Patent Description:
<NPL>) and <CIT> discloses working fluids comprising an ethoxylated phosphite compound.

An unclaimed composition having a compound having the structure:
<CHM>
wherein each R is an independently selected alkylphenol-free moiety that is a C<NUM>-<NUM> alkyl, C<NUM>-<NUM> alkenyl, C<NUM>-<NUM> cycloalkyl, C<NUM>-<NUM> cycloalkylene, C<NUM>-<NUM> methoxy alkyl glycol ether, C<NUM>-<NUM> alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C<NUM>-<NUM> alkylene, C<NUM>-<NUM> cycloalkylene, or C<NUM>-<NUM> alkyl lactone moiety; wherein m is an integer ranging from <NUM> to <NUM>; and wherein x is an integer ranging from <NUM> to <NUM>.

An unclaimed composition having a compound having the structure:
<CHM>
wherein each R is an independently selected alkylphenol-free moiety that is a C<NUM>-<NUM> alkyl, C<NUM>-<NUM> alkenyl, C<NUM>-<NUM> cycloalkyl, C<NUM>-<NUM> cycloalkylene, C<NUM>-<NUM> methoxy alkyl glycol ether, C<NUM>-<NUM> alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C<NUM>-<NUM> alkylene, C<NUM>-<NUM> cycloalkylene, or C<NUM>-<NUM> alkyl lactone moiety; wherein each Z is independently selected from the group consisting of S and O; wherein m is an integer ranging from <NUM> to <NUM>; and wherein x is an integer ranging from <NUM> to <NUM>.

A method according to the invention having the step of using the following compound as a metalworking fluid additive:
<CHM>
wherein each R is an independently selected moiety that is a C<NUM>-<NUM> alkyl, C<NUM>-<NUM> alkenyl, C<NUM>-<NUM> cycloalkyl, C<NUM>-<NUM> cycloalkylene, C<NUM>-<NUM> methoxy alkyl glycol ether, C<NUM>-<NUM> alkyl glycol ether, or Y-OH moiety; wherein each Y is an independently selected alkylphenol-free moiety that is a C<NUM>-<NUM> alkylene, C<NUM>-<NUM> cycloalkylene, or C<NUM>-<NUM> alkyl lactone moiety; wherein m is an integer ranging from <NUM> to <NUM>; and wherein x is an integer ranging from <NUM> to <NUM>; and wherein the compound has a weight ranging from <NUM> to <NUM> Daltons; or from <NUM> to <NUM> Daltons; or from <NUM> to <NUM> Daltons.

The following embodiments, which are not all claimed, are directed to compounds that are useful as metalworking-fluid additives.

An unclaimed embodiment is directed to polyhydrogen-phosphite compounds having the general structure:
<CHM>.

In some polyhydrogen-phosphite embodiments, each Y is an ethylene, propylene, or caprylactone moiety.

In some polyhydrogen-phosphite embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons. In some polyhydrogen-phosphite embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons. In some polyhydrogen-phosphite embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons.

An unclaimed embodiment is directed to phosphate compounds having the general structure:
<CHM>.

In some phosphate embodiments, each Y is an ethylene, propylene, or caprylactone moiety.

In some phosphate embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons. In some phosphate embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons. In some phosphate embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons.

An unclaimed embodiment is directed to thiophosphate compounds having the general structure:
<CHM>.

In some thiophosphate embodiments, each Y is an ethylene, propylene, or caprylactone moiety.

In some thiophosphate embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons. In some thiophosphate embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons. In some thiophosphate embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons.

An unclaimed embodiment is directed to phosphorus-containing compounds having the general structure:
<CHM>.

In some phosphorus-containing-compound embodiments, each Y is an ethylene, propylene, or caprylactone moiety.

In some phosphorus-containing-compound embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons. In some phosphorus-containing embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons. In some phosphorus-containing embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons.

An unclaimed embodiment is directed to phosphorus-containing copolymer compounds having the general structure:
<CHM>.

In some phosphorus-containing copolymer compound embodiments, each Y is an ethylene, propylene, or caprylactone moiety.

In some phosphorus-containing copolymer compound embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons. In some phosphorus-containing copolymer compound embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons. In some phosphorus-containing copolymer compound embodiments, the compound has a weight ranging from <NUM> to <NUM> Daltons.

The invention is directed to a method comprising the step: improving a metalworking fluid's anti-wear properties by adding a compound to the metalworking fluid, the phosphite compounds having the general structure:
<CHM>.

In some phosphite embodiments, each Y is an ethylene, propylene, or caprylactone moiety.

According to the invention, the phosphorus-containing copolymer compound has a weight ranging from <NUM> to <NUM> Daltons; or from <NUM> to <NUM> Daltons; or from <NUM> to <NUM> Daltons.

Methods for manufacturing phosphite compounds, polyhydrogen phosphite compounds, phosphate compounds, thiophosphate compounds, and thiophosphite-phosphate copolymer compounds can be determined by persons of ordinary skill in the art without having to exercise undue experimentation. Non-limiting examples of manufacturing methods can be found in the below Examples.

Metalworking additives are well known, and any of the above compounds, either alone or in any combination, can be used as additives for metalworking fluids. Any of the above compounds, either alone or in any combination, can be used as additives for metalworking fluids in useful amounts that can be determined by persons of ordinary skill in the art. As a non-limiting example, useful amounts of the above compounds, either alone or in any combination, range from <NUM> to <NUM> % by weight of the metalworking fluid. In an additional non-limiting example, useful amounts of the above compounds, either alone or in any combination, range from <NUM> to <NUM> % by weight of the metalworking fluid.

In any of the above sulfur-containing compounds, the amount of sulfur within the compound can range from <NUM> to <NUM> mole percent relative to the amount of phosphorus within the compound; stated differently, in any of the above sulfur-containing compounds, anywhere from half to all of the phorphorus atoms are bonded to a sulfur atom. In another embodiment, the amount of sulfur within the compound can range from <NUM> to <NUM> mole percent relative to the amount of phosphorus within the compound. In another embodiment, the amount of sulfur within the compound is <NUM> mole percent relative to the amount of phosphorus within the compound.

To a three-neck <NUM> flask equipped with a mechanical stirrer and purged with nitrogen was added <NUM> grams of triisnonylphenol phosphite (<NUM> mol), with a total nonylphenol content ranging from <NUM>% to <NUM>% with <NUM>% being the target and <NUM> grams of <NUM>,<NUM>-dimercapto-<NUM>,<NUM>,<NUM>-thiadiazole (<NUM> mol). The mixture was mixed well and heat was applied to a reaction temperature of <NUM>°F. <NUM> grams of elemental sulfur (<NUM> mol) was then added at this temperature. After one hour, the reaction temperature is increased to <NUM>°F and held for <NUM>-<NUM> hours. This reaction takes place under a nitrogen blanket. The resulting thiophosphate had the following analysis:.

To a three-neck <NUM> flask equipped with a mechanical stirrer and purged with nitrogen was added <NUM> grams of a alkylphenol-free liquid polymeric phosphite (Example #<NUM> from <CIT>) with a molecular weight of about <NUM> and <NUM> grams of <NUM>,<NUM>-dimercapto-<NUM>,<NUM>,<NUM>-thiadiazole (<NUM> mol). The mixture was mixed well and heat was applied to a reaction temperature of <NUM>°F. Then <NUM> grams of elemental sulfur (<NUM> mol) was added. After one hour, the reaction temperature is increased to <NUM>°F and held for <NUM>-<NUM> hours. This reaction takes place under a nitrogen blanket. The resulting alkyl phenol free polymeric thiophosphate had the following analysis:.

To a three-neck <NUM> flask equipped with a mechanical stirrer and purged with nitrogen was added <NUM> grams of cycloaliphatic polyphosphite (Example <NUM> from <CIT>) with a molecular weight range of about <NUM>,<NUM> and <NUM> grams of <NUM>,<NUM>-dimercapto-<NUM>,<NUM>,<NUM>-thiadiazole (<NUM> mol). The mixture was mixed well and heat was applied to a reaction temperature of <NUM>°F. <NUM> grams of elemental sulfur (<NUM> mol) was then added. After one hour, the reaction temperature is increased to <NUM>°F and held for <NUM>-<NUM> hours. This reaction takes place under a nitrogen blanket. The resulting analysis of the phenol free cycloaliphatic alkylated poly thiophosphate was:.

To a three-neck <NUM> flask equipped with a mechanical stirrer and purged with nitrogen was added <NUM> grams of a alkylphenol-free liquid polymeric phosphite (Example #<NUM> from <CIT>), with a molecular weight of about <NUM> and <NUM> grams of <NUM>,<NUM>-dimercapto-<NUM>,<NUM>,<NUM>-thiadiazole (<NUM> mol). The mixture was mixed well and heat was applied to a reaction temperature of <NUM>°F. Then <NUM> grams of elemental sulfur (<NUM> mol) was added. After one hour, the reaction temperature is increased to <NUM>°F and held for <NUM>-<NUM> hours. This reaction takes place under a nitrogen blanket. The resulting alkyl phenol free polymeric thiophosphate had the following analysis:.

To a three-neck <NUM> flask equipped with a mechanical stirrer and purged with nitrogen was added <NUM> grams of a Triisodecyl phosphite, with a molecular weight of about <NUM> and <NUM> grams of <NUM>,<NUM>-dimercapto-<NUM>,<NUM>,<NUM>-thiadiazole (<NUM> mol). The mixture was mixed well and heat was applied to a reaction temperature of <NUM>°F. Then <NUM> of elemental sulfur (<NUM> mol) was added. After one hour, the reaction temperature is increased to <NUM>°F and held for <NUM>-<NUM> hours. This reaction takes place under a nitrogen blanket. The resulting alkyl phenol free thiophosphate had the following analysis:.

Four Ball Wear: This test is used for evaluating friction- reducing and anti-wear fluids. Testing involves <NUM> stationary steel balls secured in a steel cup and a <NUM>th steel ball lowered to make contact with the <NUM> stationary balls. The fluid to be tested is poured into the cup. The <NUM>th ball is the only ball that spins. Typical rpm for the ball is <NUM> rpm. The single ball spins in contact with the <NUM> stationary balls at a constant load of <NUM>. Typical run time is <NUM> hour. The wear on the lower <NUM> balls is measured and reported in mm. The fluid to produce the smallest wear scars has the best performance.

Test results clearly show that the alkylphenol free polymeric polyphosphites give excellent results, better than the commercial trisnonylphenyl thiophosphate with excellent color. And there are no alkylphenols in the final products.

Timken Testing: Timken testing was carried out by adding weight to a lever applying pressure to a block that is in contact with a wheel. The bottom portion of the wheel is submersed in the fluid to be tested. As the wheel spins, the lubricant is carried to the interface of the block and wheel. A one pound weight is added to the lever every minute until a maximum of <NUM> pounds has been added. The wear scar on the block is measured and reported in millimeters.

The following formulae were prepared for various machine testing:.

The water based formulae were prepared using a commercial semi-synthetic. The additive was added to either the Super Concentrate (SC) prior to dilution of the semi-synthetic with water, or to the concentrate after <NUM>% dilution of the semi-synthetic with water. After the <NUM>% dilution with water, all testing was conducted with the semi-synthetic diluted in water at <NUM>%.

Four Ball Wear: This test is used for evaluating friction-reducing and anti-wear fluids. Testing involves <NUM> stationary steel balls secured in a steel cup and a <NUM>th steel ball lowered to make contact with the <NUM> stationary balls. The fluid to be tested is poured into the cup. The <NUM>th ball is the only ball that spins. Typical rpm for the ball is <NUM> rpm. The single ball spins in contact with the <NUM> stationary balls at a constant load of <NUM>. Typical run time is <NUM> hour. The wear on the lower <NUM> balls is measured and reported in mm. The fluid to produce the smallest wear scars has the best performance.

Vertical Drawbead: Vertical Drawbead is a machine used to determine a fluids ability to form a piece of metal. Vertical Drawbead works by applying pressure to a coated metal strip. The formulae to be tested is applied to a <NUM> inch metal strip which is raised between two dye. The dyes apply <NUM> psi of pressure to the bottom of the strip. The coated strip is pulled between the two dyes. The amount of force needed to pull the strip between the dyes, is plotted by an X-Y plotter and the force is calculated from this curve. In all cases, higher percent efficiency refers to the performance of the fluid being better.

In this test, all formulae were evaluated on <NUM> Steel and <NUM> Stainless Steel.

Microtap Tap and Torque Testing: Microtap testing is one method used to determine a fluids ability to remove metal. A metal bar with predrilled holes is fastened to a vice. The tap and the metal bar are coated in the fluid to be tested. The tap rotates to tap out the pre-drilled hole. The force needed to tap the hole is measured by a computer and is reported as torque in newton centimeters. In all cases, higher percent efficiency refers to the performance of the fluid being better.

In this test, all formulae were evaluated on <NUM> Steel.

Falex Pin and Vee Block Testing: Falex Pin and Vee Block measures the fluids ability to perform in more severe operations, such as cold heading, but can also apply to grinding operations. A pin is fastened using a brass shear pin. Two Vee blocks are clamped onto the pin. The pin and vee blocks are submerged in the fluid to be tested. The load applied on the pin from the vee blocks begins at <NUM> pounds. The load is increased automatically by a ratcheting arm as the pin spins between the two vee blocks. The torque generated by the load on the pin is read at <NUM> pound load and is recorded every <NUM> pounds until a final load of <NUM> pounds is reached or a failure occurs. A failure implies the pin or shear pin has broken. See <FIG> and <FIG>.

Microtap Tap and Torque Testing: Microtap testing is one method used to determine a fluids ability to remove metal. A metal bar with predrilled holes is fastened to a vice. The tap and the metal bar are coated in the fluid to be tested. The tap rotates to tap out the predrilled hole.

The force needed to tap the hole is measured by a computer and is reported as torque in newton centimeters. In all cases, higher percent efficiency refers to the performance of the fluid being better.

Claim 1:
A method comprising the step:
improving a metalworking fluid's anti-wear properties by adding a compound to the metalworking fluid, the compound having the structure:
<CHM>
wherein each R is an independently selected moiety that is a C<NUM>-<NUM> alkyl, C<NUM>-<NUM> alkenyl, C<NUM>-<NUM> cycloalkyl, C<NUM>-<NUM> cycloalkylene, C<NUM>-<NUM> methoxy alkyl glycol ether, C<NUM>-<NUM> alkyl glycol ether, or Y-OH moiety;
wherein each Y is an independently selected alkylphenol-free moiety that is a C<NUM>-<NUM> alkylene moiety, C<NUM>-<NUM> cycloalkylene moiety, or C<NUM>-<NUM> alkyl lactone moiety;
wherein m is an integer ranging from <NUM> to <NUM>; and
wherein x is an integer ranging from <NUM> to <NUM>; and
wherein the compound has a weight ranging
- from <NUM> to <NUM> Daltons; or
- from <NUM> to <NUM> Daltons; or
- from <NUM> to <NUM> Daltons.