Heat transfer fluids with low electrical conductivity containing vinylpyrrolidone polymers, methods for preparing same and uses thereof - Patents.com
Patent Information
- Application Number
- JP2023580515
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2021-06-29
- Filing Date
- 2022-06-28
- Publication Date
- 2025-06-09
- Estimated Expiration
- 2042-06-28
AI Technical Summary
Existing heat transfer fluids used in electrical applications like fuel cells suffer from increased electrical conductivity upon aging, leading to voltage drop and corrosion issues, often requiring expensive and potentially toxic additives that affect material properties.
A coolant composition comprising a base fluid and N-vinylpyrrolidone polymer, particularly polyvinylpyrrolidone, maintains low electrical conductivity by forming a film that separates metal ions, reducing the need for excessive additives and extending the fluid's useful life.
The composition effectively maintains low electrical conductivity even at elevated temperatures, minimizing voltage drop and corrosion, while reducing the amount of additives needed, thus enhancing the fluid's performance and longevity.
Abstract
Description
[Technical field]
[0001] The present invention relates to a heat transfer fluid comprising an N-vinylpyrrolidone polymer and having low electrical conductivity that is useful for a variety of applications, such as in fuel cells. The present invention further relates to a method for preparing said heat transfer fluid, as well as methods and uses of said heat transfer fluid. [Background technology]
[0002] Heat transfer fluids are widely used in heat exchange systems involving internal combustion engines, solar systems, fuel cells, electric motors, generators, electronic devices, battery devices, etc. Heat transfer fluids are generally composed of a base fluid and one or more additives.
[0003] Traditionally, water has been the preferred base fluid for heat transfer properties. In many applications, antifreeze properties are required, in which case a base fluid consisting of water mixed with a freezing point depressant such as alcohol, glycol or salt is used. The additives present in the heat transfer fluid can be used to obtain various functionalities such as (further) lowering of the freezing point, improving heat exchange properties, inhibiting corrosion, etc. Since heat transfer fluids are in continuous contact with metal parts (aluminum alloys, cast iron, steel, copper, brass, solder, etc.), they almost always contain one or more corrosion inhibitors.
[0004] Fuel cells are electrochemical cells that convert stored chemical energy into electrical energy by the controlled oxidation of fuel. Their relatively low emissions of pollutants compared to combustion engines make them an attractive option for applications such as automobiles and power plants. In most applications, several electrochemical cells are stacked together in series in so-called fuel cell stacks, allowing to produce higher voltages. The heat generated by the fuel cell stack can be removed by flowing a coolant through the channels formed by the bipolar plates.
[0005] The potential difference between the positive and negative ends of the fuel cell stack can cause a shunt current to flow in the coolant, thus reducing the voltage of the fuel cell. In addition to the harmful reduction in voltage, the shunt current can cause further problems, such as corrosion of the separator plates near the positive end of the fuel cell stack. Thus, coolants for use in electrical applications such as fuel cells must have low electrical conductivity (i.e., high electrical resistance) and be able to maintain this over the life of the coolant.
[0006] Most known heat transfer fluids (e.g. coolants) are specifically designed for internal combustion engines and are therefore unsuitable for use in electrical applications such as fuel cells, batteries or power electronics, since they either (i) have a high electrical conductivity or (ii) become significantly more electrically conductive upon aging, especially at high temperatures. The increase in electrical conductivity upon aging is generally attributed to the formation of ionic compounds due to the decomposition of alcohols, especially glycols, which are often used as base fluids, due to the decomposition of additives, due to metal corrosion and / or due to impurities in the cooling circuit.
[0007] Therefore, in recent years there has been increased interest in developing heat transfer fluids that are suitable for use in electrical applications such as fuel cells.
[0008] U.S. Patent Application Publication No. 2005 / 0109979A1 describes a heat transfer fluid for electric vehicles that includes a base agent and a rust inhibitor additive that is an amide compound, an imide compound, or an azole compound that suppresses oxidation of the base agent or prevents ions from leaching into the cooling system and prevents an increase in the electrical conductivity of the coolant.
[0009] EP 1 739 775 B1 describes a heat transfer fluid comprising a base agent and a rust inhibitor additive which is a sugar alcohol and which inhibits oxidation of the base agent and prevents an increase in electrical conductivity.
[0010] Known heat transfer fluids capable of maintaining low electrical conductivity have several disadvantages. They rely on the presence of additives that can be costly, toxic, or have other undesirable properties, for example. Furthermore, additives used in the art to maintain low electrical conductivity are often consumed in the process, so large amounts of additives are required for practical use, which can also affect other properties of the heat transfer fluid in undesirable ways.
[0011] Alcohol-based, e.g., glycol-based, heat transfer fluids have several advantages, e.g., they have low viscosity and low freezing points combined with high flash points, and the safety profiles of the different glycols have been extensively reviewed.
[0012] The inventors have found it particularly desirable to provide alcohol-based, and particularly glycol-based, heat transfer fluids that are capable of maintaining low electrical conductivity upon aging in the presence of aluminum. Due to their light weight, aluminum-based materials are often preferred for components such as cold plates and heat exchangers.
[0013] It is an object of the present invention to provide improved heat transfer fluids, preferably alcohol-based, which are suitable for use as coolants in electrical systems such as fuel cells, batteries or power electronics.
[0014] It is therefore an object of the present invention to provide heat transfer fluids, preferably alcohol-based, that have low electrical conductivity that can maintain low electrical conductivity upon aging, such as when aged at elevated temperatures.
[0015] It is a further object of the present invention to provide heat transfer fluids, preferably alcohol-based, that are capable of maintaining comparable low electrical conductivity upon aging, such as aging at elevated temperatures, while still requiring less additives than known heat transfer fluids.
[0016] It is a further object of the present invention to provide a glycol-based heat transfer fluid that has an extended useful life as compared to known heat transfer fluids. Summary of the Invention [Means for solving the problem]
[0017] The inventors have discovered that one or more of these objectives can be accomplished by using a coolant composition comprising a base fluid and an N-vinylpyrrolidone polymer, where the N-vinylpyrrolidone polymer is selected from polyvinylpyrrolidone homopolymers and polyvinylpyrrolidone copolymers, and where the composition has an electrical conductivity at 25° C. of less than 100 μS / cm.
[0018] As shown in the accompanying examples, it has been surprisingly found that N-vinylpyrrolidone polymers maintain low electrical conductivity when aged at elevated temperatures. Moreover, it has been surprisingly found that coolant compositions according to the present invention are capable of maintaining this low electrical conductivity when aged at elevated temperatures in the presence of an aluminum substrate using the test procedures described in the experimental section.
[0019] Based on this disclosure, one skilled in the art will understand that the coolant compositions according to the present disclosure effectively enable the provision of heat transfer fluids or coolants suitable for use in electrical applications that require fewer additives (especially antioxidants) and / or can maintain low electrical conductivity upon aging for a longer period of time than comparable coolant compositions known in the art. Without wishing to be bound by any theory, the inventors believe that, as can be seen from the experimental results, the electrical conductivity of the aged samples can be correlated to the amount of alcohol-related, particularly glycol-related, oxidation products, glycolates and formates present in the mixture. It is believed that the N-vinylpyrrolidone polymer interacts with the metal surface to form a (weakly bound) film that is in some way effective in separating the metal ions from the heat transfer fluid and the metal substrate.
[0020] Polyvinylpyrrolidone is known as a hard water stabilizer in antifreeze concentrates for internal combustion engines (see, for example, U.S. Patent Application Publication No. 2008 / 0001118A1). However, the use of N-vinylpyrrolidone polymers to maintain low electrical conductivity in coolant compositions has not yet been known in the art.
[0021] Thus, in a first aspect, the present invention provides coolant compositions comprising a base fluid and an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, wherein the composition has an electrical conductivity at 25° C. of less than 100 μS / cm, the base fluid consists of water and alcohol, the alcohol is present in an amount ranging from 10 to 99.5 wt % based on the weight of the base fluid, the composition comprises more than 75 wt % of the base fluid based on the total weight of the composition, and the amount of inorganic compounds is less than 100 ppm based on the total weight of the composition. As shown herein, these coolant compositions are capable of maintaining low electrical conductivity, such as when aged at elevated temperatures in the presence of an aluminum substrate (EN AC-AlSi10Mg(a)T6, DIN EN 1706) using the test procedures described in the experimental section.
[0022] In a preferred embodiment, the coolant compositions of the present invention are provided in the form of ready-to-use compositions as described herein.
[0023] In another aspect, the invention provides methods for preparing the compositions described herein.
[0024] In another aspect, the present invention provides a method for preparing the ready-to-use compositions described herein from the concentrates.
[0025] In another aspect, the present invention provides a corresponding use of an N-vinylpyrrolidone polymer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0026] A first aspect of the present invention relates to a coolant composition comprising a base fluid and an N-vinylpyrrolidone polymer selected from polyvinylpyrrolidone homopolymer and polyvinylpyrrolidone copolymer, wherein the composition has an electrical conductivity at 25° C. of less than 100 μS / cm, the base fluid consists of water and alcohol, wherein the alcohol is present in an amount ranging from 10 to 99.5 wt % based on the weight of the base fluid, the composition comprises greater than 75 wt % base fluid based on the total weight of the composition, and the amount of inorganic compounds is less than 100 ppm based on the total weight of the composition.
[0027] The coolant composition preferably has an electrical conductivity at 25° C. of less than 50 μS / cm, more preferably less than 25 μS / cm, even more preferably less than 10 μS / cm, and even more preferably less than 5 μS / cm.
[0028] basic fluid According to the invention, the base fluid consists of water and an alcohol, in a preferred embodiment the alcohol is selected from the group consisting of monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, monopropylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, hexapropylene glycol, methanol, ethanol, propanol, butanol, tetrahydrofurfuryl, ethoxylated furfuryl, dimethyl ether of glycerol, sorbitol, 1,2,6-hexanetriol, trimethylolpropane, methoxyethanol, glycerol and mixtures thereof, more preferably from the group consisting of monoethylene glycol, monopropylene glycol, 1,3-propanediol, glycerol and mixtures thereof.
[0029] As used herein, "monoethylene glycol" shall be taken to mean "ethane-1,2-diol" and are referred to interchangeably as "MEG."
[0030] As used herein, "monopropylene glycol" shall be taken to mean "propane-1,2-diol" and are interchangeably referred to as "MPG."
[0031] As used herein, the term "glycerol" means "propane-1,2,3-triol" and is synonymous with glycerin. In a preferred embodiment of the invention, the base fluid comprises water, monoethylene glycol, monopropylene glycol, 1,3-propanediol, glycerol, or mixtures thereof.
[0032] The base fluid comprises water and alcohol, wherein the alcohol is present in an amount of 10-99.5% by weight (based on the weight of the base fluid), preferably 10-80% by weight, more preferably 30-70% by weight, In certain embodiments, the alcohol is present in an amount in the range of 33-60% by weight (based on the weight of the base fluid).
[0033] In an embodiment of the invention, the base fluid comprises more than 50% water by weight (based on the weight of the base fluid), preferably more than 70% and more preferably more than 85%.
[0034] In an embodiment of the invention, the base fluid comprises more than 50% by weight (based on the weight of the base fluid) monoethylene glycol, preferably more than 70% by weight, more preferably more than 85% by weight, and most preferably more than 95% by weight.
[0035] In an embodiment of the invention, the base fluid comprises more than 50% by weight (based on the weight of the base fluid) monopropylene glycol, preferably more than 70% by weight, more preferably more than 85% by weight, and most preferably more than 95% by weight.
[0036] In an embodiment of the invention, the base fluid comprises more than 50% by weight 1,3-propanediol (based on the weight of the base fluid), preferably more than 70% by weight, more preferably more than 85% by weight, and most preferably more than 95% by weight 1,3-propanediol.
[0037] In an embodiment of the invention, the base fluid comprises more than 50% by weight glycerol (based on the weight of the base fluid), preferably more than 70% by weight, more preferably more than 85% by weight, and most preferably more than 95% by weight glycerol.
[0038] In a preferred embodiment of the invention, there is provided a composition as described herein which comprises more than 78 wt.% of base fluid (based on the total weight of the composition), more preferably more than 85 wt.%, even more preferably more than 90 wt.%, even more preferably more than 95 wt.% or more than 98 wt.% of base fluid.
[0039] As will be appreciated by those skilled in the art, the base fluid is typically added to the composition in "amounts appropriate." In an embodiment of the invention, the composition comprises less than 99.9% by weight of the base fluid (based on the total weight of the composition), such as less than 99.8%, less than 99.5% or less than 99%, less than 98%, less than 97%, less than 96%, less than 95%, less than 94%, less than 93%, less than 92%, less than 91%, less than 90%, less than 89%, less than 88%, less than 87%, less than 86%, less than 85%, less than 84%, less than 83%, less than 82%, or less than 81% by weight of the base fluid.
[0040] In preferred embodiments of the invention, there are provided compositions as described herein that comprise less than 99.9% by weight of base fluid (based on the total weight of the composition), or less than 99.5% by weight, or less than 99% by weight.
[0041] N-vinylpyrrolidone polymer According to the present invention, the composition described herein comprises an N-vinylpyrrolidone polymer, preferably a polyvinylpyrrolidone homopolymer, selected from polyvinylpyrrolidone homopolymer and polyvinylpyrrolidone copolymer. Thus, the term N-vinylpyrrolidone polymer as used herein relates to a polymer derived from a monomer comprising or consisting of N-vinylpyrrolidone, also known as N-vinyl-2-pyrrolidone. Whenever the term "polyvinylpyrrolidone" is used in this document without any additional (e.g. homopolymer or copolymer) or additional definition, polyvinylpyrrolidone homopolymer is referred to as polyvinylpyrrolidone (i.e. homopolymer), abbreviated as PVP, which is a water-soluble polymer synthesized by polymerization from the monomer N-vinylpyrrolidone, where n defines the degree of polymerization of the polymer (see diagram below). Polyvinylpyrrolidone is also commonly called polyvidone, povidone, poly[1-(2-oxo-1-pyrrolidinyl)ethylene], 1-ethenyl-2-pyrrolidone homopolymer or 1-vinyl-2-pyrrolidinone polymer. Its chemical formula is (C6H9NO) n and the CAS number is 9003-39-8. [ka]
[0042] In certain preferred embodiments, the N-vinylpyrrolidone polymer is a polyvinylpyrrolidone homopolymer, meaning that the polyvinylpyrrolidone is derived from one species of monomer, which is N-vinylpyrrolidone. In other preferred embodiments, the N-vinylpyrrolidone polymer is a polyvinylpyrrolidone copolymer, meaning that the polyvinylpyrrolidone is derived from two or more species of monomer, in particular N-vinylpyrrolidone in combination with at least one other monomer. Non-limiting examples of such other monomers are styrene, vinyl acetate, ethylene, propylene, tetrafluoroethylene, methyl methacrylate, vinyl chloride, and ethylene oxide.
[0043] In a preferred embodiment, the polyvinylpyrrolidone copolymer is derived from N-vinylpyrrolidone and at least one other monomer, where the percentage of N-vinylpyrrolidone monomer is at least 10%, more preferably at least 25%, such as at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%, based on the total number of monomers in the polyvinylpyrrolidone copolymer. As will be understood by those skilled in the art, the minimum percentage of N-vinylpyrrolidone monomer based on the total number of monomers in the polyvinylpyrrolidone copolymer is determined, inter alia, by the solubility of the polyvinylpyrrolidone copolymer in the composition, more particularly in the base fluid.
[0044] Preferred polyvinylpyrrolidone copolymers that may be applied in the composition according to the present invention include copolymers of N-vinylpyrrolidone and vinyl acetate, where the percentage of N-vinylpyrrolidone monomer is at least 25% based on the total number of monomers in the polyvinylpyrrolidone copolymer, hydrolyzed forms of copolymers of N-vinylpyrrolidone and vinyl acetate, where the percentage of N-vinylpyrrolidone monomer is at least 10% based on the total number of monomers in the polyvinylpyrrolidone copolymer, and copolymers of N-vinylpyrrolidone and N-vinylcaprolactam, where the percentage of N-vinylpyrrolidone monomer is at least 40% based on the total number of monomers in the polyvinylpyrrolidone copolymer.
[0045] It is particularly preferred according to the invention that the N-vinylpyrrolidone polymer is a polyvinylpyrrolidone homopolymer.
[0046] According to the invention, the N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, has a weight average molecular weight M in the range of 500 to 2,500,000 g / mol. w As will be appreciated by those skilled in the art, the weight average molecular weight is the weight fraction of molecules in a polymer sample, giving an average of the molecular masses of single macromolecules in the polymer sample. Weight average molecular weight as defined herein has the formula Mw =(ΣN i M i 2 ) / (ΣN i M i ) are used to determine the weight average molecular weight of polymers of various chain lengths. Those skilled in the art are aware of different techniques for determining the weight average molecular weight of polymers of various chain lengths. The weight average molecular weight and corresponding measurement methods are typically indicated on the product data sheet of the polymer under consideration.
[0047] In a particular embodiment of the present invention, the N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, has a weight average molecular weight in the range of 3,000 to 2,500,000 g / mol, preferably in the range of 5,000 to 2,250,000 g / mol, more preferably in the range of 7,500 to 2,000,000 g / mol, even more preferably in the range of 8,000 to 1,800,000 g / mol.
[0048] In a particular embodiment of the present invention, the N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, has a weight average molecular weight in the range of 3,000 to 700,000 g / mol, preferably in the range of 5,000 to 500,000 g / mol, more preferably in the range of 7,500 to 250,000 g / mol, and even more preferably in the range of 8,000 to 100,000 g / mol. N-vinylpyrrolidone polymers, preferably polyvinylpyrrolidone, having these weight average molecular weight ranges are preferred as they have a lower dynamic viscosity, thereby improving the resulting charge transport of the composition, which is beneficial for the properties of the low electrical conductivity coolant.
[0049] In a particular embodiment of the present invention, the N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, has a weight average molecular weight in the range of 700,000 to 2,500,000 g / mol, preferably in the range of 750,000 to 2,250,000 g / mol, more preferably in the range of 850,000 to 2,000,000 g / mol, even more preferably in the range of 1,000,000 to 1,800,000 g / mol.
[0050] In a preferred embodiment, the N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, has a weight average molecular weight in the range of 500 to 50,000 g / mol, more preferably in the range of 1,000 to 15,000 g / mol, even more preferably in the range of 1,500 to 10,000 g / mol, for example about 2000 g / mol, about 2500 g / mol, about 5000 g / mol or about 8000 g / mol.
[0051] N-vinylpyrrolidone polymers suitable for use as additives can be purchased from commercial sources such as BASF, Sigma-Aldrich, or Nippon Shokubai. An example of a commercially available polyvinylpyrrolidone is Luvitec K17 (M W = 9,000 g / mol), Luvitec K30 (M W = 50,000 g / mol), Luvitec K90 (M W = 1,400,000 g / mol) and PVP K30.
[0052] In an embodiment of the invention, the N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, when used as the sole additive at a concentration in the range of 0.0001-1 wt. % N-vinylpyrrolidone polymer; preferably in the range of 0.00015-0.5 wt. % N-vinylpyrrolidone polymer; most preferably in the range of 0.0002-0.5 wt. % N-vinylpyrrolidone polymer in a base fluid consisting of 30-60 wt. % MEG in water, is capable of maintaining an electrical conductivity at 25° C. of less than 50 μS / cm, preferably less than 25 μS / cm, preferably less than 10 μS / cm, more preferably less than 5 μS / cm, most preferably less than 2 μS / cm, where the electrical conductivity is measured after ageing the heat transfer fluid for 14 days at 90° C. in the presence of, for example, an aluminum substrate (EN AC-AlSi10Mg(a)T6, DIN EN 1706) using the test procedure described in the experimental section.
[0053] In certain preferred embodiments, an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, having a weight average molecular weight of 500-12,000 g / mol, when used as the sole additive at a concentration of 0.002-0.5 wt. % N-vinylpyrrolidone polymer in a base fluid consisting of 30-60 wt. % MEG in water, is capable of maintaining an electrical conductivity at 25° C. of less than 50 μS / cm, preferably less than 25 μS / cm, preferably less than 10 μS / cm, more preferably less than 5 μS / cm, and most preferably less than 2 μS / cm, where the electrical conductivity is measured after aging the heat transfer fluid for 14 days at 90° C. in the presence of, for example, an aluminum substrate (EN AC-AlSi10Mg(a)T6, DIN EN 1706) using the test procedures described in the experimental section.
[0054] In certain preferred embodiments, an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, having a weight average molecular weight of 20,000-50,000 g / mol, when used as the sole additive at a concentration of 0.002-0.5 wt. % N-vinylpyrrolidone polymer in a base fluid consisting of 30-60 wt. % MEG in water, is capable of maintaining an electrical conductivity at 25° C. of less than 50 μS / cm, preferably less than 25 μS / cm, preferably less than 10 μS / cm, more preferably less than 5 μS / cm, and most preferably less than 2 μS / cm, where the electrical conductivity is measured after aging the heat transfer fluid for 14 days at 90° C. in the presence of, for example, an aluminum substrate (EN AC-AlSi10Mg(a)T6, DIN EN 1706) using the test procedures described in the experimental section.
[0055] In an embodiment, an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, having a weight average molecular weight of 40,000-80,000 g / mol, when used as the sole additive at a concentration of 0.0002-0.5 wt. % N-vinylpyrrolidone polymer in a base fluid consisting of 30-60 wt. % MEG in water, is capable of maintaining an electrical conductivity at 25° C. of less than 50 μS / cm, preferably less than 25 μS / cm, preferably less than 10 μS / cm, more preferably less than 5 μS / cm, and most preferably less than 2 μS / cm, where the electrical conductivity is measured after aging the heat transfer fluid for 14 days at 90° C. in the presence of, for example, an aluminum substrate (EN AC-AlSi10Mg(a)T6, DIN EN 1706) using the test procedures described in the experimental section.
[0056] In a preferred embodiment, an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, having a weight average molecular weight of 500-50,000 g / mol, more preferably 1,000-15,000 g / mol, even more preferably 1,500-10,000 g / mol, when used as the sole additive at a concentration of 0.0002-0.5 wt. % of the N-vinylpyrrolidone polymer in a base fluid consisting of 30-60 wt. % MEG in water, is capable of maintaining an electrical conductivity at 25° C. of less than 50 μS / cm, preferably less than 25 μS / cm, preferably less than 10 μS / cm, more preferably less than 5 μS / cm, most preferably less than 2 μS / cm, where the electrical conductivity is measured after ageing the heat transfer fluid for 14 days at 90° C. in the presence of, for example, an aluminum substrate (EN AC-AlSi10Mg(a)T6, DIN EN 1706) using the test procedure described in the experimental section.
[0057] Electrical Conductivity In an embodiment of the invention, there is provided a coolant composition as described herein having an electrical conductivity as described elsewhere herein, as measured according to ASTM D1125 with a Radiometer Copenhagen CDM210 electrical conductivity meter using a Radiometer Copenhagen CDC745-conductivity cell and a Radiometer Copenhagen temperature sensor T201.
[0058] In an embodiment of the invention, there is provided a coolant composition as described herein having an electrical conductivity at 25° C. of less than 50 μS / cm, preferably less than 25 μS / cm, preferably less than 10 μS / cm, more preferably less than 5 μS / cm, even more preferably less than 2 μS / cm, optionally after aging for 14 days at 90° C. in the presence of aluminum (EN AC-AlSi10Mg(a)T6, DIN EN 1706) using the test procedures described in the experimental section.
[0059] In an embodiment of the invention, there is provided a coolant composition as described herein having a glycolate concentration and / or a formate concentration of less than 30 ppm, preferably less than 10 ppm, more preferably less than 5 ppm, after aging for 14 days at 90° C., optionally in the presence of aluminum (EN AC-AlSi10Mg(a)T6, DIN EN 1706) using the test procedures described in the experimental section, where the glycolate concentration and the formate concentration are measured by ion chromatography.
[0060] Corrosion inhibition As explained throughout this document, coolant compositions according to the present invention exhibit the electrical conductivity properties described herein without significantly corroding aluminum.Accordingly, in an embodiment of the present invention, there is provided a composition as described herein, in which an aluminum coupon (EN AC-AlSi10Mg(a)T6, DIN EN 1706) immersed in the composition exhibits a weight loss of less than 20 mg, preferably less than 10 mg, preferably less than 2 mg, when tested using the procedure described in the experimental section.
[0061] inorganic compounds The compositions described herein according to the present invention may contain inorganic compounds. If present, the (total) amount of inorganic compounds is less than 100 ppm based on the total weight of the coolant composition. As will be understood by those skilled in the art, inorganic compounds do not contain carbon-hydrogen bonds. In contrast, organic compounds such as organic rust inhibitors that can be used in the compositions according to the present invention do not contain carbon-hydrogen bonds.
[0062] As will be appreciated by those skilled in the art, high concentrations of inorganic compounds, especially inorganic compounds in salt form, can increase the electrical conductivity of the coolant composition, which can result in a drop in the voltage of the fuel cell and corrosion of the separator plates, making them unsuitable for use in fuel cells. Thus, the coolant compositions described herein typically have a drop in electrical conductivity when the amount of inorganic compounds is less than 100 ppm, preferably less than 75 ppm, more preferably less than 50 ppm, even more preferably less than 25 ppm, and most preferably less than 10 ppm based on the total weight of the composition.
[0063] In certain embodiments of the present invention, the coolant compositions defined herein may contain an inorganic rust inhibitor in an amount, for example, greater than 1 ppm, greater than 3 ppm, or greater than 5 ppm based on the total weight of the composition, provided that the electrical conductivity of the composition at 25° C. is less than 100 μS / cm.
[0064] In an embodiment of the invention, the coolant composition defined herein comprises an inorganic rust inhibitor selected from the group consisting of silicates, molybdates, nitrates, nitrites, borates, tungstates, sulfates, sulfites, carbonates, phosphonates, selenates and phosphates.
[0065] In a preferred embodiment, the coolant compositions defined herein are free of borax, sodium nitrate, sodium nitrite, sodium silicate and sodium benzoate.
[0066] In a preferred embodiment, the coolant compositions defined herein are carbon black-free.
[0067] In a preferred embodiment, the coolant compositions defined herein are borate and cerium nitrate free.
[0068] In a preferred embodiment, the coolant compositions defined herein are free of water soluble molybdates, nitrites and nitrates.
[0069] In a preferred embodiment, the coolant compositions defined herein do not include potassium hydroxide.
[0070] Additional Additives As will be understood by those skilled in the art, based on the teachings set forth herein, the coolant composition according to the present invention may include one or more additional additives that are conventional in the art. It is within the routine ability of a person skilled in the art to determine how much of a particular additive can be added so that the electrical conductivity of the resulting composition is in accordance with the present invention. As will be understood by those skilled in the art, non-ionic additional additives are preferred. The coolant composition includes clearly defined amounts of water, alcohol, N-vinylpyrrolidone polymer, and inorganic compound. Thus, the one or more additional additives are different from the water, alcohol, and N-vinylpyrrolidone polymer, and inorganic compound.
[0071] In certain embodiments of the present invention, the compositions provided herein comprise one or more additional additives, preferably one or more additional additives selected from the group consisting of corrosion inhibitors, liquid dielectrics, antioxidants, anti-wear agents, detergents, and anti-foam agents. In a preferred embodiment, the compositions of the present invention further comprise one or more of said additional additives in an amount in the range of 0.001 to 10 wt. %, preferably 0.01 to 5 wt. %, more preferably 0.02 to 3 wt. % (based on the total weight of the composition).
[0072] In a preferred embodiment, the coolant composition of the present invention further comprises one or more additional additives selected from the group consisting of thiazoles, triazoles, polyolefins, polyalkylene oxides, silicon oils, silicate esters (e.g., Si(OR)4, where R is a C1-C4 alkyl group), mineral oils, monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids. In a preferred embodiment, the coolant composition of the present invention further comprises one or more of said additives in an amount in the range of 0.001 to 10 wt. %, preferably 0.01 to 5 wt. %, more preferably 0.02 to 3 wt. % (based on the total weight of the composition).
[0073] In a preferred embodiment of the present invention, there is provided a coolant composition as defined herein comprising as an additional additive a corrosion inhibitor which is a thiazole or triazole, preferably an aromatic triazole or thiazole.In a preferred embodiment of the present invention, there is provided a coolant composition as defined herein comprising as an additional additive one or more triazoles selected from the group consisting of tolyltriazole, benzotriazole and combinations thereof.
[0074] In an embodiment of the present invention there is provided a coolant composition as defined herein comprising as additional additive a triazole or thiazole, preferably tolyltriazole or benzotriazole, in an amount of more than 0.001 wt.-%, preferably more than 0.01 wt.-%, preferably more than 0.1 wt.-% and / or less than 10 wt.-%, preferably less than 5 wt.-%, preferably less than 3 wt.-% (based on the total weight of the composition).
[0075] In an embodiment of the present invention, there is provided a composition as defined herein comprising as an additional additive a defoamer, preferably selected from the group consisting of polyalkylene oxides, silicone polymers (e.g. 3D silicone polymers) or silicone oils.
[0076] In an embodiment of the present invention there is provided a coolant composition as defined herein comprising as additional additive a defoamer in an amount of more than 0.001 wt.-%, preferably more than 0.005 wt.-%, preferably more than 0.01 wt.-% and / or less than 10 wt.-%, preferably less than 5 wt.-%, preferably less than 3 wt.-% (based on the total weight of the composition).
[0077] In an embodiment of the present invention, there is provided a coolant composition as defined herein which comprises as an additional additive a corrosion inhibitor selected from the group consisting of aromatic carboxylates, aliphatic monocarboxylates, aliphatic dicarboxylates, aliphatic tricarboxylates, and polymeric corrosion inhibitors.
[0078] In an embodiment of the present invention, an aliphatic monocarboxylate, preferably a C4-C 12 There is provided a coolant composition as defined herein comprising an aliphatic monocarboxylate selected from the group consisting of aliphatic monocarboxylates in an amount (based on the total weight of the composition) of more than 50 ppm, preferably more than 100 ppm, preferably more than 500 ppm and / or less than 5000 ppm, preferably less than 2500 ppm, preferably less than 1000 ppm.
[0079] In an embodiment of the present invention, an aliphatic dicarboxylate, preferably a C6-C 16 There is provided a coolant composition as defined herein comprising an aliphatic dicarboxylate selected from the group consisting of aliphatic dicarboxylates in an amount (based on the total weight of the composition) greater than 50 ppm, preferably greater than 100 ppm, preferably greater than 500 ppm and / or less than 5000 ppm, preferably less than 2500 ppm, preferably less than 1000 ppm.
[0080] In an embodiment of the present invention, an aliphatic tricarboxylate, preferably a C7-C 18There is provided a coolant composition as defined herein comprising an aliphatic tricarboxylate selected from the group consisting of aliphatic tricarboxylates in an amount (based on the total weight of the composition) greater than 50 ppm, preferably greater than 100 ppm, preferably greater than 500 ppm and / or less than 5000 ppm, preferably less than 2500 ppm, preferably less than 1000 ppm.
[0081] In an embodiment of the present invention, there is provided a coolant composition as defined herein comprising as an additional additive an aromatic carboxylate, preferably an aromatic carboxylate selected from the group consisting of benzoate, benzene-1,2-dicarboxylate, benzene-1,2,3-tricarboxylate, benzene-1,2,4-tricarboxylate, benzene-1,4-dicarboxylate and combinations thereof in an amount greater than 50 ppm (based on the total weight of the composition), preferably greater than 100 ppm, preferably greater than 500 ppm and / or less than 5000 ppm, preferably less than 2500 ppm, preferably less than 1000 ppm.
[0082] In an embodiment of the present invention, there is provided a coolant composition as defined herein comprising as an additional additive an antioxidant, preferably selected from the group consisting of phenols such as 2,6 di-t-butylmethylphenol 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-naphthalamine and alkyl-phenyl-2-naphthalamine, and sulfur-containing compounds.
[0083] In an embodiment of the present invention there is provided a coolant composition as defined herein comprising as an additional additive more than 0.001 wt.%, preferably more than 0.005 wt.%, preferably more than 0.01 wt.% and / or less than 10 wt.%, preferably less than 5 wt.%, preferably less than 3 wt.% (based on the total weight of the composition) of an antioxidant.
[0084] In an embodiment of the present invention, there is provided a coolant composition as defined herein which includes an anti-wear agent as an additional additive.
[0085] In an embodiment of the present invention there is provided a coolant composition as defined herein comprising as an additional additive an anti-wear agent in an amount of more than 0.001 wt.%, preferably more than 0.005 wt.%, preferably more than 0.01 wt.% and / or less than 10 wt.%, preferably less than 5 wt.%, preferably less than 3 wt.% (based on the total weight of the composition).
[0086] In an embodiment of the present invention, there is provided a coolant composition as defined herein comprising one or more surfactants as additional additives. In a preferred embodiment, the one or more surfactants are, for example: · Fatty acid esters such as sorbitan fatty acid esters; · Polyalkyleneamide glycols; · Polyalkylene amidoglycol esters; · Copolymers and block copolymers of ethylene oxide and propylene oxide; Polyoxyalkylene derivatives of sorbitan fatty acid esters; and Alkoxylated alcohol ethers The surfactants are selected from the group consisting of non-ionic surfactants, such as one or more non-ionic surfactants selected from the group consisting of:
[0087] In an embodiment of the present invention there is provided a coolant composition as defined herein comprising said one or more surfactants in an amount of more than 0.001 wt.-%, preferably more than 0.005 wt.-%, preferably more than 0.01 wt.-% and / or less than 10 wt.-%, preferably less than 5 wt.-%, preferably less than 3 wt.-% (based on the total weight of the composition).
[0088] In certain embodiments of the present invention, there is provided a coolant composition as defined herein which comprises as an additional additive a dielectric liquid. Preferred dielectric liquids are mineral oil, silicone oil and mixtures thereof.
[0089] In certain embodiments of the present invention, the coolant compositions provided herein comprise more than 0.0001 wt. % of dielectric liquid (based on the total weight of the composition), preferably more than 0.001 wt. %, preferably more than 0.01 wt. %, and / or less than 10 wt. %, preferably less than 5 wt. %, preferably less than 3 wt. %.
[0090] In certain embodiments of the present invention, the coolant compositions provided herein comprise 0.0001 to 10 wt % of dielectric liquid (based on the total weight of the composition), preferably 0.001 to 5 wt %, and preferably 0.01 to 1 wt %.
[0091] In a particular embodiment of the present invention, there is provided a coolant composition as defined herein comprising one or more non-ionic dyes, such as the non-ionic dyes disclosed in EP 1809718 B1 and KR 102108349 B1 as additional additives, preferably in an amount (based on the total weight of the composition) of more than 0.001 wt.-%, preferably more than 0.005 wt.-%, preferably more than 0.01 wt.-% and / or less than 10 wt.-%, preferably less than 5 wt.-%, preferably less than 3 wt.-%.
[0092] In a particular embodiment of the present invention, for safety reasons, there is provided a coolant composition as defined herein comprising one or more bittering agents as additional additives, preferably in an amount of less than 100 ppm (based on the total weight of the composition), preferably less than 80 ppm, less than 60 ppm, less than 40 ppm, or less than 20 ppm.
[0093] In a particular embodiment of the present invention, there is provided a coolant composition as defined herein comprising as additional additive one or more polymeric viscosity modifiers such as homopolymers of ethylene oxide, random copolymers of ethylene oxide and propylene oxide, 80% hydrolyzed polyvinyl alcohol, polyalkoxy grafted polyvinyl alcohol and poly(vinyl alcohol-co-ethylene), preferably in an amount (based on the total weight of the composition) of more than 0.001 wt.%, preferably more than 0.005 wt.%, preferably more than 0.01 wt.% and / or less than 10 wt.%, preferably less than 5 wt.%, preferably less than 3 wt.%.
[0094] Composition as a heat transfer fluid In highly preferred embodiments, the coolant compositions described herein, preferably ready-to-use coolant compositions, are heat transfer fluids, preferably suitable for use in solar systems, fuel cells, electric motors, generators, batteries, battery electric vehicles, power electronics or electronic devices, most preferably suitable for use in fuel cells or power electronics.
[0095] As will be appreciated by those skilled in the art, depending on (for example) the intended application, the compositions according to the present invention can be formulated and used in various concentrations. Thus, the coolant composition is not particularly limited by the concentration of the N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, or other additives described herein. Thus, depending on the anticipated application, the compositions described herein may be suitable for use as is or may require dilution with a base fluid before use. However, the inventors have found it particularly advantageous to provide the compositions of the present invention in the form of a ready-to-use composition that may be suitable for use as a fuel cell coolant, or in the form of a concentrate that is suitable for preparing said ready-to-use composition.
[0096] Ready-to-use compositions In a highly preferred embodiment of the present invention, there is provided a coolant composition as described herein in the form of a ready-to-use composition that is a heat transfer fluid, comprising: the concentration of N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, is in the range of 0.0001 to 10% by weight, preferably in the range of 0.00015 to 5% by weight, more preferably in the range of 0.0002 to 2% by weight, based on the total weight of the composition; and The composition comprises more than 90% by weight, preferably more than 95% by weight, preferably more than 98% by weight, preferably more than 99% by weight of a base fluid based on the total weight of the composition.
[0097] In an embodiment of the present invention, the ready-to-use composition provided herein comprises an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, having a weight average molecular weight in the range of 500 to 2,500,000 g / mol, preferably in the range of 3,000 to 2,500,000 g / mol, more preferably in the range of 5,000 to 2,250,000 g / mol, even more preferably in the range of 7,500 to 2,00,000 g / mol, and most preferably in the range of 8,000 to 1,800,000 g / mol; wherein the N-vinylpyrrolidone polymer has a concentration in the range of 0.0001 to 10 wt.%, preferably in the range of 0.00015 to 5 wt.%, more preferably in the range of 0.0002 to 3 wt.%, based on the total weight of the composition. In certain preferred embodiments, said N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, has a concentration in the ready-to-use composition of more than 0.0001 wt%, more than 0.0002 wt%, more than 0.0003 wt%, more than 0.0005 wt%, more than 0.001 wt%, more than 0.002 wt%, more than 0.003 wt%, more than 0.005 wt%, more than 0.01 wt%, more than 0.02 wt%, more than 0.03 wt%, more than 0.05 wt%, more than 0.1 wt%, more than 0.2 wt% and / or less than 10 wt%, less than 9 wt%, less than 8 wt%, less than 7 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.9 wt%, less than 0.8 wt%, less than 0.7 wt%, less than 0.6 wt%, less than 0.5 wt%, less than 0.4 wt%. In a highly preferred embodiment, the polyvinylpyrrolidone has a concentration in the ready-to-use composition of more than 0.0001% by weight, preferably more than 0.00015% by weight, more preferably more than 0.0002% by weight and / or less than 10% by weight, preferably less than 5% by weight, more preferably less than 2% by weight.
[0098] In a particular embodiment of the present invention, the ready-to-use composition provided herein comprises an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, having a weight average molecular weight in the range of 3,000 to 700,000 g / mol, preferably in the range of 5,000 to 500,000 g / mol, more preferably in the range of 7,500 to 250,000 g / mol, even more preferably in the range of 8,000 to 100,000 g / mol; wherein the N-vinylpyrrolidone polymer has a concentration in the range of 0.0001 to 10 wt.%, preferably in the range of 0.00015 to 5 wt.%, more preferably in the range of 0.0002 to 3 wt.%, based on the total weight of the composition. In certain preferred embodiments, said N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, has a concentration in the ready-to-use composition of more than 0.0001 wt%, more than 0.0002 wt%, more than 0.0003 wt%, more than 0.0005 wt%, more than 0.001 wt%, more than 0.002 wt%, more than 0.003 wt%, more than 0.005 wt%, more than 0.01 wt%, more than 0.02 wt%, more than 0.03 wt%, more than 0.05 wt%, more than 0.1 wt%, more than 0.2 wt% and / or less than 10 wt%, less than 9 wt%, less than 8 wt%, less than 7 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.9 wt%, less than 0.8 wt%, less than 0.7 wt%, less than 0.6 wt%, less than 0.5 wt%, less than 0.4 wt%. In a highly preferred embodiment, said N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, has a concentration in the ready-to-use composition of more than 0.0001 wt.-%, preferably more than 0.00015 wt.-%, more preferably more than 0.0002 wt.-% and / or less than 10 wt.-%, preferably less than 5 wt.-%, more preferably less than 2 wt.-%.
[0099] In a particular embodiment of the present invention, the ready-to-use composition provided herein comprises an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, having a weight average molecular weight in the range of 700,000 to 2,500,000 g / mol, preferably in the range of 750,000 to 2,250,000 g / mol, more preferably in the range of 850,000 to 2,000,000 g / mol, even more preferably in the range of 1,000,000 to 1,800,000 g / mol; wherein the N-vinylpyrrolidone polymer has a concentration in the range of 0.0001 to 10 wt.%, preferably in the range of 0.00015 to 5 wt.%, more preferably in the range of 0.0002 to 3 wt.%, based on the total weight of the composition. In certain preferred embodiments, said N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, has a concentration in the ready-to-use composition of more than 0.0001 wt%, more than 0.0002 wt%, more than 0.0003 wt%, more than 0.0005 wt%, more than 0.001 wt%, more than 0.002 wt%, more than 0.003 wt%, more than 0.005 wt%, more than 0.01 wt%, more than 0.02 wt%, more than 0.03 wt%, more than 0.05 wt%, more than 0.1 wt%, more than 0.2 wt% and / or less than 10 wt%, less than 9 wt%, less than 8 wt%, less than 7 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.9 wt%, less than 0.8 wt%, less than 0.7 wt%, less than 0.6 wt%, less than 0.5 wt%, less than 0.4 wt%. In a highly preferred embodiment said N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, has a concentration in the ready-to-use composition of more than 0.0001 wt.-%, preferably more than 0.00015 wt.-%, more preferably more than 0.0002 wt.-%.
[0100] In a particular embodiment of the present invention, the ready-to-use composition provided herein comprises an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, having a weight average molecular weight of 500 to 50,000 g / mol, more preferably 1,000 to 15,000 g / mol, even more preferably 1,500 to 10,000 g / mol; wherein the N-vinylpyrrolidone polymer has a concentration in the range of 0.0001 to 10 wt.%, preferably in the range of 0.00015 to 5 wt.%, more preferably in the range of 0.0002 to 3 wt.%, based on the total weight of the composition. In certain preferred embodiments, said N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, has a concentration in the ready-to-use composition of more than 0.0001 wt%, more than 0.0002 wt%, more than 0.0003 wt%, more than 0.0005 wt%, more than 0.001 wt%, more than 0.002 wt%, more than 0.003 wt%, more than 0.005 wt%, more than 0.01 wt%, more than 0.02 wt%, more than 0.03 wt%, more than 0.05 wt%, more than 0.1 wt%, more than 0.2 wt% and / or less than 10 wt%, less than 9 wt%, less than 8 wt%, less than 7 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.9 wt%, less than 0.8 wt%, less than 0.7 wt%, less than 0.6 wt%, less than 0.5 wt%, less than 0.4 wt%. In a highly preferred embodiment, said N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, has a concentration in the ready-to-use composition of more than 0.0001% by weight, preferably more than 0.00015% by weight, more preferably more than 0.0002% by weight and / or less than 10% by weight, preferably less than 5% by weight, more preferably less than 2% by weight.
[0101] In a preferred embodiment there is provided a ready-to-use composition as described herein, wherein the base fluid consists of water and an alcohol selected from the group consisting of monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, monopropylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, hexapropylene glycol, methanol, ethanol, propanol, butanol, tetrahydrofurfuryl, ethoxylated furfuryl, dimethyl ether of glycerol, sorbitol, 1,2,6-hexanetriol, trimethylolpropane, methoxyethanol glycerol and mixtures thereof, preferably selected from the group consisting of monoethylene glycol, monopropylene glycol, 1,3-propanediol, glycerol and mixtures thereof; and the amount of alcohol is in the range of 10-80% by weight (based on the total weight of the composition), preferably 30-70% by weight. In certain embodiments, the amount of alcohol ranges from 10 to 45% by weight (based on the total weight of the composition).
[0102] In a highly preferred embodiment, the ready-to-use composition has an electrical conductivity at 25° C. of less than 100 μS / cm, preferably less than 50 μS / cm, more preferably less than 25 μS / cm, even more preferably less than 10 μS / cm, even more preferably less than 5 μS / cm and most preferably less than 2 μS / cm, where the electrical conductivity is measured after ageing the heat transfer fluid at 90° C. for 14 days, optionally in the presence of an aluminum substrate (EN AC-AlSi10Mg(a)T6, DIN EN 1706) using the test procedure described in the experimental section.
[0103] In a preferred embodiment, the ready-to-use composition has a kinematic viscosity of 0.1 to 100 mm, measured according to ASTM standard test method D445-19a at 20°C. 2 / s range, preferably 0.5 to 50 mm 2 / s range, more preferably 1 to 10 mm 2 / s range.
[0104] concentrate In a preferred embodiment of the present invention, the compositions described herein are provided in the form of concentrates suitable for preparing the ready-to-use compositions described herein.
[0105] In a preferred embodiment, the concentrate is suitable for preparing a ready-to-use composition as described herein by the addition of water and / or alcohol; preferably by the addition of water, monoethylene glycol, monopropylene glycol, 1,3-propanediol and / or glycerol; most preferably by the addition of water. In a highly preferred embodiment, the concentrate is suitable for preparing a ready-to-use composition as described herein by the addition of water and / or alcohol alone, preferably by the addition of water, monoethylene glycol, monopropylene glycol, 1,3-propanediol and / or glycerol alone, most preferably by the addition of water alone (i.e. no other ingredients need to be added to prepare a ready-to-use composition as described herein from the concentrate).
[0106] In an embodiment of the present invention there is provided a concentrate as defined herein, wherein the concentration of N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, is greater than 0.01 wt.-%, preferably greater than 0.05 wt.-%, more preferably greater than 0.5 wt.-% and / or less than 10 wt.-%, preferably less than 5 wt.-%, more preferably less than 2 wt.-% (based on the total weight of the composition).
[0107] In a preferred embodiment, a concentrate as defined herein is provided, in which the concentration of N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, is in the range of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 2% by weight (based on the total weight of the composition).
[0108] In a preferred embodiment, the concentrate comprises a base fluid as defined herein and an N-vinylpyrrolidone polymer as defined herein, preferably polyvinylpyrrolidone, wherein the concentration of the N-vinylpyrrolidone polymer is greater than 0.01 wt.-% (based on the total weight of the composition), preferably greater than 0.1 wt.-%, more preferably greater than 0.5 wt.-%, and wherein greater than 80 wt.-%, preferably greater than 85 wt.-%, preferably greater than 90 wt.-% of the concentrate is alcohol, preferably an alcohol selected from the group consisting of monoethylene glycol, monopropylene glycol, 1,3-propanediol and glycerol, most preferably monoethylene glycol.
[0109] In a preferred embodiment, the concentrate comprises a base fluid as defined herein and an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, as defined herein, wherein the concentration of the N-vinylpyrrolidone polymer is greater than 0.01 wt.-% (based on the total weight of the composition), preferably greater than 0.1 wt.-%, more preferably greater than 0.5 wt.-%, and wherein greater than 80 wt.-%, preferably greater than 85 wt.-% of the concentrate is water.
[0110] Preparation method In another aspect of the invention: (i) providing a base fluid as defined herein; (ii) providing an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, as defined herein; (iii) optionally providing one or more additional additives as defined herein; (iv) combining the base fluid of step (i) with the N-vinylpyrrolidone polymer of step (ii) and the optional one or more additional additives of step (iii) to obtain a composition.
[0111] According to the present invention, the order of addition of the compounds is not particularly limited.
[0112] In another aspect of the invention, (i) providing a concentrate as defined herein; (ii) providing water, alcohol or a mixture thereof; (iii) optionally providing one or more additional additives as defined herein; (iv) combining the concentrate of step (i) with water, alcohol or mixtures thereof in step (ii) and optionally one or more additional additives in step (iv) to obtain a ready-to-use composition. In a preferred embodiment, step (iv) comprises combining more than 20% by weight of water (based on the weight of the concentrate), alcohol or mixtures thereof, preferably more than 30% by weight, or more than 50% by weight of water, alcohol or mixtures thereof.
[0113] In a preferred embodiment, the method comprises the steps of: (i) providing a concentrate as defined herein; (ii) providing water, alcohol or a mixture thereof; (iii) combining the concentrate of step (i) with water, alcohol or mixtures thereof of step (ii) to obtain a ready-to-use composition. In a preferred embodiment, step (iii) comprises combining more than 50% by weight (based on the weight of the concentrate) of water, alcohol or mixtures thereof, preferably more than 100%, more than 150%, more than 200% or more than 500% by weight of water, alcohol or mixtures thereof.
[0114] According to the present invention the alcohol of step (ii) is preferably selected from the group consisting of monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, monopropylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, hexapropylene glycol, methanol, ethanol, propanol, butanol, tetrahydrofurfuryl, ethoxylated furfuryl, dimethyl ether of glycerol, sorbitol, 1,2,6-hexanetriol, trimethylolpropane, methoxyethanol, glycerol and mixtures thereof, preferably selected from the group consisting of monoethylene glycol, monopropylene glycol, 1,3-propanediol, glycerol and mixtures thereof; preferably selected from the group consisting of monoethylene glycol, monopropylene glycol, 1,3-propanediol and mixtures thereof.
[0115] others In an embodiment of the present invention, the coolant composition as defined herein, preferably the ready-to-use composition, has a pH between 3 and 8, preferably between 3.5 and 7.5, more preferably between 4 and 7.
[0116] In an embodiment of the invention, the coolant composition defined herein, preferably the ready-to-use composition, has a weight ratio of N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, to alcohol contained in the base fluid of less than 0.01, preferably less than 0.001, most preferably less than 0.0001.
[0117] Use / method In another aspect of the present invention, there is provided an electrical system, preferably selected from the group consisting of solar systems, fuel cells, electric motors, generators, batteries, telephone transmission stations, radio and television broadcast stations, relay stations, electric heating or cooling devices, charging stations and high power lasers / beamers, more preferably fuel cells, wherein the electrical system further comprises a coolant composition as defined herein, preferably a ready-to-use composition as described herein. The electrical system preferably comprises aluminum in contact with a coolant composition as defined herein. In another aspect, the present invention provides the use of an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, as defined herein, in a low electrical conductivity coolant composition comprising water and an alcohol, as an electrical conductivity development inhibitor and / or antioxidant.
[0118] In another aspect, the present invention provides a method for producing a composition comprising: to inhibit the formation of glycolate or formate ions in alcohol and water based coolants, preferably in alcohol and water based coolants that are in direct contact with an electrical system containing aluminum, preferably in monoethylene glycol and water based coolants; or To maintain the low electrical conductivity of alcohol and water based coolants, preferably alcohol and water based coolants that are in direct contact with electrical systems containing aluminum; There is provided the use of an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, as defined herein.
[0119] In another aspect of the present invention there is provided the use of a coolant composition as described herein, preferably a ready-to-use composition, as a heat transfer fluid or coolant, preferably as a heat transfer fluid or coolant in an electrical system, more preferably as a heat transfer fluid or coolant in an electrical system selected from the group consisting of solar systems, fuel cells, electric motors, generators, batteries, telephone transmission stations, power electronics, radio and television broadcast stations, relay stations, electrical heating or cooling devices, preferably as a heat transfer fluid or coolant in fuel cells or power electronics.
[0120] In another aspect of the invention, a. generating heat in an electrical system comprising aluminum, preferably an electrical system selected from the group consisting of solar systems, fuel cells, electric motors, generators, batteries, telephone transmission stations, power electronics, radio and television broadcast stations, relay stations, electrical heating or cooling devices, preferably a fuel cell or power electronics; b. contacting the system of step a with a coolant composition as described herein, preferably a ready-to-use composition as described herein; c. transferring heat from the system to a coolant composition; d. passing the composition through a heat exchanger; e. transferring heat from the coolant composition. EXAMPLES
[0121] The surprising behavior of the coolant compositions according to the invention, even in the presence of aluminum, specifically their electrical conductivity upon aging, was demonstrated by immersing aluminum test specimens in various compositions according to the invention or comparative compositions as described below, and aging the compositions at 90° C. for 14 days.
[0122] Various amounts of polyvinylpyrrolidone (Luvitec K17:M w = 9,000 g / mol, Luvitec K30a:M w = 40,000 g / mol, Luvitec K30b:M w = 50,000 g / mol and Luvitec K90:M w = 1,400,000 g / mol) was added to a composition of 33 vol.% MEG in UPW (ultrapure water) to prepare 14 compositions (Examples 2-15).
[0123] Example 1 is a blank composition consisting of 33% by volume MEG in UPW, ie, no polyvinylpyrrolidone.
[0124] The prepared compositions of Examples 1 to 15 were treated with DOWEX Marathon MR3 (now Amberlite MB20 HOH), a mixed bed ion exchange resin, to remove all residual ionic compounds in the prepared compositions. For this purpose, the compositions were stirred with 0.5 w% DOWEX Marathon MR3 (now Amberlite MB20 HOH) at room temperature for 3 hours. The ion exchanger was removed by filtration after 3 hours.
[0125] The pH and electrical conductivity (eConduc) of the compositions thus treated were measured (measurements "before aging") and are listed in the table below. Afterwards, 100 mL glass bottles were rinsed with UPW and dried overnight at 90°C. Aluminum (EN AC-AlSi10Mg(a)T6, DIN EN 1706) coupons were polished using P240 sanding paper, rinsed with UPW and acetone, dried at 100°C for 1 hour and weighed (new coupons). The coupons were placed in bottles and 100 mL of the compositions of Examples 1 to 15 were added to the bottles. The bottles were then placed in an oven at 90°C. After 14 days, the bottles were removed from the oven and the electrical conductivity and pH of the aged compositions were measured. The glycolate and formate concentrations in the aged compositions were determined by ion chromatography. All coupons were gently cleaned with water and a soft-bristled brush, dried and weighed (coupons AT). Finally, all coupons were chemically cleaned by placing them in a 4:1 mixture of HNO3:UPW for 10 min. The coupons were further cleaned with water and a soft-bristled brush, dried at 100°C for 1 h5 and weighed (coupon CC). The weight change of the aluminum coupons due to aging was determined using the following formula: Δm (mg) = mass of new coupon (mg) - mass of coupon CC (mg). The experimental results are provided in Table 1.
[0126] [Table 1]
[0127] As can be seen from the above results, compositions according to the invention using polyvinylpyrrolidinone (Examples 2-15) surprisingly and unexpectedly exhibit low electrical conductivity and very limited glycol degradation upon aging in the presence of aluminum.
Claims
1. A coolant composition comprising a base fluid and an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, wherein the composition has an electrical conductivity at 25 °C of less than 100 μS / cm, the base fluid consists of water and alcohol, the alcohol is present in an amount in the range of 10 to 99.5% by weight based on the weight of the base fluid, the composition contains more than 75% by weight of the base fluid based on the total weight of the composition, and a coolant composition wherein the amount of the inorganic compound is less than 100 ppm based on the total weight of the composition.
2. The coolant composition according to claim 1, having an electrical conductivity at 25 °C of less than 50 μS / cm, preferably less than 25 μS / cm, more preferably less than 10 μS / cm, and even more preferably less than 5 μS / cm.
3. The alcohol is selected from the group consisting of monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, monopropylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, hexapropylene glycol, methanol, ethanol, propanol, butanol, tetrahydrofurfuryl, ethoxylated furfuryl, dimethyl ether of glycerol, sorbitol, 1,2,6-hexanetriol, trimethylolpropane, methoxyethanol, glycerol and mixtures thereof, preferably selected from the group consisting of monoethylene glycol, monopropylene glycol, 1,3-propanediol, glycerol and mixtures thereof, the coolant composition according to claim 1 or 2.
4. The coolant composition according to claim 1 or 2, wherein the alcohol is present in an amount in the range of 30 to 70% by weight based on the weight of the base fluid.
5. The coolant composition according to claim 1 or 2, wherein the N-vinylpyrrolidone polymer, preferably the polyvinylpyrrolidone, has a weight average molecular weight in the range of 500 to 2,500,000 g / mol.
6. The coolant composition according to claim 5, wherein the N-vinylpyrrolidone polymer, preferably the polyvinylpyrrolidone, has a weight average molecular weight in the range of 500 to 50,000 g / mol, more preferably in the range of 1,000 to 15,000 g / mol, even more preferably in the range of 1,500 to 10,000 g / mol, such as about 2000 g / mol, about 2500 g / mol, about 5000 g / mol or about 8000 g / mol.
7. The coolant composition according to claim 1 or 2, comprising one or more additional additives selected from the group consisting of thiazole, triazole, polyolefin, polyalkylene oxide, silicone oil, mineral oil, silicate ester, aliphatic monocarboxylic acid, aliphatic dicarboxylic acid and aliphatic tricarboxylic acid.
8. The coolant composition according to claim 1 or 2, wherein the amount of the inorganic compound is less than 50 ppm, preferably less than 25 ppm, more preferably less than 10 ppm.
9. The coolant composition according to claim 1, provided in the form of a composition that can be used immediately as a heat transfer fluid, - the concentration of the N-vinylpyrrolidone polymer, preferably the polyvinylpyrrolidone, is in the range of 0.0001 to 10% by weight, preferably in the range of 0.00015 to 5% by weight, more preferably in the range of 0.0002 to 2% by weight based on the total weight of the composition, and - the composition comprises a base fluid of more than 90% by weight, preferably more than 95% by weight, preferably more than 98% by weight, preferably more than 99% by weight based on the total weight of the composition.
10. The coolant composition according to claim 1, having a pH between 3 and 8, more preferably between 3.5 and 7.5, most preferably between 4 and 7.
11. The coolant composition according to claim 9 or 10, wherein the base fluid consists of water and an alcohol selected from the group consisting of monoethylene glycol, monopropylene glycol, 1,3-propanediol, glycerol and mixtures thereof, and the alcohol is present in an amount in the range of 30 to 70% by weight based on the weight of the base fluid.
12. The kinematic viscosity at 20°C, measured in accordance with ASTM standard test method D445-19a at 20°C, is in the range of 0.1 to 100 mm 2 / s, preferably in the range of 0.5 to 50 mm 2 / s, more preferably in the range of 1 to 10 mm 2 / s, and the coolant composition according to claim 9 or 10.
13. The coolant composition according to claim 10, which is provided in the form of a concentrate suitable for preparing the immediately usable composition according to claim 10 by adding only water and / or alcohol, preferably by adding only water, monoethylene glycol, monopropylene glycol, 1,3-propanediol and / or glycerol, most preferably by adding only water.
14. Use of an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone, in a coolant composition having a low electrical conductivity and containing water and alcohol as an inhibitor for suppressing the development of electrical conductivity and / or an antioxidant.
15. ・ For suppressing the formation of glycolate or formate ions in an alcohol and water-based coolant, preferably a monoethylene glycol-based coolant, or ・ For maintaining a low electrical conductivity in an alcohol and water-based coolant, Use of an N-vinylpyrrolidone polymer, preferably polyvinylpyrrolidone.