CA1210384A

CA1210384A - Metalworking with an aqueous synthetic lubricant containing polyoxypropylene-polyoxyethylene- polyoxypropylene block copolymers

Info

Publication number: CA1210384A
Application number: CA000445286A
Authority: CA
Inventors: Joseph T. Laemmle
Original assignee: Aluminum Company of America
Current assignee: Howmet Aerospace Inc
Priority date: 1983-01-20
Filing date: 1984-01-13
Publication date: 1986-08-26
Also published as: AU2361584A; BR8400247A; EP0115926A1; NO840197L

Abstract

Abstract of the Disclosure A method of metalworking including the step of applying to a metal object a synthetic aqueous lubricant composition. The composition comprises a water-soluble mixture of polyoxypropylene-polyoxyethylene-polyoxypropylene block copolymers, a water-soluble carboxylic acid, a water-soluble alkanolamine and water. The metalworking method preferably includes a step of either hot rolling or cold rolling. The method is especially suitable for use on aluminum and aluminum alloy material.

Description

3~3~

The present invention relates to metalworking operations such as the cold rolling and hot rolling of aluminum and aluminum alloys. More particularly, the invention relates to an aqueous synthetic lubricant composition for use in such metalworking operations.
In the rolling of metals such as aluminum and aluminum alloys, it is customary to flood the rolls and the workpiece with a coolant for the purpose of carrying away heat generated by the operation. It is also customary ~o employ the coolant in combination with various agents having load bearing and friction-modifying properties for reducing friction between the rolls and the workpiece. It has heretofore been the practice to use for such purpose aqueous compositions containing such lubricating agents as emulsified petroleum and non-petroleum additives. In order to perform satisfactorily on an industrial scale, an aqueous lubricant fluid must meet several important require-ments.
Among the requirements for a satisfactory metalworking lubricant are corrosion-inhibiting properties and stability under conditions of operation. While various fluids may possess such characteristics, there are also other important requirements that should be met. Among these requirements is the avoidance of deposits on the rolls and workpiece following the rolling operation. Such deposits result from drying of the fluid, and they are difficult to remove. Other important requirements include avoidance of excessive foam formation.
Metalworking lubricants in the form of aqueous solutions have generally not been able to satisfy all of the foregoing requirements prior to the present invention.

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Metalworking methods using single phase aqueous lubricant compositions are known in the prior art. ~lowever, prior to the present invention, metalworking with single phase aqueous lubricant compositions was no~ in widespread cornmercial use because of the inability of such compositions to satisy simultaneously each o~ the requirements listed above.
Beaubien et al U.S. Pa~ent No. 2,825,693 claims a metalworking lubricant concentrate comprising about 5-20% each of a block polyoxypropylene-polyoxyethylene copolymer and a random polyoxypropylene-polyoxyethylene copolymer, about 1-12%
each of sodium nitrite and ethanolamine, and about 0.01-5% of an unsaturated high molecular weight fatty acid. The block polyoxypropylene-polyoxyethylene copolymers disclosed by Beaubien et al are not conjugated in the order polyoxypropylene-polyoxyethylene-polyoxypropylene, as claimed in the present invention.
Reamer U.S. Patent No. 2,981,686 discloses an aqueous metalworking lubricant comprising a water-soluble hetero-copolymer of a mixture of oxyethylene and oxypropylene groups. The Reamer patent states that block copolymers of ethylene oxide and propylene oxide are undesirable in such lubricants because of the tendency of these copolymers to produce "undesirable frictional problems, foaming, instability, and the like".
Davis U.S. Patent No. 3,374,171 claims a cutting fluid containing about 5-40% of a water-soluble alkanolamine, about 0.1-9% of a saturated organic acid having about 6-9 carbon atoms per molecule, and about 0.5-20% of a water-soluble polyoxyalkylene glycol. The Davis patent contains no specific ~ 8 ~

teaching of the utility of polyoxyethylene-polyoxypropylene-pol~Joxyethylene block copolymers as ingre~ients of aqueous metalworking compositions. In addition, Davis cautions against the use of higher molecular weight saturated organic acids. He states that such higher organlc acids can result in poor hard water stability, reduced corrosion-inhibiting properties and high foaming tendencies. These problems are said to lead to clogged filters, poor rust protection and reduced tool life in areas where hard water is encountered.
Felton U.S. Patent No. 4,033,88~ discloses a liquid suitable for the forma~ion of a recyclable metalworking lubricant. The liquid is an aqueous solution containing a mixture of ethylene oxide-propylene oxide block copolymers, an alkanolamine cinnamate and a boron amine complex. The block copolymers have a central portion of polypropylene oxide with polyethylene o~ide on each end (see column 2, lines 32-33).
It is a principal object of the present invention to provide a metalworking method employing a lubricant composition having acceptable load bearing and friction-modifying properties, corrosion-inhibition ability and chemical stability under ordinary operating conditions, and avoidance of deposits on tools and workpieces following operations in which the lubricant composition is used.
It is a related object of ~he invention to provide a lubricant composition accomplishing the foregoing objectives while at the same time avoiding excessive production of foam.
Additional objects and advantages of the present invention will become apparent to persons skilled in the art from the following specification.

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In accordance with the present invention, there is provided a metalworking method employing an aqueous synthetic lubricant having good lubricating properties in metal fabricating operations. The lubricant is especially suitable for use in the hot rolling and cold rolling of aluminum and aluminum alloys into sheet orm.
The lubricant composition comprises a water-soluble mixture of polyoxypropylene-polyoxyethylene-polyoxypropylene block copolymers, a water-soluble carboxylic acid, a water-soluble alkanolamine and water. A preferred composition also contains an antifoam agent.
The polyoxypropylene-polyoxyethylene-polyoxypropylene block copolymers comprise about 1.0-20 wt% of the composition.
The average molecular weight of polyoxypropylene chains in the mixture is at least 900, and ~he polyoxyethylene chains constitute about 10-80 wt~ of the mixture.
The carboxylic acid comprises about 0.5-10 wt% of the composition and may be a saturated or unsaturated Cll to C36 mono- or dicarboxylic acid. The acid is preferably a saturated or monounsatruated C12 to C20 monocarboxylic acid. Two particularly preferred carboxylic acids are oleic acid and lauric acid.
The water-soluble alkanolamine comprises about 0.5-10 wt% of the composition. Some particularly preferred alkanolamines are triethanolamine, diethanolamine and ethyldiisopropanolamine.
The metalworking method of the invention is suitable for use with both errous and non-ferrous metals. The method can include such operations as rolling, drawing and ironing, ~ 2 ~ 3~

machining and others. The lubricant composition employed in the method exhibits satisfactory load bearing and riction modi~ying propertles when used for either hot rolling or cold rolling of aluminum alloys.
The term "hot rolling" refers to rolling that takes place at a metal entry temperature of approximately 450-1000F
for aluminum alloys. Hot rolling is typically used to reduce slabs of aluminum alloy material that are several inches thick into sheets having a thickness of about 1/8 inch.
The term "cold rolling" refers to rolling in which metal entry temperature may range from approximately ambient temperature to about 450F for aluminum alloys. Metal entry temperature is ordinarily about ambient temperature. Cold rolling is typically used to reduce sheets of aluminum alloy material about 1/8 inch thick into lesser thicknesses.
One ingredient of the lubricant composition is a water-soluble mixture of polyoxyethylene-polyoxypropylene block copolymers containing a single polyxoyethylene chain and two polyoxypropylene chains attached to the polyoxyethylene chain.
These block copolymers have the general ormula Ho~cH2cHo]x[cH2(~H2o]y[cH2c ]Z

The average molecular weight of polyoxypropylene chains in the mixture is at least 900, and th~ polyoxyethylene chains in the mixture constitute about 10-80 wt% of the mixture. The average molecular weight o polyoxypropylene chains in the mixture is preferably about 1000 to 3100. In a preerred mixture, -the average molecular weight o polyoxypropylene chains ln the . 5 ~2~

mixture is about 1700, and polyoxyethylene chains constitute about 20 wt% of the mixture.
Such materials are sold under the trade name "Pluronic R" by BASF Wyandotte Corporation of Wyandotte, Michigan. The mixture of block copolymers constitutes abou~ 1.0-20 wt% of the lubricant composition, generally about 2.5-10 w~%. One example contains about 5 wt% of a mixture of block polyoxypropylene-polyoxyethylene-polyoxypropylene copolymers wherein the average molecular weight of polyoxypropylene chains in the mixture is about 1700, and the polyoxyethylene chains constitute about 20 wt% of the mixture. This mixture is sold under the trade designation "17R2". The mixture of block copolymers functions as an additive solubilizer, viscosity builder and antiwear agent in the lubricant composition.
The polyoxypropylene-polyoxyethylene-polyoxypropylene block copolymers are formed by the sequential addition of ethylene oxide and then propylene oxide to an ethylene glycol base. These con~ugated or block copolymers are described in greater detail in Jackson et al U.S. Patent No. 3,036,118 issued May 22, 1962.
A second ingredient of the composition is a water-soluble carboxylic acid having the general formula CmH2m_n_r~2(COOH)r where m is an integer from 11 to 36, n = 0, 2, 4 or 6 and r = 1 or 2. The carboxylic acid is preferably a saturated or monounsaturated C12 to C20 monocarboxylic acid. Two preferred monocarboxylic acids are oleic acid and lauric acid.
An alternative formulation of the lubricant composition includes a dimeric unsaturated fatty acid, such as ~L~3L()3~

dilinoleic acid. ~imeric fatty acids are also commercially available as "dimer acids", usually containing a total of about 32 to 36 carbon atoms. These acids result rom the dimerization of polyunsaturated fatty acids containing from 16 to 18 carbon atoms.
The water-soluble carboxylic aci.d comprises about 0.5-10 wt~ of the composition, preferably about 0.5-5 wt%.
Compositions containing about 1-2 wt% of the acid are qu;te suitable. Two preferred lubricant compositions include 1 wt%
oleic acid and 2 w~% oleic acid, respectively. The carboxylic acid functions as a load bearing and riction modifying additive in the composition.
A third ingredient of the composition is a water-soluble alkanolamine. Some suitable alkanolamines are monoethanolamine, diethanolamine, triethanolamine, dimethyl-ethanolamine, diethyl-e~hanolamine, aminoethyl-ethanolamine, methyl-diethanolamine, N-acetyl ethanolamîne, phenylethanol amine, phenyldiethanolamine, mono-, di- and trii~opropanolamine, and mixtures of any of the foregoing alkanolamines. The pre-ferred alkanolamines are triethanolamine, diethanolamine andethyldiisopropanolamine.
The water-soluble alkanolamine comprises about 0.5-10 wt% of the lubricant composition, preferably about 0.5-3 wt%.
Two preferred compositions include 0.8 wt% triethanolamine and 1.6 wt% triethanolamine, respectively. The alkanolami.ne has the function of partially or completely converting the carboxylic acid into amine soap. The alkanolamine should preferably be present in sufficient concentration that at least one amine group is present for each carboxyl group in the carboxyllc acid.

In the preferred form, the lubricant composition of the invention also contains a defoaming agent. One preferred composition contains about 50-100 ppm (about .005-.01 wt%) of a non-silicone defoaming agen~. This agent comprises organic and silica derivatives dispersed in a solvent and is sold commercially by Ma~er Chemicals Inc. o:E Gurnee, Illinois under the trade name MAZU DF 2502. ~ less preferred lubricant composition comprises about 25 ppm (about .0025 wt%) of a silicon defoaming agent. The defoaming agent is chosen so as to produce suitable reductions in foam while at the same time avoiding deposits on metal surfaces that affect coating or paint adhesion.
The lubricant composition may also include about 0.5-10 wt% of a water-soluble polyoxyethylene or polyoxypropylene alcohol or a water~soluble carboxylic acid ester of such alcohol. T~o suitable esters are a monos~earate of a polyethylene glycol having a molecular weight of about 400, and a dioleate of a polyethylene glycol having a molecular weight of about 1000. These esters are typically added to form about 1 wt% of the lubricant composition. The esters add to lubricity of the composition.
Additional additives known ~o persons skilled in the art may be desirable under certain conditions. Such additives may include biocides, oxidation inhibitors and corrosion inhibitors.
Examples Some examples of suitable lubricant compositions for practicing the metalworking method of the invention are as follows:

33~34 Example Ingredient Content (wt7~) 1 A mixture of polyoxypropylene 10 polyoxyethylene-polyoxypropylene block copolymers in which the average molecular weight of the polyoxypropylene chains is about 1700 and the polyoxyethylene chains constitute about 20 wt%
of the mix~ure (Pluronic 17R2) Oleic acid 2 Triethanolamine 1.6 Non silicone defoamer 50-100 ppm *(MAZU DF 2502) Water P~emainder *[Trademark~

2 A mix~ure of polyoxypropylene- 5 po'lyoxyethylene-polyoxypropylene block copolymers in which the average molecular weight of the polyoxypropylene chains is about 1700 and the polyoxyethylene chains constitute about 20 wt%
of the mixture (Pluronic 17R2) Oleic acid Triethanolamine 0.8 Non-silicone defoamer 50-100 ppm (MAZU DF 2502) Water Remainder .: ~

3~4 Example In~redient Content (wt%) 3 A mixture of polyoxypropylene- 10 polyoxyethylene~polyoxypropylene block copolymers in which the average molecular weight of the polyoxypropylene chains is about 1700 and the polyoxyethylene : chains constitute about 20 wt%
of the mixture (Pluronic 17R2) Dimer acid 2 Triethanolamine 2.4 Polyethylene glycol (400) monostearate Non-silicone defoamer 50-100 ppm (MAZU DF 2502) Water Remainder

4 A mixture of polyoxypropylene- 5 polyoxyethylene-polyoxypropylene block copolymers in which rhe average molecular weight of the polyoxypropylene chains is about 2500 and the polyoxyethylene chains constitute about 40 wt%
of the mixture (Pluronic 25R4) Laurlc acid Ethyldiisopropanolamine 2 Polyethylene glycol (1000) Dioleate Non-silicone defoamer 50-100 ppm (MAZU DF 2502) Water Remainder )313~

Example Ingredient Content ~wt%) A mixture of polyoxypropylene- 10 polyoxyethylene-polyoxypropylene block copolymers in which the average molecular weight of the polyoxypropylene chains is about 3100 and the polyoxyethylene chains constitute about 10 wt%
of the mixture (Pluronic 31Rl) Oleic acid 2 Triethanolamine 0.5 Diethanolamine Defoamer (MAZU DF 2502) 50-100 ppm Water Remalnder 6 A mixture of polyoxypropylene- 5 polyoxyethylene-polyoxypropylene block copolymers in which the average molecular weight of the polyoxypropylene chains is about 2500 and ~he polyoxyethylene chains constitute about 50 wt%
of ~he mix~ure (Pluronic 25RS) Oleic acid 0.5 Dimer acid 0.5 Triethanolamine Defoamer (MA~U DF 2502) 50-100 ppm Water Remainder ~2~L~3t~3~

Example In~redient Content (wt%) 7 A mixture of polyoxypropylene- 7 polyoxyethylene-polyoxypropylene block copolymers in which the average molecular weight of the polyoxypropylene chains is about 3100 and the polyoxyethylene chains constitute about 40 wt%
of the mix~ure (Pluronic 31R4) Oleic acid 2 Aminoethyl-ethanolamine Polyethylene glycol (600) monolaurate Defoamer (MAZU DF 2502) 50-100 ppm Water Remainder 8 A mixture of polyoxypropylene~ 10 polyoxyethylene-polyoxypropylene block copolymers in which the average molecular weigh~ of the polyoxypropylene chains is about 1700 and the polyoxyethylene chains constitute about 40 wt%
of the mixture (Pluronic 17R4) Isostearic acid 3 Di~thanolamine Polyoxyethylene (12) lauryl ether Non-silicone de~oamer 50-100 ppm (MAZU DF 2502) Water ~emainder 3313~

Example Ingredient Content (wt%) 9 A mixture of polyoxypropylene- 10 polyoxyethylene-polyoxypropylene block copolymers in which the average molecular weight of the polyoxypropylene chains is about lO00 and the polyoxyethylene chains constitute about 50 wt%
of the mixture (Pluronic lOR5) Isostearic acid 2 Diethanolamine Non-silicone defoamer 50-100 ppm (MAZU DF 2502) Water Remainder A mixture of polyoxypropylene- 7 polyo~yethylene-polyoxypropylene block copolymers in which the average molecular weight of the polyoxypropylene chains is about 1700 and the polyoxyethylene chains cons~itute about 80 wt%
of the mixture (Pluronic 17R8) Oleic acid 2 Triethanoalmine 1.6 Defoamer (MAZU DF 2502) 50-lO0 ppm Water Remainder "~: 13 38~

Example In~redient Content (wt%) 11 A mixture of polyoxypropyl.ene- 5 polyoxyethylene-polyoxypropylene block copolymers in which the average molecular weight of the polyoxypropylene chains is about 2500 and the polyoxyethylene chains constitute about 10 wt%
of the mixture (Pluronic 25Rl) Linoleic acid Monoethanolamine 0.5 Defoamer (MAZU DF 2502) 50-100 ppm Water Remainder 12 A mixture of polyoxypropylene- 7.5 polyoxyethylene-polyoxypropylene block copolymers in which the average molecular weight of the polyoxypropylene chains is a~out 3100 and the polyoxyethylene chains constitute about 20 wt%
of the mixture (Pluronic 31R2) Oleic acid 4 Diethanolamine 1.5 Non-silicone defoamer 50-100 ppm (MAZU DF 2502) Water Remainder 38~

Example Ingredient Content (wt%) 13 A mixture of polyoxypropylene- 5 polyoxyethylene-polyoxypropylene block copolymers in which the average molecular weight of the polyoxypropylene chains is about 1000 and the polyoxyethylene chains constitute about 50 wt%
of the mixture (Pluronic lOR5) Lauric acid 1.5 Monoethanolamine Polyethylene glycol (4000) distearate Non-silicone defoamer 50-100 ppm (MAZU DF 2502) Water Remainder 14 A mix~ure of polyoxypropylene- 10 polyoxyethylene-polyoxypropylene block copolymers in which the average molecular weight of the polyoxypropylene chains is about 1700 and the polyo~yethylene chains constitute about 20 wt%
of the mixture (Pluronic 17R2) Isostearic acid Lauric acid Diethanolamine 1.5 Polyethylene glycol (400) monolaurate Defoamer ~MAZU DF 2502) 50-100 ppm Water Remainder )38~L

The method of the present invention works surprisingly well for either hot rolling or cold rolling o aluminum alloys.
Various modifications may be made in the invention without departing from the spirit thereof, or the scope of the claims, and, therefore, the specific treatment described is to be taken as illustrative only and not in a limiting sense, and it is desired that only such limitations shall be placed thereon as are imposed by the prior art, or are specifically set forth in the appended claims.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A method of metalworking including the steps of applying to a metal object a synthetic lubricant composition consisting of an aqueous solution comprising: (a) about 1.0-20 wt% of a water-soluble mixture of polyoxyethylene-polyoxypropylene block copolymers containing a single polyoxyethylene chain and two polyoxypropylene chains attached to the polyoxyethylene chain, the average molecular weight of the polyoxypropylene chains in the mixture being at least 900 and the polyoxyethylene chains in the mixture constituting about 10-80 wt% of the mixture; (b) about 0.5-10 wt% of a water soluble carboxylic acid of the general formula CmH2m-n-r+2(COOH)r where m is an integer from 11 to 36, n = 0, 2, 4 or 6 and r = 1 or 2; (c) about 0.5-10 wt% of a water-soluble alkanolamine; and (d) remainder, water.

2. The metalworking method of claim 1 wherein said metal is aluminum or an aluminum alloy.

3. The metalworking method of claim 2, further including the step of hot rolling or cold rolling the metal object.

4. The metalworking method of claim 2, further including the step of hot rolling the metal object at a temperature of about 450-1000°F.

5. The metalworking method of claim 2, further including the step of cold rolling the metal object at approximately ambient temperature to 450°F.

6. The metalworking method of claim 1 wherein the average molecular weight of polyoxypropylene chains in the mixture is about 1000 to 3100.

7. The metalworking method of claim 1 wherein the polyoxyethylene chains in the mixture constitute about 20 wt%
of the mixture.

8. The metalworking method of claim 1 wherein the mixture of polyoxyethylene-polyoxypropylene block copolymers comprises about 2.5-10 wt% of the composition.

9. The metalworking method of claim 8 wherein the mixture of polyoxyethylene-polyoxypropylene block copolymers comprises about 5 wt% of the composition.

10. The metalworking method of claim 1 wherein said carboxylic acid comprises a saturated or monunsaturated C12 to C20 monocarboxylic acid.

11. The metalworking method of claim 10 wherein said carboxylic acid comprises oleic acid or lauric acid.

12. The metalworking method of claim 1 wherein said carboxylic acid comprises about 0.5-5 wt% of the composition.

13. The metalworking method of claim 12 wherein said carboxylic acid comprises about 1-2 wt% of the composition.

14, The metalworking method of claim 1 wherein said alkanolamine is selected from the group consisting of triethanolamine, diethanolamine and ethyldiisopropanolamine.

15. The metalworking method of claim 14 wherein said alkanolamine is triethanolamine.

16. The metalworking method of claim 1 wherein said aqueous solution further comprises: (e) an antifoam agent.

17. The metalworking method of claim 16 wherein said antifoam agent comprises about 50-100 ppm of the composition.

18. The metalworking method of claim 1 wherein said aqueous solution further comprises: (f) about 0.5-10 wt% of a water-soluble polyoxyethylene or polyoxypropylene alcohol or a water-soluble carboxylic acid ester of a polyoxyethylene or polyoxypropylene alcohol.

19. The metalworking method of claim 18 wherein said alcohol or ester comprises about 1 wt% of the composition.

20. A synthetic aqueous solution metalworking lubricant composition comprising: (a) about 1.0-20 wt% of a water-soluble mixture of polyoxyethylene-polyoxypropylene block copolymers containing a single polyoxyethylene chain and two polyoxypropylene chains attached to the polyoxyethylene chain, the average molecular weight of the polyoxypropylene chains in the mixture being at least 900 and the polyoxyethylene chains in the mixture constituting about 10-80 wt% of the mixture;
(b) about 0.5-10 wt% of a water-soluble carboxylic acid of the general formula CmH2m-n-r+2(COOH)r where m is an integer from 11 to 36, n = 0, 2, 4 or 6 and r = 1 or 2; (c) about 0.5-10 wt% of a water-soluble alkanolamine; and (d) remainder, water.

21. The lubricant composition of claim 20 wherein the average molecular weight of polyoxypropylene chains in the mixture is about 1000 to 3100.

22. The lubricant composition of claim 20 wherein the polyoxyethylene chains in the mixture constitute about 20 wt% of the mixture.

23. The lubricant composition of claim 20 wherein the mixture of polyoxyethylene-polyoxypropylene block copolymers comprises about 2.5-10 wt% of the composition.

24. The lubricant composition of claim 20, further comprising: (e) a non-silicone antifoam agent.

25. The lubricant composition of claim 24 wherein said antifoam agent comprises about 50-100 ppm of the composition.

26. The lubricant composition of claim 20, further comprising: (f) about 0.5-10 wt% of a water-soluble polyoxyethylene or polyoxypropylene alcohol or a water-soluble carboxylic acid ester of a polyoxyethylene or polyoxypropylene alcohol.