US2355995A - Water-soluble cutting composition - Google Patents

Description

range, and asmall stream of chlorine gas Patented Aug. 15, 1944 2,3 5,! WATER-SOLUBLE OUTING COMPOSITION Iohn n. Morgan, South Oran and amen '11.

1. East I orange, Service Oil Company,

lvania ration of Penny 3., alaignors to Cities New York, N. 1., a corpo- No application March 9, 1942,

Sel'lnlNo. 438,988

llclalml.

This invention relates to improvements in metal cutting compositions adapted to cool and lubricate metal cutting tools and the metal being out. More particularly the invention relates to improved water soluble bases adapted to be introduced into the bottom of the retort and bubbled through the oil therein at a rate of about one gram per minute. After the fiow of chlorine used in the preparation of metal cutting compositions.

The present application is a continuation-ln- 11 7 part of the applicants pending application Serial 1 No. 389,760, flled April 22, 1941, for watei'joliible cutting compound and method or manufac 1 withintherangcoi300to850F.

ture."

It has been discovered that certain of the intermediate reaction products obtained in accordance with the disclosure of this prior application may be used in conjunction with the water soluble material thereof in the making of improved cutting compositions.

According to the present invention, the improved'cutting compositions or bases include: (1) as a principal constituent a water soluble mate rial obtained by chlorinating, phosphorizing and sulfonating a heavy petroleum oil (hereinafter had been started through the retort, the upper end thereof being vented, 5 cc. of P011 was slowly introduced into the bottom of the retort and flushed in with an additional 50 cc. of the Duvall crude oil. These steps required eight or ten minutes, after which the introduction or the chlorine was continued for a period of thirty minutes, a

while the temperaturein the retort was held The intermediate reaction product iormed by the above procedure was withdrawn from the retort through a drawofi valve at the bottom and comprised apprordmately 323 cc. or liquid having a specific gravity or 0.93 (300 gms.). The retort identified as product 0); (2) a substantial proportion of a chlorinated, phosphorized andsulionated oil (hereinafter identified as product B) (3); a relatively small proportion of a glycol ester such for example as diglycol laurate; (4) a relatively small proportion of a high molecular weight fatty acid such for example as oleic acid, and (5) a relatively small proportion (0.2 to a 0.6%) of an oxidation inhibitor such as triethanolamine or other water soluble organic amine. The cutting composition or base may also include from a relatively small proportion up to a substantial proportion of a'chlorinated and phosphorized oil (hereinaiteridentified as product A) Since some of the products used in the compositions of the present invention are preferably -made in accordance with the disclosure of the above-mentioned pending application, it will be 1 noted that according to the procedure therein disclosed, a crude petroleum oil is converted to produce an intermediate reaction product by reacting the crude oil at moderate temperature with an active inorganic halide and chlorine in the presence of a catalyst. The intermediate reaction product is thereupon subjected to a sulfonation operation to produce a tarry mass which. is diluted with water, neutralized to Congo red indicator and concentrated to provide the'base for the metal cutting compound.

.The pending application describes a specific example in which a batch of Duvall crude oil having an A. P. I. gravity of about 21 and comprising 275 cc., was heated to a temperature or from 300 to 350F. and introduced into a vertical retort substantially filled with loose graphite chips. The retort was maintained in this temperature was found to be clean and free of any sludge. The 300 grams of intermediate product (product A referred to above) was cooled to room temperature and then treated with grams or chlorosulfonic acid, added slowly to avoid overheating and. foaming, and the resulting mixture was permitted to react with mild stirring for a period of about two hours. The resulting material comprised an upper layer of black tarry viscous material, and a lower liquid oil layer which was separated'out and recovered. This oil is the product B referred to above and is used directly in the improvedcomposltions. The tar-like material comprising 138 gms. was dissolved in 290 cc.

of water, by warming, and was then neutralized to Congo red with a 25% solution of sodium hydroxide, 1'7 grams of NaOH being required.

The neutralized material comprising approximately 493 gms. was concentrated by evaporation to about 146 gms. The resulting concentrate separated into two layers, the upper of which was a brown viscous mass, while the lower layer comprised a highly fluorescent aqueous solution. The upper layer of 123 gms. and comprising the desired product, was dissolved in water to give a specific gravity of from 1.055 to 1.065, then settled (centrifuging may be used) to remove any water-insoluble residue. In this instance 350 gms. of water were required to give the solution a specific gravity of 1.060. This material is a concentrate which may have a gravity of from 1.040 to 1.065, and is not intended to be used directly, but should be diluted to at least approximately 20 to 1 with water.

This concentrate is the water soluble product C referred-to above. This material is a water solution comprising about /4 water and upon lurther dilution gives a clear or transparent solution even with rather hard water. The product 7 was i eluding rusting of iron and steel. I The concenthen incorporated into the water solution. Fi-

nally the triethanolamine is added to complete to be superior'to a known commercial cutting composition.

The pending application describes the characteristics of Duvall crude oil and points out that while the use of naphthenic petroleum oils were preferred (of the type of DuvalD, other heavy petroleum oils could be used in the process described above. Placedo crude oil has been used.

the base composition. While the above dilution of three to one applies in the case of products from Duvall crude, a corresponding dilution of four to one was used in the case of Placedo crude with the same specific gravity of 1.050 for the concentrate.

A cutting composition for special and extreme conditions is made with one part of the above base mixture and ten parts of water. A stand- It was also pointed out that the conversion reaction may becarried out in the presence of other catalysts which are equivalent to graphite, as for example, activated carbon, activated charcoal, silica gel and other adsorbent catalysts such as activated clays and fullers earth; that such reaction carried out in the retort may also be promoted by other active inorganic halides which are equivalent to the preferred PClz, such for example as A1013, BCls, FeCla, AlBra, SbCla, SnCla. and ZnCla; that instead of using chlorine, other equivalent chlorinating agents adapted to chlorinate some of the constituents in the oil could V be employed; and that other suli'onating agents such as S03, fuming sulfuric acid, and other equivalent agents may be used for the sulfonation operation.

The pending application also points out that the chemical constitution of the water soluble material, product C, was not known, but that its exceptional quality and eflectiveness was believed to be due at least in part to the simultaneous treatment of the high gravity oil with the chlorinating agent and the active inorganic halide; and that the preferred product comprised carbon compounds containing chemically combined phosphorus, chlorine and sulfonate groups, other electropositive atoms or active inorganic halides being useful in place of phosphorus,

From the foregoing description of the procedure for making certain 01' the improved ingredients for use in the cutting compositions of the present invention, it should be apparent that considerable variation in the compositions may be'made. However, the following examples will serve to illustrate cutting composition bases in accordance with the present invention, the percentages being by volume.

- Example 1 uct C) .83.75 (2) 011 containing combined phosphorus,

chlorine and sulfonate groups (product B) 12 (3) Diglycol laurate 3 (4) Oleic acid 1 (5) Triethanolamine 0.25

In preparing the cutting composition base from these constituents, the concentrate, product C,

is preferably diluted three to one with water, a I

mixture is made of the oil product B, the diglycol laurate and the oleic acid and this mixture is 78 ard productwill have a dilution ratio of 1 to 20. Example 2 3 A water soluble base for preparing cutting compositions by addition constituents:

( 1) Mixture of water-soluble carbon compounds containing combined phosphorus, chlorine and sulfonate groups in a water solution of 1.050 sp. gr. (product C) (2) 011 containing combined phosphorus, chlorine and sulfonate groups (product B) 10 (3) 'Digly'collaurate 3.0 (4) Ofleicac'id 1 (5) Triethanolamine 0.25 (6) Heavy hydrocarbon oil containing chemically combined chlorine and phosphorusgroups (product A) 4 The oils A and B, the diglycol laurate and the oleic acid-are preferably mixed and then added to the diluted product C, as in Example 1, the triethanolamine being added last.

The cutting compositions may have the same,

dilutions as in Example 1.

Example 3 s1 (2) 011 containing combined phosphorus,

chlorine and sulfonate groups (product B) 8 (3) Diglycol laurate 3 (4) Oleicacid 1 (5) Triethanolamine 0,25 (6) Heavy hydrocarbon oil containing chemically combined chlorine and phosphorus groups (product A) 6.75

The base composition is preferably made up in accordance with the procedure of Examples 1 and 2; The dilutions of the base for the preparation of the cutting compositions may be. the same as in Example 1.

The oil products A and B, used as constituents in the bases of the foregoing examples are not normally soluble in water-but are brought into solutioh or into a very intimate colloidal dispersion in water by the water soluble product 0, the diglycol laurate, thetriethanolamine, and the oleic acid. The product C is a water solution of which only a small proportion is carbon compounds, produced by the above described process. Cutting compositions which include both of the oils A and B are practically clear solutions but in of water has the following Per cent some cases may have a slight opalescentappearance. The oil product A is preferably only used in making up the bases to replace a portion of theoil product B so that the proportion of'the water plasticizer. The plasticlzing action of the laurate is made use of primarily after the cutting operation is completed and the work is left coated with the coating composition. The laurate prevents p the formation of a dry brittle coating. The oleic.

acid functions primarily as a dispersing agent for the oil products A and B and as a plasticizing aid.

vVarious other base compositions may be made from the constituents listed above or their equivalents. The content of product C orits equivalent may vary from about 80% to 85%, that of product B from 8% to 12%, and that of product A when used, from 1 to 7%. Instead of using diglycol laurate, other diglycol esters of high molecular weight fatty acids may be used, and these or the laurate may comprise from about 2% to 4% of the base mixture, 3% however being preferred. Other fatty acids than oleic acid may be used, such as other well-known high molecular weight fatty acids, as stearic and linoleic. The percentage of this constituent may vary from 0.5% to 1.5%. The final diluted product'should preferably have a pH value of from 7.2 to about Having described the invention in its preferred form, what is claimed as new is:

1. A metal cutting base composition comprising approximately 83.75% of a water-soluble product including chlorinated, phosphorized and sulfonated mineral oil, approximately 12% of a normally water-insoluble oil product including a chlorinated, phosphorized and sulfonated mineral oil, 3% of diglycol laurate, 1% of oleic acid,

and approximately ganic amine.

2. A metal cutting base composition comprising approximately 82% of a water-soluble product including chlorinated, phosphorized and sulfonated mineral oil compounds, approximately 10% of a normally water-insoluble chlorinated,

0.25% of a water soluble orphosphorized and sulfonated mineral 'oil, 'aping from about to about of a watersoluble product including chlorinated, phosphorized and sulfonated constituents of mineral oil, from about 8% to about 12% of a normally water-insoluble chlorinated. phosphorized and snlfonated mineral oil, from about 2% to 4% of di-glycol laurate, from 0.5% to 1.5% of oleic acid, and from 0.2% to 0.6% of a water-soluble organic amine.

4. A metal cutting base composition comprising from about 80% to about 85% of a watersoluble product including chlorinated, phospho-' rized and sulfonated constituents of mineral oil, from about 8% to about 12% of a normally water-insoluble chlorinated, phosphorized and sulfonated mineral oil, from 1% to about 7% of a normally water-insoluble chlorinated and phosphorized mineral oil, from about 2% to 4% of a di-glycol ester, and from 0.5% tov 1.5% of a high molecular weight fatty acid. I

5. A metal cutting base composition as defined by claim 3 in which said water-soluble product is asolution, at least about three-fourths of which is water.

6. A metal cutting base composition as defined by claim 3 in which said mineral oil is a naphthenic base petroleum.

7. A metal cutting base composition as defined by claim 4 in which said water-soluble product is a solution of which about three-fourths is water.

8. A metal cutting base composition as defined by claim 4 in which said mineral oil is a naphthenic base petroleum.

9. A metal cuttingibase composition as defined .by claim 3 in which said water soluble product is substantially diluted wilth water, a mixture made of said water insoluble oil, said laurate and said oleic acid, and the resulting mixture incorporated into said diluted product.

10. A metal cutting base composition as defined by claim 4 in which said composition is made up by diluting said water-soluble product substantially with water, mixing said waterinsoluble oils, di-glycol ester and said fatty acid together, and thereafter incorporating the resulting mixture into the diluted water-soluble