CA1283400C - Hydraulic fluid - Google Patents
Hydraulic fluidInfo
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- CA1283400C CA1283400C CA000537916A CA537916A CA1283400C CA 1283400 C CA1283400 C CA 1283400C CA 000537916 A CA000537916 A CA 000537916A CA 537916 A CA537916 A CA 537916A CA 1283400 C CA1283400 C CA 1283400C
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- solution
- sodium
- methylphenoxide
- trifluoroethoxide
- hydraulic fluid
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Abstract
ABSTRACT
HYDRAULIC FLUID
A polyphosphazene hydraulic fluid that remains solids-free on storage at temperatures down to -30°C over an extended period can be made by reacting a solution of sodium phenoxide, sodium m-methylphenoxide, sodium p-methylphenoxide and sodium trifluoroethoxide with a small stoichiometric excess of cyclic phosphonitrilic chloride oligomer, mainly trimer, and then reacting the remaining replaceable chlorine atoms with a solution of sodium trifluoroethoxide.
HYDRAULIC FLUID
A polyphosphazene hydraulic fluid that remains solids-free on storage at temperatures down to -30°C over an extended period can be made by reacting a solution of sodium phenoxide, sodium m-methylphenoxide, sodium p-methylphenoxide and sodium trifluoroethoxide with a small stoichiometric excess of cyclic phosphonitrilic chloride oligomer, mainly trimer, and then reacting the remaining replaceable chlorine atoms with a solution of sodium trifluoroethoxide.
Description
1~34(~3 Case 5581 HYDRAULIC FLUID
Hydraulic fluids are used to trans~er energy through fluid conduits to cause a force to be exerted against a moveable object such as a piston resulting in 5 work. In order to function efficiently, it is necessary that such fluids be stable and preferably fire resistant.
A very important property is that the fluid have a low pour point and that it does not form any solid precipitate ; _ when maintained at low temperature for an extended 10 period. Solids could plug orifices and cause a malfunc-tion in the hydraulic system.
Because of their fire resistance, polyphosphazenes have been investigated for some time in an attempt to prepare a suitable hydraulic fluid. Kober et al., U.S.
15 3,291,865 describes the preparation of hydraulic fluids by reacting mixtures of phenols or substituted phenols and fluoroalcohols with cyclic phosphonitrilic chloride trimer.
Lederle et al., J. Chem. & Eng. Data, Vol. 11, No.
20 2, April 1966, page 221 describes fire resistant hydraulic fluids made in a manner similar to Kober et al. Ottmann et al., Ind. ~ Eng. (Chem. Prod. Res. & Dev.j, Vol. 5, No.
Hydraulic fluids are used to trans~er energy through fluid conduits to cause a force to be exerted against a moveable object such as a piston resulting in 5 work. In order to function efficiently, it is necessary that such fluids be stable and preferably fire resistant.
A very important property is that the fluid have a low pour point and that it does not form any solid precipitate ; _ when maintained at low temperature for an extended 10 period. Solids could plug orifices and cause a malfunc-tion in the hydraulic system.
Because of their fire resistance, polyphosphazenes have been investigated for some time in an attempt to prepare a suitable hydraulic fluid. Kober et al., U.S.
15 3,291,865 describes the preparation of hydraulic fluids by reacting mixtures of phenols or substituted phenols and fluoroalcohols with cyclic phosphonitrilic chloride trimer.
Lederle et al., J. Chem. & Eng. Data, Vol. 11, No.
20 2, April 1966, page 221 describes fire resistant hydraulic fluids made in a manner similar to Kober et al. Ottmann et al., Ind. ~ Eng. (Chem. Prod. Res. & Dev.j, Vol. 5, No.
2, June 1966, page 202 describe arylamino polyfluoro-alkoxy-substituted phosphonitrilic cyclic trimers made by 25 the addition of N-methylanilin~ and triethylamine to a stoichiometric excess o~ phosphonitrilic chloride trimer.
This in turn is then added to a solution of sodium fluoro-alkoxide to complete the reaction.
Singler et al., "Army Science Conference Paper", 5 A117298 describe the synthesis and evaluation of phospha-zene fluid in an attempt to find a replacement for triaryl-phosphates under military specification MIL-H-19457c.
This research involved the us~ of trifluoroethoxy-substituted cyclic phosphonitrilates which were also 10 substituted with either m-chlorophenoxy or m-trifluoro-_ _ methylphenoxy groups. Three modes of synthesis are described:
(1) addition of trimer to a mixture of sodiumaryloxide and sodium trifluoroethoxide, ~2) addition of a mixture of sodium aryloxide and trifluoroethoxide to trimer, and (3) sequential addition of sodium aryloxide followed by sodium trifluoroethoxide to trimer.
Crystallization appears to have been encountered in all 20 cases but oil recovery was increased by following the methods of modes tws or three.
Singler, "Potential of Phosphazenes as Hydraulic Fluids", Hydraulic Fluids Meeting, NASA Ames Research Center, February 1976 summarizes the effect of various 25 substituents on the substituted cyclic phosphonitrilate trimers and tetramers. -4(3~
More recently, Singler et al., Ind. Eng. Chem.(Prod. Res. & Dev.), Vol. 25, No.1 (1986) describe hydraulic fluids made by substituting cyclic phospho-nitrilic chloride with both aryloxy groups and trifluoro-5 ethoxy groups. Reference is again made to the three modesof synthesis; "which yielded widely di~ferent ratios of solids to fluids". For example, mode two in which an equal mole mixture of sodium m-chlorophenate and sodium trifluoroethoxide was added to trimer increased the oil lOrecovery from 18% up to 62%.
_ Carr, Eur. Pat. Appl. 0 145 002, published June 19, 1985 discloses a phosphazene fluid prepared by reacting cyclic phosphonitrilic chloride trimer with a phenol, a polyfluoroalcohol or mixtures thereof in a two-phase medium comprising water and a water-immiscible soivent.
The reaction is promoted by use of a base such as sodium hydroxide, and a phase transfer catalyst. In Example 4, the process carried out with trifluoroethanol and phenol is said to form an almost colorless clear liquid.
It has now been discovered that a clear substan-tially solids-free polyphosphazene hydraulic fluid can be made by reacting a mixture of sodium phenoxide,- sodium m-methylphenoxide, sodium p-methylphenoxide and sodium trifluoroethoxide with a slight stoichiometric excess of 2scyclic phosphonitrilic chloride trimer followed by a V
second stage in which residual chlorine substituents a~e reacted with a second quantity of sodium trifluoro-ethoxide. The recovered fluid remains solids-free on cold storage cycling between -10 and -30C.
A preferred embodiment o~ the invention is a process for making a polyphosphazene hydraulic fluid that remains solids-free on storage at temperatures down to -30C, said process comprising:
(A) prèparing a solution of 0.2-0~3 mole parts of sodium phenoxide, 0.12-0.22 mole parts of ._ sodium m-methylphenoxide, 0.02-0.15 mole parts of sodium p-methylphenoxide and 0.3-0.9 mole parts of sodium 2,2,2-trifluoroethoxide in an inert solvent, the total parts being 0.85-0.95 i moles for each equivalent of replaceable chlorine in the cyclic phosphonitrilic chloride oligomer, (B) preparing a solution of about 0.2 mole parts of a cyclic phosphonitrilic chloride oligomer comprising pre~ominantly trimer in an inert solvent, (C~ mixing the solution of step (A) wit-h the solution of step (B), (D) reactîng the resultant mixture until the reaction is substantially complete, (E) preparing a solution of sodium 2,2,2-trifluoro-ethoxide in an inert solvent, ~334~
(F) in a second stage, mixing the trifluoro-ethoxid~ solution of step (E) with the reaction mixture of step (D), the amount of said trifluoroethoxide solution being an amount which when taken together with the sodium phenoxide, m-methylphenoxide, p-methylphenoxide and trifluoroethoxide of step (A), totals at least 1.01 moie parts per each equivalent of replaceable chlorine in _._ 10 said cyclic phosphonitrilic chloride oligomer, (G) reacting the mixture until substantially all replaceable chlorine has reacted and (H) recovering the polyphosphazene hydraulic fluid.
More preferably, the total amount of sodium phenoxide, sodium m-methylphenoxide, sodium p-methyl-phenoxide and sodium trifluoroethoxide including that added in the second stage is at least 1.05 moles per each equivalent of replaceable chlorine in the cyclic phospho-nitrilic chloride trimer (hereinafter referred to as "trimer") in the initial charge. A still more preferred total amount of aryloxide and trifluoroethoxide is 1.01-1.05 mole parts per each equivalent of replaceable chlorine in the trimer charge. One mole of trimer con-tains six equivalents of replaceable chlorine.
34(3~3 In a more preferred embodiment, the composition of the solution used in step (A) comprises 0.23-0.27 mole parts of sodium phenoxide, 0.15-0.2 mole parts sf sodium m-methylphenoxide, 0.0~-0.11 mole parts of p-methyl-phenoxide and 0.5-0.7 mole parts of sodium trifluoro-ethoxide.
In the most preferred embodiment, the hydraulic fluid i5 prepared by:
(A) preparing a solution of about 0.25 moles of sodium phenoxide, 0.. 18 moles of sodium _ m-methylphenoxide, 0.08 moles of sodium p-methylphenoxide and 0.6 moles of sodium 2,2,2-trifluoroethoxide in tetrahydrofuran, (B) preparing a solution of about 0.2 mole parts of cyclic phosphonitrilic chloride trimer in cyclohexane, (C) adding the solution of step (A) to the solution of step (B) over an extended period of time, (D) heating the resultant mixture at reflux, (E) preparing a solution of about 0.13 mole parts of sodium 2,2,2-trifluoroethoxide in tetrahydrofuran, (F) mixing the solution of step (E) with the reaction mixture of step ~D~, (G) heating the mixture at reflux until substan-tially all replaceable chlorine has reacted and (H) recovering the polyphosphazene hydraulic fluid.
The inert solvent used in step (A) and (E) can be any inert solvent in which the aryloxides and the trifluoroethoxides are soluble. The sodium salts are soluble in most ethers such as diethyl ether, dioxane, tetrahydrofuran (THF), dimethoxyethane, and diethylene _-_ glycol dimethyl ether. The preferred ether solvent is THF.
The amount of solvent used in steps (A) and (E) should be an amount sufficient to dissolve the aryloxides and trifluoroethoxide. A useful range is 200-500 parts by weight solvent per 100 parts sodium aryloxide and sodium trifluoroethoxide. A more useful range when using THF is 250-300 parts THF per each 100 parts sodium aryloxide and sodium trifluoroethoxide.
The inert solvent used to dissolve the trimer in step (B) can be any solven~ that is substantially inert to the trimer and to the sodium aryloxide and sodium trifluoroethoxide. ~These can include aromatic hydro-carbons, cycloalkanes, haloalkanes, and haloaromatics.
~epresentative examples are benzene, toluene, xylene, cyclohexane, methyl cyclohexane, sym-tetrachloroethane, ~34()~
1,1,1-trichloroethane, carbon tetrachloride, chloro-benzene, chlorotoluene, di-chlorobenzene, dichlorotoluene and mixtures thereof. The most preferred solvent for the trimer is cyclohexane.
The amount of trimer solvent used in step ~B) should be a solvent amount. ~ useful range is 3-lO parts by weight of solvent per each part by weight trimer. With cyclohexane, good results have been achieved using about 4 parts cyclohexane per part trimer.
The trimer used in the process need not be pure _ trimer. Trimer is made by reacting phosphorus penta-chloride with ammonium chloride in a solvent such as monochlorobenzene at or near reflux. An excess of ammonium chloride favors cyclics. After removal of solids and linears, the cyclic oligomers are predominantly trimer ~usually 75-90 weight percent trimer) with lesser amounts of tetramers and higher cyclics. The trimer can be purified by distillation and/or crystallization.
Extensive purification is not required and the trimer can contain up to lO weight percent tetramer although preferably the amount is less than 5 weight percent.
The sodium aryloxides can be made by reacting sodium metal in an ether solvent with a mixture of phenol, m~cresol and p-cresol in the desired ratio. The reaction proceeds readily at room temperatures but may be conducted up to reflux.
3LX~;~4~0 g The sodium trifluoroethoxide can be prepared by carefully adding sodium dispersion to an ether solution of trifluoroethanol. A suitable process is described in Sulzer et al., U.S. 4,568,779. Since metallic sodium can react with the fluorine substituents, (Wurz reaction) it is important to minimize the amount of unreacted sodium present in the system at any one time.
The ether solution of the aryloxides and tri~luoro-ethoxides is added to the trimer solution over an extended period. The purpose of this is to always maintain an excess of trimer so that the desired group distribution occurs. Depending upon reaction scale, this addition can take from about 5 minutes up to 8 hours or more.
At the start of the addition, the trimer solution is preferably at ambient temperature. The heat of reaction causes the temperature to rise during the addition. Heat is supplied towards the end of the reaction to bring the mixture to reflux. With a THF-cyclohexane system this is about 71C. Reflux is continued until the reaction is substantially complete.
Reflux is not necessary to complete the reaction since it will go to completion at lower temperatures ove~ a long~r time period Since the total mole parts of aryloxide and trifluoroethoxide is O.~5-0.95 per each equivalent of replaceable chlorine in the trimer, there will still remain 0.05-0.15 equivalents of replaceable chlorine in the reaction mixture.
4~3t3 In a second stage, a solution of sodium trifluoro-ethoxide is prepared in an inert solvent and this is mi~ed with the first reaction mixture. The amount of sodium trifluoroethoxide used in this stage is sufficient to react with the remaining replaceable chlorine. Preferably the total amount of aryloxide and trifluoroethoxide used in the overall process is at least about 1.01 moles per each e~uivalent of chlorine in the initial trimer charge.
A useful range is 1.01-1.05 mole parts aryloxide and tri-fluoroethoxide per each equivalent of chlorine.
The second stage reaction mixture is then heated tocomplete the substitution reaction. Preferably it is refluxed for about 15 minutes up to an hour.
The hydraulic fluid preparation is then complete and it can be recovered by any conventional procedure that removes solvents and salt byproducts. In a preferred procedure the mixture is first washed with water and the water layer removed. Next the mixture is washed with 5%
aqueous caustic followed by a second water wash. Residual solvent is then distilled out under vacuum leaving the hydraulic fluid. The fi~al fluid may be filtered if there are any solids present.
The following example shows how the hydraulic fluid can be prepared.
In a dry reaction vessel was placed 69.48 grams (0.2 moles) phosphonitrilic chloride trimer (97.4 mole 4~
percent trimer, 2.6 mole percent tetramer) and 282 grams of cyclohexane. Following this, 385 grams of a THF
solution containing 29.5 grams (0.25 moles) sodium phenoxide, 22.9 grams (0.18 moles) sodium m-methyl-phenoxide, 9.96 grams (0.077 moles) of sodium p-me~hyl-phenoxide and 73.1 grams (0.6 moles) sodium 2,2,2-tri-fluoroethoxide was added over a 25 minute period as the temperature climbed from 29C up to 62C. The mixture ~las then heated to reflux (71C) and held at reflux for 1 1~ hour. Following this, a solution of 0.13 moles of sodium _ trifluoroethoxide in tetrahydrofuran was added and the mixture refluxed for 70 minutes. Following this, the mixture was washed with about 250 grams of water and the water layer removed. The mixture was then washed with 5%
a~ueous caustic. Following this, the mixture was washed a second time with water. The mixture was transferred to a distillation apparatus and solvents were distilled out under vacuum up to a liquid temperature of 70C at 1-2 torr. This yielded 144.7 grams of a clear fluid.
The U.S. Navy has establishPd certain criteria for phosphazene hydraulic fluids. These ar~ published in "Information to Offerors Or Quoters" Solicitation No.
N00167-86-R-0065. These physical properties compare to those of the hydraulic fluid prepared above are as follows:
Navv Spec.Prepared Fluid Appearance clear, colorless Viscosity (40) 32-38 cSt 38.1 cSt (100) 3.7 cSt min. 4.4 cSt 5 Pour Point -21C max. -21C
Density 1.5 g/ml max. 1.446 Acid Mo. ~0.1 mg KOH/g Demulsibility 40/40 3 min.
separation 10 Flash Point > 275C
The fluid was placed in a cold box which cycled between -30C and -10C. After ten weeks the fluid remained clear and solids-free.
The present process provides a hydraulic fluid having excellent physical properties which remain solids-free after extended storage at very low temperatures.
This in turn is then added to a solution of sodium fluoro-alkoxide to complete the reaction.
Singler et al., "Army Science Conference Paper", 5 A117298 describe the synthesis and evaluation of phospha-zene fluid in an attempt to find a replacement for triaryl-phosphates under military specification MIL-H-19457c.
This research involved the us~ of trifluoroethoxy-substituted cyclic phosphonitrilates which were also 10 substituted with either m-chlorophenoxy or m-trifluoro-_ _ methylphenoxy groups. Three modes of synthesis are described:
(1) addition of trimer to a mixture of sodiumaryloxide and sodium trifluoroethoxide, ~2) addition of a mixture of sodium aryloxide and trifluoroethoxide to trimer, and (3) sequential addition of sodium aryloxide followed by sodium trifluoroethoxide to trimer.
Crystallization appears to have been encountered in all 20 cases but oil recovery was increased by following the methods of modes tws or three.
Singler, "Potential of Phosphazenes as Hydraulic Fluids", Hydraulic Fluids Meeting, NASA Ames Research Center, February 1976 summarizes the effect of various 25 substituents on the substituted cyclic phosphonitrilate trimers and tetramers. -4(3~
More recently, Singler et al., Ind. Eng. Chem.(Prod. Res. & Dev.), Vol. 25, No.1 (1986) describe hydraulic fluids made by substituting cyclic phospho-nitrilic chloride with both aryloxy groups and trifluoro-5 ethoxy groups. Reference is again made to the three modesof synthesis; "which yielded widely di~ferent ratios of solids to fluids". For example, mode two in which an equal mole mixture of sodium m-chlorophenate and sodium trifluoroethoxide was added to trimer increased the oil lOrecovery from 18% up to 62%.
_ Carr, Eur. Pat. Appl. 0 145 002, published June 19, 1985 discloses a phosphazene fluid prepared by reacting cyclic phosphonitrilic chloride trimer with a phenol, a polyfluoroalcohol or mixtures thereof in a two-phase medium comprising water and a water-immiscible soivent.
The reaction is promoted by use of a base such as sodium hydroxide, and a phase transfer catalyst. In Example 4, the process carried out with trifluoroethanol and phenol is said to form an almost colorless clear liquid.
It has now been discovered that a clear substan-tially solids-free polyphosphazene hydraulic fluid can be made by reacting a mixture of sodium phenoxide,- sodium m-methylphenoxide, sodium p-methylphenoxide and sodium trifluoroethoxide with a slight stoichiometric excess of 2scyclic phosphonitrilic chloride trimer followed by a V
second stage in which residual chlorine substituents a~e reacted with a second quantity of sodium trifluoro-ethoxide. The recovered fluid remains solids-free on cold storage cycling between -10 and -30C.
A preferred embodiment o~ the invention is a process for making a polyphosphazene hydraulic fluid that remains solids-free on storage at temperatures down to -30C, said process comprising:
(A) prèparing a solution of 0.2-0~3 mole parts of sodium phenoxide, 0.12-0.22 mole parts of ._ sodium m-methylphenoxide, 0.02-0.15 mole parts of sodium p-methylphenoxide and 0.3-0.9 mole parts of sodium 2,2,2-trifluoroethoxide in an inert solvent, the total parts being 0.85-0.95 i moles for each equivalent of replaceable chlorine in the cyclic phosphonitrilic chloride oligomer, (B) preparing a solution of about 0.2 mole parts of a cyclic phosphonitrilic chloride oligomer comprising pre~ominantly trimer in an inert solvent, (C~ mixing the solution of step (A) wit-h the solution of step (B), (D) reactîng the resultant mixture until the reaction is substantially complete, (E) preparing a solution of sodium 2,2,2-trifluoro-ethoxide in an inert solvent, ~334~
(F) in a second stage, mixing the trifluoro-ethoxid~ solution of step (E) with the reaction mixture of step (D), the amount of said trifluoroethoxide solution being an amount which when taken together with the sodium phenoxide, m-methylphenoxide, p-methylphenoxide and trifluoroethoxide of step (A), totals at least 1.01 moie parts per each equivalent of replaceable chlorine in _._ 10 said cyclic phosphonitrilic chloride oligomer, (G) reacting the mixture until substantially all replaceable chlorine has reacted and (H) recovering the polyphosphazene hydraulic fluid.
More preferably, the total amount of sodium phenoxide, sodium m-methylphenoxide, sodium p-methyl-phenoxide and sodium trifluoroethoxide including that added in the second stage is at least 1.05 moles per each equivalent of replaceable chlorine in the cyclic phospho-nitrilic chloride trimer (hereinafter referred to as "trimer") in the initial charge. A still more preferred total amount of aryloxide and trifluoroethoxide is 1.01-1.05 mole parts per each equivalent of replaceable chlorine in the trimer charge. One mole of trimer con-tains six equivalents of replaceable chlorine.
34(3~3 In a more preferred embodiment, the composition of the solution used in step (A) comprises 0.23-0.27 mole parts of sodium phenoxide, 0.15-0.2 mole parts sf sodium m-methylphenoxide, 0.0~-0.11 mole parts of p-methyl-phenoxide and 0.5-0.7 mole parts of sodium trifluoro-ethoxide.
In the most preferred embodiment, the hydraulic fluid i5 prepared by:
(A) preparing a solution of about 0.25 moles of sodium phenoxide, 0.. 18 moles of sodium _ m-methylphenoxide, 0.08 moles of sodium p-methylphenoxide and 0.6 moles of sodium 2,2,2-trifluoroethoxide in tetrahydrofuran, (B) preparing a solution of about 0.2 mole parts of cyclic phosphonitrilic chloride trimer in cyclohexane, (C) adding the solution of step (A) to the solution of step (B) over an extended period of time, (D) heating the resultant mixture at reflux, (E) preparing a solution of about 0.13 mole parts of sodium 2,2,2-trifluoroethoxide in tetrahydrofuran, (F) mixing the solution of step (E) with the reaction mixture of step ~D~, (G) heating the mixture at reflux until substan-tially all replaceable chlorine has reacted and (H) recovering the polyphosphazene hydraulic fluid.
The inert solvent used in step (A) and (E) can be any inert solvent in which the aryloxides and the trifluoroethoxides are soluble. The sodium salts are soluble in most ethers such as diethyl ether, dioxane, tetrahydrofuran (THF), dimethoxyethane, and diethylene _-_ glycol dimethyl ether. The preferred ether solvent is THF.
The amount of solvent used in steps (A) and (E) should be an amount sufficient to dissolve the aryloxides and trifluoroethoxide. A useful range is 200-500 parts by weight solvent per 100 parts sodium aryloxide and sodium trifluoroethoxide. A more useful range when using THF is 250-300 parts THF per each 100 parts sodium aryloxide and sodium trifluoroethoxide.
The inert solvent used to dissolve the trimer in step (B) can be any solven~ that is substantially inert to the trimer and to the sodium aryloxide and sodium trifluoroethoxide. ~These can include aromatic hydro-carbons, cycloalkanes, haloalkanes, and haloaromatics.
~epresentative examples are benzene, toluene, xylene, cyclohexane, methyl cyclohexane, sym-tetrachloroethane, ~34()~
1,1,1-trichloroethane, carbon tetrachloride, chloro-benzene, chlorotoluene, di-chlorobenzene, dichlorotoluene and mixtures thereof. The most preferred solvent for the trimer is cyclohexane.
The amount of trimer solvent used in step ~B) should be a solvent amount. ~ useful range is 3-lO parts by weight of solvent per each part by weight trimer. With cyclohexane, good results have been achieved using about 4 parts cyclohexane per part trimer.
The trimer used in the process need not be pure _ trimer. Trimer is made by reacting phosphorus penta-chloride with ammonium chloride in a solvent such as monochlorobenzene at or near reflux. An excess of ammonium chloride favors cyclics. After removal of solids and linears, the cyclic oligomers are predominantly trimer ~usually 75-90 weight percent trimer) with lesser amounts of tetramers and higher cyclics. The trimer can be purified by distillation and/or crystallization.
Extensive purification is not required and the trimer can contain up to lO weight percent tetramer although preferably the amount is less than 5 weight percent.
The sodium aryloxides can be made by reacting sodium metal in an ether solvent with a mixture of phenol, m~cresol and p-cresol in the desired ratio. The reaction proceeds readily at room temperatures but may be conducted up to reflux.
3LX~;~4~0 g The sodium trifluoroethoxide can be prepared by carefully adding sodium dispersion to an ether solution of trifluoroethanol. A suitable process is described in Sulzer et al., U.S. 4,568,779. Since metallic sodium can react with the fluorine substituents, (Wurz reaction) it is important to minimize the amount of unreacted sodium present in the system at any one time.
The ether solution of the aryloxides and tri~luoro-ethoxides is added to the trimer solution over an extended period. The purpose of this is to always maintain an excess of trimer so that the desired group distribution occurs. Depending upon reaction scale, this addition can take from about 5 minutes up to 8 hours or more.
At the start of the addition, the trimer solution is preferably at ambient temperature. The heat of reaction causes the temperature to rise during the addition. Heat is supplied towards the end of the reaction to bring the mixture to reflux. With a THF-cyclohexane system this is about 71C. Reflux is continued until the reaction is substantially complete.
Reflux is not necessary to complete the reaction since it will go to completion at lower temperatures ove~ a long~r time period Since the total mole parts of aryloxide and trifluoroethoxide is O.~5-0.95 per each equivalent of replaceable chlorine in the trimer, there will still remain 0.05-0.15 equivalents of replaceable chlorine in the reaction mixture.
4~3t3 In a second stage, a solution of sodium trifluoro-ethoxide is prepared in an inert solvent and this is mi~ed with the first reaction mixture. The amount of sodium trifluoroethoxide used in this stage is sufficient to react with the remaining replaceable chlorine. Preferably the total amount of aryloxide and trifluoroethoxide used in the overall process is at least about 1.01 moles per each e~uivalent of chlorine in the initial trimer charge.
A useful range is 1.01-1.05 mole parts aryloxide and tri-fluoroethoxide per each equivalent of chlorine.
The second stage reaction mixture is then heated tocomplete the substitution reaction. Preferably it is refluxed for about 15 minutes up to an hour.
The hydraulic fluid preparation is then complete and it can be recovered by any conventional procedure that removes solvents and salt byproducts. In a preferred procedure the mixture is first washed with water and the water layer removed. Next the mixture is washed with 5%
aqueous caustic followed by a second water wash. Residual solvent is then distilled out under vacuum leaving the hydraulic fluid. The fi~al fluid may be filtered if there are any solids present.
The following example shows how the hydraulic fluid can be prepared.
In a dry reaction vessel was placed 69.48 grams (0.2 moles) phosphonitrilic chloride trimer (97.4 mole 4~
percent trimer, 2.6 mole percent tetramer) and 282 grams of cyclohexane. Following this, 385 grams of a THF
solution containing 29.5 grams (0.25 moles) sodium phenoxide, 22.9 grams (0.18 moles) sodium m-methyl-phenoxide, 9.96 grams (0.077 moles) of sodium p-me~hyl-phenoxide and 73.1 grams (0.6 moles) sodium 2,2,2-tri-fluoroethoxide was added over a 25 minute period as the temperature climbed from 29C up to 62C. The mixture ~las then heated to reflux (71C) and held at reflux for 1 1~ hour. Following this, a solution of 0.13 moles of sodium _ trifluoroethoxide in tetrahydrofuran was added and the mixture refluxed for 70 minutes. Following this, the mixture was washed with about 250 grams of water and the water layer removed. The mixture was then washed with 5%
a~ueous caustic. Following this, the mixture was washed a second time with water. The mixture was transferred to a distillation apparatus and solvents were distilled out under vacuum up to a liquid temperature of 70C at 1-2 torr. This yielded 144.7 grams of a clear fluid.
The U.S. Navy has establishPd certain criteria for phosphazene hydraulic fluids. These ar~ published in "Information to Offerors Or Quoters" Solicitation No.
N00167-86-R-0065. These physical properties compare to those of the hydraulic fluid prepared above are as follows:
Navv Spec.Prepared Fluid Appearance clear, colorless Viscosity (40) 32-38 cSt 38.1 cSt (100) 3.7 cSt min. 4.4 cSt 5 Pour Point -21C max. -21C
Density 1.5 g/ml max. 1.446 Acid Mo. ~0.1 mg KOH/g Demulsibility 40/40 3 min.
separation 10 Flash Point > 275C
The fluid was placed in a cold box which cycled between -30C and -10C. After ten weeks the fluid remained clear and solids-free.
The present process provides a hydraulic fluid having excellent physical properties which remain solids-free after extended storage at very low temperatures.
Claims (9)
1. A process for making a polyphosphazene hydraulic fluid that remains solids-free on storage at temperatures down to -30°C, said process comprising:
(A) preparing a solution of 0.2-0.3 mole parts of sodium phenoxide, 0.12-0.22 mole parts of sodium m-methylphenoxide, 0.02-0.15 mole parts of sodium p-methylphenoxide and 0.3-0.9 mole parts of sodium 2,2,2-trifluoroethoxide in an inert solvent, the total parts being 0.85-0.95 moles for each equivalent of replaceable chlorine in the cyclic phosphonitrilic chloride oligomer, (B) preparing a solution of about 0.2 mole parts of a cyclic phosphonitrilic chloride oligomer comprising predominantly trimer in an inert solvent, (C) mixing the solution of step (A) with the solution of step (B), (D) reacting the resultant mixture at a tem-perature in the range of ambient up to reflux until the reaction is substantially complete, (E) preparing a solution of sodium 2,2,2-tri-fluoroethoxide in an inert solvent, (F) in a second stage, mixing the trifluoro-ethoxide solution of step (E) with the reaction mixture of step (D), the amount of said trifluoroethoxide solution being an amount which when taken together with the sodium phenoxide, m-methylphenoxide, p-methylphenoxide and trifluoroethoxide of step (A), totals at least 1.01 mole parts per each equivalent of replaceable chlorine in said cyclic phosphonitrilic chloride oligomer, (G) reacting the mixture at an elevated temperature up to reflux until substantially all replaceable chlorine has reacted and (H) recovering the polyphosphazene hydraulic fluid.
(A) preparing a solution of 0.2-0.3 mole parts of sodium phenoxide, 0.12-0.22 mole parts of sodium m-methylphenoxide, 0.02-0.15 mole parts of sodium p-methylphenoxide and 0.3-0.9 mole parts of sodium 2,2,2-trifluoroethoxide in an inert solvent, the total parts being 0.85-0.95 moles for each equivalent of replaceable chlorine in the cyclic phosphonitrilic chloride oligomer, (B) preparing a solution of about 0.2 mole parts of a cyclic phosphonitrilic chloride oligomer comprising predominantly trimer in an inert solvent, (C) mixing the solution of step (A) with the solution of step (B), (D) reacting the resultant mixture at a tem-perature in the range of ambient up to reflux until the reaction is substantially complete, (E) preparing a solution of sodium 2,2,2-tri-fluoroethoxide in an inert solvent, (F) in a second stage, mixing the trifluoro-ethoxide solution of step (E) with the reaction mixture of step (D), the amount of said trifluoroethoxide solution being an amount which when taken together with the sodium phenoxide, m-methylphenoxide, p-methylphenoxide and trifluoroethoxide of step (A), totals at least 1.01 mole parts per each equivalent of replaceable chlorine in said cyclic phosphonitrilic chloride oligomer, (G) reacting the mixture at an elevated temperature up to reflux until substantially all replaceable chlorine has reacted and (H) recovering the polyphosphazene hydraulic fluid.
2. A process as claimed in Claim 1 in which in step (C) the solution of step (A) is added to the solution of step (B).
3. A process as claimed in Claim 1 in which the amount of trifluoroethoxide solution added in step (F) is an amount which when taken together with the sodium phenoxide, m-methylphenoxide, p-methylphenoxide and tri-fluoroethoxide of step (A) totals 1.01-1.05 mole parts per each equivalent of replaceable chlorine in said cyclic phosphonitrilic chloride oligomer.
4. A process as claimed in Claim 3 in which in step (C) the solution of step (A) is added to the solution of step (B) over an extended period of time.
5. A process as claimed in Claim 4 in which said inert solvent in steps (A) and (E) is tetrahydrofuran and said inert solvent in step (B) is cyclohexane.
6. A polyphosphazene hydraulic fluid made by the process as claimed in Claims 1, 2 or 3.
7. A polyphosphazene hydraulic fluid made by the process as claimed in Claims 4 or 5.
8. A process for making a polyphosphazene hydraulic fluid that remains solids-free on storage at -30°C, said process comprising:
(A) preparing a solution of about 0.25 moles of sodium phenoxide, 0.18 moles of sodium m-methylphenoxide, 0.08 moles of sodium p-methylphenoxide and 0.6 moles of sodium 2,2,2-trifluoroethoxide in tetrahydrofuran, (B) preparing a solution of about 0.2 mole parts of cyclic phosphonitrilic chloride trimer in cyclohexane, (C) adding the solution of step (A) to the solution of step (B) over an extended period of time, (D) heating the resultant mixture at reflux, (E) preparing a solution of about 0.13 mole parts of sodium, 2,2,2-trifluoroethoxide in tetrahydrofuran, (F) mixing the solution of step (E) with the reaction mixture of step (D), (G) heating the mixture at reflux until substantially all replaceable chlorine has reacted and (H) recovering the polyphosphazene hydraulic fluid.
(A) preparing a solution of about 0.25 moles of sodium phenoxide, 0.18 moles of sodium m-methylphenoxide, 0.08 moles of sodium p-methylphenoxide and 0.6 moles of sodium 2,2,2-trifluoroethoxide in tetrahydrofuran, (B) preparing a solution of about 0.2 mole parts of cyclic phosphonitrilic chloride trimer in cyclohexane, (C) adding the solution of step (A) to the solution of step (B) over an extended period of time, (D) heating the resultant mixture at reflux, (E) preparing a solution of about 0.13 mole parts of sodium, 2,2,2-trifluoroethoxide in tetrahydrofuran, (F) mixing the solution of step (E) with the reaction mixture of step (D), (G) heating the mixture at reflux until substantially all replaceable chlorine has reacted and (H) recovering the polyphosphazene hydraulic fluid.
9. A polyphosphazene hydraulic fluid made by the process as claimed in Claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000537916A CA1283400C (en) | 1987-05-25 | 1987-05-25 | Hydraulic fluid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000537916A CA1283400C (en) | 1987-05-25 | 1987-05-25 | Hydraulic fluid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1283400C true CA1283400C (en) | 1991-04-23 |
Family
ID=4135742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000537916A Expired - Lifetime CA1283400C (en) | 1987-05-25 | 1987-05-25 | Hydraulic fluid |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1283400C (en) |
-
1987
- 1987-05-25 CA CA000537916A patent/CA1283400C/en not_active Expired - Lifetime
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