Antifreeze compositions

Abstract

Compositions of matter that are antifreeze composition, coolants, heat transfer fluids, and de-icing fluids based on the use of coalescent efficient glycol ethers.

Claims

1. A non-flammable antifreeze composition comprising incipient materials: A. water; B. a coalescent efficient glycol ether selected from a group of materials having the general formula: ##STR00003## wherein in (i.), RO is selected from a group consisting of an alkoxy group of 1 to 6 carbon atoms or phenoxy; R′ is H, or —C(O)CH.sub.3, and .sub.y has a value of 1 to 6, and wherein in (ii.), RO is an alkoxy group of 1 to 4 carbon atoms, the phenoxy group or acetoxy group; R′ is H or —C(O)CH.sub.3, and .sub.y has a value of 1 to 3, wherein a boiling point of the coalescent efficient glycol ether is 190° C. or greater at 760 mm Hg; C. a non-flammable compound selected from a group consisting of: a. sodium formate, b. potassium formate, c. lithium formate, d. rubidium formate, e. cesium formate, f. beryllium formate, g. magnesium formate, h. calcium formate, i. strontium formate, j. barium formate, k. mixtures of a. to j, wherein the composition is not a colloidal solution and does not comprise a viscoelastic surfactant: and wherein the non-flammable compound is present from greater than 10 weight percent based on a weight of the total composition.

2. The non-flammable antifreeze composition as claimed in claim 1, wherein A. is present from 0.1 to 95 weight percent; B. is present from 0.1 to 85 weight percent; C. is present from 10 to 73 weight percent, each based on the weight of the total composition.

3. The non-flammable antifreeze composition as claimed in claim 1, wherein, in addition, there is a corrosion inhibitor present.

4. The non-flammable antifreeze composition as claimed in claim 3, wherein the corrosion inhibitor is present from 0.1 to 10 weight percent based on the weight of the total composition.

5. The non-flammable antifreeze composition as claimed in claim 3, wherein the corrosion inhibitor is at least one of sodium silicate, potassium silicate, and sodium trihydroxysilylpropylmethyl-phosphonate.

6. The non-flammable antifreeze composition as claimed in claim 1, wherein, in addition, there is wax present.

7. The non-flammable antifreeze composition as claimed in claim 6, wherein the wax is present from 0.1 to 10 percent based on the weight of the total composition.

8. The non-flammable antifreeze composition as claimed in claim 1, wherein, in addition, there is a thickener present.

9. The non-flammable antifreeze composition as claimed in claim 8, wherein the thickener is present from 0.1 to 10 percent based on the weight of the total composition.

10. The non-flammable antifreeze composition as claimed in claim 1, wherein the water is ultra-pure water.

11. The non-flammable antifreeze composition as claimed in claim 1, wherein the water is a mixture of ultra-pure water and water other than ultra-pure water.

12. The non-flammable antifreeze composition as claimed in claim 6, wherein, in addition, there is a wax present which are used primarily at about 0.2 weight percent to about 10.0 weight percent.

13. A non-flammable antifreeze composition consisting of incipient materials: A. water; B. a coalescent efficient glycol ether selected from a group of materials having a general formula: ##STR00004## wherein, in (i.), RO is selected from a group consisting of an alkoxy group of 1 to 6 carbon atoms or phenoxy; R′ is H, or —C(O)CH.sub.3, and .sub.y has a value of 1 to 6, and wherein in (ii.), RO is an alkoxy group of 1 to 4 carbon atoms, the phenoxy group or acetoxy group; R′ is H or —C(O)CH.sub.3, and .sub.y has a value of 1 to 3, said coalescent efficient glycol ether having a boiling point of 190° C. or greater at 760 mm Hg; C. a compound selected from a group consisting of: a. sugar, b. glycerin, c. polyethylene glycol, d. polypropylene glycol, e. sodium chloride, f. sea salt, g. diethylene glycol, and, h. mixtures of (i) to (vii); D. a non-flammable compound selected from a group consisting of: a. sodium formate, b. potassium formate, c. lithium formate, d. rubidium formate, e. cesium formate, f. beryllium formate, g. magnesium formate, h. calcium formate, i. strontium formate, j. barium formate, k. mixtures of a. to j; and E. at least one additive selected from a group consisting of: a. at least one wax, b. at least one silicate stabilizer, c. at least one thickener, d. at least one rheology modifier, e. at least one dye, f. at least one corrosion inhibitor, and g. a mixture of a. to f, wherein the non-flammable compound is present from greater than 10 weight percent based on a weight of the total composition.

14. The non-flammable antifreeze composition as claimed in claim 13, wherein the at least one wax is at least one of a carnauba wax, a paraffin wax, a polyethylene wax, a polypropylene wax, a polytetrafluoroethylene wax, and a microcrystalline wax.

15. The non-flammable antifreeze composition as claimed in claim 13, wherein the at least one corrosion inhibitor is at least one of a sodium silicate, a potassium silicate, and a sodium trihydroxysilylpropyl methylphosphonate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1A is a graph showing conductivity end freezing points of aqueous solutions without potassium formate. FIG. 1B is a graph of various properties of aqueous solutions without potassium formate.

(2) FIG. 1C is a graph of conductivity and freezing point of aqueous solutions with potassium formate.

(3) FIG. 1D is a graph of various properties of aqueous solutions with potassium formate.

(4) FIG. 1E is a graph of freezing point comparison with and without potassium formate.

(5) FIG. 2A is a comparison of samples 130, 131, and 132, initial properties compared to commercial antifreeze.

(6) FIG. 2B is a comparison of sample 130, 131, and 132, at 30 days at high ambient temperature stability 70° C. for 30 days.

(7) FIG. 2C is a comparison of sample 130, 131, and 132, at 90 days at high ambient temperature stability 70° C. for 90 days.

(8) FIG. 2D is a comparison of sample 130, 131, and 132, at 40 cycles high ambient temperature stability 66° C.

(9) FIG. 3A is a graph of corrosion rate at 30 days.

(10) FIG. 3B is a graph of weight loss rate at 30 days.

(11) FIG. 3C is a graph of corrosion rate for 60 days.

(12) FIG. 3D is a graph of weight loss for 60 days.

(13) FIG. 3E is a graph of corrosion for 90 days.

(14) FIG. 3F is a graph of weight loss for 90 days.

(15) FIG. 4A is a table showing corrosion rate and weight loss data at 30 days

(16) FIG. 4B is a table showing corrosion rate and weight loss date at 60 days

(17) FIG. 4C is a table showing corrosion rate and weight loss data at 90 days

(18) FIG. 5A is a graph showing % volume changes for formulation 130 and various rubbers and plastics.

(19) FIG. 5B is a graph showing % weight change for formulation 130 and various rubbers and plastics.

(20) FIG. 5C is a graph showing % volume change for formulation 131 and various rubbers and plastics.

(21) FIG. 5D is a graph showing % weight change for formulation 131 and various rubbers and plastics.

(22) FIG. 5E is a graph showing % volume change for formulation 132 and various rubbers and plastics.

(23) FIG. 5F is a graph showing % weight change for formulation 132 and various rubbers and plastics.

(24) FIG. 6A is a table showing data for formulation 130 and various rubbers and plastics.

(25) FIG. 6B is a table showing data for formulation 131 and various rubbers and plastics.

(26) FIG. 6C is a table showing data for formulation 132 and various rubbers and plastics.

DETAILED DESCRIPTION OF THE INVENTION

(27) It has now been discovered that antifreeze compositions can be formulated that are essentially low cost, non-flammable, have very low freezing points, and are essentially non-corrosive to metal components of systems used for handling such antifreeze compositions.

(28) What is disclosed herein are non-flammable antifreeze compositions comprising the incipient materials, water; a coalescent efficient glycol ether selected from a group of materials having the general formula:
RO(CH.sub.2CH.sub.2O).sub.yR′ or,

(29) ##STR00001##

(30) In the first formula, RO is selected from a group consisting of an alkoxy group of 1 to 6 carbon atoms or phenoxy; R′ is H, or —C(O)CH.sub.3, and .sub.y has a value of 1 to 6. In the second formula, RO is an alkoxy group of 1 to 4 carbon atoms, the phenoxy group or acetoxy group; is R′ or —C (O)CH.sub.3, and .sub.y has a value of 1 to 3, wherein the boiling point of the coalescent efficient glycol ether is 190° C. or greater at 760 mm Hg.

(31) A third component is a non-flammable compound selected from the group consisting of sodium formate, potassium formate, lithium formate, rubidium formate, cesium formate, beryllium formate, magnesium formate, calcium formate, strontium formate, barium formate, and mixtures of these components.

(32) In addition, it is contemplated within the scope of this invention to use one or more additional adjuvants and materials in the formulation. Such materials comprise such materials as waxes, silicate stabilizers, thickeners, dyes, and the like. It is also contemplated within the scope of this invention to use mixtures of these materials with the basic formulation.

(33) Another embodiment is the use of the basic formula set forth Supra in conjunction with other sources of carbinol, such as sugar, glycerin, polyethylene glycol, polypropylene glycol, diethylene glycol, and, salts such as sodium chloride and sea salt. Also contemplated within the scope of this invention are mixtures of these materials.

DETAILED DESCRIPTION OF THE DISCLOSURE

(34) Thus what is disclosed and claimed herein are non-flammable antifreeze compositions based on water. the amount of each of the components here is based on the total weight of the components, and the amount of water that can be used herein is 0.1 to 95% weight percent. A preferred amount of water is from about 15 weight percent to about 75 weight percent and the most preferred embodiments is water at 40 weight percent to 65 weight percent.

(35) A second component of the antifreeze composition is a group of materials that are coalescent efficient glycol ethers having the general formula RO(CH.sub.2CH.sub.2O).sub.yR′ or,

(36) ##STR00002##
wherein in the first formula, RO is selected from a group consisting of an alkoxy group of 1 to 6 carbon atoms or phenoxy; R′ is H, or —C(O)CH.sub.3, and .sub.y has a value of 1 to 6, and in the second formula, RO is an alkoxy group of 1 to 4 carbon atoms, the phenoxy group or acetoxy group; R′ is H or —C(O)CH.sub.3, and .sub.y has a value of 1 to 3.

(37) These materials can be used singularly or combined in two or more combinations. They are used in this composition at from 0.1 to 85 weight percent, based on the total weight of the composition. Preferred is from 20 to 60 weight percent and most preferred is from 40 to 55 weight percent based on the total weight of the final composition.

(38) A third component of the antifreeze composition is a non-flammable compound selected from group consisting of sodium formate, rubidium formate, cesium formate, beryllium formate, magnesium formate, calcium formate, strontium formate, barium formate, potassium formate, lithium formate, and, mixtures of these compounds. These compositions are used in the antifreeze compositions at from 0.1 to 85 weight percent of the total composition. Preferred is a weight of from 0.1 weight percent to 70 weight percent and most preferred is the use at 0.1 to 50 weight percent based on the weight of the final composition.

(39) In addition, it is contemplated within the scope of this invention to use corrosion inhibitors, such as, for example, sodium silicate, potassium silicate, and sodium trihydroxysilylpropyl methylphosphonate. The corrosion inhibitors are used at 0.1 to 10 weight percent based on the weight of the total composition. Preferred is from about 3 percent to about 8 percent and most preferred is from about 5 percent to 7 percent by weight based on the total weight of the final composition.

(40) Other adjuvants include waxes, such as carnauba, paraffin, polyethylene wax or polypropylene wax, PTFE, microcrystalline waxes and blends of waxes which are used primarily at about 0.2 weight percent to about 10.0 weight percent based on the total weight of the final composition. Such waxes can be obtained from a variety of commercial sources such as Michelman, INC. Cincinnati, Ohio.

(41) In addition, there can be used thickeners or rheology modifiers, for example for use on de-iceing airplanes wings. Any conventional thickener can be used. Cellulosics such as CMC, HMC, HPMC, and others, that are chemically substituted cellulose macromolecules, polyvinyl alcohol, metal oxides such as silica, clays: attapulgite which also disperses suspensions, bentonite (both flocculating and non-flocculating), and other montmorillonite clays. Preferred for this invention is carboxymethylcellulose which is used primarily at about 0.2 weight percent to about 5.0 weight percent based on the total weight of the final composition.

(42) As indicated Supra, ultra-pure water can be used in this invention and it can be used is conjunction with other water, such as well water, city water, river, lake and pond water.

(43) When the coalescent efficient glycol ethers are mixed with the other carbinol materials, the ratio of the other carbinol materials to the coalescent efficient glycol ethers is in the range of from 0.1:99.9 to 25:75. The salts can be managed in the same manner.

(44) The compositions of the invention are easily prepared by simple mixing of the ingredients at room temperature and, the compositions can be stored indefinitely at room temperature.

(45) The following examples illustrate the disclosure.

EXAMPLES

(46) In accordance with UL 2901: Outline of Investigation for Antifreeze Solutions for Use in Fire Sprinkler Systems initial testing on potential solutions includes Pour Point—ASTM D97, Standard Test Method for Pour Point of Petroleum Products Viscosity—ASTM D2983, Standard Test Method for Low-Temperature Viscosity of Lubricants Measured by Brookfield Viscometer; Specific Gravity—ASTM D1429, Standard Test Methods for Specific Gravity of Water and Brine; pH—ASTM D1293, Standard Test Methods for pH of Water; Freeze Point—ASTM D6660, Standard Test Method for Freezing Point of Aqueous Ethylene Glycol Base Engine Coolants by Automatic Phase Transition Method or equivalent differential scanning calorimetric methods. All of these methods were used in acquiring the data in the following examples.

(47) After these required tests are met and quantified, the following further testing is required: High Ambient Temperature Stability; Temperature Cycling Stability; Electrical Conductivity; Corrosion Rate; Exposure to Elastomeric Materials; Compatibility with Polymeric Materials, and Exposure to Fire.

(48) In these examples, all data is in grams; Temperatures are measured in Centigrade (degrees C); Freeze Point at −20° C. was determined by placing samples in a refrigerated chamber for 24 hours at a constant −20° C. After 24 hours the sample was evaluated for flow; pH was tested using the Standard Methods for examination of water and wastewater standard 4500-H.

(49) Exotherm or endotherm was measured using a NIST certified thermometers; Viscosity was tested using ASTM D2983, Standard Test Method for Low-Temperature Viscosity of Lubricants Measured by Brookfield Viscometer Model DV-II; Spindle 2 @100 rpm or Ubbleode tubes for low viscosity measurements.

(50) Freeze Point at −40° C. (or lower) was determined by placing samples in a bath of Dow Corning® 10 cst 200 fluid chilled to temperature using either a bath of dry ice in acetone or a Neslab Bath Cooler Model PBC 2-II; Pour point was determined by placing samples in a bath of Dow Corning® 10 cst 200 fluid™ chilled to temperature using either a bath of dry ice in acetone or a Neslab Bath Cooler Model PBC 2-II and observing the temperature at which the sample was no longer fluid.

(51) Corrosion rate was determined by placing pre-weighed samples into the test solution, aged at 49° C., and re-weighed at the prescribed times; Exposure to Elastomeric Materials was determined by placing pre-weighed samples into the test solution, aged at 70° C., and reweighed at the prescribed times, and, Unless specified otherwise all raw materials were purchased form Aldrich Chemical Company.

(52) Tables 1 and 2 represent the development work done to arrive at the lowest freezing point achievable. This effort centered on dissociative salts trying to achieve a freezing point of at least −40° C.

(53) The compositions of this invention can have conductivity properties that can be manipulated at will as will be obvious from the data infra. For example, city water, in the inventor's laboratory, has a conductivity of 300 μS. A requirement for the materials used for antifreeze for outdoor file suppression systems is 1000 μS or less. Table 3 sets forth conductivity for the various components and combinations useful in this invention. H+H.sub.2O is ultra-pure water. “Water” indicates tap water.

(54) TABLE-US-00001 TABLE 1 sample No. A B C D E F G Water 100 100 100 100 100 100 100 KC.sub.2H.sub.3O.sub.2 269 201 135 70 269 NaC.sub.2H.sub.3O.sub.2 94.9 Glycerol, 100 25 50 75 100 pure FPt, −20 C. OK SOLID OK OK OK OK OK initial pH 8.5 7 4.5 final pH 7 7 7 7 7 7 7 Exotherm, @ mix Init temp 23 23 23 final temp 9 20 23 pour point , −52 C. , −52 C. FPt, −40 C. solid solid OK OK , −48 C. OK OK

(55) TABLE-US-00002 TABLE 2 Sample No. H K L M O P Water 100 100 100 100 100 KC.sub.2H.sub.3O.sub.2 269 33.7 Glycerol, 100 50 10 100 raw S.G. 1.55 1.2 1.25 FPt, −20 C. OK Slice 2 solid solid v phase thick initial pH 9 7.5 4.5 5 final pH 8 7 5 5 4.53 Exotherm, @ mix Init temp 22 22 22 22 final temp 11 21 22 22 Viscosity, 32 5 20 3 cps Sp 2 @ 100 rpm Freezing , −40 C. point

(56) TABLE-US-00003 TABLE 3 Sample 9 10 11 12 13 H + H.sub.2O 100 50 50 Glycerin 50 DPM 100 50 TPNB 100 Conductivity uS 1.8 3.6 4.5 0.08 1 FPt, −20 C. solid OK <−75 −83 OK Flash Pt 126 75 Density 0.93 0.95

(57) TABLE-US-00004 TABLE 4 Sample I J K L Water 100 90 45 49 KC2H3O2 135 10 5 1 Glycerol 50 50 Wt. % KCHO 57 11 5 3.6 Conductivity, uS 76000 14400 8500 3600

(58) Table 4 contains data regarding the level of Potassium Formate as it relates to the conductivity vs concentration in solution. Tables 5 and 6 illustrate conductivity as it relates to three lower levels of Potassium Formate, no Potassium Formate, and the addition of specialty fluids to lower the freezing point of the formulation. The formulations in Table 7 contain date regarding the levels of water in the formulation and its effect on conductivity and pH.

(59) TABLE-US-00005 TABLE 5 Sample 15 16 17 H + H.sub.2O 50 50 50 DPM 47.75 47.75 47.75 TPNB 2.25 2.25 2.25 KCHO 1 0.6 0.2 % H.sub.2O 50 50 50 Conductivity uS 3600 1955 785

(60) TABLE-US-00006 TABLE 6 Sample 15 16 17 14 18 19 H + H.sub.2O 50 50 50 50 50 50 DPM 47.75 47.75 47.75 47.75 40 30 TPNB 2.25 2.25 2.25 2.25 10 20 KCHO 1 0.6 0.2 0 Conductivity 3600 1955 785 2.5 5.4 2 uS phase FPt, −20 C. OK OK OK OK OK

(61) TABLE-US-00007 TABLE 7 Sample 20 21 22 14 23 24 25 H + H.sub.2O 450 150 100 50 25 10 5 DPM 47.75 47.75 47.75 47.75 47.75 47.75 47.75 TPNB 2.25 2.25 2.25 2.25 2.25 2.25 2.25 % H.sub.2O 90 75 66 50 36 16 9 Conductivity 13.9 8.01 5.07 2.5 6.2 5.81 5.51 uS pH 7.57 7.3 7.02 6.6 6.2 5.8 5.5

(62) Tables 8 and 9 are miscellaneous salt additives as they relate to freezing point while Table 10 shows the optimum formulations that have resulted in low conductivity and low freezing point depression. Additionally an added corrosion inhibitor to further improve the formulation was incorporated, i. e. CH.sub.3COOK and/or CH.sub.3COONa.

(63) TABLE-US-00008 TABLE 8 Sample 20 21 22 Water 100 100 100 CH.sub.3COOK 200 CH.sub.3COONa 125 NaCl 35 ppt FPt, −20 C. OK solid some ice initial pH 9 9 6.8 final pH 9 8 6.8 Exotherm, @ mix Init temp 21 21 21 final temp 26 32 19

(64) TABLE-US-00009 TABLE 9 Sample a-13 a-14 a-20 a-21 a-3 a-4 a-7 Water 100 100 100 100 100 100 KC.sub.2H.sub.3O.sub.2 269 135 269 33.7 prop glycol 100 100 50 Na Lactate 100 100 Na Silicate 26.9 13.5 FPt, −20 C. Solid Solid OK OK OK OK OK

(65) TABLE-US-00010 TABLE 10 Sample 29 30 17 15 H + H.sub.2O 50 50 50 50 DPM 47.75 47.75 47.75 47.75 TPNB 2.25 2.25 2.25 2.25 DCC 6083 1 0.5 KCHO 0.1 0.2 1 % H.sub.2O 50 50 50 50 Conductivity uS 967 857 785 3600 FPt, −20 C. OK OK OK OK FPt, −C. −20 R.I. 1.3907 1.4255 pH 11.5 10.7

(66) TABLE-US-00011 TABLE 11 Aging Study Formulations 130 131 132 same as 30 24 32 H + H.sub.2O 50 10 10 DPM 47.5 47.75 47.75 TPNB 2.25 2.25 2.25 DCC 6083 0.5 0.5 KCHO 0.1 0.1 % H.sub.2O 50 16.7 16.5

(67) High Ambient Temperature Stability at 70° C. for 90 days. The Pour Point, Viscosity, Specific Gravity, pH and Freeze Point will remain stable within 10 percent of the initial properties (FIG. 2). Temperature Cycling Stability at 66° C. for 40 cycles. One cycle was equal to 24 hours at 66° C. and 24 hours at room temperature. The Pour Point, Viscosity, Specific Gravity, pH and Freeze Point will remain stable within 10 percent of the initial properties (FIG. 2). Corrosion Rate. The corrosion rate should not exceed 1.0 mils/year. Corrosion rate was tested according to NFPA 18A-2011. Metal alloy samples were submerged in the test solutions and incubated at 45° C. for 30, 60 and 90 days. The corrosion rate (Cr) was calculated using the following equation:

(68) $\frac{\mathrm{Cr}=\mathrm{weight}\mathrm{loss}\left(g\right)\times K}{\mathrm{alloy}\mathrm{density}\times \mathrm{exposed}\mathrm{area}\times \mathrm{exposure}\mathrm{time}}$
where K=5.34*10.sup.5
Percent Weight Loss was also calculated for these samples where:

(69) $\%\mathrm{Weight}\mathrm{Loss}=\frac{\mathrm{initial}\mathrm{weight}-\mathrm{final}\mathrm{weight}\times 100}{\mathrm{initial}\mathrm{weight}}$
See FIG. 3.

(70) Exposure to Elastomeric Materials: A volume change of minus 1 to plus 25 percent and a maximum loss of weight of 10 percent (See the Figures).

(71) Tables 12, 13, and, illustrate a few of the compositions of this disclosure.

(72) TABLE-US-00012 TABLE 12 sample No. A B C D E F G Water 100 100 100 100 100 100 100 KC.sub.2H.sub.3O.sub.2 269 201 135 70 269 NaC.sub.2H.sub.3O.sub.2 94.9 Glycerol, pure 100 25 50 75 100 Freeze Pt, OK SOLID OK OK OK OK OK −20 C. initial pH 8.5 7 4.5 final pH 7 7 7 7 7 7 7 Exotherm, @ mix Init temp 23 23 23 final temp 9 20 23 Ratio 100/0 0/100 75/25 50/50 25/75 100/100 Viscosity S.G. pour point −52 C. −52 C. R.I. Freeze Pt, solid solid OK OK −40 C. −48 C. OK OK

(73) TABLE-US-00013 TABLE 13 Sample No. H K L M O p Water 100 100 100 100 100 KC.sub.2H.sub.3O.sub.2 269 33.7 Glycerol, raw 100 50 10 100 S.G. 15.5 1.2 1.25 Freeze Pt, −20 C. OK Slice 2 solid solid v phase thick initial pH 9 7.5 4.5 5 final pH 8 7 5 5 4.53 Exotherm, @ mix Init temp 22 22 22 22 final temp 11 21 22 22 Viscosity 32 5 20 3

(74) TABLE-US-00014 TABLE 14 a = 8 a-9 a-10 a-13 a-14 Water 100 100 100 100 KC.sub.2 H.sub.3 O.sub.2 269 135 135 prop glycol eth glycol Glycerol 50 Corr. In @ 43% 26.9 13.5 13.5 Na Lactate 100 100 S.G. FPt, −20 C. OK OK OK Solid Solid initial Ph Corrosion inhibitor = sodium trihydroxysilylpropyl methylphosphonate