulsifier or emulsifier mixture were, before mixing, heated for 18 hours up to C. After the emulsifier-bearing mineral oil had been mixed with water, the emulsion was left to stand for one-half hour, after which the surface creaming was measured; it is stated as a percentage of the emulsion.

A very important factor is the solubility of the emulsifier, or emulsifier mixture, in the mineral oil. In order to arrive at a good, even emulsification and, above all, a long storage life, the emulsifier or emulsifier mixture should be clearly dissolved in the mineral oil. To allow comparison of the results obtained, the content of the emulsifier or emulsifier mixture in the mineral oil was at all times maintained at 3 percent by weight.

EXAMPLE 1 97 Parts by weight of a paraffin-based oil were mixed with 3 parts by weight of an emulsifier mixture containing 90 percent lauryl alcohol polyglycol ether with 3 mols of ethylene oxide per mol of lauryl alcohol, and 10 percent 50/55 oleyl/cetyl alcohol. A clear and translucent oil mixture was obtained. After mixing the emulsion, creaming amounted to 3-4 percent after one-half h.

With another, identically composed sample a heat resistance test was carried out; after formation of the emulsion this oil has showed 3-4 percent creaming after one-half h. Thus, the emulsifying capacity of the oil mixture was not reduced by heating it for 18 h to For purposes of comparison an ethoxylated nonyl phenol of the same proportions as mentioned above containing 6 mols of ethylene oxide was added to the paraffin-based oil. This mixture was, however, cloudy, unlike the preceding one which was completely clear. Cloudiness means, as has been already mentioned, that there is a great risk that the emulsion will separate under storage.

As regards the emulsifying capacity both before and after heating, which was carried out in the same way as mentioned above, creaming amounted to 3-4 percent in both cases.

EXAMPLE 2 3 Parts by weight of an emulsifier mixture containing EXAMPLE 3 3 Parts by weight of an emulsifier mixture containing 90 percent lauryl alcohol polyglycol ether with 3 mols of ethylene oxide per mol of lauryl alcohol and 10 percent coconut fatty acid diethanolamide were added to 97 parts by weight of paraffin-based oil. The emulsifier mixture dissolved completely clearly in the paraffinbased oil. The emulsifying capacity was the same as was mentioned in the preceding Examples.

EXAMPLE 4 97 Parts by weight of a paraffin-based oil were mixed with 3 parts by weight of an emulsifier mixture containing 90 percent oleyl amine polyglycol ether with 7 mols of ethylene oxide per mol of oleyl amine and 10 percent 50/55 oleyl/cetyl alcohol. The emulsifier mixture dissolved clearly in the mineral oil.

EXAMPLE 5 97 Parts by weight of a naphthene-based oil were mixed with 3 parts by weight of an emulsifier mixture containing 90 percent lauryl alcohol polyglycol ether with 3 mols of ethylene oxide per mol of lauryl alcohol and 10 percent oleyl/cetyl alcohol.

The oil mixture dissolved completely clearly in the mineral oil. As was mentioned in Example 1, the emulsifying capacity was tested first with the abovementioned oil mixture per se and secondly with the abovementioned oil mixture heated for 18 h to 180C. In both cases the emulsions indicated l-2 percent creaming after one-half h.

For purposes of comparison, a nonyl phenol polyglycol ether containing 6 mols of ethylene oxide per mol of nonyl phenol was used as an emulsifier also in this case. This product, in the proportions 97 parts by weight naphthene-based oil to 3 parts by weight emulsifier, was not clearly soluble in the mineral oil. The

emulsifying capacity, tested as described previously,

was 1-2 percent both before and after heating.

EXAMPLE 6 97 Parts by weight of a naphthene-based oil were added to 3 parts by weight of an emulsifier mixture containing 90 percent lauryl alcohol polyglycol ether 1 with 3 mols of ethylene oxide per mol of lauryl alcohol and 10 percent coconut fatty acid diethanol amide. The product dissolved clearly in the naphthene-based oil, and had the same emulsifying capacity as the emulsifier mixture mentioned in Example 5.

EXAMPLE 7 97 Parts by weight of a paraffih-based oil were mixed with 3 parts by weight of an emulsifier mixture containing 90 percent oleyl cetyl polyglycol ether with 5 mols of ethylene oxide per mol of oleyl/cetyl alcohol and 10 percent of a fatty alcohol mixture with 20 or more C- atoms in the alkyl group. The emulsifier mixture dissolved almost clearly in the oil. A 5 percent emulsion indicated.4.5 percent creaming one-halfh after mixing and One-half h after heat treatment.

The same test carried out with naphthene-based oil gave a clear solution of the emulsifier mixture in the mineral oil and the emulsion indicated 2 percent creaming before and after heat treatment.

Thus, the emulsifying capacity was'not impaired either in paraffin-based or naphthene-based oil.

EXAMPLE 8 97 Parts by weight of paraffin-based oil were mixed with 3 parts by weight of an emulsifier mixture containing 79 percent tallow diamine polyglycol ether with 3 mols of ethylene oxide per mol of tallow diamine,,20 percent oleyl/cetyl alcohol, 1 percent tallow diamine as a corrosion inhibitor. The emulsifier mixture was clearly soluble in the mineral oil and gave a fine emulsion. After one-half h before and after heating creaming amounted to 3 percent.

The same test in the naphthene-based oil gave a clear solution of the emulsifier mixture in the mineral oil, a fine emulsion, and 1 percent cream before and after heating.

Thus, the emulsifying capacity showed no change either in paraffin-based or in naphthene-based oil.

EXAMPLE 9 97 Parts by Weight of paraffin-based oil were mixed with 3 parts by weight of an emulsifier mixture containing percent ethoxylated oleic acid diethanolamide with 10 mols of ethylene oxide per mol of oleic acid diethanolamide and 30 percent oleyl/cetyl alcohol. The emulsifier mixture was clearly soluble in the oil and resulted in rapid emulsion, and the emulsion produced 5 percent cream oil before and after heating.

The test with the same emulsifier mixture in naphtheme-based oil gave an opaque solution of the emulsifier-in the oil and the emulsion produced 4 percent cream oil before and after heating.

The emulsifying capacity of the mixture was inferior to that of the preceding examples; the heating, however, did not result in any deterioration.

EXAMPLE 1O 97 Parts by weight of paraffin-based oil were mixed with 3 parts of an emulsifier mixture containing 88 percent lauryl alcohol polyglycol ether, 10 percent oleyl/- cetyl alcohol and 2 percent stearyl amine. The emulsifier mixture dissolved clearly in the mineral oil and the emulsion produced, before heating, 4.5 percent cream oil and, after heating, 5 percent cream.

The same emulsifier mixture in naphthene-based oil gave a clear solution and the emulsion produced, before and after heating, 3.5 percent cream.

EXAMPLE 1 l 97 Parts by weight of paraffin-based oil were mixed with 3 parts of an emulsifier mixture containing 90 percent ethoxylated coconut fatty acid monoethanolamide with 2 mols of ethylene oxide per mol of coconut fatty acid mono-ethanolamide and percent olive oil. The emulsifier mixture dissolved almost clearly in the oil, gave a fine emulsion and produced, before and after heating, 4.5 percent cream.

The same emulsifier mixture was almost clearly soluble in naphthene-based oil and the emulsion indicated before and after heating 3.5 percent creaming.

EXAMPLE 12 97 Parts by weight of naphthene-based oil were mixed with 3 parts by weight of an emulsifier mixture containing 67 percent oleic acid polyglycol ester and 33 percent oleyl amine. The oleic acid polyglycol ester contained 6 mols of ethylene oxide per mol of oleic acid. The emulsifier mixture dissolved opaquely in the oil and the emulsion indicated, before heating, 2 percent and, after heating, 2.5 percent creaming.

EXAMPLE 13 97 Parts by weight of paraffin-based oil were mixed with 3 parts by weight of an emulsifier mixture containing 67 percent oleic acid polyglycol ester with 6 mols of ethylene oxide per mol of oleic acid and 33 percent coconut fatty diamine. The emulsifier mixture dissolved opaquely in the oil and gave a fine emulsion indicating, before heating, 4 percent and, after heating, 4.5 percent creaming.

EXAMPLE 14 97 Parts by weight of paraffin-based oil containing 1 percent by weight oleyl amine as a corrosion inhibitor were mixed with 3 parts by weight of an emulsifier mixture containing 90 percent oleic acid polyglycol ester with 6 mols of ethylene oxide per mol of oleic acid and 10 percent oleyl/cetyl alcohol. The emulsifier mixture gave an opaque solution in the mineral oil and a fine emulsion indicating 4.5 percent creaming before and after heating.

97 Parts by weight of naphthene-based oil containing 1 percent by weight of coconut fatty diamine as a corrosion inhibitor were added to 3 parts by weight of the same emulsifier mixture. The dissolved opaquely in the oil and gave a fine emulsion indicating 2 percent creaming before and after heating.

Thus, by adding a corrosion inhibitor directly to the oil and by heating, the emulsifying capacity did not deteriorate.

What I claim and desire to secure by Letters Patent l. A method of improving a mineral oil-based oil for use in cooling metallic objects by rapidly immersing said objects in said oil, said method comprising adding to said oil l-lO percent, by weight of said oil, of a mixture consisting of:

A. 60-95 percent by weight of an emulsifier, said emulsifier being a biodegradable, ethoxylated, acyclic compound selected from the group consisting of esters, alkyl ethers, fatty acid amides and alkylamine-ethylene oxide adducts, wherein said compound contains 8-20 carbon atoms in alkyl groups and 2-15 hydrophilic, ethylene oxide units; and

B. 40-5 percent by weight of a C -C film-forming,

acyclic compound selected from the group consisting of esters, alcohols, amides and amines, said film-forming compound being neither soluble in nor dispersible by water.

2. A method of improving a mineral oil-based oil for use in cooling metallic objects by rapidly immersing said objects in said oil, said method comprising adding to said oil 1-10 percent, by weight of said oil, of a mixture consisting of:

A. 60-95 percent by weight of an emulsifier, said emulsifier being a biodegradable, ethoxylated, acyclic compound selected from the group consisting of esters, alkyl ethers, fatty acid amides and alkylamine-ethylene oxide adducts, wherein said compound contains 8-20 carbon atoms in alkyl groups and 2-15 hydrophilic, ethylene oxide units;

B. 40-5 percent by weight of a C -C film-forming,

acyclic compound selected from the group consisting of esters, alcohols, amides and amines, said film-forming compound being neither soluble in nor dispersible by water; and

C. an antioxidant selected from the group consisting of dibutyl phenol and dibutyl methyl phenol.

3. A method of improving a mineral oil-based oil for use in cooling metallic objects by rapidly immersing said objects in said oil, said method comprising adding to said oil l-lO percent, by weight of said oil, of a mixture consisting of:

B. 40-5 percent by weight of a C -C film-forming,

acyclic compound selected from the group consisting of esters, alcohols, amides and amines, said film-forming compound being neither soluble in nor dispersible by water;

C. an antioxidant selected from the group consisting of dibutyl phenol and dibutyl methyl phenol; and

D. a corrosion inhibitor selected from the group consisting of C -C acyclic amines.

4. A method of improving a mineral oil-based oil for use in cooling metallic objects by rapidly immersing said objects in said oil, said method comprising adding to said oil 2-5 percent by weight of said oil, of a mixture consisting of:

A. 60-95 percent by weight of an emulsifier, said emulsifier being a biodegradable, ethoxylated, acyclic compound selected from the group consisting of esters, alkyl ethers, fatty acid amides and alkylamine-ethylene oxide adducts, wherein said compound contains 8-20 carbon atoms in alkyl groups and 2-l5 hydrophilic, ethylene oxide units; and

B. 40-5 percent by weight of a C -C film-forming,

acyclic compound selected from the group consisting of esters, alcohols, amides and amines, said of esters, alkyl ethers, fatty acid amides and alkylamine-ethylene oxide adducts, wherein said compound contains 8-20 carbon atoms in alkyl groups and 2-8 hydrophilic, ethylene oxide units; and

B. 405 percent by weight of a C -C film-forming,

acyclic compound selected from the group consisting of esters, alcohols, amides and amines, said film-forming compound being neither soluble 'in nor dispersible by water.

Claims

1. A METHOD OF IMPROVING A MINERAL OIL-BASED OIL FOR USE IN COOLING METALLIC OBJECTS BY RAPIDLY IMMERSING SAID OBJECTS IN SAID OIL, SAID METHOD COMPRISING ADDING TO SAID OIL 1-10 PERCENT, BY WEIGHT OF SAID OIL, OF A MIXTURE CONSISTING OF: A. 60-95 PERCENT BY WEIGHT OF AN EMULSIFIER, SAID EMULSIFIER BEING A BIODEGRADABLE, ETHOXYLATED, ACYCLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF ESTERS, ALKYL ETHERS, FATTY ACID AMIDES AND ALKYLAMINE-ETHYLENE OXIDE ADDUCTS, WHEREIN SAID COMPOUND CONTAINS 8-20 CARBON ATOMS IN ALKYL GROUPS AND 2-15 HYDROPHILIC, ETHYLENE OXIDE UNITS, AND B. 40-5 PERCENT BY WEIGHT OF A C10-C26, FILM-FORMING, ACYCLIC COMPOUND SELECTED FROM THE GROUP CONSITING OF ESTERS, ALCOHOLS, AMIDES AND AMINES, SAID FILM-FORMING COMPOUND BEING NEITHER SOLUBLE IN NOR DISPERSIBLE BY WATER.

2. A method of improving a mineral oil-based oil for use in cooling metallic objects by rapidly immersing said objects in said oil, said method comprising adding to said oil 1-10 percent, by weight of said oil, of a mixture consisting of: A. 60-95 percent by weight of an emulsifier, said emulsifier being a biodegradable, ethoxylated, acyclic compound selected from the group consisting of esters, alkyl ethers, fatty acid amides and alkylamine-ethylene oxide adducts, wherein said compound contains 8-20 carbon atoms in alkyl groups and 2-15 hydrophilic, ethylene oxide units; B. 40-5 percent by weight of a C10-C26, film-forming, acyclic compound selected from the group consisting of esters, alcohols, amides and amines, said film-forming compound being neither soluble in nor dispersible by water; and C. an antioxidant selected from the group consisting of dibutyl phenol and dibutyl methyl phenol.

3. A method of improving a mineral oil-based oil for use in cooling metallic objects by rapidly immersing said objects in said oil, said method comprising adding to said oil 1-10 percent, by weight of said oil, of a mixture consisting of: A. 60-95 percent by weight of an emulsifier, said emulsifier being a biodegradable, ethoxylated, acyclic compound selected from the group consisting of esters, alkyl ethers, fatty acid amides and alkylamine-ethylene oxide adducts, wherein said compound contains 8-20 carbon atoms in alkyl groups and 2-15 hydrophilic, ethylene oxide units; B. 40-5 percent by weight of a C10-C26, film-forming, acyclic compound selected from the group consisting of esters, alcohols, amides and amines, said film-forming compound being neither soluble in nor dispersible by water; C. an antioxidant selected from the group consisting of dibutyl phenol and dibutyl methyl phenol; and D. a corrosion inhibitor selected from the group consisting of C10-C20 acyclic amines.

4. A method of improving a mineral oil-based oil for use in cooling metallic objects by rapidly immersing said objects in said oil, said method comprising adding to said oil 2-5 percenT by weight of said oil, of a mixture consisting of: A. 60-95 percent by weight of an emulsifier, said emulsifier being a biodegradable, ethoxylated, acyclic compound selected from the group consisting of esters, alkyl ethers, fatty acid amides and alkylamine-ethylene oxide adducts, wherein said compound contains 8-20 carbon atoms in alkyl groups and 2-15 hydrophilic, ethylene oxide units; and B. 40-5 percent by weight of a C10-C26, film-forming, acyclic compound selected from the group consisting of esters, alcohols, amides and amines, said film-forming compound being neither soluble in nor dispersible by water.

5. A method of improving a mineral oil-based oil for use in cooling metallic objects by rapidly immersing said objects in said oil, said method comprising adding to said oil 1-10 percent, by weight of said oil, of a mixture consisting of: A. 60-95 percent by weight of an emulsifier, said emulsifier being a biodegradable, ethoxylated, acyclic compound selected from the group consisting of esters, alkyl ethers, fatty acid amides and alkylamine-ethylene oxide adducts, wherein said compound contains 8-20 carbon atoms in alkyl groups and 2-8 hydrophilic, ethylene oxide units; and B. 40-5 percent by weight of a C10-C26, film-forming, acyclic compound selected from the group consisting of esters, alcohols, amides and amines, said film-forming compound being neither soluble in nor dispersible by water.