Classifications

• • 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
• • 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
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
  • C09K3/185—Thawing materials
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
  • C23F11/12—Oxygen-containing compounds
  • C23F11/124—Carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
  • C23F11/12—Oxygen-containing compounds
  • C23F11/124—Carboxylic acids
  • C23F11/126—Aliphatic acids

Definitions

• the invention relates generally to antifreeze compositions exhibiting improved thermal stability at low temperatures.
• antifreeze compositions in heat exchanging systems and/or for de-icing applications.
• the antifreeze compositions come in contact with various metals, alloys, and other components forming the different parts of the heat exchanging system or the system to be de-iced.
• Efforts have been made towards the protection from corrosion of parts and components in contact with the antifreeze compositions.
• Prior art solutions include the addition of various corrosion inhibitors and/or the use of different organic acids for multiple metal protection systems.
• Corrosion protection is critical at all temperature ranges. However, at low temperatures, other factors important to the performance of antifreeze compositions come into play, including the unwanted formation of scale and/or deposits.
• Water is often used to dilute antifreeze compositions. Water quality varies greatly with geographic location, population and degree of industrialization. When hard water is used, scales can be formed from alkaline earth metal carbonate and phosphate deposition. These inorganic films tend to inhibit thermal transfer and thus reduce the heat transfer efficiency of the system.
• certain corrosion inhibitors contributes to the formation of deposits, e.g., silicate gellation.
• silicate/phosphate corrosion inhibitors are used to help protect metal cooling system parts and also as a buffer to control the pH of the antifreeze.
• a composition containing silicates/phosphates is mixed with hard water, copious precipitates develop in a short period of time. These precipitates may clog a cooling system, resulting in reduced antifreeze/coolant flow, increased engine operating temperatures and shorter service life.
• Deposit formation can also result in the physical damage of soft material parts, e.g., water pump seals, engine head seals, hoses, etc. used in the parts and components of the system.
• silicate stabilizers can be added to antifreeze compositions.
• some additives are not soluble thus further compounding the problem.
• antifreeze compositions should remain transparent and free of insoluble materials in operation as the unwanted formation of deposits/soluble materials decreases the heat transfer property of the composition.
• the antifreeze composition should be environmentally and toxicological friendly.
• a toxicological friendly antifreeze composition i.e., a non-glycol based composition having improved thermal stability at low temperatures with minimal salt/deposition formation.
• This formulation is particularly effective at inhibiting corrosion in coolants which are free of borates, primary and secondary amines, phosphates, silicates, as well as those coolants which are free of p-tertbutyl benzoic acid.
• U.S. Pat. No. 6,080,331 is directed to a silicate-, borate- and nitrate-free antifreeze concentrate which is based on alkylene glycols or derivatives thereof and consists essentially of: (a) from 0.05 to 10% by weight, based on the total amount of concentrate, of a mixture of two monocarboxylic acids each of 3 to 16 carbon atoms in the form of their alkali metal salts, ammonium salts or substituted ammonium salts, the first acid being an aliphatic monocarboxylic acid, and the second acid being a hydroxy aromatic monocarboxylic acid, selected from the group consisting of o-, m- or p-hydroxybenzoic acid and o-, m- or p-(hydroxymethyl)benzoic acid, and (b) from 0.01 to 3% by weight, based on the total amount of concentrate, of at least one hydrocarbon-triazole and/or hydrocarbon-thiazole.
• U.S. Pat. No. 6,398,984 is directed to corrosion inhibitor formulation comprising, in a preferred embodiment alkylene glycols such as ethylene or propylene glycol as freezing point depressants.
• an antifreeze composition comprising from 50 to 99.8 wt. % of a freezing point depressant comprising at least one of an aqueous medium alkali metal salt of anions selected from acetates, formats, proprionates, adipiates, and succinates; 0.1 to 5 wt. % of at least a branched organic acid (C 5 -C 16 ) or alkali- or amino salt of a branched organic acid (C 5 -C 16 ); and 0.1 to 5 wt.
• the composition is employed as a concentrate, in admixture with an aqueous antifreeze solution comprising 10 to 90 wt. % by weight of water.
• an antifreeze concentrate composition comprising 50 to 99.8 wt. % of a freezing point depressant selected from the group of alkali metal salts of anions selected from acetates, formats, proprionates, adipiates, and succinates and mixtures thereof, 0.1 to 10 wt. % of at least one of a 2-ethylhexanoic acid, isononanoic acid and 3,5,5-trimethylhexanoic acid; and 0.1 to 10 wt.
• a freezing point depressant selected from the group of alkali metal salts of anions selected from acetates, formats, proprionates, adipiates, and succinates and mixtures thereof
• 0.1 to 10 wt. % of at least one of a 2-ethylhexanoic acid, isononanoic acid and 3,5,5-trimethylhexanoic acid and 0.1 to 10 wt.
• a corrosion inhibitor system comprising: a) 0.1 to 10 wt. % of at least a branched organic acid (C 5 -C 16 ) or alkali- or amino salt of a branched organic acid (C 5 -C 16 ); and b) 0.1 to 10 wt.
• antifreeze refers to a composition which reduces the freezing point of an aqueous solution, or is an aqueous solution with a reduced freezing point with respect to water, e.g., a composition comprising a freezing point depressant.
• coolant refers to a category of liquid antifreeze compositions which have properties that allow an engine to function effectively without freezing, boiling, or corrosion.
• the performance of an engine coolant must meet or exceed standards set by the American Society for Testing and Materials (A.S.T.M.) and the Society of Automotive Engineers (S.A.E.).
• heat transfer fluid refers to a fluid which flows through a system in order to prevent its overheating, transferring the heat produced within the system to other systems or devices that can utilize or dissipate the heat.
• de-icing fluid refers to a fluid which makes or keeps a system, a device, or a part free of ice, or a fluid which melts ice.
• antifreeze composition composition (or fluid or concentrate) may be used interchangeably with “heat transfer,” “coolant,” or “de-icing” fluid (composition or concentrate).
• an antifreeze composition with excellent thermal stability properties is provided.
• the composition remains relatively clear with minimal deposit formation (that can be visually observed).
• the composition comprises a combination of corrosion inhibitors in a non-glycol based freezing point depressant.
• Non-Glycol Based Freezing Point Depressant Matrix is free of glycol and consists of at least an aqueous medium alkali metal salt of anions selected from acetates, formats, proprionates, adipiates, and succinates, in an amount of 50 to 99.8 wt. % of total weight of a final concentrate composition.
• the composition is in admixture with an aqueous antifreeze solution comprising 10 to 90 wt. % by weight of water. Suitable examples include but are not limited to potassium formate, potassium propionate, potassium acetate, dipotassium adipinate, and mixtures thereof.
• the matrix further comprises additional water soluble organic compounds such as formamide and/or urea, containing an intensively hydrophilic substituent, for an extreme reduction in freezing point.
• additional water soluble organic compounds such as formamide and/or urea, containing an intensively hydrophilic substituent, for an extreme reduction in freezing point.
• some glycol may be added to the non-glycol freezing point depressant for a matrix with a glycol:non-glycol base ratio of 1:2 to 1:20.
• the non-glycol matrix is a mixture of some, if not all the alkali metal salts described above.
• the combinations result in an extreme reduction in freezing point which is not even approached when the individual alkali metal salt components are employed.
• a concentrate aqueous solution of potassium acetate (40:0) has a freezing point of ⁇ 38° C.
• a potassium formate (40:0) in water solution freezes at ⁇ 35° C. If these two potassium compounds are “dissolved” in water in combination with each other, a composition is obtained that is liquid at ⁇ 70° C.
• a concentrate sodium proprionate (40:0) in water has a freezing point of ⁇ 32° C.
• a mixture of sodium proprionate and potassium formate (at a ratio 20:20) in water has a freezing point of ⁇ 48° C., which is remarkably lower than the expected mid-point of ⁇ 34° C. calculated using the addition rule.
• potassium formate is used as the freezing point depressant.
• a mixture of potassium formate and potassium propionate is employed in the matrix for a formate: propionate ratio of 1:5 to 1:20.
• a mixture of potassium acetate and monoethylene glycol is employed in the matrix.
• dipotassium adipinate is used as the freezing point depressant.
• the non-glycol matrix comprises a mixture of potassium succinate and sodium polyaspartate in a ratio of 90:10 to 99:1.
• the non-glycol matrix component comprises >40 wt. % of alkali metal acetates or formates.
• the matrix has a formate-acetate anion concentration ratio of 1:6, when diluted with water (for a water content of 65 wt. %), the matrix has a freezing point of ⁇ 25° C., and ⁇ 80° C. when diluted with water for a 30 wt. % water content.
• the antifreeze composition further comprises a combination of: a) 0.1 to 10 wt. % of one or more branched organic acids (C 5 -C 16 ) or alkali- or amino salt of the branched organic acids as a first component; and b) 0.1 to 10 wt. % of one or more linear aliphatic mono- or di-basic acids (C 5 -C 12 ), aromatic organic acids (C 7 -C 18 ), or substituted aromatic organic acids (C 7 -C 18 ) or alkali- or amino salt of the foregoing acids as a second component.
• the combination improves the thermal stability of the antifreeze compositions as compared to prior art compositions that contain only aliphatic organic acids or substituted aromatic acids.
• the first component comprising at least one of branched organic acids, salts of branched organic acids, and mixtures thereof.
• branched organic acids examples include but are not limited to the following branched C 4 -C 18 -carboxylic acids and salts thereof: isobutanoic acid, 2-ethylhexanoic acid, isononanoic acid and 3,5,5-trimethylhexanoic acid.
• the branched organic first component is 2-ethylhexanoic acid or 3,5,5-trimethylhaxanoic acid.
• the second component is selected from the group of aliphatic mono acids; aliphatic dibasic acids; aromatic organic acids; substituted aromatic organic acids; alkali metal, ammonium, or amine salt of the aforementioned acids; and mixtures thereof.
• the aliphatic mono acid component includes at least a C 5 -C 12 aliphatic monobasic acid or the alkali metal, ammonium, or amine salt thereof.
• the acids or isomers include but are not limited to octanoic, nonanoic, decanoic, undecanoic and dodecanoic, and mixtures thereof. Any alkali metal, ammonium, or amine can be used to form the monobasic acid salt.
• the second component comprises at least an alkali metal of the aliphatic mono acids with sodium and potassium being used as the alkali metals for use in forming the monobasic acid salt.
• octanoic acid is used as the second component.
• the dibasic acid component includes at least a hydrocarbyl C 5 -C 12 dibasic acid or the alkali metal, ammonium, or amine salt of such dibasic acid.
• examples include but are not limited to suberic, sebacic, undecanedioic, dodecanedioic, malonic, succinic, glutaric, adipic, pimelic, azelaic, undecanedioic acid, dodecanedioic, dicyclopentadienedicarboxylic, phthalic, terephthalic and mixtures thereof.
• the second component comprises at least an alkali metal of the dibasic acid with sodium and potassium being used as the alkali metals for use in forming the acid salt.
• sebacic acid is used as the second component.
• aromatic organic acids and hydroxyl-substituted aromatic organic acids include but not limited to benzoic acids, C 1 -C 8 -alkylbenzoic acids/salts thereof, for example o-, m- and p-methylbenzoic acid or p-tert-butylbenzoic acid, C 1 -C 4 -alkoxybenzoic acids, for example o-, m- and p-methoxybenzoic acid, hydroxyl-containing aromatic monocarboxylic acids, for example o-, m- or p-hydroxybenzoic acid, o-, m- and p-(hydroxymethyl)benzoic acid, and halobenzoic acids, for example o-, m- or p-fluorobenzoic acid.
• the aromatic organic acid is selected from 2-hydroxybenzoic acid, p-terbutylbenzoic acid, mandelic acid and homophthalic acid and salts thereof.
• the carboxylic acids mentioned are present as alkali metal salts, e.g., sodium or potassium salts, or as ammonium salts or substituted ammonium salts (amine salts), for example with ammonia, trialkylamines or trialkanolamines.
• the approximate proportions (based on the amount of the water non-glycol freezing point depressant present) of the combination package are about 0.1 to 15.0 wt. % of the first component and about 0.1 to 15.0 wt. % of the second component.
• the amount of either the first or the second component is in the range of 0.1 to 5 wt. %.
• either component is present in an amount of 0.5 to 3 wt. %.
• the system comprises 1-3 wt. % of the first component and 1-3 wt. % of the second component, with the ratio of the first to the second component in the range of 3:1 to 1:3.
• the antifreeze composition comprises 1 to 3 wt. % of a branched acid selected from 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; 1 to 3 wt. % of at least one of: benzoic acid, octanoic acid, p-tertbutylbenzoic acid, adipic acid, sebacic acid, and mixtures thereof, in a matrix of 40-55 wt. % (based on the final weight of the diluted composition) of at least one of potassium format, potassium propionate, potassium acetate, dipotassium adipinate, and mixtures thereof.
• a branched acid selected from 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid
• the diluted composition comprises about 40-50 wt. % of at least a non-glycol freezing point depressant material, 1-2 wt. % 2-ethylhexanoic acid and 1-2 wt. % 3,5,5-trimethylhexanoic acid.
• the antifreeze composition further comprises one or more additional conventional corrosion inhibitors in combination with the above-described components, at concentrations of 0.01-5.0 wt. % (based on the weight of the non-glycol freezing point depressant matrix).
• additional conventional corrosion inhibitors include alkali metal borates, alkali metal silicates, alkali metal benzoates, alkali metal nitrates, alkali metal nitrites, alkali metal molybdates, and hydrocarbyl thiazoles.
• the additional corrosion inhibitor is selected from hydrocarbyl triazoles, hydrocarbyl thiazoles, sodium metasilicate pentahydrate, organosilane stabilizers, and mixtures thereof.
• Suitable hydrocarbyl triazoles include aromatic triazoles or alkyl-substituted aromatic triazoles, e.g., benzotriazole or tolyltriazole, at a concentration of 0.1-0.5 wt. % and combinations thereof.
• the antifreeze composition comprises 0.2 to 5 wt. % of a sulfite or an alkali metal salt of sulfurous acid as an additional corrosion inhibitor.
• the antifreeze composition further contains other additives in an amount of 0.05 to about 0.1 wt. % (based on the weight of the non-glycol freezing point depressant matrix) such as antioxidants, anti-wear agents, detergents, antifoam agents, acid-base indicators, dyes and the like, provided that the additives are soluble and thermally stable at low temperatures.
• additives such as antioxidants, anti-wear agents, detergents, antifoam agents, acid-base indicators, dyes and the like, provided that the additives are soluble and thermally stable at low temperatures.
• antifoam agents include but are not limited to polyalkylene oxide having a molecular weight of from about 1,000 to about 4,000; silicone oils such as dimethylpolysilozane; and organic silicon compounds such as diethyl silicates.
• antioxidants include but are not limited to phenols, such as 2,6di-t-butyl methylphenol and 4,4′-methylene-bis(2,6-di-t-butylphenol); aromatic amines, such as p,p-dioctylphenylamine, monooctyldiphenylamine, phenothiazine, 3,7-dioctylphenothiazine, phenyl-1-naphthylamine, phenyl-2-naphthylamine, alkylphenyl-1-naphthatalamines and alkyl-phenyl-2-naphthal-amines, as well as sulphur-containing compounds, e.g. dithiophosphates, phosphitest, sulphides and dithio metal salts, such as benzothiazole, tin-dialkyldithiophosphates and zinc diaryldithiophosphates.
• antiwear agents include but are not limited to phosphates, phosphate esters, phosphites, thiophosphites, e.g. zinc dialkyl dithiophosphates, zinc diaryldithiophosphates, tricresyl phosphates, chlorinated waxes, sulphurised fats and olefins, such as thiodipropionic esters, dialkyl sulphides, dialkyl polysulphides, alkyl-mercaptanes, dibenzothiophenes and 2,2′-dithiobis(benzothiazole); organic lead compounds, fatty acids, molybdenum complexes, such as molybdenum disulphide, halogen substituted organosilicon compounds, organic silicon compounds, borates and halogen-substituted phosphorus compounds.
• phosphates phosphate esters, phosphites, thiophosphites, e.g. zinc dialkyl
• detergents include but are not limited to sulphonates, aromatic sulphonic acids, which are substituted with alkyl having a long chain, phosphonates, thiophosphonates, phonolates, metal salts of alkylphenols, and alkyl sulphides.
• a sufficient amount of at least a base e.g., NaOH is added to the composition to modify the pH of the formulation to between 7 and 10.
• a sufficient amount of at least a base is added for the pH to be between 7 and 9.
• the corrosion inhibitor combination, optional additives, optional glycol depressant can be blended into the non-glycol based freezing point depressant matrix individually or in various sub-combinations to formulate the antifreeze composition.
• the composition can be in the form of a “concentrate,” which can be used as is or to be further diluted.
• an anti-freeze concentrate with 50-90 wt. % of aqueous freezing point depressant is further diluted with about 10-90 vol. % water prior to being used in cooling system or as an anti-freeze/de-icing fluid.
• the anti-freeze composition is diluted with 25 to 60 vol. % water.
• the amount of water added is between 30% to 50 wt. %.
• water is added to the antifreeze concentrate for a composition comprising 3 to 9 parts by weight water, from 1 to 2 parts by weight potassium formate, from 1 to 9 parts by weight potassium acetate, optionally up to 1.5 parts by weight urea and optionally up to 1.5 parts by weight of a glycol, and 1 to parts by weight of the corrosion inhibitor combination.
• the antifreeze composition provides improved heat transfer properties and lower viscosities (as compared to a glycol-based system) for the same level of frost protection.
• the composition is characterized as exhibiting excellent protection against the corrosion of metals.
• the composition is further characterized as being thermally stable.
• thermally-stable means a sample of the antifreeze composition forms less than 2% precipitate when chilled at 0° C. for at least 24 hours.
• the term means that the composition is relatively free of precipitates (as visually observed) after being chilled at ⁇ 15° C. for at least 24 hours.
• thermalally-stable means that less than 2% of the composition forms precipitates when chilled at ⁇ 15° C. for at least 24 hours.
• the term means that less than 1% of the composition forms precipitates when chilled at ⁇ 15° C. for at least 24 hours.
• the composition forms less than 1 wt. % precipitates when chilled at ⁇ 25° C. for at least 24 hours.
• precipitate means broadly to include insolubles, coagulants, flocculants, solids and/or fine particles, needles (from crystallization), crystals, gels, colloidal formations, aggregated or precipitated lumps, clusters, or granules which may suspend, deposit, or settle in the antifreeze composition.
• the composition further exhibits improved thermal stability properties compared to the compositions of the prior art, wherein the composition remains relatively free of insolubles/precipitates at a freezing or sub-freezing temperature and after a period of at least 24 hours. In one embodiment, the composition remains relatively transparent after at least 24 hours at a temperature of less than 0° C. In one embodiment, the composition remains thermally stable at a temperature of less than ⁇ 5° C. In a second embodiment, the composition remains thermally stable at a temperature of less than ⁇ 10° C. In a third embodiment, the composition remains thermally stable at a temperature of less than ⁇ 20° C.
• the antifreeze composition is especially useful in applications where it is desirable to provide long service life with minimal fluid change-outs or fluid modifications once in service.
• the antifreeze composition is used in applications in which heat is to be supplied to petroleum materials drilled or transported in cold climates to improve the fluidity and decrease the viscosity of the petroleum materials.
• the composition is also useful in conventional applications for heat transfer fluids, such as coolants in industrial engines.
• the composition can be used in operating cooling towers of thermal power stations, industrial and household refrigerators and freezers, open and closed heat exchangers, solar collectors, doublers and autoclaves used in the chemical industry, generally providing equipment with protection against frost damage in case of freezing, and in the foodstuffs sector for indirect cooling (e.g., freeze-drying, deep-freeze cabinet).
• the composition can also be used in de-icing applications for melting ice away from aircrafts, equipment, etc.
• compositions are prepared by mixing the components in the amounts indicated in Table 2.
• the components used in the Examples and the corresponding “code” in Table 1 are listed below. All components are commercially available from a number of sources.
• TMHA 3,5,5-trimethylhexanoic acid
• Sebacic acid C10b.
• Adipic acid C6b.
• Benzoic acid BA.
• PTBA p-tertButylbenzoic acid
• Potassium format (KFormate), potassium propionate (Kpropionate), potassium acetate (KAcetate), and dipotassium adipinate: non-glycol-based freezing point depressants used in the Examples.
• Mono ethylene glycol (MEG) optional glycol-based freezing point depressant used in some of the Examples.
• the antifreeze compositions were placed in glass vials and placed in climate chambers maintained at the specified temperatures in the Table. After 24 hours, the glass vials were taken out and visually assessed. Observations about the liquid samples in the examples (as indicated in the Table) were made according to the guidelines in Table 1
• a code of “TH” is used. If the liquid is very hazy with trace of precipitate, then “SH+TP” is used. If the liquid is clear, but needles are observed inside (more than just a few) then a code “MN” is used. If the liquid is slightly hazy, with a lot of gel on the glasswall, and with a trace of flocculation, combinations of codes can be used, e.g., “TH+SG+TF.” Lastly, if the liquid is clear (no instability) then the “OK” code is used.
• each antifreeze composition employs 43 wt. % potassium formate (based on the final weight on the composition), the organic acid content in wt. % as specified in the table, a sufficient amount of KOH for the sample pH to be between 10.8 and 11.2, and the remainder water.
• each example employs 22 wt. % potassium formate (based on the final weight of the composition), 16 wt. % potassium propionate, specified organic acid contents, a sufficient amount of KOH for the sample pH to be between 9.8 and 10.2, and water.
• each example employs 21 wt. % potassium acetate (based on the final weight on the composition), 28 wt.
• each example employs 22.8 wt. % dipotassium adipinate (based on the final weight of the composition), specified organic acid contents, a sufficient amount of KOH for the sample pH to be between 9.8-10.2, and water.

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