US009145613B2

(12) United States Patent (10) Patent No.: US 9,145,613 B2

Yang et al. (45) Date of Patent: *Sep. 29, 2015
(54) HEAT TRANSFER FLUIDS AND CORROSION 4,370.255. A 1/1983 Plueddemann
INHIBITOR FORMULATIONS FOR USE 4,517,110 A 5, 1985 Suzuki et al.
THEREOF 4,629,602 A 12/1986 Gousetis et al.
4,701.277 A 10, 1987 Mohr et al.
4,772.408 A 9, 1988 Mohr et al.
(71) Applicant: Prestone Products Corporation, Lake 5,018,577 A 5/1991 Pardue et al.
Forest, IL (US) 5,338.477 A 8, 1994 Chen et al.
5,567,346 A 10, 1996 Kakiuchi et al.
(72) Inventors: Bo Yang, Ridgefield, CT (US); Aleksei 5,606,105 A 2f1997 Davis et al.
5,866,042 A 2f1999 Chen et al.
Gershun, Southbury, CT (US); Peter M. 6,126,852 A * 10/2000 Turcotte et al. ................. 252/76
Woyciesjes, Woodbury, CT (US) 6,235,217 B1 5, 2001 Turcotte et al.
6,391,257 B1 5/2002 Woycieses
(73) Assignee: Prestone Products Corporation, Lake 6,572,789 B1 6/2003 Yang et al.
Forest, IL (US) 7,588,694 B1 9, 2009 Bradshaw et al.
7,608,198 B2 10/2009 Jeffcoate et al.
(*) Notice: Subject to any disclaimer, the term of this 7,645,331 B2 1/2010 Yang et al.
7,662,304 B2 2/2010 Woyciesjes et al.
patent is extended or adjusted under 35 7,820,066 B2 10/2010 Jeffcoate et al.
U.S.C. 154(b) by 0 days. 7,854.253 B2 12/2010 Woyciesjes et al.
7,985,349 B2 7/2011 Yang et al.
This patent is Subject to a terminal dis 8,216,383 B2 7/2012 Yang et al.
claimer. 2004/0227124 A1 11/2004
Turcotte et al.
2006, OO 17044 A1 1/2006
Zhang et al.
(21) Appl. No.: 14/087,796 2007.0034825 A1 2/2007 Wenderoth et al.
2009,0266519 A1 10/2009 Marinho et al.
2009,0294.102 A1 12/2009 Yang et al.
(22) Filed: Nov. 22, 2013 2010, 0006796 A1 1/2010 Yang et al.
2010.00597O3 A1* 3/2010 Yang et al. ...................... 252/76
(65) Prior Publication Data 2010, 0116473 A1* 5/2010 Yang et al. ................. 165,134.1
US 2014/O1 19983 A1 May 1, 2014 FOREIGN PATENT DOCUMENTS
Related U.S. Application Data CN 10.105055 10/2007
EP O245557 11, 1987
(63) Continuation of application No. 13/606,452, filed on
Sep. 7, 2012, now Pat. No. 8,617,416. OTHER PUBLICATIONS

(51) Int. Cl. Non-final Office Action dated Mar. 15, 2013 in U.S. Appl. No.
C09K 5/10 (2006.01) 13/606,516.
Non-final Office Action dated Mar. 15, 2013 in U.S. Appl. No.
C23F II/8 (2006.01) 13/606,452.
C09K5/20 (2006.01) International Search Report and Written Opinion of PCT/US2013/
C23F II/08 (2006.01) 56267 dated Sep. 13, 2013.
(52) U.S. Cl. International Search Report and Written Opinion of PCT/US2013/
CPC ................. C23F 11/184 (2013.01); C09K 5/10 56262 dated Oct. 16, 2013.
(2013.01); C09K5/20 (2013.01); C23H II/08 International Search Report and Written Opinion of PCT/US2013/
(2013.01) 56268 dated Sep. 19, 2013.
(58) Field of Classification Search * cited by examiner
None
See application file for complete search history. Primary Examiner — Necholus Ogden, Jr.
(56) References Cited
(74) Attorney, Agent, or Firm — Barnes & Thornburg LLP:
Gregory H. Zayia
U.S. PATENT DOCUMENTS
(57) ABSTRACT
3, 198,820 A 8, 1965 Pines et al. Disclosed herein is a heat transfer fluid concentrate compris
3,203,969 A 8, 1965 Pines et al. ing: greater than or equal to 90 weight percent of a freezing
3.248,329 A 4, 1966 Pines et al.
3,312,622 A 4, 1967 Pines et al. point depressant; 16 to 80 ppm of magnesium ions; an azole
3,337.496 A 8, 1967 Pines et al. compound; an inorganic phosphate; a carboxylate; and an
3,341,469
4,093,641
A
A
9, 1967
6, 1978
Pines et al.
Plueddemann
acrylate based polymer, wherein the heat transfer fluid con
4,287,077 A 9/1981 Wing centrate has a pH of 7-9.5 and the weight ratio of acrylate
4.333,843. A 6/1982 Wing et al. based polymer to magnesium ions is 1 to 25. The heat transfer
4,352,742 A 10, 1982 Davis et al. fluid concentrate can be used to make a heat transfer fluid.
4,354,002 A 10, 1982 Davis et al.
4,362,644 A 12/1982 Davis et al. 45 Claims, No Drawings
 US 9,145,613 B2
1. 2
HEAT TRANSFER FLUIDS AND CORROSION good corrosion performance. The effect of calcium ions on
INHIBITOR FORMULATIONS FOR USE the solubility of magnesium ions in the phosphate containing
THEREOF heat transfer fluid is particularly Surprising. The highly
insoluble nature of various calcium phosphate salts in aque
CROSS REFERENCE TO RELATED ous solutions at pH between 7 and 9.5 would lead one of skill
APPLICATION in the art to predict poor solubility due to solution thermody
namic considerations.
This application is a continuation of co-pending U.S. appli The heat transfer fluid concentrate and heat transfer fluid
cation Ser. No. 13/606,452, filed Sep. 7, 2012, the entire can be free of silicate, borate and amines. The nitrate content
disclosure of which is hereby incorporated by reference. 10 can be less than 50 ppm by weight based on the total weight
of the heat transfer fluid concentrate or heat transfer fluid.
BACKGROUND The freezing point depressant can be an alcohol or mixture
ofalcohols. Exemplary alcohols include monohydric or poly
Modern vehicle engines generally require a heat transfer hydric alcohols and mixtures thereof. The alcohol can be
fluid (liquid coolant) to provide long-lasting, year-round pro 15 selected from the group consisting of methanol, ethanol, pro
tection of their cooling systems. The primary requirements of panol, butanol, furfurol, furfuryl alcohol, tetrahydrofurfuryl
the heat transfer fluids are that they provide efficient heat alcohol, ethoxylated furfuryl alcohol, ethylene glycol, propy
transfer to control and maintain engine temperature for effi lene glycol. 1,3-propanediol, glycerol, diethylene glycol, tri
cient fuel economy and lubrication, and prevent engine fail ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,
ures due to freeze-up, boiling-over, or over-heating. An addi dipropylene glycol, butylene glycol, glycerol-1,2-dimethyl
tional key requirement of a heat transfer fluid is that it ether, glycerol-1,3-dimethyl ether, monoethylether of glyc
provides corrosion protection of all cooling system metals erol, Sorbitol, 1.2.6-hexanetriol, trimethylopropane, alkoxy
over a wide range of temperature and operating conditions. alkanols such as methoxyethanol, and combinations of two or
Aluminum corrosion protection for engine block, cylinder more of the foregoing.
head, water pump, heat exchangers and other components 25 In the heat transfer fluid concentrate the freezing point
from aluminum or aluminum alloys is particularly important. depressant is present in an amount greater than or equal to 85
Beyond metal protection, corrosion protection helps the heat weight percent (wt %) and less than or equal to 99 wt %, based
transfer fluid to fulfill its primary function of transferring on the total weight of the heat transfer fluid concentrate.
excess heat from the engine to the radiator for dissipation. Within this range, the amount of freezing point concentrate
There is an ongoing need for heat transfer fluids having 30 can be greater than or equal to 86 wt %, greater than or equal
good heat transfer and corrosion protection. to 87 wt %, greater than or equal to 88 wt %, greater than or
equal to 89 wt %, greater than or equal to 90 wt %, greater than
BRIEF DESCRIPTION or equal to 91 wt %, greater than or equal to 92 wt %, greater
than or equal to 93 wt %, greater than or equal to 94 wt %,
This need is met, at least in part, by a heat transfer fluid 35 greater than or equal to 95 wt %, greater than or equal to 96
concentrate comprising: greater than or equal to 85 weight wt %, greater than or equal to 97 wt %, or greater than or equal
percent of a freezing point depressant; 16 to 80 ppm of mag to 98 wit 9/6.
nesium ions; an azole compound; an inorganic phosphate; a The carboxylate has 6 to 20 carbon atoms. The term “car
carboxylate; and an acrylate based polymer, wherein the heat boxylate' is inclusive of carboxylic acid, salt thereof, and
transfer fluid concentrate has a pH of 7 to 9.5 and the weight 40 combinations of a carboxylic acid and carboxylic acid salt.
ratio of acrylate based polymer to magnesium ions is 1 to 25. The carboxylate may comprise a single or multiple carboxyl
The heat transfer fluid concentrate can be diluted to form a groups and may be linear or branched. It is expressly contem
heat transfer fluid coolant comprising: less than 90 weight plated that combinations of carboxylates may be used and are
percent of a freezing point depressant; water, 8 to 60 ppm of encompassed by the term “carboxylate' or “carboxylic acid”.
magnesium ions; an azole compound; an inorganic phos 45 Exemplary aliphatic carboxylates include 2-ethylhexanoic
phate; a carboxylic acid; greater than 0.5 ppm of calcium acid, hexanoic acid, heptanoic acid, octanoic acid, neode
ions; and an acrylate based polymer, wherein the heat transfer canoic acid, decanoic acid, nonanoic acid, isoheptanoic acid,
fluid has a pH of 7-9.5 and the weight ratio of acrylate based dodecanoic acid, sebacic acid, adipic acid, pimelic acid,
polymer to magnesium ions is 1 to 25. Suberic acid, azelaic acid, dodecanedioic acid, and combina
Also described herein is a heat transfer system comprising 50 tions of two or more of the foregoing. Exemplary aromatic
a heat transfer fluid concentrate or heat transfer coolant as carboxylates include benzoic acid, toluic acid or methylben
described herein and a heat transfer apparatus. Zoic acid, tert-butylbenzoic acid, alkoxybenzoic acid, e.g.,
methoxybenzoic acid (or o, p, m-anisic acid), salicylic acid,
DETAILED DESCRIPTION phthalic acid, isophthalic acid, terephthalic acid, phenylace
55 tic acid, mandelic acid, 1,2,4-benzenetricarboxylic acid, and
Disclosed herein are heat transfer fluid concentrate and combinations of two or more of the foregoing.
heat transfer fluid compositions that demonstrate a synergis In the heat transfer fluid concentrate the carboxylate is
tic effect between the components of the composition. In a present in an amount of 1 to 10 wt %, based on the total weight
heat transfer fluid comprising ethylene glycol, water, a car of the heat transfer fluid concentrate. Within this range, the
boxylate, inorganic phosphate, and an azole compound the 60 amount can be greater than or equal to 1.5 wt %, or, more
synergistic effect is observed between magnesium ions and specifically, greater than or equal to 2 wt %. Also within this
acrylate based polymer, as shown in the corrosion tests and range, the amount can be less than or equal to 7 wt %, or, more
storage test. The optimal performance is observed when the specifically, less than or equal to 5 wt %.
ratio of acrylate-based polymer to magnesium ion (both in The inorganic phosphate can be phosphoric acid, Sodium
ppm or wt %) in the heat transfer fluid concentrate is 1 to 25. 65 orthophosphate, potassium orthophosphate, sodium pyro
In the case of a heat transfer fluid, the results show that adding phosphate, potassium pyrophosphate, Sodium polyphos
1-15 ppm of calcium ions can ensure storage stability and phate, potassium polyphosphate, Sodium hexametaphos
 US 9,145,613 B2
3 4
phate, potassium hexametaphosphate, or a combination of acrylate based polymers, copolymers, terpolymers, and quad
two or more of the foregoing inorganic phosphates. polymers, such as acrylate/acrylamide copolymers, poly
In the heat transfer fluid concentrate, the inorganic phos methacrylates, polymaleic acids or maleic anhydride poly
phate can be present in an amount of 0.10 wt.% to 0.60 wt %, mers, maleic acid based polymers, their copolymers and
based on the total weight of the heat transfer fluid concentrate. terpolymers, modified acrylamide based polymers, including
Within this range, the amount can be greater than or equal to polyacrylamides, acrylamide based copolymers and terpoly
0.11 wt %, or, more specifically, greater than or equal to 0.12 mers. In general, water soluble polymers Suitable for use
wt %. Also within this range, the amount can be less than or include homo-polymers, copolymers, terpolymer and inter
equal to 0.45 wt %, or, more specifically, less than or equal to polymers having (1) at least one monomeric unit containing
O40 wit 9/6. 10 C. to C monoethylenically unsaturated mono- or dicar
The heat transfer fluid additive composition comprises an boxylic acids or their salts; or (2) at least one monomeric unit
azole. Exemplary azoles include benzotriazole, tolyltriazole, containing C to C monoethylenically unsaturated mono- or
methylbenzotriazole (e.g., 4-methylbenzotriazole and 5-me dicarboxylic acid derivatives such as amides, nitriles, car
thylbenzotriazole), butylbenzotriazole, and other alkylben boxylate esters, acid halides (e.g., chloride), and acid anhy
Zotriazoles (e.g., the alkyl group contains from 2 to 20 carbon 15 drides, and combination thereof. In some embodiments, the
atoms), mercaptobenzothiazole, thiazole and other Substi acrylate based polymer comprises a phosphinopolyacrylate.
tuted thiazoles, imidazole, benzimidazole, and other substi In the heat transfer fluid concentrate (and the heat transfer
tuted imidazoles, indazole and Substituted indazoles, tetra fluid made from the concentrate), the amount of acrylate
Zole, tetrahydrotolyltriazole, and substituted tetrazoles. based polymer is chosen based on the amount of the magne
Combinations of two or more of the foregoing azoles may sium ions. The ratio of acrylate-based polymer to magnesium
also be used and combinations of azoles are included in the ions is greater than 1 and less than 25. Within this range, the
term “azole'. ratio can be greater than or equal to 2 or, more specifically,
In the heat transfer fluid concentrate, the azole compound greater than or equal to 3. Also within this range, the ratio can
can be present in an amount of 0.01 wt % to 3 wt %, based on be less than or equal to 20, or, more specifically, less than or
the total weight of the heat transfer fluid concentrate. Within 25 equal to 15. The ratio of acrylate ions is determined using the
this range, the azole compound can be present in an amount amount (the weight) of acrylate-based polymer dissolved in
greater than or equal to 0.05 wt %, or, more specifically, the concentrate.
greater than or equal to 0.1 wt %. Also within this range, the The heat transfer fluid concentrate can further comprise
azole compound can be present in an amount less than or calcium ions. The calcium ions are derived from a calcium
equal to 2 wt %, or, more specifically, less than or equal to 1 30 compound that can produce calcium ions upon dissolving in
wt %. a water containing solution at room temperature. The calcium
The magnesium ions are derived from a magnesium com compound can be an inorganic calcium compound Such as
pound that can produce magnesium ions upon dissolving in a calcium nitrate, calcium chloride, calcium perchlorate, cal
water containing Solution at room temperature. The magne cium molybdate, calcium tungstate, calcium Vanadate, cal
sium compound can be an inorganic magnesium compound 35 cium hydroxide, or a combination thereof. The calcium com
Such as magnesium nitrate, magnesium Sulfate, magnesium pound is soluble in the heat transfer fluid. Soluble, as used
molybdate, magnesium tungstate, magnesium Vanadate, herein, is defined as dissolving Such that no particulate matter
magnesium perchlorate, magnesium hydroxide or a combi is visible to the naked eye. The calcium compound can also be
nation thereof. The magnesium compound is soluble in the calcium salt formed between calcium ions and an organic acid
heat transfer fluid. Soluble, as used herein, is defined as 40 containing one or more carboxylic acid groups, such as cal
dissolving Such that no particulate matter is visible to the cium polyacrylate, calcium polymaleate, calcium lactate, cal
naked eye. The magnesium compound can also be magne cium citrate, calcium tartrate, calcium gluconate, calcium
sium salt formed between magnesium ions and an organic glucoheptonate, calcium glycolate, calcium glucarate, cal
acid containing one or more carboxylic acid groups, such as cium Succinate, calcium hydroxysuccinate, calcium adipate,
magnesium polyacrylate, magnesium polymaleate, magne 45 calcium oxalate, calcium malonate, calcium sulfamate, cal
sium lactate, magnesium citrate, magnesium tartrate, magne cium formate, calcium acetate, calcium propionate, calcium
sium gluconate, magnesium glucoheptonate, magnesium salts of aliphatic tri-carboxylic acid or aliphatic tetra-car
glycolate, magnesium glucarate, magnesium Succinate, mag boxylic acid, and combinations of the foregoing calcium
nesium hydroxySuccinate, magnesium adipate, magnesium compounds.
oxalate, magnesium malonate, magnesium sulfamate, mag 50 The calcium compound is present in an amount Such that
nesium formate, magnesium acetate, magnesium propionate, the heat transfer fluid concentrate has a calcium ion concen
magnesium salt of aliphatic tri-carboxylic acid or aliphatic tration of greater than 0.5 parts per million, based on the total
tetra-carboxylic acid, and combinations of the foregoing weight of the heat transfer fluid. Within this range, the amount
magnesium compounds. of calcium ions can be less than 20 ppm. Also within this
In the heat transfer fluid concentrate, the magnesium com 55 range, the amount of calcium ions can be less than or equal to
pound is present in an amount Such that the heat transfer fluid 10 ppm.
has a magnesium ion concentration of 16 to 80 parts per The heat transfer fluid can further comprise lithium ions.
million by weight (ppm) of the heat transfer fluid concentrate. The lithium ions are derived from a lithium compound that
Within this range, the magnesium ion concentration can be can produce lithium ions upon dissolving in a water contain
greater than or equal to 20 ppm, or, more specifically, greater 60 ing solution at room temperature. The lithium compound can
than or equal to 22 ppm. Also within this range, the magne be an inorganic lithium compound Such as lithium hydroxide,
sium ion concentration can be less than or equal to 75 ppm, or, lithium phosphate, lithium borate, lithium nitrate, lithium
more specifically, less than or equal to 70 ppm. perchlorate, lithium sulfate, lithium molybdate, lithium vana
The heat transfer fluid concentrate comprises an acrylate date, lithium tungstate, lithium carbonate or a combination
based polymer. The acrylate based polymer is a water soluble 65 thereof. The lithium compound is soluble in the heat transfer
polymer (average molecular weight of 200 to 200,000 Dal fluid. Soluble, as used herein, is defined as dissolving such
tons). Exemplary acrylate polymers include polyacrylates, that no particulate matter is visible to the naked eye. The
 US 9,145,613 B2
5 6
lithium compound can also be lithium salt formed between The heat transfer fluid concentrate may further comprise a
lithium ions and an organic acid containing one or more phosphinocarboxylate. Phosphinocarboxylates are com
carboxylic acid groups, such as lithium acetate, lithium ben pounds having the general formula
Zoate, lithium polyacrylate, lithium polymaleate, lithium lac
tate, lithium citrate, lithium tartrate, lithium gluconate, HICHRCHR) P(OM)-ICHRCHRH
lithium glucoheptonate, lithium glycolate, lithium glucarate, wherein at least one R' group in each unit is a COOM,
lithium Succinate, lithium hydroxyl Succinate, lithium adi CHOH, sulphono or phosphono group and the other R'
pate, lithium oxalate, lithium malonate, lithium Sulfamate, group which may be the same as, or different from, the first R'
lithium formate, lithium propionate, lithium salt of aliphatic 10 group, is a hydrogen or a COOM, hydroxyl, phosphono,
mono-, di- or tri-carboxylic acid or aromatic mono-, di- or Sulphono, Sulphato, C, alkyl, C, alkenyl group or a car
tri-carboxylic acid, and combinations of the foregoing boxylate, phosphono, Sulphono, Sulphato and/or hydroxyl
lithium compounds. Substituted C-7 alkyl or C, alkenyl group, n is an integer
The lithium compound can be present in an amount Such equal to or greater than 1, and each M is hydrogen oran alkali
that the heat transfer fluid concentrate has a lithium ion con
centration of 50 to 2000 parts per million by weight (ppm) of
15 metal ion Such as a sodium ion, potassium ion and the like.
the heat transfer fluid. Within this range, the lithium ion
Similarly, at least one R group in each unit is a COOM,
concentration can be less than or equal to 1500 ppm, or more
CH-OH, sulphono or phosphono group and the other R
specifically, less than or equal to 1000 ppm. Also within this group which may be the same as, or different from, the first R
group, is a hydrogen or a COOM, hydroxyl, phosphono,
range, the lithium ion concentration can be greater than or Sulphono, Sulphato, C, alkyl, C, alkenyl group or a car
equal to 60 ppm, or more specifically, greater than or equal to boxylate, phosphono, Sulphono, Sulphato and/or hydroxyl
65 ppm. Substituted C-7 alkyl or C, alkenyl group, m is an integer
The pH of the heat transfer fluid concentrate is 7 to 9.5 at equal to or greater than 0. Furthermore, at least one COOM
room temperature. Within this range, the pH can be greater group will be present in one of the R' and R groups. Exem
than or equal to 7.5, or, greater than or equal to 7.8. Also 25 plary phosphinocarboxylates include phosphinicosuccinic
within this range, the pH can be less than or equal to 9.0, or, acid and water soluble salts, phosphinicobis(Succinic acid)
less than or equal to 8.8. and water soluble salts and phosphinicosuccinic acid oligo
The heat transfer fluid concentrate can further comprise a mer and salts as described in U.S. Pat. Nos. 6,572,789 and
phosphonocarboxylate. Phosphonocarboxylates are phos 5,018,577. The phosphonocarboxylates can be a mixture of
phonated compounds having the general formula 30 compounds having the preceding formula with differing Val
ues for “n” and “m'. The phosphinocarboxylates are separate
HCHRCHR). POM, and different from the carboxylates described above.
wherein at least one R group in each unit is a COOM, In the heat transfer fluid concentrate, the phosphinocar
CH2OH. Sulphono orphosphono group and the other R group boxylate can be present in an amount of 10 to 500 ppm, based
which may be the same as, or different from, the first R group, 35 on the total weight of the heat transfer fluid concentrate.
is a hydrogen or a COOM, hydroxyl, phosphono, Sulphono, Within this range, the phosphinocarboxylate can be present in
Sulphato, C, alkyl, C, alkenyl group or a carboxylate, an amount greater than or equal to 20 ppm, or, greater than or
phosphono, Sulphono, Sulphato and/or hydroxyl Substituted equal to 40 ppm. Also within this range, the phosphinocar
C, alkyl or C, alkenyl group, n is 1 or an integer greater boxylate can be present in an amountless than or equal to 400
than 1, and each M is hydrogen oran alkali metal ion Such as 40 ppm, or, less than or equal to 300 ppm.
a sodium ion, potassium ion and the like. Furthermore, at least The heat transfer fluid concentrate (and hence the heat
one COOM group will be present in one of the R groups. transfer fluid) may optionally comprise one or more of an
Preferably, the phosphonocarboxylates are phosphonated oli antifoaming agent or defoamer, dispersant, Scale inhibitor,
gomers or mixture of phosphonated oligomers of maleic acid, Surfactant, colorant and other coolant additives.
of the formula HCH(COOM)CH(COOM). POM, 45 Exemplary antifoam agents include polydimethylsiloxane
where n is 1 or an integer greater than 1, and M is a cationic emulsion based antifoams. They include PC-545ONF from
species (e.g., alkali metal cations) such that the compound is Performance Chemicals, LLC in Boscawen, N.H., CNC anti
water soluble. Exemplary phosphonocarboxylates include foam XD-55 NF and XD-56 from CNC International in
phosphonoSuccinic acid, 1-phosphono-1,2,3,4-tetracarbox Woonsocket in RI. Other antifoams suitable for use in the
ybutane, and 1-phosphono-1,2,3,4,5,6-hexacarboxyhexane. 50 instant invention include copolymers of ethylene oxide (EO)
The phosphonocarboxylates can be a mixture of compounds and propylene oxide (PO), such as Pluronic L-61 from BASF.
having the preceding formula with differing values for “n”. Generally, the optional antifoam agents may comprise a
The mean value of “n” can be 1 to 2, or, more specifically, 1.3 silicone, for example, SAG 10 or similar products available
to 1.5. The synthesis of the phosphonocarboxylates is known from OSI Specialties, Dow Corning or other suppliers; an
and described in U.S. Pat. No. 5,606,105. The phosphonocar 55 ethylene oxide-propylene oxide (EO-PO) block copolymer
boxylates are separate and different from the carboxylates and a propylene oxide-ethylene oxide-propylene oxide (PO
described above. The carboxylate described above consists of EP-PO) block copolymer (e.g., Pluronic L61, Pluronic L81,
carbon, hydrogen and oxygen and are free of non-oxygen or other Pluronic and Pluronic C products); poly(ethylene
heteroatoms. oxide) or poly(propylene oxide), e.g., PPG 2000 (i.e.,
In the heat transfer fluid concentrate, the phosphonocar 60 polypropylene oxide with an average molecular weight of
boxylate can be present in an amount of 10 to 500 ppm, based 2000); a hydrophobic amorphous silica; a polydiorganosilox
on the total weight of the heat transfer fluid concentrate. ane based product (e.g., products containing polydimethylsi
Within this range, the phosphonocarboxylate can be present loxane (PDMS), and the like); a fatty acids or fatty acid ester
in an amount greater than or equal to 20 ppm, or, greater than (e.g., Stearic acid, and the like); a fatty alcohol, analkoxylated
or equal to 40 ppm. Also within this range, the phosphono 65 alcohol and a polyglycol, a polyether polylol acetate, a poly
carboxylate can be present in an amount less than or equal to ether ethoxylated sorbital hexaoleate, and a poly(ethylene
400 ppm, or, less than or equal to 300 ppm. oxide-propylene oxide)monoallyl ether acetate; a wax, a
 US 9,145,613 B2
7 8
naphtha, kerosene and an aromatic oil; and combinations less than or equal to 40 wt %, less than or equal to 50 wt %,
comprising one or more of the foregoing antifoam agents. less than or equal to 55 wt %, less than or equal to 60 wt %,
Exemplary Surfactants include fatty acid esters, such as less than or equal to 70 wt %, less than or equal to 75 wt %,
Sorbitan fatty acid esters, polyalkylene glycols, polyalkylene less than or equal to 80 wt %, less than or equal to 85 wt %,
glycol esters, copolymers of ethylene oxide (EO) and propy less than or equal to 86 wt %, less than or equal to 87 wt %,
lene oxide (PO), polyoxyalkylene derivatives of a sorbitan less than or equal to 88 wt %, or less than or equal to 89 wt %,
fatty acid ester, and mixtures thereof. The average molecular but more than 1 wt % based on the total weight of the heat
weight of the non-ionic surfactants can be 55 to 300,000, or, transfer fluid.
more specifically 110 to 10,000. Suitable sorbitan fatty acid In the heat transfer fluid, the carboxylate is present in an
esters include Sorbitan monolaurate (e.g., sold under trade 10 amount of 0.5 to 8 wt %, based on the total weight of the heat
name Span(R) 20, Arlacel(R) 20, S-MAZR 20M1), sorbitan transfer fluid. Within this range, the amount can be greater
monopalmitate (e.g., SpanR 40 or Arlacel(R) 40), sorbitan than or equal to 0.6 wt %, or, more specifically, greater than or
monostearate (e.g., SpanR) 60, Arlacel(R) 60, or S-MAZR) equal to 0.7 wt %. Also within this range, the amount can be
60K), sorbitan monooleate (e.g., SpanR 80 or Arlacel(R) 80), less than or equal to 7 wt %, or, more specifically, less than or
sorbitan monosesquioleate (e.g., SpanR 83 or Arlacel(R) 83), 15 equal to 6 wt %.
sorbitan trioleate (e.g., SpanR 85 or Arlacel(R) 85), sorbitan In the heat transfer fluid, the inorganic phosphate can be
tridtearate (e.g., S-MAZR 65K), sorbitan monotallate (e.g., present in an amount of 0.05 wt % to 0.4 weight percent,
S-MAZR 90). Suitable polyalkylene glycols include polyeth based on the total weight of the heat transfer fluid. Within this
ylene glycols, polypropylene glycols, and mixtures thereof. range, the amount can be greater than or equal to 0.07 wt %,
Examples of polyethylene glycols suitable for use include or, more specifically, greater than or equal to 0.08 wt %. Also
CARBOWAXTM polyethylene glycols and methoxypolyeth within this range, the amount can be less than or equal to 0.35
ylene glycols from Dow Chemical Company, (e.g., CARBO wt %, or, more specifically, less than or equal to 0.30 wt %.
WAX PEG 200, 300, 400, 600, 900, 1000, 1450, 3350, 4000 In the heat transfer fluid, the azole compound can be
& 8000, etc.) or PLURACOL(R) polyethylene glycols from present in an amount of 0.005 wt % to 2 wt %, based on the
BASF Corp. (e.g., Pluracol RE 200, 300, 400, 600, 1000, 25 total weight of the heat transfer fluid. Within this range, the
2000, 3350, 4000, 6000 and 8000, etc.). Suitable polyalky azole compound can be present in an amount greater than or
lene glycol esters include mono- and di-esters of various fatty equal to 0.007 wt %, or, more specifically, greater than or
acids, such as MAPEG(R) polyethylene glycol esters from equal to 0.01 wt %. Also within this range, the azole com
BASF (e.g., MAPEG(R) 200ML or PEG 200 Monolaurate, pound can be present in an amount less than or equal to 1.5
MAPEG(R) 400 DO or PEG 400 Dioleate, MAPEG.R. 400 MO 30 wt %, or, more specifically, less than or equal to 1 wt %.
or PEG 400 Monooleate, and MAPEG(R) 600 DO or PEG 600 In the heat transfer fluid, the magnesium compound is
Dioleate, etc.). Suitable copolymers of ethylene oxide (EO) present in an amount such that the heat transfer fluid has a
and propylene oxide (PO) include various Pluronic and Plu magnesium ion concentration of 2 to 60 parts per million by
ronic Rblock copolymer surfactants from BASF, DOWFAX weight (ppm) of the heat transfer fluid. Within this range, the
non-ionic surfactants, UCONTM fluids and SYNALOX lubri 35 magnesium ion concentration can be greater than or equal to
cants from DOW Chemical. Suitable polyoxyalkylene 4 ppm, or, more specifically, greater than or equal to 6 ppm.
derivatives of a sorbitan fatty acid ester include polyoxyeth Also within this range, the magnesium ion concentration can
ylene 20 Sorbitan monolaurate (e.g., products sold under be less than or equal to 65 ppm, or, more specifically, less than
trademarks TWEEN 20 or T-MAZ 20), polyoxyethylene 4 or equal to 60 ppm.
sorbitan monolaurate (e.g., TWEEN 21), polyoxyethylene 20 40 The calcium compound can be present in an amount Such
sorbitan monopalmitate (e.g., TWEEN 40), polyoxyethylene that the heat transfer fluid has a calcium ion concentration of
20 sorbitant monostearate (e.g., TWEEN 60 or T-MAZ60K), greater than 0.5 parts per million, based on the total weight of
polyoxyethylene 20 sorbitan monooleate (e.g., TWEEN80 or the heat transfer fluid. Within this range, the amount of cal
T-MAZ80), polyoxyethylene 20tristearate (e.g., TWEEN 65 cium ions can be less than 60 ppm. Also within this range, the
or T-MAZ 65K), polyoxyethylene 5 sorbitan monooleate 45 amount of calcium ions can be less than or equal to 40 ppm.
(e.g., TWEEN 81 or T-MAZ81), polyoxyethylene 20 sorbi The lithium compound can be present in an amount Such
tan trioleate (e.g., TWEEN 85 or T-MAZ 85K) and the like. that the heat transfer fluid has a lithium ion concentration of
The heat transfer fluid concentrate can be diluted, typically 20 to 1800 parts per million by weight (ppm) of the heat
with water, to form a heat transfer fluid. For example, the heat transfer fluid. Within this range, the lithium ion concentration
transfer fluid concentrate can be diluted by 10 to 75 volume 50 can be less than or equal to 1200 ppm, or more specifically,
percent to form the heat transfer fluid. In some embodiments, less than or equal to 900 ppm. Also within this range, the
the water used for dilution is deionized water as described in lithium ion concentration can be greater than or equal to 30
Section 4.5 of ASTM D3306-10. ppm, or more specifically, greater than or equal to 65 ppm.
In the heat transfer fluid the freezing point depressant is The pH of the heat transfer fluid is 7 to 9.5 at room tem
present in an amount of 1 wt % to less than 90 wt %, based on 55 perature. Within this range, the pH can be greater than or
the total weight of the heat transfer fluid. Within this range, equal to 7.5, or, greater than or equal to 7.8. Also within this
the amount of the freezing point depressant can be greater range, the pH can be less than or equal to 9.0, or, less than or
than or equal to 30 wt %, greater than or equal to 40 wt %, equal to 8.8.
greater than or equal to 50 wt %, greater than or equal to 55 A method of preventing corrosion comprises contacting a
wt %, greater than or equal to 60 wt %, greater than or equal 60 heat transfer fluid as described herein with a heat transfer
to 70 wt %, greater than or equal to 75 wt %, greater than or system. The heat transfer system can comprise components
equal to 80 wt %, greater than or equal to 85 wt %, greater than made by controlled atmosphere brazing. The heat transfer
or equal to 86 wt %, greater than or equal to 87 wt %, greater system may comprise aluminum.
than or equal to 88 wt %, or greater than or equal to 89 wt %, It is also contemplated that in Some applications, such as
but less than 90 wt % based on the total weight of the heat 65 heavy duty engines, it may be desirable to incorporate one or
transfer fluid. Also, within this range, the amount of the more additional corrosion inhibitors such as nitrites, molyb
freezing point depressant can be less than or equal to 30 wt %, dates, and salts thereof.
 US 9,145,613 B2
10
The heat transfer fluid is further demonstrated by the fol not denote any order, quantity, or importance, but rather are
lowing non-limiting examples. used to distinguish one element from another. The various
embodiments and ranges described herein are combinable to
EXAMPLES the extent that the description is not contradictory.
5 While typical embodiments have been set forth for the
The examples Were made using the materials shown in purpose of illustration, the foregoing descriptions should not
Table 1. be deemed to be a limitation on the scope herein. Accordingly,
various modifications, adaptations, and alternatives may
TABLE 1. occur to one skilled in the art without departing from the spirit
Component Description 10 and scope herein.
EG Ethylene glycol The invention claimed 1S
Natolyltriazole 50 wt % solution of sodium tolyltriazole 1. A method of preventing corros1on comprising contacting
Nahydroxide 50 wt % solution of sodium hydroxide a heat transfer system with a heat transfer fluid comprising:
Neodecanoic acid Neodecanoic acid
2-ethylhexanoic acid 2-ethylhexanoic acid
is a) thereof
a freezing point depressant, water, or a combination
PM-5150 An anti-foam EMCO s
HPO A 75 wt % of HPO. b) a carboxylate:
DIHO Deionized water c) an inorganic phosphate:
Mg(NO3)6HO
:
Hexahydrated magnesium nitrate; (MW = 256.30) d) an azole compound;
Mg(Ac).*4H2O stylgleim acetoacetate; 2O e) magnes1um 10ns; and
Ca(Ac).*HO Tetrahydrated calcium acetoacetate; f) al acrylate based polymer
(MW = 176.18) wherein the heat transfer fluid has a pH of 7 to 9.5; and
AR-940 Sodium polyacrylate (MW =2600) wherein a weight ratio of the acrylate based polymer to
aqueous solution, 40% solid, pH = 8.3 the magnesium ions is from 1 to 25
Acumer 3100 AA/AM/AMPS terpolymer, (MW = 4500), 43.5% 9.
solid, pH = 2.1-3.0 as 2. The method of claim 1, wherein the heat transfer system
Acumer 4161 Phosphino polycarboxylic acid, (MW = 3600), comprises a component made by controlled atmosphere braZ
51% solid, pH = 3.3 ing.
BTCA 1,2,3,4-butane tetracarboxylic acid 3. The method of claim 1, wherein the heat transfer system
comprises aluminum.
The concentrate compositions shown in Table 2 were made to 4. The method of claim 1, wherein the heat transfer fluid
by mixing the listed ingredients and less than 0.03 weight further comprises lithium ions.
percent of a dye. The concentrate was diluted to 25 volume 5. The method of claim 1, wherein the heat transfer fluid
percent with deionized water and 100 ppm of chloride was further comprises an additional corrosion inhibitor selected
added. A modified GM9066P test was run on the diluted from the group consisting of nitrites, molybdates, nitrates,
Solution using sand cast aluminum 319 at 263-3 degrees alkali metal nitrates, alkaline earth metal nitrates, salts
Fahrenheit. Results are shown below in Table 2. thereof, and combinations thereof.

Example 1: 2: 3 4 5 6 7 8 9
EG 93.12 92.91 93.48 93.43 93.41 93.43 93.56 93.49 93.47
Natolyltriazole O.47 O.47 O.47 O.47 O.47 O.47 O.47 O.47 O.47
Nahydroxide 2.19 2.28 2.07 2.07 2.07 2.05 2.00 2.03 2.066
Neodecanoic acid O.96 O.95 O.85 O.90 O.90 O.89 O.86 O.86 O.86
2-ethylhexanoic acid 2.87 2.87 2.56 2.70 2.70 2.68 2.58 2.58 2.58
PM-5150 O.2O O.20 O.18 O.19 O.19 O.18 O.19 O.18 O.18
HPO. O.17 O.25 O.25 O.17 O.17 O.17 O.25 O.25 O.25
DIH2O O.OS O.O3 O.O3 O.O3 O.O3 O.O2 O.O2 O.O2
Mg(NO3)2*6H2O O.O3
Mg(Ac)2*4H2O O.O3 O.O3 O.O3 O.O2 O.O2 O.O2
Ca(Ac)2*H2O O.O1 O.OO2 O.OO2
AR-940 O.O6 O.O1 O.O1 O.04 O.O3 O.O7 O.O7
Acumer 3100 O.O1 O.O1
Acumer 4161 O.O2
BTCA
Calculated Mg concentration, mg/kg O.O O.O 34.0 34.01 34.O1 28.4 22.67 2SO 24.9
Calculated Ca concentration, mg/kg O.O 28.7 3.5 3.6
ppm Polyacrylate, ppm Mg O.OO O.OO 7.06 1.76 1.18 S.62 6.18 1122 11.23
1 hr LPR CorrRate, mpy (a 263 F. 9.8524 9.1596 O4406 0.7125 0.9555 O428O O.4351 O.7588 0.5979
1 hr Ecorr, VAgAgCl -O.9378 -0.9771 -O.8828 -O.88SS -O.8894 -0.856O -0.8271 -0.8660 -0.8578
3 hr LPR CorrRate, mpy (a 263 F. 8.9671 9.1923 0.2657 O.2719 O.4519 O.2809 0.5152 O5404 0.3614
3 hr Ecorr, VAgAgCl -0.9141 -0.9196 -0.8357 -O.84.95 -O.8608 -0.8173 -0.82O1 -0.841O -0.8344
5 hr LPR CorrRate, mpy (a 263 F. 8.4252 9.11OO O.2231 O.3036 O.3930 O.2074 0.4127 O.4572 O.3984
5 hr Ecorr, VAgAgCl -O.90SS -O.9036 O.8304 -0.8268 -0.8423 -0.7988 -0.8310 -0.8312 -0.8187
*Comparative example

The singular forms “a,” “an and “the include plural 6. The method of claim 1, wherein the heat transfer fluid
referents unless the context clearly dictates otherwise. The comprises less than 60 parts per million by weight (ppm)
endpoints of all ranges reciting the same characteristic or magnes1um 10ns.
component are independently combinable and inclusive of 65
the recited endpoint. All references are incorporated herein by 7. The method of claim 1, further comprising calcium ions,
reference. The terms “first,” “second, and the like herein do wherein the calcium ions are greater than 0.5 ppm.
 US 9,145,613 B2
11 12
8. The method of claim 1, wherein the magnesium ions are 24. The method of claim 22, wherein the calcium com
about 2 to about 60 ppm. pound is a calcium salt.
9. The method of claim 1, wherein the carboxylate has 6 to 25. The method of claim 24, wherein the calcium salt is
20 carbon atoms. selected from the group consisting of calcium polyacrylate,
10. The method of claim 1, wherein the carboxylate is calcium polymaleate, calcium lactate, calcium citrate, cal
linear or branched. cium tartrate, calcium gluconate, calcium glucoheptonate,
11. The method of claim 1, wherein the carboxylate is calcium glycolate, calcium glucarate, calcium Succinate, cal
selected from the group consisting of 2-ethylhexanoic acid, cium hydroxysuccinate, calcium adipate, calcium oxalate,
hexanoic acid, heptanoic acid, octanoic acid, neodecanoic calcium malonate, calcium sulfamate, calcium formate, cal
acid, decanoic acid, nonanoic acid, isoheptanoic acid, dode 10 cium acetate, calcium propionate, calcium salt of aliphatic
canoic acid, sebacic acid, adipic acid, pimelic acid, Suberic tri-carboxylic acid, calcium salt of aliphatic tetra-carboxylic
acid, azelaic acid, dodecanedioic acid, benzoic acid, toluic acid, and combinations thereof.
acid, methylbenzoic acid, tert-butylbenzoic acid, an alkoxy 26. The method of claim 4, wherein the lithium ions are
derived from a lithium compound.
benzoic acid, Salicylic acid, phthalic acid, isophthalic acid, 15 27. The method of claim 26, wherein the lithium compound
terephthalic acid, phenylacetic acid, mandelic acid, 1,2,4- is an inorganic lithium compound.
benzenetricarboxylic acid, and combinations thereof. 28. The method of claim 27, wherein the inorganic lithium
12. The method of claim 1, wherein the inorganic phos compound is selected from the group consisting of lithium
phate is selected from the group consisting of phosphoric nitrate, lithium perchlorate, lithium molybdate, lithium tung
acid, Sodium orthophosphate, potassium orthophosphate, state, lithium Vanadate, lithium hydroxide, lithium phos
Sodium pyrophosphate, potassium pyrophosphate, sodium phate, lithium borate, lithium sulfate, lithium carbonate, and
polyphosphate, potassium polyphosphate, sodium hexameta a combination thereof.
phosphate, potassium hexametaphosphate, and a combina 29. The method of claim 26, wherein the lithium compound
tion thereof. is a lithium salt.
13. The method of claim 1, wherein the azole compound is 25 30. The method of claim 29, wherein the lithium salt is
selected from the group consisting of benzotriazole, tolyltria selected from the group consisting of lithium acetate, lithium
Zole, methyl benzotriazole, butylbenzotriazole, mercapto benzoate, lithium polyacrylate, lithium polymaleate, lithium
benzothiazole, thiazole, a Substituted thiazole, imidazole, a lactate, lithium citrate, lithium tartrate, lithium gluconate,
Substituted imidazole, indazole, a Substituted indazole, tet lithium glucoheptonate, lithium glycolate, lithium glucarate,
rahydrotolyltriazole, tetrazole, a substituted tetrazole, and a 30 lithium Succinate, lithium hydroxyl Succinate, lithium adi
combination thereof. pate, lithium oxalate, lithium malonate, lithium Sulfamate,
14. The method of claim 1, wherein the heat transfer fluid lithium formate, lithium propionate, and combinations
further comprises calcium ions. thereof.
15. The method of claim 1, wherein the weight ratio of 31. The method of claim 1, wherein the heat transfer fluid
acrylate based polymer to magnesium ions is 1 to 15. 35 further comprises a phosphonocarboxylate or a phosphi
16. The method of claim 1, wherein the magnesium ions nocarboxylate.
are derived from a magnesium compound. 32. The method of claim 1, wherein the heat transfer fluid
17. The method of claim 16, wherein the magnesium com further comprises an antifoaming agent, dispersant, scale
pound is an inorganic magnesium compound. inhibitor, Surfactant, or colorant.
18. The method of claim 17, wherein the inorganic mag 40 33. The method of claim32, wherein the antifoaming agent
nesium compound is selected from the group consisting of comprises a polydimethylsiloxane emulsion antifoaming
magnesium nitrate, magnesium sulfate, magnesium molyb agent, an ethylene oxide, a propylene oxide, an ethylene
date, magnesium tungstate, magnesium Vanadate, magne oxide-propylene oxide block copolymer, a propylene oxide
sium perchlorate, magnesium hydroxide, and a combination ethylene oxide-propylene oxide block copolymer, a fatty
thereof. 45 acid, a fatty acid ester, a fatty alcohol, an alkoxylated alcohol,
19. The method of claim 16, wherein the magnesium com a polyglycol, a polyether polyol acetate, a polyether ethoxy
pound is a magnesium salt. lated Sorbital hexaoleate, a poly(ethylene oxide-propylene
20. The method of claim 19, wherein the magnesium salt is oxide)monoallyl ether acetate, a wax, a naphtha, kerosene, an
selected from the group consisting of magnesium polyacry aromatic oil, a silicone product, and a combination thereof.
late, magnesium polymaleate, magnesium lactate, magne 50 34. The method of claim 32, wherein the surfactant is
sium citrate, magnesium tartrate, magnesium gluconate, selected from the group consisting of Sorbitan fatty acid
magnesium glucoheptonate, magnesium glycolate, magne esters, polyalkylene glycols, polyalkylene glycol esters,
sium glucarate, magnesium Succinate, magnesium hydrox copolymers of ethylene oxide (EO) and propylene oxide
ySuccinate, magnesium adipate, magnesium oxalate, magne (PO), polyoxyalkylene derivatives of a sorbitan fatty acid
sium malonate, magnesium sulfamate, magnesium formate, 55 ester, and mixtures thereof.
magnesium acetate, magnesium propionate, magnesium salt 35. The method of claim 1, wherein the heat transfer fluid
of aliphatic tri-carboxylic acid, magnesium salt of aliphatic comprises 1 wt % to less than 90 wt % of the freezing point
tetra-carboxylic acid, and combinations thereof. depressant, based on the total weight of the heat transfer fluid.
21. The method of claim 14, wherein the calcium ions are 36. The method of claim 1, wherein the heat transfer fluid
derived from a calcium compound. 60 comprises 0.5 wt % to 8 wt % of the carboxylate, based on the
22. The method of claim 21, wherein the calcium com total weight of the heat transfer fluid.
pound is an inorganic compound. 37. The method of claim 1, wherein the heat transfer fluid
23. The method of claim 22, wherein the inorganic calcium comprises 0.05 wt % to 0.4 wt % of the inorganic phosphate,
compound is selected from the group consisting of calcium based on the total weight of the heat transfer fluid.
nitrate, calcium chloride, calcium perchlorate, calcium 65 38. The method of claim 1, wherein the heat transfer fluid
molybdate, calcium tungstate, calcium Vanadate, calcium comprises 0.005 wt % to 2 wt % of the azole compound, based
hydroxide, and a combination thereof. on the total weight of the heat transfer fluid.
 US 9,145,613 B2
13
39. The method of claim 4, wherein the lithium ions are 20
to 1800 ppm.
40. The method of claim39, wherein the lithium ions are 20
to 1200 ppm.
41. The method of claim39, wherein the lithium ions are 20 5
to 900 ppm.
42. The method of claim39, wherein the lithium ions are 30
to 1800 ppm.
43. The method of claim 42, wherein the lithium ions are 65
to 1800 ppm. 10
44. The method of claim 1, wherein the freezing point
depressant is ethylene glycol; propylene glycol; 1,3-pro
panediol; glycerin; or combinations thereof.
45. A method of preventing corrosion comprising contact
ing a heat transfer system with a heat transfer fluid compris- 15
1ng:
a) ethylene glycol;
b) water;
c) a carboxylate;
d) an inorganic phosphate; 2O
e) an azole compound;
f) calcium ions;
g) magnesium ions; and
h) an acrylate based polymer;
wherein the heat transfer fluid has a pH of 7 to 9.5; and 25
wherein the weight ratio of acrylate based polymer to
magnesium ions is 1 to 15.
k k k k k