US2697072A

US2697072A - Emulsion type drawing compounds containing carboxyalkyl cellulose salts

Info

Publication number: US2697072A
Application number: US230710A
Authority: US
Inventors: Roden Harry
Original assignee: Texaco Inc
Current assignee: Texaco Inc
Priority date: 1951-06-08
Filing date: 1951-06-08
Publication date: 1954-12-14
Anticipated expiration: 1971-12-14

Description

United States Patent EMULSION TYPE DRAWING COMPOUNDS CON- TAlNlNG CARBOXYALKYL CELLULOSE SALTS HarryT-Roden, Port Nec'hes, 'Tex., assignor to The Texas Company, New York, N. Y., a corporation of Delaware No Drawing. Application June 8,1951, Serial No. 230,710

'13 Claims. '(Cl. 252-18) This inyentionrelates to lubricants for metal working processes. ,More particularly it relates to lubricants of the emulsion type containing a solid tiller and a water soluble salt-of carboxyalkyl cellulose.

In metal working processes such as drawing, rolling, pms FP Q SmE, .itis nec ss ry t mplo alub cant .to seduce thefnctiqn be w en the sl d n metal ,surfaces {to prevent .stickin and scoring of thewwork and excessive --.w.ear.-on the ie. ;In order to .efiectiyely separate -.th e ;metal.;-s urfiaces under the high pressures em ploy dan such proc s s, i i rusual yn c s ry to. e 11103 lubricants -,co,ntaining .inert ,fillers such .asflgraphite, talc, bentomte, chalk, .etc. These inert materials are \usuallyapplied-to the surface of ,the workin th form .of asuspension inaliquid carrier, suchas water, a light minerahoilqor eanemnlsion.

.The emulsion-type lubricant containing an inert filler is the; most; generallysatiefactory lubricant for cold ,metal itonnmeap cesscs, (s nc y reas n of in both i y d sohd snspension ingredients it serves .as .a .kdouble-functioning lubricant, and in addition is easily remoyed after :;use bywashing'ewith watenor-With. analkali solution. For

:.the sake of convenience randieconomy, lubricantsof this type :are ordinarily prepared "by :themanufacturer in the :consistency of a soft grease concentratehaving the S lid --fil.en.d1s;persed therein and; containing only a small, amount of; Water suflicient @to form a stable composition. This concentrate is then further diluted with water in vthe -Shop .to the :desired concentration of lubricant accord.

'ingwtothe;specificmequirements. of the operation in which ,itdsito beemployed. v

while-a numberiof different compositions-of thea-bove type whiclrihave; been. employed heretoforetin metal .workng operations ;have;ag-iyen satisfactory .lubrication .in rela- ;t1vely -.concent rated form, as for example in -,a dilution 'rat-ioof: 1 (0 E1- or less, 1 they sare:-generallyunsatisfactory at gh-igher idilutions, schiefly -;be ca,us.e ,the emulsions thus ,producedhave-insufiicient viscosityand adhesiveness tonietal to form lubricating films-.oftthe .necessary thickness upon .the surface-ofwthe work. Another difficultyis thatthe remulsionfbreaks down ,either on standingor in useso that --an.-o.i .o.-fihnrwhich cannot be removedbywashing with another difficulty is that the particles ofjfiller material tend to separate and sediment when the emulsionfis pers-mitted-togstand'iimdilutediform.

zstn. accordance-:Wi-tb-nnyyention, fan improved ;lnbri- .1oating;;composition :for zthetzcold forming of -meta-ls. com- :prisessan r aqueousemulsion of .-:a mineral lubricating :Qi containing asolid :filler and a small amount of a water soluble salt-ofa carboxyalkyl cellulose. M-y.-..preferr ed composition is/an'aqueous emulsion ofa mineral'lubricating oil-containing aifatty acidsoap as an -;emulsif-yi ng agent and'a solidfillercomprising in major proportion .calciumca'rbonate in'finely *dividedform 'The'composition is pre'ferably. siighftly alkaline with a small-amount of free alkali.

l ica ing;c mp n .cf. .thelah rcmcompos ion f mco hw dh nt. thick. filmsup nmeta .surtace when employe v in either. concentr ed -.or.. ilut Q m' "the :emulsify, readily with .Water andiform uniform and {emulsions-of goodyisces-ity tBIid'JQ h-Q d sir b 1 :characteristics oveni-aawide range of ehaidasennifcrmn t iorlys ouiponent.

ice

erties do not deteriorate upon standing by loss of emulsion or by settling fontof the solid particles.

The water soluble salts of carboxya'lkyl cellulose employed are chiefly alkali metal or alkaline earth metal 5 salts of cellulose derivatives in .Which a portion of thehydroxy groups are ether-ified with carboxy-containing aliphatic groups. As examples .of such compounds which may be mentioned are sodium carboxymethyl cellulose, ammonium carboxyethyl cellulose, calcium carboxypropyl cellulose and potassium carboxyhexyl cellulose. The preferred compound of this ,class is sodium carboxyrne'thyl cellulose, which may be readily obtained in the known manner by dissolving cellulose fibers in sodium hydroxide solution to accomplish some degradation in lthe molecular chain length and to form sodiiim cellulose, which is then treated with monochloracetic acid. In order to obtain a water soluble product, the'proce'ss is carried out in such a manner {that at least about :10 per cent and preferably about 13 per cent of thehydroxy groups are .etherified.

A number of products of this character areavailable commercial-ly, a particularly suitable product being .the'water soluble sodium carboxymethyl cellulose sold by the Drilling Specialties Co, Bartlesv ille, Oklahoma, under the trade name of Driscose. This has been employed extensiyely-as a drilling mud additive. i

The carboxyalkyl cellulosesalts may be present in extremely smallarnounts, such as 0.05 per cent or less, or in amounts above 1 per centWhe're-the compositions are to'be diluted with water in high dilution ratios such as 1:3 ;or higher. For {most purposes they are employed i i-amounts betweenabout 0.1 and l.pe r cent,.and.pre ferably from about 0,2 to 0.5 per cent by Weight based o'nflthe weight of the undiluted composition.

"The emulsifying agentemployed in these compositions is preferably an alkali metal fatty acid soap, obtained by saponifying a fat of animal, jyegetable or synthetic origin with tan :alkali metal hydroxide or other compound.

A particularly suitable soap' is the sodium soap of Wool fat. in additionto-the fat'tyacid soap other emulsifying 40 agents may be employed such as petroleumsulfonates.

The "lubricating oil component may be any suitable medium viscosity fraction from a paraffinic, naphthenic or mixed base crude, obtained by simple distillation or by any of the usualrefini-ng-methodssuch assolvent-treating,

4.5 acid treating, etc. It is preferably a distillate oil fraction from -a naphthenic base crude {raving an SUS viscosity atlOO" ---F.'"in the range from about 275 to about 325.

The solid filler is preferably calcium carbonate or calcium carbonate mixed with'a-minor amount of a different soli gsuch as tflg "oyster shellorclays of various .tynes- (Eli calc um ce bcnatam y b bt n y g inding 1 a natural {material i such as chalk. to suitable particle s z c ma b qrr a c 'ehs c l Az e ip t ca ciu eca bona is p ef rably ed, hav n a pa t cle bstantially below -about-325 mesh but not ,rnore than ab 4 th i ;-.c

- 10 :micr

cha c r.

Julonf czthcr mponsat recite a v at ewmpositioninay also ontaimminor amounts .of .otherrnate al c e yp 'c ti r n emp o e n l i .Mine compositions-of -,this ;ch aracter such as anti foarn, agents, extrem p e u a ent ucha st u tcon a n c mpound materi i m qccmp u s 5 :0 mp ve X th app .ance oro'dorLnfthe composi on. .and \SOxfQIllh.

gin concentrated form, the lubricating remulsions of this invention may cornprise about 110. to per cent 1 by weight of solid filler cornprising ,in major proportion larly uit able materiali [of this all Ae t e eas men 70 calcium .11' Q a o t .0 pe c n by W h atty -.-acid,soapcontainingia small amount of .free :BJE IQlltfOJ -;to l percentormore by .we ghLof ,alkali,

a Wat l0 --Wetc an th 19b I1 medium viscosity.

Composit ons of fil hau ed? t ,by .yyeight .of particles .beloyv.

eisoluble; salt,. ofearboxyalkyl; cellulose, about 0.5

about 0.1 to 0.5 per cent by weight of sodium carboxymethyl cellulose, about 1 to 5 per cent of water and a naphthene base lubricating oil having an SUS viscosity at 100 F. of about 275 to 325. For more severe d awing operations the emulsion preferably contains about 32 to 38 per cent by weight of calcium carbonate, about to 16 per cent by weight of the fatty acid soap and about 0.1 to 0.5 per cent by weight of sodium carboxymethyl cellulose. For deep drawing operations, the emulsion preferably contains about 52 to 5 8 per cent by weight of calcium carbonate, about 8 to 14 per cent by weight of the fatty acid soap and about 0.2 to 1 per cent by weight of sodium carboxymethyl cellulose.

The above compositions may be used directly in the form of a paste by spreading them over the surface of the metal to be pressed, rolled or otherwise shaped, or they may be diluted with water to form free-flowing emulsions. For example, they may be diluted with water in a dilution ratio of l to l or higher, such as in a dilution ratio 1 to 2 or even 1 to 3 in some cases.

The emulsion may be made up by conventional procedures. For example, a fat such as tallow, palm oil, degras or other suitable saponifiable material may be saponified with an alkaline solution such as sodium or potassium hydroxide, and the oil, filler, water and carboxyalkyl cellulose salt worked in gradually.

According to my preferred method for preparing these lubricating compounds, the saponification is carried out at 2903l0 F. employing a small excess of alkali, amounting to from about 0.1 to about 0.5 per cent excess based on the weight of the finished product as calculated from the saponification number of the fat, and in the presence of a portion of the oil which forms the oil phase in the final product. Following the saponification, the mixture is maintained at this temperature until the soap is dehydrated and the remainder of the mineral oil added with stirring. The calcium carbonate is then added slowly with continued stirring at a temperature of 260-280 F. When the temperature has dropped below about l90200 F., an odorant material, water and carboxyalkvl cellulose salt are added and the mix cooled to l05-ll0 F. with continued stirring until the compound is uniform and of a soft buttery consistency of about 300 penetration at 77 F. The product is drawn atl 513111; temperature and is not reheated in excess of The following example is given to illustrate the preparation of a typical compound of my invention and to demonstrate its superior properties as compared with a drawing compound of the usual type employed at the present time.

EXAMPLE A ch arge comprising 950 pounds of degras having a saponification number of 120, 182 pounds of naphthene base lubricating oil having an SUS viscosity at 100 F. of 300, 400 pounds of water, and 182.5 pounds of a 49 per cent solution of caustic soda, corresponding to an excess of 0.1 per cent of alkali based on the weight of the finished product, was introduced into a steam heated kettle and heated with stirring for 2 to 3 hours at 290 F. to acconiplish saponification and dehydration. The materiatwas then maintained at this temperature for an additional 3 hours while 3704 pounds of the naphthene base lubricating oil was worked in slowly. The heating was then discontinued and 2700 pounds of S wansdown calcium carbonate added gradually with stirring. In order to improve the odor of the composition 25 pounds of pine tar was added also, when the temperature had dropped below 200 F. With continued stirring, 194 pounds of water was next added gradually during 1 hour while the temperature was maintained at 190 F., and finally 16 pounds of Driscose in admixture with 100 pounds of the calcium carbonate while the temperature was about 140 F. The stirring was continued for two hours after the "Driscose was added, and the batch finally drawn at 105 F.

The product obtained by the procedure described above was a soft paste, light brown in color and of a smooth, non-grainy texture, having a penetration at 77 F. of 331. The test results given in the following table show the improved coverage and adhesion properties of this compound in comparison with those of an emulsion type lubricant of the usual composition. of the table is that described above. Lubricant No. l was prepared with the same lubricating oil base and Lubricant No. 2

with the same soap, but with a dilferent type of filler and without the sodium carboxymethyl cellulose.

Table Lubricant N0 a 1 Comoosltion, percent by weight:

Sidinm soup of degr'ts Lubricating oil Calcium cerbona Talc Pine tar Tests:

Emulsifiability Viscosity, 77F., cps. 1:1 dilution After 24 hours Film weight, gm./sq. in., 1:1 diluti0n Sedimentation at 77 F., 1:2 di1utiou After 24 hours After 7 days After 14 days Visibile sedimentation.

The viscosity values in centipoises given in the above table were obtained by means of the Brookfield Synchro Electric Viscometer upon samples which were prepared by mixing together grams of the test material with 100 grams of distilled water at 77 F. until uniform.

The film weight values of the table were obtained in the following manner: A thin piece of polished steel plate, about 1.75 inches by 4 inches by 0.05 inch thick was weighed to the nearest 0.1 gram and immersed 2 inches into a beaker of the compound diluted one to one with distilled water and at a temperature of 77 Ir. After a few seconds it was removed, drained in a vertical position for one minute and reweighed. The weight of diluted compound retained on the plate was calculated from the increase in weight and the square inches 01 immersed surface.

The sedimentation test of the table was carried out by gradually diluting a 100 gram sample of the test compound with 200 grams of distilled water and permitting the diluted compound to stand in a stoppered graduate for 2 weeks at 77 F. At the end of the indicated periods the amount of sedimentation was observed.

The results given in the above table show the outstandingly superior adhesive and coverage properties of a typical compound of my invention over those of an emulsion type lubricant of conventional composition. These superior lubricating properties are strikingly demonstrated by the increase film weight obtained with my compound, amounting to over 10 times that obtained with the known compound. In addition, no sedimentation of filler occurred after 14 days with my compound in a 1:2 dilution with water, whereas in the case of the other compound sedimentation took place within 24 hours.

Obviously many modifications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

I claim:

1. An improved lubricating composition for metal working which consists essentially of an aqueous emulsion of a naphthene base lubricating oil having an SUS viscosity at 100 F. of about 275 to 325, containing about 5 to 20 per cent by weight based on the weight of the composition of a soap obtained by saponifying wool grease with a small excess of alkali, about 10 to 70 per cent by weight based on the weight of the composition of finely divided calcium carbonate, about 0.1 to 1 per cent by weight based on the weight of the composition of sodium carboxymethyl cellulose, and about 0.5 to 10 per cent by weight based on the weight of the composition of water.

2. An improved lubricating composition for metal working which consists essentially of an aqueous emulsion of a naphthene base lubricating oil having an SUS viscosity at 100 F. of about 275 to 325, containing about 12 to 18 per cent by weight based on the weight of the composition of a soap obtained by saponifying wool greasewith a small excess of alkali, about 15 to 20 per cent by weight based on the weight of the composition of calcium carbonate having a particle size below about 325 mesh, about 0.1 to 0.5 per cent by weight based on the weight of the composition of sodium carboxymethyl cellulose, and about 1 to 5 per cent by weight based on the weight of the composition of water.

3. An improved lubricating composition for metal working which consists essentially of an aqueous emulsion of a naphthene base lubricating oil having an SUS viscosity at 100 F. of about 275 to 325, containing about to 16 per cent by weight based on the weight of the composition of a soap obtained by saponifying wool grease with a small excess of alkali, about 32 to 3.8 per cent by Weight based on the weight of the composition of calcium carbonate having a particle size below about 325 mesh, about 0.1 to 0.5 per cent by weight based on the weight of the composition of sodium carboxymethyl cellulose, and about 1 to 5 per cent by weight based on the weight of the composition of water.

4. An improved lubricating composition for metal working which consists essentially of an aqueous emulsion of a naphthene base lubricating oil having an SUS viscosity at 100'F. of about 275 to 325, containing about 8 to 14 per cent by weight based on the weight of the composition of a soap obtained by saponifying wool grease with a small excess of alkali, about 52 to 58 per cent by weight based on the weight of the composition of calcium carbonate having a particle size below about 325 mesh, about 0.2 to 1 per cent by weight based on the weight of the composition of sodium carboxymethyl cellulose, and about 1 to 5 per cent by weight based on the weight of the composition of water.

5. Claim 1 wherein the lubricating composition is diluted with water in a dilution ratio of from about 1:1 up to about 1:3.

6. An improved lubricating composition for cold metal working which consists essentially of an aqueous emulsion of a mineral lubricating oil, containing about 10 to 70 per cent by weight based on the weight of the composition of calcium carbonate in finely divided form, about 5 to per cent by weight based on the weight of the composition of an alkali metal soap, about 0.1 to

1 per cent by weight based on the weight of the com- -1 position of a water soluble salt of carboxyalkyl cellulose wherein the alkyl group contains from 1 to 6 carbon atoms, and about 0.5 to 10 per cent by weight based on the weight of the composition of water, said composition being free from excess fatty acid and slightly alkaline with a small amount of free alkali metal hydroxide.

7. An improved lubricating composition for cold metal working which consists essentially of an aqueous emulsion of a mineral lubricating oil, containing about 10 to per cent by weight based on the weight of the composition of calcium carbonate in finely divided form, about 5 to 20 per cent by weight based on the weight of the composition of an alkali metal soap, about 0.1 to l per cent by weight based on the weight of the composition of a water soluble salt of carboxymethyl cellulose, and about 0.5 to 10 per cent by weight based on the weight of the composition of water, said composition being free from excess fatty acid and containing about 6 0.05-0.5 per cent by weight of free alkali metal hydroxide.

8. A lubricating composition according to claim 7 in which the water soluble salt of carboxymethyl cellulose is sodium carboxymethyl cellulose.

9. A lubricating composition according to claim 7 in which the soap is an alkali metal soap obtained by saponifying wool grease.

10. A lubricating composition according to claim 7 in which the mineral lubricating oil is a naphthene base lubricating oil having an SUS viscosity at F. of about 275 to 325.

11. An improved lubricating composition for metal working which consists essentially of an aqueous emulsion of a mineral lubricating oil, containing about 5 to 20 per cent by weight based on the weight of the composition of an alkali metal fatty acid soap, about 10 to 70 per cent by weight based on the weight of the composition of an inert finely divided filler, about 0.1 to 1 per cent by weight based on the weight of the composition of a water soluble salt of carboxyalkyl cellulose wherein the alkyl group contains from 1 to 6 carbon atoms, and about 0.5 to 10 per cent by Weight based on the weight of the composition of water, said inert filler being selected from the group consisting of finely divided calcium carbonate, and a major proportion of finely divided calcium carbonate mixed with a minor amount of another inert filler selected from the group consisting of talc, oyster shell and clay.

12. Claim 11 wherein the lubricating composition is diluted with water in a dilution ratio of from about 1:1 up to about 1:3.

13. An improved lubricating composition for metal working which consists essentially of an aqueous emulsion of a mineral lubricating oil, containing about 5 to 20 per cent by weight based on the weight of the composition of an alkali metal fatty acid soap, about 10 to 70 per cent by weight based on the weight of the composition of finely divided calcium carbonate, about 0.1 to 1 per cent by weight based on the weight of the composition of a water soluble salt of carboxyalkyl cellulose wherein the alkyl group contains from 1 to 6 carbon atoms, and about 0.5 to 10 per cent by weight based on the weight of the composition of water.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,409,658 Brann Mar. 14, 1922 1,449,379 Bullock Mar. 27, 1923 1,617,455 Montgomery Feb. 15, 1927 2,003,564 Thorpe June 4, 1935 2,112,632 Montgomery Mar. 29, 1938 OTHER REFERENCES CarboxymethylcelluloseUses and Applications, Hollabaugh et al., Ind. and Eng. Chem., Oct. 1945, vol. 37, No. 10, pages 943-947. (Copy in Div. 64.)

Claims

1. AN IMPROVED LUBRICATING COMPOSITION FOR METAL WORKING WHICH CONSISTS ESSENTIALLY OF AN AQUEOUS EMULSION OF A NAPHTHENE BASE LUBRICATING OIL HAVING AN SUS VISCOSITY AT 100* F. OF ABOUT 275 TO 325, CONTAINING ABOUT 5 TO 20 PER CENT BY WEIGHT BASED ON THE WEIGHT OF THE COMPOSITION OF A SOAP OBTAINED BY SAPONIFYING WOOL GREASE WITH A SMALL EXCESS OF ALKALI, ABOUT 10 TO 70 PER CENT BY WEIGHT BASED ON THE WEIGHT OF THE COMPOSITION OF FINELY DIVIDED CALCIUM CARBONATE, ABOUT 0.1 TO 1 PER CENT BY WEIGHT BASED ON THE WEIGHT OF THE COMPOSITION OF SODIUM CARBOXYMETHYL CELLULOSE, AND ABOUT 0.5 TO 10 PER CENT BY WEIGHT BASED ON THE WEIGHT OF THE COMPOSITION OF WATER.