WATER-BASED METALWORK1NG FLUID INCORPORATING POLYMERIC BORON MATERIALS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority of United States Provisional Patent Application Serial No. 60/741,205 filed December 1, 2005, entitled "Water-Based Metal working Fluid Incorporating Polymeric Boron Materials," and United States Patent Application Serial No. 1 1/564,442 filed November 29, 2006, both of which are incorporated herein by reference.

FIELD OF THE INVENTION

[0002] This invention relates generally to metalworking fluids. More specifically, the invention relates to water-based, recyclable metalworking fluids which incorporate boron-based polymers as well as to methods for making such compositions, and their use in metalworking processes.

BACKGROUND OF THE INVENTION

[0003] Metalworking fluids are employed in metalworking operations such as cutting, forming, stamping and rolling to provide cooling and lubrication to both the workpiece and the metalworking apparatus. The metalworking fluids also function to flush away oil and debris from the worksite and they provide corrosion protection to both the workpiece and the metalworking apparatus. Metalworking fluids were initially formulated from hydrocarbon oils and solvents. However, water-based metalworking fluids are coming to be widely used. [0004] Water-based metalworking formulations typically comprise emulsified structures incorporating both water-soluble and water-insoluble materials in a stable, emulsified composition. Water-based metalworking fluids are more environmentally acceptable than are hydrocarbon oil-based fluids. Water-based fluids can be easily recycled, and waste handling and pollution control is minimized when such fluids are utilized. Problems do occur with water- based fluids, however, since such fluids may have lower lubricity than do oil-based fluids. Furthermore, various additive packages incorporated in water-based fluids are subject to depletion in the use of the fluids. Often, the depletion of the various components of the fluid does not proceed at the same rate, and it is frequently difficult to monitor the compositional state of the fluids.

[0005] As will be explained hereinbelow, the present invention provides for a class of water-based metalworking fluids which incorporate boron-based inorganic polymers. These

boron-based polymers are very stable and hence are not prone to break down during use and storage of the compositions; hence, the compositions are stable and can be readily recycled and replenished. In addition, such materials can provide a high degree of lubricity to water-based compositions.

BRIEF DESCRIPTION OF THE INVENTION

[0006] Disclosed is a metalworking fluid which comprises a polymeric boron species which includes at least B, N and H, together with water and a surfactant in an amount operable to provide an emulsion of the polymeric boron species and the water. In some instances, the polymeric boron species comprises a polyborane or a borazine polymer. In particular instances, the polymeric boron species comprises a backbone of a polyborane or a borazine polymer having side chains pendent thereupon. The side chains may include silicon and/or phosphorous and, in particular instances, at least some of the side chains comprise a halogenated alkyl silane. In other instances, at least some of the side chains include a siloxane polymer which is optionally halogenated. In a specific instance, the siloxane polymer side chain is a linear polydimethyl siloxane. Other polymeric boron species may comprise polyaminoboranes or polyiminoboranes. In particular instances, the polymeric boron species has a liquid crystal structure.

[0007] In some instances, the fluid may further include one or more of an alkanolamine, a polyol surfactant, a glycol ether, a polyglycol surfactant, or a corrosion inhibitor. In particular instances, the fluid may further include a fluoroalkyl silane.

[0008] Also disclosed are some specific compositions in accord with the foregoing, as well as methods for using the composition and methods for making the composition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0009] The present invention is directed to a novel class of metalworking fluids comprised of water-based compositions which incorporate polymeric boron materials therein. A number of polymeric boron materials are known in the art, and these materials typically comprise boron, nitrogen and hydrogen. One such group of materials are polyboranes, and specific members of this group are polyaminoboranes as well as polyiminoboranes. Borazine polymers are another group of such materials known in the art. These polymeric boron materials are stable, inert, and water insoluble. They are resistant to bacterial degradation, chemical breakdown and are stable under high temperature, high pressure conditions such as are encountered in metalworking processes. Depending upon the degree of polymerization, compositions with various viscosities

can be prepared from these polymeric materials, and in many instances, such materials have a high degree of lubricity.

[0010] In some instances, the polymeric boron materials may be configured as a backbone comprised of the boron polymer, further including pendent side chains such as silicon or phosphorus-based side chains. Materials of this type are shown in U.S. Patent 4,581,468 which describes borazine polymers having side chains based upon silicon or other materials. A similar disclosure is found in U.S. Patent 6,103,178. A particular group of boron-based polymeric materials having very good lubricating properties are disclosed in U.S. Patent 7,125,499, which is incorporated herein by reference. This particular group of materials has specific silicon and/or phosphorus-based side chains and has a particular liquid crystal structure. These materials can have very high lubricity and the prior art recognizes their utility in metalworking applications.

[0011] However, the prior art has not heretofore recognized the possibility of, or advantages of utilizing polymeric boron species in water-based metalworking fluids. In fact, while the aforementioned 7,125,499 patent specifically teaches the use of boron polymer compositions as lubricants or cutting fluids in metalworking operations, it does not teach or suggest that such polymers can be incorporated into water-based metalworking fluids. In fact, all teaching therein is of the water immiscibiliry of the disclosed compounds, and as such suggests their incompatibility with aqueous-based compositions.

[0012] As will be explained in further detail hereinbelow. the present invention recognizes that polymeric boron materials may be successfully incorporated into water-based metalworking fluids so as to form stabilized emulsions. It is to be understood within the context of this disclosure that the term "emulsion" is to be interpreted broadly to encompass compositions of water and water-soluble materials with water-insoluble boron polymers, which compositions are homogenized or otherwise stabilized to produce a macroscopically homogeneous fluid structure which is stable during its intended period of use. Such structures may be characterized as oil-in- water or water-in-oil, and may include various micellar structures, lamellar structures, simple emulsions, complex emulsions, and various intermediate dispersions of the mutually insoluble materials.

[0013] One particular group of compositions is comprised of a mixture of one or more surfactants, such as a polyol and/or polyglycol surfactants, together with an alkanolamine, the boron polymer, and a biocide, which may comprise a single biocidal material or a combination of biocides. The composition typically also includes a corrosion inhibitor package which may

also comprise a single corrosion inhibitor or a mixture of corrosion inhibitors. The foregoing ingredients are mixed with water for use. In some instances, the composition may be provided as a concentrate which is subsequently diluted for use. Materials of this type provide very good lubricity and cooling in metalworking operations. In addition, they function very well to sequester and remove contaminants, including oils, from metalworking apparatus and workpieces. The compositions are stable in use and resistant to biological contamination. The compositions are free of hazardous material such as phenols, cresols and the like, and they can be fabricated to be free of fatty acids which can react with certain metals and form unwanted soapy deposits. The compositions are compatible with a wide variety of metals including ferrous and nonferrous metals, and it is a notable feature of the present invention that the compositions can be formulated so as to be non-corrosive toward copper, zinc or lead, and hence are very useful in the machining of brass.

[0014] Fluoroalkyl silanes such as fluoropropyl silanes can further enhance the performance of water-based, boron polymer-containing metalworking fluids. The presence of the fluoroalkyl silane enhances the water washability of the metalworking fluid, which is significant since it facilitates cleaning the metalworking fluid from the finished parts. The presence of the fluoroalkyl silane also enhances the high pressure lubricity of the compositions. Thus, fluoroalkyl silanes are beneficial adjuncts in boron-based polymer-containing metalworking fluids. The fluoroalkyl silane component may be a discrete molecular species in the formulation, or it may comprise a pendent group on the boron polymer, and such materials are described hereinbelow. In either instance, the beneficial effects of the fluoroalkyl silane will be realized.

[0015] In specific embodiments, the metalworking fluid comprises, on a weight basis, 1- 10% of the boron material, 1-15% of an alkanolamine, and 0.1 -10% of a surfactant. In those instances where corrosion inhibitors are included they may be present in an amount of 10-30%, and biocides, when included, are typically present in an amount of 0.5-1.0%. The composition may also include ancillary ingredients such as anti-foam agents, coloring agents and the like. The remainder of the composition is water.

[0016] The metalworking fluids may also include an alkanolamine. There are a number of alkanolamines which may be used either singly or in combination in the compositions. Preferred alkanolamines are generally C1-C4 alkanolamines, and primary, secondary and tertiary alkanolamines may all be employed. One specific group of alkanolamines comprises isopropanolamines. Other alkanolamines include ethanolamines. The alkanolamines may be

used either singly or in combination, and generally comprise 1-15%, and in certain embodiments 13-15% of the composition.

[0017] The metalworking fluid can include a polyol surfactant. It has been found that this group of surfactants provides superior sequestering performance and facilitates the removal of oils and other such hydrophobic materials from the workpiece and machinery. One polyol having utility in the compositions comprises a poly(oxy-l,2-ethanediyl), alpha-(4-nonylphenyl)- omega-hydroxy-, branched material. Such polyols are available from the Superior Chemical Corporation of Indianapolis, Indiana, under the designation Superwet 9.5. Other surfactants having utility are polyglycols. One such polyglycol surfactant comprises a block copolymer of polyoxypropylene and polyoxyethylene. Surfactants of this type are commercially available from a number of sources, and one specific material comprises the product sold under the designation Pluronic 17R2. This material is available from The BASF Corporation. Other such surfactants include P-41-300 sold by the Hoescht Celanese Corporation, and Triton EF- 14 sold by Rohm and Haas. Yet other materials will be apparent to those of skill in the art. [0018] The boron-based polymer, in one group of embodiments, comprises a liquid crystal boron polymer of the type disclosed in U.S. Patent 7,125,499, the disclosure of which is incorporated herein by reference. Such materials are of the general formulae: -(B-H-N-R-BH- NR'-) _n ; (-BH ₂ -NHR-BH-NHR'-) _n ; and

where n is in the range of about 1-130, and R and R' are linear polydϊmethyl siloxane polymers (including halogenated siloxane polymers). In certain instances, n is approximately 70. In other instances, the R and R' may comprise hydrocarbon-based moieties such as organic acids, esters, alcohols and the like. In yet other instances, the chains R and R' may comprise biocidal moieties, anticorrosion agents or other active species.

[0019] The metalworking fluid may include a biocide which can be a single material or a mixture of materials having a biocidal effect against both bacteria and fungi. One preferred biocide comprises a morpholine compound. One preferred morpholine biocidal compound comprises 4-(2-nitrobutyl) morpholine. Other morpholine materials include 4,4'-(2-ethyl-2- nitrotrimethylene)dimorpholine and methylene dimorpholine. Biocidal morpholine mixtures are

available from the Angus Chemical Company of Buffalo Grove, Illinois under the designation Bioban P-1487 and Bioban CS-1 135. The material sold by Rohm and Haas under the designation Kaython EDC 1.5 may also be used in this regard. This material comprises poly(oxy-l,2-ethanediyl(dimethylimino)-l,2-ethanediyl (dimethylimino)-l,2-ethanediyl dichloride). Equivalent compositions are sold under the designation Bioban TS by Angus Chemical Company, and the aforementioned Kaython EDC 1.5. Other compositional ranges of these materials, as well as other combinations of materials, are also useful in the practice of the present invention.

[0020] The compositions can also include a corrosion inhibitor. The specific corrosion inhibitor employed will depend, to some degree, upon the nature of the metals with which the material is being employed. One class of compounds having utility as corrosion inhibitors comprise thiazoles, and one specific thiazole material is sodium 2-mercaptobenzothiazole. Such material is available from the Lubrizol Corporation of Wickliffe, Ohio in a formulation sold under the designation Aqualox. Yet another corrosion inhibitor which may be used in these formulations comprises a boramide such as the product sold under the designation Addco CP-B-2 by the Lubrizol Corporation. Other corrosion inhibitors include the materials sold by Lubrizol Corporation under the designation Alox. Typically, the corrosion inhibitor will be present in an amount of about 10-30%, and in specific embodiments in a range of 8-10%. [0021J In addition to the foregoing, the metalworking fluids of the present invention may include other active components. One material often employed in the metalworking fluid compositions comprises diethylene glycol monobutyl ether. This material is often referred to the in art as glycol ether DB ₅ and is typically present in an amount of approximately .5-2%. Other ingredients in the compositions may include isoalkyloxy amine oxide. This material may be present in an amount of approximately 10-12%. Additionally, amounts of benzotriazole, either in the form of the free base or as salts, may also be added to the compositions. [0022] The metalworking fluids may also include ancillary ingredients such as coloring agents, fragrances, viscosity or rheology control agents, defoamers, scents and the like. [0023] Various compositions may be prepared in accord with the teaching presented herein. One specific group of compositions is as follows:

Percent

CAS# Ingredient bv Weight

7732-18-5 Water 22-59

000078-96-6 Monoisopropanolamine 1-3

00001 10-97-4 Diisopropanolamine 4-7

0000122-20-3 Triisopropanolamine 4-7

Proprietary Amine Oxide (Tomah AO-455) 12-18

Proprietary Aqualox 232 8-12

Proprietary Addco CP-B-2 4-8

Proprietary Boron Polymer 4-8

015217-42-2 Benzotriazole 2-5

000112-34-5 Glycol Ether DB 1-3

EPA# 48301-7 Bioban P-1487 0.25-2.5

071662-44-7 Polyether Phosphate 0.1-1.0

Proprietary Foam Ban HP-710 0.1-1.0

127087-87-0 Poly(oxy-1 ,2-ethanediyl), Alpha-(4- 0.1 -1.0 nonylphenyl)-omega-hydroxy-, branched

67762-90-7 Silicone Compound 0.1-1.0

[0024] Yet other compositions may be implemented in accord with the teaching presented herein. Modifications of the foregoing composition may be prepared, for example, by adding 1.25-1.75% of glycol ether DB to the mixture. Relatively small amounts of an anti-foaming agent, such as a polysiloxane defoamer, may be added to the composition. Typically, defoamers are employed in approximately .05-.25%. Yet other compositions may be implemented in accord with the teachings presented herein.

[0025] It has been found that the foregoing compositions function very well as metalworking fluids for cutting or otherwise shaping a wide variety of materials including leaded brass. The compositions provide a high degree of lubricity even under high-pressure conditions, and thus are compatible with high volume, high speed metalworking systems. The fluids are stable against biological contamination, and do not form metallic soap deposits. They readily clean and sequester oils and are non-corrosive to brass. The service life of the materials is long, and they may be readily recycled. In that regard, spent fluid may be collected and filtered to remove impurities and debris. Oils and other contaminants may be removed by

skimming and/or filtering, and the resultant fluid reused in the metal working process. In some instances, the recycled fluid will have certain of its components replenished before reuse. The boron polymer may be readily reclaimed from the spent fluid by breaking the emulsion and separating the boron phase. The extreme non-reactivity of the boron fluids facilitates their separation and purification.

[0026] Various other formulations may be prepared in accord with the present invention. While the foregoing has primarily described compositions based upon a specific group of liquid crystal, boron-based polymer fluids, a variety of other boron-based polymer materials are known in the art and such materials may likewise be utilized in the practice of the present invention. The foregoing is illustrative of specific embodiments of the invention, but is not meant to be a limitation upon the practice thereof. It is the following claims, including all equivalents, which define the scope of the invention.