USOO7387748B2

(12) United States Patent (10) Patent No.: US 7,387,748 B2

(54) ANTIFREEZE COOLANT COMPOSITION 4,241,015 A 12, 1980 Hirozawa et al. ............. 422/13
FOR HIGH TEMPERATURE APPLICATIONS 4,241,016 A 12/1980 Hirozawa et al.
4,460,478 A 7/1984 Mohr et al.
(75) Inventors: Regis Joseph Pellet, 5,085,793 A ck 2f1992 Burns et al.
Croton-on-Hudson, NY (US); Paul Otto 5,387.360 A 2, 1995 Uekusa et al. ................ 252/73
5,711,894 A * 1/1998 Miyake et al. ................ 252/76
Fritz, Newburgh, NY (US); Leonard 5.718,836
Kw A 2f1998 Nakatani
tani et al.
sistman Bartley, Jr., Newburgh, NY 5,851.419 A 12/1998 Miyake et al.
FOREIGN PATENT DOCUMENTS
(73) Assignee: Texaco Inc., San Ramon, CA (US)
EP O348.303 A1 12, 1989
(*) Notice: Subject to any disclaimer, the term of this RO 115535 B 4f1999
patent is extended or adjusted under 35 RU 2050397 C1 12/1995
U.S.C. 154(b) by 0 days.
* cited by examiner
(21) Appl. No.: 10/307,683 Primary Examiner Necholus Ogden
(22) Filed: Dec. 2, 2002 (74) Attorney, Agent, or Firm—Steven R. Ellinwood
(65) Prior Publication Data (57) ABSTRACT
US 2004/O104375 A1 Jun. 3, 2004 The present invention comprises an improved antifreeze
coolant composition with certain additives that serve to
(51) Int. Cl. increase the thermal stability of the glycol component of a
C09K 50/00 (2006.01) glycol/water coolant composition and to reduce the tendency
(52) U.S. Cl. ............................. 252/73; 252/75; 252/76 of the glycol component to degrade under elevated thermal
(58) Field of Classification Search .................. 252/73, conditions. These additives comprise organic compounds
252/74, 75, 76, 77, 78.1, 79; 106/13 with a carboxylic acid moiety and a hydroxyl moiety, and
See application file for complete search history. also tricarballylic acid. Another aspect of this invention
(56) References Cited
concerns a method for improving the stability of the glycol
component of a glycol/water coolant composition in engine
U.S. PATENT DOCUMENTS cooling/heating systems by formulating a glycol/water cool
ant composition with the thermal stability additive to form
4,209,415 A * 6/1980 Hirozawa et al. ...... ... 252/76 an improved coolant composition, and contacting the engine
4,210,548 A * 7/1980 Hirozawa et al. ...... ... 252/76 cooling/heating system with the improved coolant compo
4,210,549 A * 7/1980 Hirozawa et al. ...... ... 252/76 sition.
4,234,440 A * 11/1980 Hirozawa et al. ...... ... 252/76
4,241,011 A 12, 1980 Hirozawa et al. ............. 422/13
4,241,012 A 12, 1980 Hirozawa et al. ............. 422/13 8 Claims, No Drawings
 US 7,387,748 B2
1. 2
ANTIFREEZE COOILANT COMPOSITION Moreover, the coolant base fluid, often composed of
FOR HIGH TEMPERATURE APPLICATIONS glycols can itself degrade to glycol breakdown products
Such as formate and glycolate through a process of oxida
BACKGROUND OF THE INVENTION tion, perhaps catalyzed by metal Surfaces. These oxidation
products tend to be acidic and can themselves attack cooling
1. Field of the Invention system components. Thus, the presence of glycolates and
The present invention relates to an engine antifreeze formates can enhance iron corrosion processes.
coolant composition which improves the thermal stability of Prior art automotive and heavy-duty coolant technology
the glycol component of a glycol/water coolant composition was designed for use at temperatures that typically ranged
in engine cooling/heating Systems. 10 from about 180-220 F., while heat rejecting surfaces that
2. Background of the Invention emanate heat and need to be cooled, such as the engine
It is well known to use heat transfer fluids in heat block, turbo chargers, exhaust gas coolers and fuel injectors,
exchanging systems, such as the central heating circuits and can develop Surface temperatures which contact the coolant
engine cooling systems of internal combustion engines and that range from about 230° F. to about 275° F. As trends
diesel engines. Generally, the heat transfer fluid contacts 15 continue, it is expected that coolant operating temperatures
various metals, alloys and other components that form the will increase to greater than 230 F. and that the temperature
different parts of the heat exchanging circuits in these of the heat rejecting surfaces can be on the order of about
systems. Most typically, coolants that are used in the internal 450° F. to about 600°F.
combustion engines and heavy duty diesel engine applica At the temperatures for which they were designed, prior
tions are relied upon to remove the excess heat produced by art coolants resist metal corrosion by means of inorganic or
the internal combustion process. carboxylate inhibition. They are also effective to some
The coolants, which are also referred to as antifreeze extent at buffering against the deleterious effects of acidic
compositions, usually comprise a water-soluble organic glycol breakdown products. However, at the anticipated
fluid to lower the freezing point of the heat transfer fluid. increase in operating temperatures of automotive cooling
The water-soluble organic fluid is also referred to as an 25 systems, prior art corrosion protection, inhibitor depletion
organic freezing point depressant. This water-soluble and glycol stability can be negatively impacted.
organic fluid is typically a glycol, for example, monoethyl U.S. Pat. No. 5,851,419 to Miyake et al discloses an
ene glycol or monopropylene glycol. Other equivalent gly antifreeze composition containing a Succinic acid derivative
cols can also be used. Such as 1,3-butylene glycol, hexylene in combination with a benzoic acid derivative to provide
glycol, diethylene glycol, glycerin, dipropylene glycol and 30 improved corrosion protection and greater buffering capac
1.3propanediol. Corrosion inhibitors are also generally ity. Improved buffer capacity is exemplified by titrating the
added to the antifreeze compositions. antifreeze composition with acid and noting that increased
Glycol-based antifreeze compositions are generally acid is needed to reduce the pH of the coolant. When glycol
diluted with water in order to prepare a ready-to-use aqueous degrades to acidic product, the composition will resist pH
heat transfer fluid. The weight ratio of the amount of the 35 drop due to enhanced buffer capacity.
organic freezing point depressant component to that of water U.S. Pat. No. 4.241,016, to Hirozawa discloses a process
in the antifreeze composition is determined by the desired of inhibiting the corrosion of metals, especially aluminum,
freezing point temperature of the antifreeze composition. using hydroxybenzoic acids as corrosion inhibitors in com
Specific combinations of water and organic freezing point bination with an organosiloxane silicate copolymer and pH
depressant components are chosen for desired heat transfer, 40 buffering agents capable of buffering in the pH range of 9 to
freezing point and boiling point properties. 11.
Antifreeze coolant compositions also contain additives to U.S. Pat. No. 4,460,478, to Mohr et al. discloses a coolant
prevent corrosion, foaming and scale formation, as well as composition containing an orthosilicate ester in a pH range
dyes for fluid identification purposes, and buffering agents to of 6 to 8 containing between 25 to 4000 ppm silicon. Mohr
control the pH of the composition. 45 also discloses hydroxybenzoate as a corrosion inhibitor.
A current trend in engine manufacture is toward higher U.S. Pat. No. 5,085,793, to Burns et al discloses an
efficiency and reduced environmental impact. Higher effi antifreeze composition wherein hydroxybenzoates are used
ciency can be achieved by increasing power output while for corrosion protection. The antifreeze composition com
reducing engine size and weight. This in turn has the effect prises glycol and at least one hydroxyl-Substituted aromatic
of increasing the thermal load to the engine cooling system 50 carboxylic acid, having the carboxyl radical proximate to the
while often reducing the volume of the cooling system. Such hydroxyl radical. Also disclosed is a process for inhibiting
changes result in higher coolant operating temperatures. metal corrosion. The corrosion inhibitor comprises hydroxy
However, gains in efficiency are often accompanied by benzoate and at least one of borates, silicates, benzoate,
increased degradation of the coolant. nitrates, nitrites, molybdates, thiazoles, and a aliphatic
The antifreeze coolant composition can degrade in a 55 diacid or its salt.
number of ways. Higher temperatures can accelerate the U.S. Pat. No. 5,718,836 to Nakatani discloses a coolant
depletion of the coolants corrosion inhibitors, prematurely composition containing calcium and/or magnesium salts as
shortening the useful life of the coolant. Thus, corrosion well as other corrosion inhibitors, including benzoates.
inhibitors which undergo chemical reaction to protect metal European patent 0 348 303 discloses improved corrosion
Surfaces can undergo reaction at accelerated rates at elevated 60 protection at elevated temperatures from the addition of
temperatures. For example, nitrite inhibitors added to protect salicylate or acetylsalicylate to glycol based antifreeze cool
cast iron typically convert to nitrate in use and will convert ants. The examples show increased pH in comparative
the iron Surfaces to a passivated State. Higher temperatures coolants when thermally aged due to the formation of basic
will accelerate the conversion of nitrite to nitrate, resulting degradation products. The addition of Salicylate appears to
in inhibitor depletion followed by reduced iron surface 65 repress increase in basicity as indicated by the repressed pH
protection and increased iron corrosion. Ultimately, coolant rise during thermal treatment. Repression of metal corrosion
life is shortened. is also noted. Although pH rise is undesirable because it
 US 7,387,748 B2
3 4
indicates metal corrosion, a pH drop also is a matter of Dihydroxybenzoic acids include 2,3-dihydroxybenzoic
concern because an overly acid coolant will itself induce acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic
corrosion of metal to which it is exposed. Therefore, pre acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic
venting the formation of acidic products is an important and acid, and 3,5-dihydroxybenzoic acid.
different function than prevention of metal corrosion. Trihydroxybenzoic acids include gallic acid (3,4,5-trihy
U.S. Pat. No. 5,387,360 to Uekusa et al discloses an droxybenzoic acid) and 2,4,6-trihydroxybenzoic acid.
antifreeze coolant composition comprising glycols as the
main constituent, for example, ethylene glycol, propylene Benzenediols include 1,2-benzenediol (pyrocatechol),
glycol. 1,3-butylene glycol, hexylene glycol, diethylene 1,3-benzenediol (resorcinol), and 1,4-benzenediol (p-hyro
glycol and glycerin. Uekusa’s water-free antifreeze compo 10 quinone).
sition also includes at least one conventional corrosion Especially effective are the alkali salts of tricarboxylic
inhibitor except silicates, and about 0.005 weight% to about acids such as citric, isocitric and tricarballylic acids.
0.5 weight % of citric acid and/or its corresponding salts. It has been found that such additives improve coolant
Uekusa discloses that when an organic acid other than stability as evidenced by decreased inhibitor depletion and
citric acid and its salts, or a tribasic acid, or a dibasic acid 15
reduced glycol degradation. The beneficial effects of the
is employed in place of citric acid, the resulting coolant has present invention are applicable to glycol/water antifreeze
little corrosion inhibiting effect, whether or not the organic coolants which rely on organic inhibitor technology as well
acid has a hydroxyl group in the molecule. Uekusa also as inorganic inhibitor technology. Organic inhibitor technol
notes that when the amount of citric acid or its correspond ogy depends upon carbon based, organic additives Such as
ing salts are less than 0.005 weight %, the resulting coolant
does not have a satisfactory corrosion preventing effect on carboxylate salts for corrosion protection. Inorganic inhibi
metallic materials such as aluminum alloys, resulting in tor technology depends upon inorganic additives such as
increased weight loss of metallic materials due to corrosion. silicate, phosphate and borate for corrosion inhibition and
Uekusa further notes that when the concentration of citric buffering effects.
acid or its corresponding salts is greater than 0.5 weight 96, 25 The additives can be present in amounts which vary from
the resulting coolant does not have desirable corrosion about 0.01 to about 5 weight %, based on the overall
preventing properties, resulting in increased weight loss of glycol/water composition, and preferably about 0.05 to
cast aluminum test pieces due to corrosion. The Surface of about 1.5 weight%. The additives are present as neutralized
the cast aluminum alloys also turns black. Uekusa does not alkali metal salts if they possess a carboxylic or acidic
address the influence or effect of citric acid and its corre 30 functionality.
sponding salts or other additives in a glycol/water antifreeze Glycol coolant formulations can contain a weight ratio of
coolant composition on glycol stability in high temperature water to glycol which varies from about 95:5 to about 5:95,
applications. respectively. However, most glycol coolant formulations
SUMMARY OF THE INVENTION
35
will contain a ratio of water to glycol which varies from
about 60:40 to about 40:60 respectively.
The present invention comprises an improved antifreeze The present invention has discovered that such high
coolant composition with certain additives that serve to temperature stability improving additives in antifreeze com
increase the thermal stability of the glycol component of a positions provide beneficial effects upon the rate of glycol
glycol/water coolant composition and to reduce the tendency 40
degradation in a water based glycol coolant at elevated
of the glycol component to degrade under elevated thermal temperature. The results are most effective when the amount
conditions. These additives comprise organic compounds of additive component varies from about 0.05 weight % to
with a carboxylic acid moiety and a hydroxyl moiety, and about 1.5 weight % in a water based glycol antifreeze
also tricarballylic acid. Another aspect of this invention composition comprising about 40 weight % to about 60
concerns a method for improving the stability of the glycol 45
weight% glycol. Other known ingredients such as corrosion
component of a glycol/water coolant composition in engine inhibitors, antifoams, Scale inhibitors, dyes and buffering
cooling/heating systems by formulating a glycol/water cool agents to control the pH of the composition can also be
ant composition with the thermal stability additive to form included. The pH of the present invention can vary from
an improved coolant composition, and contacting the engine about seven to about 11. In one embodiment of the present
cooling/heating system with the improved coolant compo 50 invention the pH was adjusted to about 8.0 (Table 2).
sition. The following examples demonstrate the efficacy of the
DESCRIPTION OF THE PREFERRED invention on glycol stability as evidenced by resistance to
EMBODIMENTS breakdown to acid products under thermal treatment. All
parts and percentages are by weight unless otherwise noted.
In accordance with the present invention, it has been 55
found that the high temperature stability of glycol-based EXAMPLE 1.
antifreeze coolant compositions can be enhanced by the
addition of certain additives comprising organic compounds 150 grams of ethylene glycol and 150 grams of water
with a carboxylic acid moiety and a hydroxyl moiety, and were mixed to produce a 50 weight % ethylene glycol
also tricarballylic acid. Examples of such additives include 60 solution in water. The pH of the glycol/water solution was
alkali salts of the mono-, di- and trihydroxy benzoic acids adjusted to 10 by the addition of 45% potassium hydroxide
and their derivatives. These include but are not limited to the Solution. Ten separate 30 gram glycol/water Solution por
salts of Salicylic acid, acetylsalicylic acid, the resorcylic tions were divided out. Eight of the solutions were each
acids and gallic acid. mixed with 0.0226 gram moles of an additive listed in Table
Monohydroxybenzoic acids include salicylic acid (2-hy 65 1. These solutions are referred to as “additized solutions'.
droxybenzoic acid), 3-hydroxybenzoic acid, and 4-hydroxy No additives were mixed in the two remaining 30 gram
benzoic acid. glycol/water Solutions.
 US 7,387,748 B2
5 6
Each additized solution was again adjusted with 45% EXAMPLE 2
potassium hydroxide to a pH in the range of 10-11, which is
typical of fresh unaged glycol/water automotive coolants. Coolant compositions were prepared by diluting with
The pH adjustment converted each acidic additive to the water an organic acid technology glycol-based, commercial
corresponding alkali salt. coolant concentrate from Chevron sold as Delo TM Extended
The thermal stability of each solution was evaluated by Life Coolant/Antifreeze to obtain a 50 weight% solution of
placing 20 grams of each additized glycol/water Solution and the commercial coolant concentrate in water having a pH of
one non-additized glycol/water solution in separate Teflon R about 8. Additives of the present invention were added to the
lined Parr reactors (Parr, Inc.). Each solution was also mixed coolant composition to yield an additive concentration of
with 3 grams of powdered iron. The Parr reactors were 10 0.0226 gram moles per 30 grams of coolant.
sealed and placed in an oven at 450° F. and aged for 8 days. Additives were added either as their alkali metal salt of
At the end of this period, the reactors were cooled and the corresponding substituted benzoic acid. If the additives
opened, and the aged samples were collected and analyzed were added as the acid, the resulting solution pH was
on a High Pressure Liquid Chromatograph (“HPLC) Model adjusted by the addition of potassium hydroxide solution So
1050 (Hewlett Packard Co.). Also analyzed was the unaged 15
that the final pH approximated that of the unadditized
additive-free glycol/water solution. coolant, that is about 8.
Each sample was eluted for approximately 38 minutes The pH and the reserve alkalinity of all solutions were
through the HPLC. Samples of each fresh and each aged measured in their fresh states and these results appear in
solution were analyzed by this method. The unaged additive Table 2. Reserve alkalinity was determined by titrating 10 cc
free glycol/water sample was free of decomposition com of each solution, diluted to 100 cc with deionized water, with
ponents which register as peaks on the HPLC chromato 0.1N hydrochloric acid until a solution pH of 5.5 was
gram. The aged additive-free glycol/water sample exhibited obtained. The reserve alkalinity was recorded as the volume
four major decomposition peaks attributable only to the of HCl solution needed to achieve the 5.5 pH. Again initial
thermal degradation of ethylene glycol in the presence of the results are recorded in Table 2.
powdered iron at elevated temperatures. Iron powder was Thirty grams of each solution were placed in 125 ml
added to simulate the action occurring in the cooling system 25 Teflon(R) lined Parr reactors and sealed. An additional 30
of an automotive engine with heat rejecting Surfaces Such as gram portion of 50 weight % solution of the commercial
the cast iron Surface of an operating automotive engine. coolant was also placed in a Parr reactor for comparative
The four major decomposition peaks in the non-additized purposes. The sealed reactors were placed in an oven at 400°
ethylene glycol solution on the HPLC chromatogram F. and maintained at that temperature for 40 hours. The
occurred at retention times of 5.26, 8.54, 11.74 and 31.46 30 reactors were cooled and the thermally aged coolant samples
minutes, respectively. Analysis of each of the fresh, were analyzed for pH and for reserve alkalinity. Final
additized solutions were found to have no component peaks reserve alkalinity and final pH results for the aged coolants
in the areas of these decomposition peaks. Thus these four also appear in Table 2.
peaks were selected based on minimal interference from the From the data in Table 2, the 50 weight % solution of the
additives of the present example. The same four peaks were 35
commercial coolant with no additive had an initial pH of 7.8
found however, to varying extent in all of the aged additized and a reserve alkalinity of 2.06. After aging, the non
solutions and were used to indicate the extent of ethylene additized 50 weight % solution of the commercial coolant
glycol degradation that occurred during thermal aging in the had a pH of 6.75 and a reserve alkalinity of 1.37. Degrada
presence of the various additives of this example. Specifi tion of the ethylene glycol component of the 50 weight %
cally, the total “counts of the four peaks are integrated Solution of the commercial coolant generated acidic degra
unitless areas attributed to each degradation component and 40 dation products which caused the pH of coolant to decrease
serve as useful indicators of the extent of ethylene glycol and also reduced the reserve alkalinity of the aged 50 weight
degradation. The integrated areas for non-additized ethylene % solution of the commercial coolant.
glycol in water as well as the other test Solutions are From the data in Table 2, it can also be seen that the 50
summarized in Table 1. weight % solutions of the commercial coolant which were
45 additized with hydroxybenzoates or their derivatives,
TABLE 1. present as the Sodium salt, were prepared so that their intial
Aged 50% Glycol/Water Solutions
pH values were nearly the same as that of the non-additized
50 weight % solutions of the commercial coolant, or about
Additive 8. More importantly, the coolants modified with the addi
HPLC 4 Peak Weight gram-moles 50 tives of the present invention had reserve alkalinities of
Additive Area (counts) (grams) 1000 grams about 2, approximately equivalent to the non-additized 50
Ole 984
weight '% solutions of the commercial coolant comparative
tricarballyic acid 192 O.O36 O.O226 example. This signifies that the additives used in the present
gallic acid 244 O.O3S O.O226 invention did not increase the buffer capacity of the coolants
acetylsalicylic acid 26S O.O37 O.O226
55
since there was no increase in reserve alkalinity.
Sodium salicylate S4O O.O34 O.O226
Sodium citrate 952 O.O62 O.O226 TABLE 2
Sodium tartarate 979 O.049 O.O226
Thermal Aged, Additized 50 weight % Commercial
Coolant: pH and Reserve Alkalinity Properties
The non-additized ethylene glycol/water solution with a 60
total peak area of 984 counts provided a basis in which to Initial Final
evaluate the effect of each additive on the thermal stability Initial Reserve Final Reserve
of the glycol component. The data indicates that the thermal Additive pH Alkalinity pH Alkalinity
stability improving additives such as tricarballyate, citrate, None 7.8 2.06 6.75 1.37
gallate, acetylsalicylate and Salicylate were particularly Salicylate 7.87 2.06 6.95 1.83
effective in repressing glycol breakdown or degradation as 65 Acetylsalicylate 7.84 2.08 6.79 1.75
indicated by the reduced counts of the four peak HPLC areas 4-hydroxybenzoate 8.1 2.13 6.98 2.05
of the additized glycol solutions.
 US 7,387,748 B2
7 8
2.01 due to the formation of acids from glycol degradation.
TABLE 2-continued The pH of the salicylate/water/glycol solution also dropped
but only to a pH of 3.74. Since pH is a logarithmic scale, the
Thermal Aged, Additized 50 weight % Commercial 1.73 unit difference in acidity represents a nearly 100 fold
Coolant: pH and Reserve Alkalinity Properties difference in acidity.
Initial Final In order to determine the amount of acid products formed,
Initial Reserve Final Reserve each solution was titrated by adding a base solution, 0.1N
Additive pH Alkalinity pH Alkalinity sodium hydroxide in water until the resulting pH returned to
Acetylbenzoate 8.24 2.22 6.79 1.57
the initial solution pH of 11. The amount of base added was
2,4-dihydroxybenzoate 8.03 2.5 7.18 2.44 10
equivalent to the amount of degradation acid formed when
2,6-dihydroxybenzoate 8.06 2.3 7.00 2.2 the Solution pH was returned to its starting value, that is, all
acid products were neutralized. The results of these titrations
are summarized in Table 3.
After thermal aging of these coolants, a somewhat Smaller
pH drop was observed. More importantly, the reserve alka TABLE 3
linity of the coolants of the present invention remained 15
significantly higher. Thus, the 50 weight % solutions of the pH and Acid Content: Ethylene Glycol Solutions
commercial coolant modified with 4-hydroxybenzoate, as
the sodium salt, had an initial reserve alkalinity before aging Titration,
Initial pH, Aged Volume of
of 2.13. After aging it maintained a reserve alkalinity of Solution pH Solution 0.1N Base
2.05, virtually unchanged. While the initial reserve alkalin
ity of the 4-hydroxybenzoate modified 50 weight% solution Ethylene glycol, 11.OO 2.01 9.88
of the commercial coolant was the same as the non-modified Water
Sodium salicylate? 11.01 3.74 3.96
50 weight % solution of the commercial coolant, which glycoli water
indicated comparable buffer capacity, the aged reserve alka
linity of 2.05 was significantly greater than that of the aged 25 *volume of potassium hydroxide (KOH) required to restore pH to 11
non-additized 50 weight % solution of the commercial
coolant with a reserve alkalinity of 1.37. This demonstrates The titration data indicate 9.88 ml of 0.1N sodium
that far fewer acidic glycol breakdown products formed hydroxide solution were needed to restore the pH of the
upon thermal aging of the coolant of the present invention. non-additized ethylene glycol water solution to its initial pH
Note that with 4-hydroxybenzoate, the hydroxy moiety is value of 11.00. In contrast, only 3.96 ml of base were needed
not proximate to the carboxylate moiety on the benzene ring. 30 to return the solution of the present invention to its initial
To varying degrees similar improvements were observed for pH. Again, the volume of base needed to neutralize the acid
all other additives in Table 2. degradation products is an exact measure of the amount of
It appears that the multiple hydroxylated benzoates were ethylene glycol degradation that occurred. The data of Table
even better than the single hydroxy substituted benzoates in 3 indicate that acid production was reduced by more than a
stabilizing coolant against thermal degradation as indicated 35 factor of two for the solution of the present invention. Unlike
by improved reserve alkalinity properties. The triply substi the prior art where additional additives are required to obtain
tuted hydroxybenzoates, such as the alkali Salt of gallic acid increased buffer capacity or increased corrosion resistance,
were even more effective as shown in Table 1. this example demonstrates that the additives of the present
invention are effective without additional components to
EXAMPLE 3
40
repress glycol degradation.
Thermal aging of glycol/water Solutions causes acidic EXAMPLE 4
breakdown products formed from the degradation of ethyl
ene glycol. The amount of these acid products can be Three coolant compositions were prepared to demonstrate
quantified by titration with base and the quantification can the unexpected effect of increasing the additive citrate
be used as a measure of the extent of glycol degradation. In 45
content beyond the level disclosed in U.S. Pat. No. 5,387,
the following experiments, water/glycol Solutions were ther 360 to Uekusa. The first coolant composition was prepared
mally aged and then titrated to quantify the extent of thermal by diluting with water an organic acid technology glycol
degradation in the presence of and in the absence of an based coolant concentrate available commercially from
additive of the present invention. Chevron as DeloTM Extended Life Coolant to obtain a 50
A water/glycol solution was prepared by mixing 50.0 50 weight 96 solution of the commercial coolant concentrate in
grams of deionized water with 50.0 grams of ethylene glycol water. The 50 weight % or 50:50 water/glycol commercial
to yield a 50 weight percent solution of ethylene glycol in coolant solution was then used to prepare two additional
water. A 50.0 gram portion of this 50% solution was treated coolant compositions. The second coolant composition was
by dissolving in it 0.054 grams of sodium salicylate. The pH modified by adding 0.2 weight% sodium citrate to the 50:50
of this solution and the non-additized portion were adjusted 55 water/glycol coolant solution. This coolant represents a
to 11.0 using a potassium hydroxide solution. The pH of composition within the scope of the Uekusa patent because
each Solution was adjusted so that each solution would have on a water-free basis the second coolant composition would
the same acid/base content prior to thermal aging. contain 0.4 weight percent sodium citrate. The third coolant
Each solution was thermally aged as follows. A thirty composition was modified by adding 0.4 weight percent
gram portion of the water/glycol mixture was added to one 60
sodium citrate to the 50:50 water/glycol solution which
Teflon R lined Parr reactor while another thirty gram portion would be equivalent to 0.8 weight percent sodium citrate in
of the salicylate/water/glycol solution was added to a second a water-free glycol concentrate. The third coolant composi
Teflon(R) lined Parr reactor. Both reactors had a 125 ml tion with the sodium citrate additive is outside the scope of
capacity. Both reactors were sealed and placed in an oven at the 0.5 weight % maximum concentration on a water-free
400° F for 15 hours. basis disclosed in the Uekusa patent.
After thermal treatment, the reactors were cooled and the 65 The three coolant compositions were evaluated for glycol
pH of each aged solution was measured and listed in Table stability using a modified ASTM 4340 test. The ASTM 4340
3. The pH of the water/glycol solution dropped from 11.0 to Hot Surface Test is designed to measure corrosion rates on
 US 7,387,748 B2
9 10
an electrically heated aluminum Surface exposed to coolant. The 50 weight% solution of the commercial coolant, with
In this test an aluminum coupon was heated to 275° F. and no citrate added, had a reserve alkalinity of about 6 and a pH
exposed to the test coolant diluted to 25% concentration of about 8.3 in its fresh state, before testing.
with corrosive water containing chloride. Measurement of As seen from Table 4, when citrate content was raised
the aluminum coupon weight before and after exposure to s from 0 to 0.4 to 0.8 weight percent, the reserve alkalinity
coolant for a 1 week period yields a weight loss measure maintained by the aged coolant increased from 2.3 to 3.8 to
ment which is directly related to the high temperature 5.2. For the same series, Table 4 shows that the coolant pH
aluminum corrosion rate.
For purposes of demonstrating the advantages of the weight after aging increased from 7.1 to 8.2 to 8.7. Fresh, unused 50
current invention, the ASTM 4340 test was modified by 10 alkalinity% of solution of the commercial coolant had a reserve
replacing the aluminum coupon in the test apparatus with a indicate that about 5-6.0 and a pH of about 8-8.5. The data
cast iron coupon to allow accelerated aging of coolant. Cast coolant without citrateweight
the 50 % solution of the commercial
and the 50 weight % solution of the
iron was employed to simulate typical engine block Surfaces
where some of the highest engine temperatures are encoun commercial coolant with 0.4% citrate significantly reduced
tered. The modifications were made to obtain information pH and reserve alkalinity. The 50 weight % solution of the
about the stability of the coolants inhibitors and the cool- 15 commercial coolant with 0.8% citrate maintained a pH and
ant's glycol component at elevated temperature conditions reserve alkalinity equivalent to unused 50 weight% solution
to accelerate degradation. of the commercial coolant, indicating far less degradation.
The coupon assembly was placed on top of the electrical The glycol stabilization achieved by the present invention
heating unit in the test apparatus of ASTM 4340. A cylin is not disclosed in the Uekusa patent.
drical glass reservoir was placed above the coupon assem The Uekusa patent teaches away from coolant composi
bly. The glass reservoir and the coolant passage were then tions containing more than 0.5 weight percent citrate on a
filled with 500 grams of coolant to be evaluated at a pressure water-free basis. According to Uekusa, the ability to protect
of 25-30 psig. The coupon was then heated to a temperature against corrosion is negatively impacted at higher citrate
of 275° F. and maintained at that temperature for 500 hours, levels.
or approximately 3 weeks. The 275° F. test temperature was 25 This example demonstrates that when citrate was added to
selected to accelerate thermal degradation which occurs over an organic additive coolant, the resultant coolant had
hot metal Surfaces in real world applications. improved resistance to glycol degradation. More impor
Each of the three coolant compositions described above tantly, this example showed the unexpected beneficial effect
were aged in the modified ASTM 4340 apparatus by expos of elevated citrate concentrations on glycol stabilization.
ing the coolant to the cast iron assembly, heated to 275° F. 30 Coolants containing citrate at concentrations outside the
for 500 hours at pressures ranging from 25 to 30 psi. range disclosed in the Uekusa patent were shown to be
Following aging, the aged coolant was analyzed for inhibitor
content, pH, reserve alkalinity (RA) and for the typical superior to coolants containing citrate within the range
glycol breakdown products, glycolate and formate. The disclosed by Uekusa. The Uekusa patent does not disclose
presence of glycolate and formate indicates degradation or advantages for glycol or for elastomers when using coolants
breakdown of the glycol coolant component due to thermal 35 with citrate additives. These benefits are obtained without
and/or oxidative treatment. adversely affecting other coolant properties. Surprisingly,
This modified test yielded information on glycol break the aluminum corrosion resistance of a coolant containing
down or degradation induced by exposure of the coolant to citrate in excess of the level claimed in the Uekusa patent,
the cast iron coupons heated to 275°F. over the 500 hour test as measured by aluminum corrosion current in Table 4, was
period. The test yielded information regarding changes to 40 actually better than the aluminum protection afforded by
the coolant pH and to the coolant reserve alkalinity. Both of using citrate at levels specified by Uekusa.
these parameters changed as a result of glycol degradation.
As glycol degrades, acidic degradation products, such as EXAMPLE 5
glycolic and formic acid were generated resulting in a
decrease in coolant pH as well as a decrease to coolant 45 The electrochemical techniques detailed in ASTM D
reserve alkalinity. Reserve alkalinity is measured by titration 6208-97 "Test Method for Repassivation Potential of Alu
with 0.1N hydrochloric acid and is the volume in milliliters minum and Its Alloys by Galvanostatic Measurement” are
of acid needed to titrate 10 milliliters of coolant to a pH of generally used in the industry to evaluate the ability of
5.5. This increased acidity is to be avoided because of the
detrimental effect it has on cooling system components. At 50 metallic Surfaces to resist pitting corrosion. Metal corrosion
is electrolytically accelerated in ASTM D 6208-97 in an
reduced pH, acid attack on metal and elastomeric parts anodic process wherein metal is oxidized to metal ions and
becomes a significant cause of degradation. the metal surface becomes pitted in a fashion similar to the
The results obtained in evaluating the three coolant com pitting which occurs during the corrosion process.
positions described above in the modified ASTM 4340 test At a given or constant applied potential, the metal Sur
are summarized in Table 4. 55
faces which exhibit increased current will also exhibit
TABLE 4 increased pitting corrosion. Thus the current observed at an
aluminum electrode immersed in coolant under applied
Reserve potential will indicate the extent of corrosion induced by the
Alkalinity Aluminum applied potential. Metallic Surfaces exhibiting increased
weight % after Aging pH Corrosion 60 current will be corroding at a faster rate. Conversely, Sur
Citrate in (volume, ml after Current
Base Coolant Concentrate of 0.1N HCI) Aging (micro amps) faces protected by the coolant inhibitors will exhibit reduced
current relative to an unprotected Surface.
50 weight % O.00% 2.3 7.1 2.19 The three coolant compositions prepared in Example 4
wateriglycol O.40% 3.8 8.18 3.59
commercial O.80% 5.2 8.66 2.67 were replicated to evaluate their ability to protect aluminum
Solution 65 against corrosion. Aluminum coupons or electrodes com
mercially available from Metal Samples, Inc., having an
exposed surface area of 1.0 cm were prepared from alumi
 US 7,387,748 B2
11 12
num 3003 alloy and were cleaned and polished with 600 solutions at 0.1 volts above the open circuit potential of each
mesh sand paper to remove Surface coatings and to prepare coupon.
a reproducible Surface for evaluation. The aluminum cou As a 0.1 volt anodic potential was applied, current was
pons thus prepared were placed in a cellholder available as induced and corrosion began. The rate of corrosion is
EG&G's 5/8 inch Teflon(R) disk holder and immersed in each 5 indicated by the amount of current induced. As the coolant
of the three replicated test coolants prepared in Example 4. citrate level was raised from 0 to 0.4% to 0.8% the corrosion
Test solutions were prepared by further diluting each of current varied from 2.2 to 3.6 to 2.7 microamps. This is an
the three test coolant compositions with ASTM D-1384 extremely small current and is relatively the same for all
corrosive water containing 100 ppm portions of Sulfate, three solutions. This indicates that for coolants of the present
chloride and bicarbonate ions introduced as Sodium salts. 10 invention, aluminum corrosion protection was not impaired
The final solution contained about 17 weight % of the by the presence of citrate in excess of the range claimed by
original glycol concentrate. the Uekusa patent.
Dilution of the corrosion inhibitor is necessary to enhance What is claimed is:
the severity of this test and to magnify difference in inhibitor 1. A thermally stable coolant composition having a pH
performance. Specifically, the corrosive ions present in the 15 from about 7.8 to about 11.1 and consisting of water and a
corrosive water accelerate the pitting of the aluminum glycol in a weight ratio of about 95:5 to about 5:95 respec
specimen immersed in the coolants of this example. The tively, and about 0.01 weight % to about 5.0 weight % of at
coolants that offer improved corrosion protection will better least one additive selected from the group consisting of
resist pitting tendencies caused by the presence of the 3-hydroxybenzoic acid: 4-hydroxybenzoic acid; 2,3-dihy
corrosive water. Those coolants with improved corrosion droxybenzoic acid; 2,4-dihydroxybenzoic acid; 2,5-dihy
protection will exhibit reduced electrical current and droxybenzoic acid; 2,6-dihydroxybenzoic acid; 3,4-dihy
improved corrosion protection. droxybenzoic acid; 3,5-dihydroxybenzoic acid; 2.4.6-
The cell holder with the aluminum coupon was electri trihydroxybenzoic acid; isocitric acid; acetylsalicylic acid;
cally connected to the anodic (positive) terminal of a poten resorcylic acid and the alkali salts of each of said acids.
tiometer while a graphite working electrode was connected 25 2. The composition of claim 1, wherein the weight ratio
to the cathodic (negative) terminal. The potentiometer was of glycol to water is about 50:50.
used to apply a precisely controlled potential (voltage) 3. The composition of claim 1, wherein the initial pH
varies from about 7.8 to about 9.0.
between the metal test specimen, that is, the aluminum 4. The composition of claim 1, wherein the glycol is at
electrodes and the graphite electrode. 30 least one selected from the group consisting of monoethyl
For purposes of studying the corrosion tendencies in the ene glycol, monopropylene glycol, 1,3-propylenediol, dieth
coolants of this example, a positive charge was applied to the ylene glycol, dipropylene glycol, butylene glycol, hexylene
aluminum electrode (anode) relative to the graphite counter glycol and glycerin.
electrode (cathode). A standard calomel electrode was also 5. A method for improving the high temperature stability
used and served as a reference against which, the precise 35 of a water and glycol antifreeze coolant composition con
potential of the aluminum electrode was measured. sisting of the steps of:
In addition to measuring the potentials or Voltage differ (a) forming a water and glycol antifreeze coolant mixture
ences, the potentiometer measured the current generated with a water to glycol weight ratio of about 95:5 to
between two electrodes as the potential or voltage was about 5:95 respectively,
applied. The amount of current generated is a measure of the 40 (b) adding to said antifreeze coolant composition about
amount of corrosion occurring at the aluminum Surface. 0.01 weight % to about 5.0 weight % of at least one
When the coolants provided improved corrosion protec thermal stability improving additive selected from the
tion, the aluminum electrode exhibited reduced current at a group consisting of 3-hydroxybenzoic acid, 4-hydroxy
controlled, applied potential, thereby showing improved benzoic acid: 2,3-dihydroxybenzoic acid; 2,4-dihy
corrosion protection. 45 droxybenzoic acid; 2,5-dihydroxybenzoic acid; 2,6-
Each aluminum coupon was allowed to equilibrate by dihydroxybenzoic acid; 3,4-dihydroxybenzoic acid;
placing it in each of the three test solutions for thirty 3,5-dihydroxybenzoic acid; 2,4,6-trihydroxybenzoic
minutes. After equilibration, the anodic potential of the acid; isocitric acid; acetylsalicylic acid; resorcylic acid
aluminum was increased relative to the graphite cathode. and the alkali salts of each of said acids,
The anodic potential was increased to +0.1 Volts greater than 50 (c) adjusting the pH of said antifreeze coolant mixture
the open circuit potential of the aluminum electrode from about 7.8 to about 11.1.
immersed in each test solution. The open circuit potential is 6. The method of claim 5, wherein the weight ratio of
the potential observed relative to a standard calomel elec glycol to water is about 50:50.
trode when the aluminum electrode is immersed in the test 7. The method of claim 5, wherein the initial pH varies
coolant with no applied potential. The open circuit potential 55 from about 7.8 to about 9.0.
is the potential observed when the aluminum electrode is at 8. The method of claim 5, wherein the glycol is at least
equilibrium with the coolant environment in which it is one selected from the group consisting of monoethylene
immersed. The actual potential of the anode was determined glycol, monopropylene glycol, 1,3-propylenediol, diethyl
by comparison to a saturated calomel electrode. ene glycol, dipropylene glycol, butylene glycol, hexylene
Table 4 in Example 4 lists anodic currents in microamps
60 glycol and glycerin.
for aluminum coupons immersed in each of the three test