CA2183220C - Process for the preparation of a propylene glycol antifreeze containing an alkali metal silicate - Google Patents
Process for the preparation of a propylene glycol antifreeze containing an alkali metal silicate Download PDFInfo
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- CA2183220C CA2183220C CA002183220A CA2183220A CA2183220C CA 2183220 C CA2183220 C CA 2183220C CA 002183220 A CA002183220 A CA 002183220A CA 2183220 A CA2183220 A CA 2183220A CA 2183220 C CA2183220 C CA 2183220C
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- silicate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
Abstract
The preparation of propylene glycol compositions containing alkali metal silicates having improved gel resistance is provided by forming a silicate premix having effective amounts of inorganic base compound(s) and water. The silicate premix is then added to the propylene glycol.
Description
~ 18320 The invention relates to a process for preparing an improved propylene glycol antifreeze containing silicate which is resistant to gellation of the silicate.
Antifreeze compositions comprising ethylene glycol and a wide variety of corrosion inhibitors are well known in the prior art as evidenced by U.S.
Patent Nos.
3,341.469, 3,337,496, 4,241,014 and 4,664,833. Although prior art patents disclose the use of a wide variety of glycols in antifreeze compositions, such patents primarily deal with and provide working examples for ethylene glycol based antifreeze compositions.
Further, the prior art has not generally disclosed any criticality of the mixing order of the corrosion inhibitors to the ethylene glycol. Two exceptions to this are found in U.S. Patent Nos. 3,282,84b (Scott) and 4,149,985 (Wilson). Scott discloses a method for manufacturing an antifreeze involving the mixing order of ethylene glycol, borate, silicate, and sodium mercaptobenzotriazole. Wilson discloses a method for manufacturing an antifreeze involving the mixing order of ethylene glycol, borate, basic inorganic compound (until a pH of from 9.5 to 10.5) and then silicate.
It has been found that the order of mixing disclosed in the Scott and Wilson patents is not applicable to all types of alkylene glycols and is particularly inapplicable for manufacturing propylene glycol antifreeze compositions. U.S. Patent No. 5, 422,026 (Greaney) discloses a phosphate-free corrosion inhibited antifreeze prepared by admixing an aqueous solution comprising silicate, silicate stabilizer (polysiloxane), molybdate, and a relatively small amount of a basic compound, with a solution of an alkylene glycol, preferably, propylene glycol, and the various corrosion inhibitors typically employed, e.g., mercaptobenzotriazole, borate, nitrate, sebacate, tolyltriazole, and the like.
Greaney does 2183~~0 not recognize or disclose the need for a high pH in the initial silicate premix in achieving long term silicate stability without gel formation. Applicants' invention overcomes the prior art limitations and provides a process for preparing gel resistant propylene glycol antifreeze compositions containing alkali metal silicate.
It has been discovered that the preparation of propylene glycol antifreeze containing an alkali metal silicate can be improved so as to provide enhanced gel resistance by controlling the amount of basic compound and water of the silicate mixture at the time the propylene glycol and alkali metal silicate are admixed. Such compositions are useful in the manufacture of antifreeze/coolant compositions for use in the cooling systems for internal combustion engines. The invention correlates the concentration of basic compounds) and water to the alkali metal silicate in a premixed additive ("silicate premix") whereby the silicate has improved gel resistance when added to the propylene glycol.
The instant invention achieves this improvement in resistance to gel formation by use of a "silicate premix" which is employed to prepare compositions containing 85 to 98 weight percent propylene glycol, a corrosion inhibiting amount of an alkali metal silicate, basic compound, water and a silicone. The process of the invention comprises:
(a) preparing a "silicate premix" by admixing an alkali metal silicate, a basic inorganic compound (preferably as an aqueous base solution) to provide a silica to alkali metal oxide mole ratio (Si02: MZO) where M is an alkali metal cation, of less than about 0.25, preferably less than about 0.22, and adding an effective amount of water to said premix to provide at least about 60 weight percent water in the silicate premix; and (b) adding the silicate premix of step (a) to said propylene glycol.
Antifreeze compositions comprising ethylene glycol and a wide variety of corrosion inhibitors are well known in the prior art as evidenced by U.S.
Patent Nos.
3,341.469, 3,337,496, 4,241,014 and 4,664,833. Although prior art patents disclose the use of a wide variety of glycols in antifreeze compositions, such patents primarily deal with and provide working examples for ethylene glycol based antifreeze compositions.
Further, the prior art has not generally disclosed any criticality of the mixing order of the corrosion inhibitors to the ethylene glycol. Two exceptions to this are found in U.S. Patent Nos. 3,282,84b (Scott) and 4,149,985 (Wilson). Scott discloses a method for manufacturing an antifreeze involving the mixing order of ethylene glycol, borate, silicate, and sodium mercaptobenzotriazole. Wilson discloses a method for manufacturing an antifreeze involving the mixing order of ethylene glycol, borate, basic inorganic compound (until a pH of from 9.5 to 10.5) and then silicate.
It has been found that the order of mixing disclosed in the Scott and Wilson patents is not applicable to all types of alkylene glycols and is particularly inapplicable for manufacturing propylene glycol antifreeze compositions. U.S. Patent No. 5, 422,026 (Greaney) discloses a phosphate-free corrosion inhibited antifreeze prepared by admixing an aqueous solution comprising silicate, silicate stabilizer (polysiloxane), molybdate, and a relatively small amount of a basic compound, with a solution of an alkylene glycol, preferably, propylene glycol, and the various corrosion inhibitors typically employed, e.g., mercaptobenzotriazole, borate, nitrate, sebacate, tolyltriazole, and the like.
Greaney does 2183~~0 not recognize or disclose the need for a high pH in the initial silicate premix in achieving long term silicate stability without gel formation. Applicants' invention overcomes the prior art limitations and provides a process for preparing gel resistant propylene glycol antifreeze compositions containing alkali metal silicate.
It has been discovered that the preparation of propylene glycol antifreeze containing an alkali metal silicate can be improved so as to provide enhanced gel resistance by controlling the amount of basic compound and water of the silicate mixture at the time the propylene glycol and alkali metal silicate are admixed. Such compositions are useful in the manufacture of antifreeze/coolant compositions for use in the cooling systems for internal combustion engines. The invention correlates the concentration of basic compounds) and water to the alkali metal silicate in a premixed additive ("silicate premix") whereby the silicate has improved gel resistance when added to the propylene glycol.
The instant invention achieves this improvement in resistance to gel formation by use of a "silicate premix" which is employed to prepare compositions containing 85 to 98 weight percent propylene glycol, a corrosion inhibiting amount of an alkali metal silicate, basic compound, water and a silicone. The process of the invention comprises:
(a) preparing a "silicate premix" by admixing an alkali metal silicate, a basic inorganic compound (preferably as an aqueous base solution) to provide a silica to alkali metal oxide mole ratio (Si02: MZO) where M is an alkali metal cation, of less than about 0.25, preferably less than about 0.22, and adding an effective amount of water to said premix to provide at least about 60 weight percent water in the silicate premix; and (b) adding the silicate premix of step (a) to said propylene glycol.
The above process provides compositions that have improved resistance to gel formation sometimes observed in alkylene glycol-containing antifreeze compositions containing alkali metal silicates.
The order of mixing of the ingredients described herein is significantly different than that taught in the prior art so that the pH and water content associated with the alkali metal silicate can be controlled. This is to be contrasted with the prior art. For example, U.S. Patent No. 4,149,985 teaches the importance of adding borate to an alkylene glycol while maintaining a neutral, acidic or slightly alkaline pH, then raising the pH to from 9.5 to 10.5 by adding a basic inorganic compound, followed by addition of an alkali metal silicate.
The instant invention teaches that it is not necessary to add alkali metal borate to a neutral alkylene glycol as taught by U.S. Patent No. 4,149,985, if an alkali metal borate or other corrosion inhibitors are to be employed. In fact, it is preferred to add borate, if present, after addition of a silicate premix to the propylene glycol, as will be further discussed hereinafter.
The instant invention provides compositions which are resistant to silicate gel formation by providing the alkali metal silicate in a form wherein it may be added to the propylene glycol with improved resistance to silicate gel formation. The stable form of the silicate employed herein is achieved by forming an "over-alkalized"
silicate premix, i.e., an alkali metal silicate solution containing sufficient base to achieve a silica to alkali metal oxide mole ratio (SiOZ: M20), where "M" is an alkali metal cation, of less than about 0.25, preferably less than about 0.22, with an effective amount of water to solubilize the alkali metal silicate and inorganic basic compound so as to provide the total weight percent ~_ 21 Q~220 (wt 9c) of water in the premix of at least about 60 wt. 90 or higher, and preferably, at least about 63 wt. %.
As used herein the term "propylene glycol" shall be understood to mean propylene glycol and mixtures of propylene glycol with one or more of dipropylene glycol, ethylene glycol and diethylene glycol, wherein the propylene glycol comprises greater than about 95 weight percent of any such mixture. As is well known, however, propylene glycol and the propylene glycol mixtures referred to herein can contain up to about 5 weight percent added water.
The basic inorganic compound can be an alkali metal hydroxide, allcali metal carbonate, alkali metal phosphate, and the like, and is preferably sodium or potassium hydroxide.
Alkali metal silicates useful herein include, for example, sodium metasilicate, potassium metasilicate, lithium metasilicate, the corresponding orthosilicates, and the like, and mixtures thereof.
Optional additives can be employed in minor amounts of less than 10 weight percent based on the total weight of the antifreeze composition.
Typical optional additives can include, for example, known corrosion inhibitors for metals such as, for example, tungstates, selenates, carbonates and bicarbonates, monocarboxylic acids, sebacates and other dicarboxylic acids, molybdates, borates, phosphates and benzoates, hydroxy benzoates or acids thereof, silicones, alkali metal nitrates, alkali metal nitrites, tolyltriazole, mercaptobenzotriazole, benzotriazole, and the like, or mixtures thereof. If one or more of the known inhibitors are employed together with the inhibitors present in the instant invention, the sum total of all inhibitors should be used in an effective inhibitory amount, i.e., an amount sufficient to provide some corrosion inhibition with respect to the metal surfaces to be protected. Other typical optional additives would m 218 322 0 include buffers, such as alkali metal borates, phosphates and carbonates;
wetting agents and surfactants, such as, for example, known ionic and non-ionic surfactants such as poly (oxyalkylene) adducts of fatty alcohols; anti-foaming agents and/or lubricants such as the well known polysiloxanes and the polyoxyallcylene glycols, as well as any other minor ingredients known in the antifreezelcoolant art.
For the purposes of this invention, the gel resistance of the composition is determined by observing the presence or absence of gel formation immediately upon _ mixing or after sitting quiescently in a closed bottle at 55°C for a determinate period of time (until gel formation is observed).
As can be seen from the examples, the order of addition of an over-alkalized aqueoussilicate premix is a critical feature of the invention, and is not taught by the prior art. The order of addition is related to maintaining silicate solubility in the propylene glycol. First, silicate requires a high pH to be stable. The premix of the present invention maximizes the pH during silicate addition and never allows the pH to be less than the final buffer pH. Second, silicate will condense if dehydrated. The premix of the present invention ensures that a sufficient amount of water is present during admixture with the propylene glycol. While the order of mixing is especially advantageous with propylene glycol, which is less soluble than ethylene glycol, this order of mixing also can be useful in the preparation of other alkylene glycol antifreezes.
Once the silicate is in solution in the premix, further silicate stabilization can be achieved through use of a conventional silicate stabilizer, e.g., the organic and/or inorganic silanes and/or siloxanes disclosed in U.S. Patent Nos. 4,772,408, 4,725,405, 4,414,126, 5,064,552 and the patents referred to therein. The silicate stabilizer can be added directly to the C
~18~2~0 propylene glycol or to the premix or to the resulting admixture obtained upon adding the premix to the propylene glycol solution.
The present invention involves the stabilization of the alkali metal silicate with basic inorganic compound and water to form a silicate premix which is then added to the propylene glycol.
Although it is preferred to add corrosion inhibitor compounds to the resultant silicate-containing propylene glycol mixture, the corrosion inhibitor compounds can, if desired, be added to the propylene glycol solution prior to the addition of the silicate premix. Since the corrosion inhibitor compounds can lower the pH, it is preferred that in such instance, additional basic inorganic compounds be added to bring the pH
of the propylene glycol solution at least back to the normal pH of propylene glycol, i.e., about 6Ø In this manner, the pH in the final silicate-containing propylene glycol mixture will be at least about 9.0 and, preferably, between about 9.5 and about 11.5.
In one embodiment a mixture is prepared containing between about 92 and 93 weight percent propylene glycol and between about 3.7 and about 3.9 weight percent of a silicate premix (the premix containing between about 0.34 and about 0.35 weight percent basic inorganic compound, and about 0.25 weight percent added water such that the total water content of the premix is at least 60% by weight or higher).
The rate of addition of the silicate premix to the propylene glycol is related to the pH and water content of the propylene glycol and silicate premix. It is preferred to add the silicate premix either slowly or stepwise in two or more aliquots to the propylene glycol, allowing any cloudiness which may form to clear before continuing the addition of the silicate premix to the propylene glycol. This rate of addition becomes more important where the pH of the propylene glycol or propylene glycol/inhibitors mixture may be low, e.g., having a pH below that of the propylene glycol.
The order of mixing of the ingredients described herein is significantly different than that taught in the prior art so that the pH and water content associated with the alkali metal silicate can be controlled. This is to be contrasted with the prior art. For example, U.S. Patent No. 4,149,985 teaches the importance of adding borate to an alkylene glycol while maintaining a neutral, acidic or slightly alkaline pH, then raising the pH to from 9.5 to 10.5 by adding a basic inorganic compound, followed by addition of an alkali metal silicate.
The instant invention teaches that it is not necessary to add alkali metal borate to a neutral alkylene glycol as taught by U.S. Patent No. 4,149,985, if an alkali metal borate or other corrosion inhibitors are to be employed. In fact, it is preferred to add borate, if present, after addition of a silicate premix to the propylene glycol, as will be further discussed hereinafter.
The instant invention provides compositions which are resistant to silicate gel formation by providing the alkali metal silicate in a form wherein it may be added to the propylene glycol with improved resistance to silicate gel formation. The stable form of the silicate employed herein is achieved by forming an "over-alkalized"
silicate premix, i.e., an alkali metal silicate solution containing sufficient base to achieve a silica to alkali metal oxide mole ratio (SiOZ: M20), where "M" is an alkali metal cation, of less than about 0.25, preferably less than about 0.22, with an effective amount of water to solubilize the alkali metal silicate and inorganic basic compound so as to provide the total weight percent ~_ 21 Q~220 (wt 9c) of water in the premix of at least about 60 wt. 90 or higher, and preferably, at least about 63 wt. %.
As used herein the term "propylene glycol" shall be understood to mean propylene glycol and mixtures of propylene glycol with one or more of dipropylene glycol, ethylene glycol and diethylene glycol, wherein the propylene glycol comprises greater than about 95 weight percent of any such mixture. As is well known, however, propylene glycol and the propylene glycol mixtures referred to herein can contain up to about 5 weight percent added water.
The basic inorganic compound can be an alkali metal hydroxide, allcali metal carbonate, alkali metal phosphate, and the like, and is preferably sodium or potassium hydroxide.
Alkali metal silicates useful herein include, for example, sodium metasilicate, potassium metasilicate, lithium metasilicate, the corresponding orthosilicates, and the like, and mixtures thereof.
Optional additives can be employed in minor amounts of less than 10 weight percent based on the total weight of the antifreeze composition.
Typical optional additives can include, for example, known corrosion inhibitors for metals such as, for example, tungstates, selenates, carbonates and bicarbonates, monocarboxylic acids, sebacates and other dicarboxylic acids, molybdates, borates, phosphates and benzoates, hydroxy benzoates or acids thereof, silicones, alkali metal nitrates, alkali metal nitrites, tolyltriazole, mercaptobenzotriazole, benzotriazole, and the like, or mixtures thereof. If one or more of the known inhibitors are employed together with the inhibitors present in the instant invention, the sum total of all inhibitors should be used in an effective inhibitory amount, i.e., an amount sufficient to provide some corrosion inhibition with respect to the metal surfaces to be protected. Other typical optional additives would m 218 322 0 include buffers, such as alkali metal borates, phosphates and carbonates;
wetting agents and surfactants, such as, for example, known ionic and non-ionic surfactants such as poly (oxyalkylene) adducts of fatty alcohols; anti-foaming agents and/or lubricants such as the well known polysiloxanes and the polyoxyallcylene glycols, as well as any other minor ingredients known in the antifreezelcoolant art.
For the purposes of this invention, the gel resistance of the composition is determined by observing the presence or absence of gel formation immediately upon _ mixing or after sitting quiescently in a closed bottle at 55°C for a determinate period of time (until gel formation is observed).
As can be seen from the examples, the order of addition of an over-alkalized aqueoussilicate premix is a critical feature of the invention, and is not taught by the prior art. The order of addition is related to maintaining silicate solubility in the propylene glycol. First, silicate requires a high pH to be stable. The premix of the present invention maximizes the pH during silicate addition and never allows the pH to be less than the final buffer pH. Second, silicate will condense if dehydrated. The premix of the present invention ensures that a sufficient amount of water is present during admixture with the propylene glycol. While the order of mixing is especially advantageous with propylene glycol, which is less soluble than ethylene glycol, this order of mixing also can be useful in the preparation of other alkylene glycol antifreezes.
Once the silicate is in solution in the premix, further silicate stabilization can be achieved through use of a conventional silicate stabilizer, e.g., the organic and/or inorganic silanes and/or siloxanes disclosed in U.S. Patent Nos. 4,772,408, 4,725,405, 4,414,126, 5,064,552 and the patents referred to therein. The silicate stabilizer can be added directly to the C
~18~2~0 propylene glycol or to the premix or to the resulting admixture obtained upon adding the premix to the propylene glycol solution.
The present invention involves the stabilization of the alkali metal silicate with basic inorganic compound and water to form a silicate premix which is then added to the propylene glycol.
Although it is preferred to add corrosion inhibitor compounds to the resultant silicate-containing propylene glycol mixture, the corrosion inhibitor compounds can, if desired, be added to the propylene glycol solution prior to the addition of the silicate premix. Since the corrosion inhibitor compounds can lower the pH, it is preferred that in such instance, additional basic inorganic compounds be added to bring the pH
of the propylene glycol solution at least back to the normal pH of propylene glycol, i.e., about 6Ø In this manner, the pH in the final silicate-containing propylene glycol mixture will be at least about 9.0 and, preferably, between about 9.5 and about 11.5.
In one embodiment a mixture is prepared containing between about 92 and 93 weight percent propylene glycol and between about 3.7 and about 3.9 weight percent of a silicate premix (the premix containing between about 0.34 and about 0.35 weight percent basic inorganic compound, and about 0.25 weight percent added water such that the total water content of the premix is at least 60% by weight or higher).
The rate of addition of the silicate premix to the propylene glycol is related to the pH and water content of the propylene glycol and silicate premix. It is preferred to add the silicate premix either slowly or stepwise in two or more aliquots to the propylene glycol, allowing any cloudiness which may form to clear before continuing the addition of the silicate premix to the propylene glycol. This rate of addition becomes more important where the pH of the propylene glycol or propylene glycol/inhibitors mixture may be low, e.g., having a pH below that of the propylene glycol.
EXAMPLES
The following examples were conducted to demonstrate the improved gel resistance of silicate-containing alkylene glycol compositions formed according to the process of the instant invention as compared to the processes of the prior art.
In the following examples, the following nomenclature is employed.
NOMENCLATURE MEANING ~ SUPPLIER
PG Propylene Glycol Silicone A Organosiloxane, tradeOSi Specialties name Sil uest~ Y-556- silaneDanbu , CT
Silicone B Organosiloxane, tradeDow Corning Corporation name DC- 2-6083 Midland, MI
NaTTZ Sodium Tol ltriazole NaMBT Sodium Merca tobenzothiazole a ueous Antifoam A Polypropylene glycol Union Carbide Corporation type antifoaming agent, Danbury, CT
trade name Antifoam B Organosiloxane type Dow Corning Corporation antifoaming agent, Midland, MI
trade name Nasil Gr 40 CL Mixture of Silicate, Occidental Chemical (trade KOH, and name) water having a SiOz/M20Dallas, TX
mole ratio of 3.22 Kasil #6 (trade Mixture of Silicate, The PQ Corporation name) KOH, and water having a SiO~/M20Valley Forge, PA
mole ratio of 3.29 DI water Deionized Water Examples A and C are comparative examples. Examples B, D, E, F, G. H, I
and J were carried out according to the instant invention. The compositions discussed in the following examples are set forth in Table l and Table 2.
_7_ COMPARATIVE EXAMPLE A:
Example A is a comparative example which demonstrates the effect of adding inhibitors to an alkylene glycol in a "conventional" manner as taught in the prior art. This order of mixing may work for ethylene glycol in some instances but is not generally applicable to other alkylene glycols. This example will be contrasted with Example B, below, where the inhibitor content is identical to that used in this Comparative Example A, but the inhibitors are added according to the process of the instant invention.
A composition was formed by placing propylene glycol in a mixing vessel.
Under constant stirring, 20 wt% borax in propylene glycol and phosphoric acid were added. The required amount of basic inorganic compound, 45% KOH in this case, was then added to neutralize acids and provide a pH of about 10.8. Next the silicone is added.
Upon addition of the high mole ratio silica/alkali metal oxide mixture (SiOz:
MZO = 1.81) the mixture turns cloudy as a silicate gel forms. Although some clearing is noted as additional silicate mixture is added, the mixture is never completely clear of a silicate gel.
The final pH of the mixture is about 11.3. Additional components were then added as shown in Table 1.
EXAMPLE B
Example B demonstrates an alkali metal silicate-containing alkylene glycol made according to the process of the instant invention. the chemical concentrations are substantially the same as employed in Example A, but the mixing order is according to the instant invention.
The selected amount of propylene glycol was placed in a mining vessel.
Next, under constant stirring, a silicate premix consisting of alkali metal silicate, basic inorganic compound, and water was added slowly. (The SiOZ: MZO mole ratio was 0.13).
Addition of the silicate premix to the propylene glycol was achieved by adding a small _g_ 21 ~ 3220 aliquot of the silicate premix and waiting for the mixture to substantially clear before adding the next silicate premix aliquot. Addition of the silicate premix took about 2 hours and about 12 aliquot additions in substantially equal amounts. The silicone was then added. The remaining components, e.g., the inhibitors and any additional components were then added. No silicate gel formation was observed after completing the silicate premix addition. No silicate gel was observed after storage at 55°C for one year.
COMPARATIVE EXAMPLE C
Comparative Example C demonstrates how silicate gel formation can arise if the process of the instant invention is not employed in the manufacture of silicate-containing propylene glycol compositions. Comparative Example C exhibited a persistent silicate gel upon addition of the silicate to the propylene glycol.
In Comparative Example C, the selected amount of propylene glycol was placed in a mixing vessel. The benzoic acid and phosphoric acid were mixed and then added to the mixture, followed by addition of the silicone. The silicate premix contained alkali metal silicate, all required basic inorganic compound (with a SiOz: M20 ratio of 0.12 as shown in Table 1), and water. The pH was observed to rise from less than 3 initially to about 10.8 after all the silicate premix was added. Comparative Example C was always cloudy and contained a silicate gel after storage.
EXAMPLE D:
Example D has the same composition as Comparative Example C, however, the composition is prepared according to the process of the instant invention.
The selected amount of propylene glycol was placed in a mixing vessel.
The silicate premix was added over time in a number of aliquots. The initial aliquot was added and produced a slight cloudiness which quickly cleared. Subsequent aliquots produced less and less cloudiness upon addition. The silicone, corrosion inhibitors, and ~ ~ 83~Z0 additional components were then added. No cloudiness was observed for the mixture and no silicate gels are detected after storage at 55° C. for 3 months.
Table 1. (Wei ht Percents) I
'I Component ComparativeExample B ComparativeExample Exam le Exam le D
A C
Propylene 95.1783 95.1783 93.4176 93.3194 glycol (PG) -'~ Benzoic 0.9703 0.9703 Acid 'i 20~7c Borax1.5000 1.5000 in PG
~
' 759c H,PO, 0.6000 0.6000 1.1411 1.1411 Silicone A 0.0775 0.0775 Silicone B 0.0282 0.0282 459c KOH 1.3777 50~c NaOH 0.0313 Nasil Gr 40 0.1601 CI
Silicate premix* 1.6535 3.7190 3.157 509c NaTTZ 0.1100 0.1100 0.2330 0.2330 (aq.l 509c NabfBT 0.1100 0.1100 409c Nall0, 0.5000 0.5000 35.19c NaMoo,0.3000 0.3000 Alizarine 0.0015 0.0030 Dye Antifoam A 0.4400 0.4400 Antifoam B 0.0200 0.0200 The silicate remix in each of the above exam les was:
*Silicate A B C D
pmmiz Nasil GR 40 0.1601 Cl 509c NaOH 0.0313 0.3418 0.3418 459c KoH 1.3777 3.1272 3.2239 DI water (added) 0.0844 0.2500 0.2500 Mole Ratio, 1.81 0.13 0.12 0.11 Si0_/M:O
~' Total 9c Water in 73.4 I 64.1 ~ 64.7 ~ 64.6 ~n"'~ I
EXAMPLES E TO I:
Examples E to I, Table 2, demonstrate the gel resistance benefits derived by use of the instant invention for a wide variety of antifreeze formulations.
The compositions of Examples E to I, inclusive, were prepared according to the instant invention by adding an aqueous mixture of highly alkalized silicate directly to the propylene glycol.
TABLE
2. (Wei ht Percents _ _ Com nent Exam le Exam le Exam le Exam le Exam le E F G H I
Propylene Glycol 92.8859 92.5322 94.2936 95.7276 9 ("PG> 4.6493 Benzoic 0.9703 1.9406 _ Acid Boric 0.8918 Acid 20% Borax in 1.9875 1.9875 PG
75~ H,PO,1.1411 0.7607 0.6602 0.1625 0.6602 Silicone 0.0775 0.0775 A
Silicone 0.3100 0.0652 0.1550 B
Silicate p~n""* 3.5657 3.8125 2.1322 2.4079 1.9248 50% f~IaTIZ
0.3495 0.1165 0.1165 0.2200 0.1165 ao% rrarro,0.7500 0.7500 0.5000 0.5250 0.5000 Alizarine0.0030 0.0030 Dye Antifoam 0.0070 0.0070 0.0067 A
The silicate remix in each of the above exam Ies was:
*SilicateE F G H I
remix 0.3418 0.3418 0.3418 0.1778 0.1709 45~ KoH 3.2239 3.4707 1.6195 2.1001 1.5830 21 ~3 224 Dl Watet ~a~~~ 0.2500 I ~ 0.1709 0.1300 0.1709 Mole Ratio SiO:/M:O 0.I1 0.10 0.22 0.09 0.11 Total % Water ~.6 62.1 65.1 64.2 65.5 in premix The above compositions can be employed as antifreeze compositions for the cooling systems of internal combustion engines and were observed to be gel resistant both during their preparation and after storage at 55°C for 3 months.
EXAMPLE J:
The corrosion protection properties of the compositions prepared in Examples B and E were evaluated according to ASTM D 4340-89, "Standard Test Method for Aluminum alloys in Engine Coolants Under Heat-Rejecting Conditions" and ASTM D
1384-93, "Standard Test Method for Corrosion Test for Engine Coolants in Glassware" to demonstrate the improved corrosion protection of compositions prepared according to the instant invention.
The ASTM D 4340 and D 1384 results for Examples B and E, as compared to the ASTM D 3306 and D 5216 requirements for new coolants, demonstrates the excellent protection of aluminum under heat transfer conditions and the overall general corrosion protection afforded to the other metals typically found in an engine cooling system. This excellent protection can be attributed directly to the stable, fully formulated nature of the coolant.
ASTM D 3306(a)ASTM D 5216(b) Exam le Exam le re uirementsre uirements B E
Test Results (c) Corrosion Rate,0.36 0.33 1.0 max. 1.0 max.
mg/cm~/week Test Results (d) Weight loss, mg/specimen Copper 6 6 10 max. 10 max.
Solder 5 3 30 max. 30 max.
Brass 7 3 10 max. 10 max.
Steel 3 0 10 max. 10 max.
Cast Iron 0 -1 10 max. 10 max.
Cast Aluminum 2 3 30 max. 30 max.
a) ASTM D 3306-89, "Standard Specification for Ethylene Glycol Base Engine Coolant for Automobile and Light Duty Service."
b) ASTM D 5216-91, "Standard Specification for Propylene Glycol Base Engine Coolant for Automobile and Light Duty Service."
c) The values reported are the average of two runs.
d) The values reported are the average of three runs. Scrubbing weight losses were not subtracted out. A minus value indicates a weight gain.
The following examples were conducted to demonstrate the improved gel resistance of silicate-containing alkylene glycol compositions formed according to the process of the instant invention as compared to the processes of the prior art.
In the following examples, the following nomenclature is employed.
NOMENCLATURE MEANING ~ SUPPLIER
PG Propylene Glycol Silicone A Organosiloxane, tradeOSi Specialties name Sil uest~ Y-556- silaneDanbu , CT
Silicone B Organosiloxane, tradeDow Corning Corporation name DC- 2-6083 Midland, MI
NaTTZ Sodium Tol ltriazole NaMBT Sodium Merca tobenzothiazole a ueous Antifoam A Polypropylene glycol Union Carbide Corporation type antifoaming agent, Danbury, CT
trade name Antifoam B Organosiloxane type Dow Corning Corporation antifoaming agent, Midland, MI
trade name Nasil Gr 40 CL Mixture of Silicate, Occidental Chemical (trade KOH, and name) water having a SiOz/M20Dallas, TX
mole ratio of 3.22 Kasil #6 (trade Mixture of Silicate, The PQ Corporation name) KOH, and water having a SiO~/M20Valley Forge, PA
mole ratio of 3.29 DI water Deionized Water Examples A and C are comparative examples. Examples B, D, E, F, G. H, I
and J were carried out according to the instant invention. The compositions discussed in the following examples are set forth in Table l and Table 2.
_7_ COMPARATIVE EXAMPLE A:
Example A is a comparative example which demonstrates the effect of adding inhibitors to an alkylene glycol in a "conventional" manner as taught in the prior art. This order of mixing may work for ethylene glycol in some instances but is not generally applicable to other alkylene glycols. This example will be contrasted with Example B, below, where the inhibitor content is identical to that used in this Comparative Example A, but the inhibitors are added according to the process of the instant invention.
A composition was formed by placing propylene glycol in a mixing vessel.
Under constant stirring, 20 wt% borax in propylene glycol and phosphoric acid were added. The required amount of basic inorganic compound, 45% KOH in this case, was then added to neutralize acids and provide a pH of about 10.8. Next the silicone is added.
Upon addition of the high mole ratio silica/alkali metal oxide mixture (SiOz:
MZO = 1.81) the mixture turns cloudy as a silicate gel forms. Although some clearing is noted as additional silicate mixture is added, the mixture is never completely clear of a silicate gel.
The final pH of the mixture is about 11.3. Additional components were then added as shown in Table 1.
EXAMPLE B
Example B demonstrates an alkali metal silicate-containing alkylene glycol made according to the process of the instant invention. the chemical concentrations are substantially the same as employed in Example A, but the mixing order is according to the instant invention.
The selected amount of propylene glycol was placed in a mining vessel.
Next, under constant stirring, a silicate premix consisting of alkali metal silicate, basic inorganic compound, and water was added slowly. (The SiOZ: MZO mole ratio was 0.13).
Addition of the silicate premix to the propylene glycol was achieved by adding a small _g_ 21 ~ 3220 aliquot of the silicate premix and waiting for the mixture to substantially clear before adding the next silicate premix aliquot. Addition of the silicate premix took about 2 hours and about 12 aliquot additions in substantially equal amounts. The silicone was then added. The remaining components, e.g., the inhibitors and any additional components were then added. No silicate gel formation was observed after completing the silicate premix addition. No silicate gel was observed after storage at 55°C for one year.
COMPARATIVE EXAMPLE C
Comparative Example C demonstrates how silicate gel formation can arise if the process of the instant invention is not employed in the manufacture of silicate-containing propylene glycol compositions. Comparative Example C exhibited a persistent silicate gel upon addition of the silicate to the propylene glycol.
In Comparative Example C, the selected amount of propylene glycol was placed in a mixing vessel. The benzoic acid and phosphoric acid were mixed and then added to the mixture, followed by addition of the silicone. The silicate premix contained alkali metal silicate, all required basic inorganic compound (with a SiOz: M20 ratio of 0.12 as shown in Table 1), and water. The pH was observed to rise from less than 3 initially to about 10.8 after all the silicate premix was added. Comparative Example C was always cloudy and contained a silicate gel after storage.
EXAMPLE D:
Example D has the same composition as Comparative Example C, however, the composition is prepared according to the process of the instant invention.
The selected amount of propylene glycol was placed in a mixing vessel.
The silicate premix was added over time in a number of aliquots. The initial aliquot was added and produced a slight cloudiness which quickly cleared. Subsequent aliquots produced less and less cloudiness upon addition. The silicone, corrosion inhibitors, and ~ ~ 83~Z0 additional components were then added. No cloudiness was observed for the mixture and no silicate gels are detected after storage at 55° C. for 3 months.
Table 1. (Wei ht Percents) I
'I Component ComparativeExample B ComparativeExample Exam le Exam le D
A C
Propylene 95.1783 95.1783 93.4176 93.3194 glycol (PG) -'~ Benzoic 0.9703 0.9703 Acid 'i 20~7c Borax1.5000 1.5000 in PG
~
' 759c H,PO, 0.6000 0.6000 1.1411 1.1411 Silicone A 0.0775 0.0775 Silicone B 0.0282 0.0282 459c KOH 1.3777 50~c NaOH 0.0313 Nasil Gr 40 0.1601 CI
Silicate premix* 1.6535 3.7190 3.157 509c NaTTZ 0.1100 0.1100 0.2330 0.2330 (aq.l 509c NabfBT 0.1100 0.1100 409c Nall0, 0.5000 0.5000 35.19c NaMoo,0.3000 0.3000 Alizarine 0.0015 0.0030 Dye Antifoam A 0.4400 0.4400 Antifoam B 0.0200 0.0200 The silicate remix in each of the above exam les was:
*Silicate A B C D
pmmiz Nasil GR 40 0.1601 Cl 509c NaOH 0.0313 0.3418 0.3418 459c KoH 1.3777 3.1272 3.2239 DI water (added) 0.0844 0.2500 0.2500 Mole Ratio, 1.81 0.13 0.12 0.11 Si0_/M:O
~' Total 9c Water in 73.4 I 64.1 ~ 64.7 ~ 64.6 ~n"'~ I
EXAMPLES E TO I:
Examples E to I, Table 2, demonstrate the gel resistance benefits derived by use of the instant invention for a wide variety of antifreeze formulations.
The compositions of Examples E to I, inclusive, were prepared according to the instant invention by adding an aqueous mixture of highly alkalized silicate directly to the propylene glycol.
TABLE
2. (Wei ht Percents _ _ Com nent Exam le Exam le Exam le Exam le Exam le E F G H I
Propylene Glycol 92.8859 92.5322 94.2936 95.7276 9 ("PG> 4.6493 Benzoic 0.9703 1.9406 _ Acid Boric 0.8918 Acid 20% Borax in 1.9875 1.9875 PG
75~ H,PO,1.1411 0.7607 0.6602 0.1625 0.6602 Silicone 0.0775 0.0775 A
Silicone 0.3100 0.0652 0.1550 B
Silicate p~n""* 3.5657 3.8125 2.1322 2.4079 1.9248 50% f~IaTIZ
0.3495 0.1165 0.1165 0.2200 0.1165 ao% rrarro,0.7500 0.7500 0.5000 0.5250 0.5000 Alizarine0.0030 0.0030 Dye Antifoam 0.0070 0.0070 0.0067 A
The silicate remix in each of the above exam Ies was:
*SilicateE F G H I
remix 0.3418 0.3418 0.3418 0.1778 0.1709 45~ KoH 3.2239 3.4707 1.6195 2.1001 1.5830 21 ~3 224 Dl Watet ~a~~~ 0.2500 I ~ 0.1709 0.1300 0.1709 Mole Ratio SiO:/M:O 0.I1 0.10 0.22 0.09 0.11 Total % Water ~.6 62.1 65.1 64.2 65.5 in premix The above compositions can be employed as antifreeze compositions for the cooling systems of internal combustion engines and were observed to be gel resistant both during their preparation and after storage at 55°C for 3 months.
EXAMPLE J:
The corrosion protection properties of the compositions prepared in Examples B and E were evaluated according to ASTM D 4340-89, "Standard Test Method for Aluminum alloys in Engine Coolants Under Heat-Rejecting Conditions" and ASTM D
1384-93, "Standard Test Method for Corrosion Test for Engine Coolants in Glassware" to demonstrate the improved corrosion protection of compositions prepared according to the instant invention.
The ASTM D 4340 and D 1384 results for Examples B and E, as compared to the ASTM D 3306 and D 5216 requirements for new coolants, demonstrates the excellent protection of aluminum under heat transfer conditions and the overall general corrosion protection afforded to the other metals typically found in an engine cooling system. This excellent protection can be attributed directly to the stable, fully formulated nature of the coolant.
ASTM D 3306(a)ASTM D 5216(b) Exam le Exam le re uirementsre uirements B E
Test Results (c) Corrosion Rate,0.36 0.33 1.0 max. 1.0 max.
mg/cm~/week Test Results (d) Weight loss, mg/specimen Copper 6 6 10 max. 10 max.
Solder 5 3 30 max. 30 max.
Brass 7 3 10 max. 10 max.
Steel 3 0 10 max. 10 max.
Cast Iron 0 -1 10 max. 10 max.
Cast Aluminum 2 3 30 max. 30 max.
a) ASTM D 3306-89, "Standard Specification for Ethylene Glycol Base Engine Coolant for Automobile and Light Duty Service."
b) ASTM D 5216-91, "Standard Specification for Propylene Glycol Base Engine Coolant for Automobile and Light Duty Service."
c) The values reported are the average of two runs.
d) The values reported are the average of three runs. Scrubbing weight losses were not subtracted out. A minus value indicates a weight gain.
Claims (22)
1. A process for the preparation of propylene glycol-containing antifreeze compositions having improved gel resistance comprising 85 to 98 weight percent propylene glycol, a corrosion inhibiting amount of an alkali metal silicate, at least one basic inorganic compound and water which comprises:
(a) forming a silicate premix containing alkali metal silicate, a basic inorganic compound selected from the group consisting of alkali metal hydroxide, alkali metal carbonate and alkali metal phosphate, and water, wherein the silica to alkali metal oxide mole ratio (SiO2: M2O) is less than about 0.25, and adding an effective amount of water to said premix to provide at least about 60 weight percent water in the premix, to thereby prevent gel formation when said silicate premix is added to said propylene glycol; and (b) adding the silicate premix of step (a) to said propylene glycol.
(a) forming a silicate premix containing alkali metal silicate, a basic inorganic compound selected from the group consisting of alkali metal hydroxide, alkali metal carbonate and alkali metal phosphate, and water, wherein the silica to alkali metal oxide mole ratio (SiO2: M2O) is less than about 0.25, and adding an effective amount of water to said premix to provide at least about 60 weight percent water in the premix, to thereby prevent gel formation when said silicate premix is added to said propylene glycol; and (b) adding the silicate premix of step (a) to said propylene glycol.
2. A process according to claim 1 wherein said silica to alkali metal oxide ratio is less than about 0.22 and said water is present in an amount of at least about 63 percent by weight.
3. A process according to claim 1 or 2 wherein at least one silicate stabilizer is added to the propylene glycol prior to addition of the silicate premix.
4. A process according to claim 1 or 2 wherein at least one silicate stabilizer is added to the silicate premix prior to said premix being added to the propylene glycol.
5. A process according to claim 1 or 2 wherein at least one silicate stabilizer is added to the mixture of step (b).
6. A process according to any one of claims 1 to 5 wherein said alkali metal (M) is sodium or potassium.
7. A process according to any one of claims 1 to 6 wherein an additional process step comprises (c) adding to the mixture of step (b) an effective inhibitory amount of at least one additional corrosion inhibitor.
8. A process according to claim 7 wherein said corrosion inhibitor is at least one member selected from the group consisting of tungstates, molybdates, selenates, carbonates, bicarbonates, monocarboxylic acids, dicarboxylic acids, borates, phosphates, benzoates, alkali metal nitrates, alkali metal nitrites, tolytriazole, mercaptobenzotriazole, benzotriazole and mixtures thereof.
9. A process according to any one of claims 1 to 8 wherein the pH of the mixture formed in step (b) is at least 9Ø
10. A process according to claim 9 wherein the pH is between about 9.5 and 11.5.
11. A process according to any one of claims 1 to 10 wherein, in step (b), said silicate premix of step (a) is added to said propylene glycol in two or more aliquots.
12. A process according to claim 11 wherein, in step (b), each aliquot is added at an effective rate of addition to prevent gel formation.
13. A process according to any one of claims 1 to 10 wherein, in step (b), said silicate premix of step (a) is slowly added to said propylene glycol to prevent gel formation.
14. A process according to any one of claims 1 to 13 wherein an additional process step comprises adding to the propylene glycol prior to step (b) an effective inhibitory amount of at least one corrosion inhibitor.
15. A process according to claim 14 wherein after the addition of said at least one corrosion inhibitor and before the addition of said silicate premix, at least one inorganic base compound is added to the propylene glycol to raise the pH above about 6Ø
16. A process according to claim 15 wherein the final pH of the silicate-containing propylene glycol mixture is at least about 9Ø
17. A process according to claim 16 wherein the pH is between about 9.5 and about 11.5.
18. A process for the preparation of propylene glycol-containing compositions having improved gel resistance comprising 85 to 98 weight percent propylene glycol, an aqueous base solution, a corrosion inhibiting amount of an alkali metal silicate, a basic inorganic compound, water and a silicate stabilizer which comprises:
(a) adding a basic inorganic compound selected from the group consisting of alkali metal hydroxide, alkali metal carbonate and alkali metal phosphate, to said propylene glycol;
(b) adding to the propylene glycol of step (a) a silicate premix comprising at least one alkali metal silicate, at least one basic inorganic compound selected from the group consisting of alkali metal hydroxide, alkali metal carbonate and alkali metal phosphate, and water, said silicate premix having a silica to alkali metal oxide mole ratio of about 0.25 or less and at least 63 percent by weight water; and (c) adding an effective amount of silicate stabilizer to the mixture of step (b).
(a) adding a basic inorganic compound selected from the group consisting of alkali metal hydroxide, alkali metal carbonate and alkali metal phosphate, to said propylene glycol;
(b) adding to the propylene glycol of step (a) a silicate premix comprising at least one alkali metal silicate, at least one basic inorganic compound selected from the group consisting of alkali metal hydroxide, alkali metal carbonate and alkali metal phosphate, and water, said silicate premix having a silica to alkali metal oxide mole ratio of about 0.25 or less and at least 63 percent by weight water; and (c) adding an effective amount of silicate stabilizer to the mixture of step (b).
19. A process for the preparation of propylene glycol-containing compositions having improved gel resistance comprising 85 to 98 weight percent propylene glycol, an aqueous base solution, a corrosion inhibiting amount of an alkali metal silicate, a basic inorganic compound, water and a silicate stabilizer which comprises:
a) adding to the propylene glycol a silicate premix comprising at least one alkali metal silicate, at least one basic inorganic compound selected from the group consisting of alkali metal hydroxide, alkali metal carbonate and alkali metal phosphate, and water, said silicate premix having a silica to alkali metal oxide mole ratio of about 0.25 or less and at least 63 percent by weight water; and (b) adding an effective amount of silicate stabilizer to the mixture of step (a).
a) adding to the propylene glycol a silicate premix comprising at least one alkali metal silicate, at least one basic inorganic compound selected from the group consisting of alkali metal hydroxide, alkali metal carbonate and alkali metal phosphate, and water, said silicate premix having a silica to alkali metal oxide mole ratio of about 0.25 or less and at least 63 percent by weight water; and (b) adding an effective amount of silicate stabilizer to the mixture of step (a).
20. A process according to claim 18 wherein one or more additional corrosion inhibitors are added in an effective corrosion inhibiting amount to the mixture of step (c).
21. A process according to claim 19 wherein one or more additional corrosion inhibitors are added in an effective corrosion inhibiting amount to the mixture of step (b).
22. A process according to claim 18 wherein one or more corrosion inhibitors are added in an effective corrosion inhibiting amount in step (a) and sufficient basic inorganic compound is then added to raise the pH
of the propylene glycol to at least about 6Ø
of the propylene glycol to at least about 6Ø
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/518,154 | 1995-08-23 | ||
| US08/518,154 US5651916A (en) | 1995-08-23 | 1995-08-23 | Process for the preparation of a propylene glycol antifreeze containing an alkali metal silicate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2183220A1 CA2183220A1 (en) | 1997-02-24 |
| CA2183220C true CA2183220C (en) | 2001-06-12 |
Family
ID=24062797
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002183220A Expired - Fee Related CA2183220C (en) | 1995-08-23 | 1996-08-13 | Process for the preparation of a propylene glycol antifreeze containing an alkali metal silicate |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5651916A (en) |
| EP (1) | EP0761797A3 (en) |
| JP (1) | JP3205266B2 (en) |
| KR (1) | KR100190977B1 (en) |
| CA (1) | CA2183220C (en) |
| MX (1) | MX9603621A (en) |
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| US5709813A (en) * | 1996-03-21 | 1998-01-20 | Janke; George A. | Deicing composition and method |
| US5709812A (en) * | 1996-04-25 | 1998-01-20 | Janke; George A. | Deicing composition and method |
| AT405408B (en) * | 1996-08-26 | 1999-08-25 | Lang Chem Tech Prod | FREEZER AND ICE SOLVENTS |
| US6759050B1 (en) | 1998-12-03 | 2004-07-06 | Avigen, Inc. | Excipients for use in adeno-associated virus pharmaceutical formulations, and pharmaceutical formulations made therewith |
| KR100573963B1 (en) * | 1999-12-31 | 2006-04-25 | 에스케이케미칼주식회사 | Antifreeze composition |
| MXPA02012231A (en) * | 2000-06-10 | 2004-05-21 | Evans Cooling Systems Inc | Non-toxic ethylene glycol-based antifreeze/heat transfer fluid concentrate and antifreeze/heat transfer fluid. |
| CN1511187A (en) * | 2000-07-19 | 2004-07-07 | 埃文斯冷却系统公司 | Non-aqueous heat transfer fluid and use thereof |
| US20020033470A1 (en) * | 2000-07-19 | 2002-03-21 | Evans John W. | Non-aqueous heat transfer fluid and use thereof |
| US20020171063A1 (en) | 2001-03-10 | 2002-11-21 | Evans John W. | Reduced toxicity ethylene glycol-based antifreeze/heat transfer fluid concentrates and antifreeze/heat transfer fluids |
| US6841647B2 (en) * | 2001-11-06 | 2005-01-11 | National Starch And Chemical Investment Holding Corporation | Fluid resistant silicone encapsulant |
| WO2004091028A1 (en) * | 2003-04-02 | 2004-10-21 | Shishiai-Kabushikigaisha | Cooling liquid composition for fuel cell |
| JP4771351B2 (en) * | 2004-03-18 | 2011-09-14 | 大阪瓦斯株式会社 | Heat transfer medium and heat transfer system using the same |
| KR100748779B1 (en) * | 2005-12-12 | 2007-08-13 | 현대자동차주식회사 | Composition of Antifreezing Liquid |
| DE102009038398A1 (en) | 2009-08-24 | 2011-03-03 | Uhde Gmbh | Process and apparatus for the preparation of alkylene oxides and of alkylene glycols |
| US8357310B2 (en) * | 2010-11-10 | 2013-01-22 | Hamilton Sundstrand Space Systems International, Inc. | Aqueous based cooling of components having high surface area levels of aluminum or nickel |
| CN102703039B (en) * | 2012-06-07 | 2015-08-05 | 青岛康普顿科技股份有限公司 | The nano-fluid cooling fluid of a kind of nano-fluid cooling fluid preparation method and preparation thereof |
| US20140070134A1 (en) * | 2012-09-07 | 2014-03-13 | Prestone Products Corporation | Heat transfer fluid concentrate |
| JP7017612B1 (en) * | 2020-08-13 | 2022-02-08 | トヨタ自動車株式会社 | Coolant composition |
| KR20230121388A (en) | 2022-02-11 | 2023-08-18 | (주) 에스엠아이앤씨 | Conductivity carbon black facturing apparatus and method using waste rubber scrap |
| KR102613684B1 (en) * | 2023-07-27 | 2023-12-19 | 양표서진산업주식회사 | Composition of Long Life Antifreezing Liquid and Manufacturing Method Of It |
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| US2726215A (en) * | 1952-04-19 | 1955-12-06 | Atlantic Refining Co | Rust inhibitors for aqueous systems |
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| DE2235093C2 (en) * | 1972-07-18 | 1974-07-04 | Bayer Ag, 5090 Leverkusen | Anti-corrosive agents |
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| DE3832592A1 (en) * | 1988-09-24 | 1990-03-29 | Basf Ag | NITRITE AND PHOSPHATE-FREE COOLANT MIXTURES ON GLYCOL BASE |
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-
1995
- 1995-08-23 US US08/518,154 patent/US5651916A/en not_active Expired - Lifetime
-
1996
- 1996-08-13 CA CA002183220A patent/CA2183220C/en not_active Expired - Fee Related
- 1996-08-20 EP EP96420273A patent/EP0761797A3/en not_active Withdrawn
- 1996-08-23 JP JP22281996A patent/JP3205266B2/en not_active Expired - Fee Related
- 1996-08-23 MX MX9603621A patent/MX9603621A/en not_active IP Right Cessation
- 1996-08-23 KR KR1019960034957A patent/KR100190977B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0761797A2 (en) | 1997-03-12 |
| KR100190977B1 (en) | 1999-06-15 |
| US5651916A (en) | 1997-07-29 |
| JP3205266B2 (en) | 2001-09-04 |
| EP0761797A3 (en) | 1997-07-30 |
| JPH09221663A (en) | 1997-08-26 |
| CA2183220A1 (en) | 1997-02-24 |
| MX9603621A (en) | 1997-05-31 |
| KR970010924A (en) | 1997-03-27 |
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