Coolant for cooling systems in electric vehicles having fuel cells and/or batteries containing azole derivatives and additional corrosion protectants

Abstract

Coolants based on alkylene glycols or derivatives thereof are useful for cooling systems in electric vehicles having fuel cells and/or batteries, preferably for motor vehicles, particularly preferably for passenger cars and commercial vehicles (known as light and heavy duty vehicles). The coolants contain additional corrosion inhibitors for improved corrosion protection in addition to specific azole derivatives.

Claims

1. A coolant composition having a conductivity of not more than 50 μS/cm, the coolant composition comprising: at least one alkylene glycol or derivative thereof; one or more five-membered heterocyclic compounds, which are azole derivatives, and which have 2 or 3 heteroatoms selected from the group consisting of nitrogen and sulfur, and comprise no or at most one sulfur atom and can bear an aromatic or saturated six-membered fused-on ring; ion free water; at least one compound of formula (V) ##STR00007## wherein R.sup.1 is an organic radical having from 7 to 21 carbon atoms, n is a positive integer from 10 to 60, and each X.sub.i for i=1 to n is selected independently from the group consisting of —CH.sub.2—CH.sub.2—O—, —CH.sub.2—CH(CH.sub.3)—O—, —CH(CH.sub.3)—CH.sub.2—O—, —CH.sub.2—C(CH.sub.3).sub.2—O—, —C(CH.sub.3).sub.2—CH.sub.2—O—, —CH.sub.2—CH(C.sub.2H.sub.5)—O—, —CH(C.sub.2H.sub.5)—CH.sub.2—O—, —CH(CH.sub.3)—CH(CH.sub.3)—O—, —CH.sub.2—CH.sub.2—CH.sub.2—O—, and —CH.sub.2—CH.sub.2—CH.sub.2—CH.sub.2O—; and optionally, at least one ortho-silicic ester.

2. The coolant composition according to claim 1, wherein the structural element R.sup.1—COO— in the formula (V) is derived from an acid selected from the group consisting of 2-ethylhexanoic acid, octanoic acid (caprylic acid), pelargonic acid (nonanoic acid), 2-propylheptanoic acid, decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, palmitic acid (hexadecanoic acid), palmitoleic acid [(9Z)-hexadec-9-enoic acid], margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), oleic acid [(9Z)-octadec-9-enoic acid], elaidic acid [(9E)-octadec-9-enoic acid], linoleic acid [(9Z,12Z)-octadeca-9,12-dienoic acid], linolenic acid [(9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid], eleostearic acid [(9Z,11E,13E)-octadeca-9,11,13-trienoic acid], ricinoleic acid ((R)-12-hydroxy-(Z)-octadec-9-enoic acid), isoricinoleic acid [(S)-9-hydroxy-(Z)-octadec-12-enoic acid], nonadecanoic acid, arachidic acid (eicosanoic acid), behenic acid (docosanoic acid), and erucic acid [(13Z)-docos-13-enoic acid].

3. The coolant composition according to claim 1, wherein the structural element R.sup.1—COO— in the formula (V) originates from a fatty acid mixture originating from a work-up of linseed oil, coconut oil, palm kernel oil, palm oil, soy oil, peanut oil, cocoa butter, shea butter, cottonseed oil, maize oil, sunflower oil, rapeseed oil, or castor oil.

4. The coolant composition according to claim 1, wherein n is a positive integer from 12 to 50.

5. The coolant composition according to claim 1, wherein n is a positive integer from 15 to 40.

6. The coolant composition according to claim 1, wherein n is a positive integer from 18 to 30.

7. The coolant composition according to claim 1, wherein n is a positive integer from 20 to 25.

8. The coolant composition according claim 1, wherein X.sub.i is —CH.sub.2—CH.sub.2—O—.

9. The coolant composition according claim 1, wherein X.sub.i is selected from the group consisting of —CH.sub.2—CH.sub.2—O—, —CH.sub.2—CH(CH.sub.3)—O—, and —CH(CH.sub.3)—CH.sub.2—O—.

10. The coolant composition according to claim 1, comprising benzimidazole, benzotriazole, tolutriazole, and/or hydrogenated tolutriazole as the azole derivatives.

11. The coolant composition according to claim 1, further comprising at least one ortho-silicic ester in such an amount that a silicon content in the coolant composition is from 2 to 2000 ppm by weight when in a ready-to-use state.

12. The coolant composition according to claim 1, wherein the coolant composition consists essentially of: (a) from 10 to 90% by weight of the at least one alkylene glycol or derivative thereof; (b) from 90 to 10% by weight of the ion free water; (c) from 0.005 to 5% by weight of the one or more azole derivatives; (d) optionally, at least one ortho-silicic ester, and (e) from 0.05 to 5% by weight of the at least one compound of formula (V), and wherein a sum of all components (a) to (e) is 100% by weight.

13. The coolant composition according to claim 1, having a conductivity of not more than 30 μS/cm.

14. A method for producing a coolant composition having a conductivity of not more than 50 μS/cm, the method comprising: admixing at least one antifreeze concentrate with water, wherein the antifreeze concentrate comprises: at least one alkylene glycol or derivative thereof, one or more five-membered heterocyclic compounds, which are azole derivatives, and which have 2 or 3 heteroatoms selected from the group consisting of nitrogen and sulfur, and comprise no or at most one sulfur atom and can bear an aromatic or saturated six-membered fused-on ring, at least one compound of formula (V): ##STR00008## wherein R.sup.1 is an organic radical having from 7 to 21 carbon atoms, n is a positive integer from 10 to 60, and each X.sub.i for i=1 to n is selected independently from the group consisting of —CH.sub.2—CH.sub.2—O—, —CH.sub.2—CH(CH.sub.3)—O—, —CH(CH.sub.3)—CH.sub.2—O—, —CH.sub.2—C(CH.sub.3).sub.2—O—, —C(CH.sub.3).sub.2—CH.sub.2—O—, —CH.sub.2—CH(C.sub.2H.sub.5)—O—, —CH(C.sub.2H.sub.5)—CH.sub.2—O—, —CH(CH.sub.3)—CH(CH.sub.3)—O—, —CH.sub.2—CH.sub.2—CH.sub.2—O—, and —CH.sub.2—CH.sub.2—CH.sub.2—CH.sub.2O—; and optionally, at least one ortho-silicic ester.

15. A coolant composition produced according to the method of claim 14, wherein the structural element R.sup.1—COO— in the formula (V) is derived from an acid selected from the group consisting of 2-ethylhexanoic acid, octanoic acid (caprylic acid), pelargonic acid (nonanoic acid), 2-propylheptanoic acid, decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, palmitic acid (hexadecanoic acid), palmitoleic acid [(9Z)-hexadec-9-enoic acid], margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), oleic acid [(9Z)-octadec-9-enoic acid], elaidic acid [(9E)-octadec-9-enoic acid], linoleic acid [(9Z,12Z)-octadeca-9,12-dienoic acid], linolenic acid [(9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid], eleostearic acid [(9Z,11E,13E)-octadeca-9,11,13-trienoic acid], ricinoleic acid ((R)-12-hydroxy-(Z)-octadec-9-enoic acid), isoricinoleic acid [(S)-9-hydroxy-(Z)-octadec-12-enoic acid], nonadecanoic acid, arachidic acid (eicosanoic acid), behenic acid (docosanoic acid), and erucic acid [(13Z)-docos-13-enoic acid].

16. A coolant composition produced according to the method of claim 14, wherein the structural element R.sup.1—COO— in the formula (V) originates from a fatty acid mixture originating from a work-up of linseed oil, coconut oil, palm kernel oil, palm oil, soy oil, peanut oil, cocoa butter, shea butter, cottonseed oil, maize oil, sunflower oil, rapeseed oil, or castor oil.

17. A coolant composition produced according to the method of claim 14, wherein the coolant composition consists essentially of: (a) from 10 to 90% by weight of the at least one alkylene glycol or derivative thereof; (b) from 90 to 10% by weight of the ion free water; (c) from 0.005 to 5% by weight of the one or more azole derivatives; (d) optionally, at least one ortho-silicic ester, and (e) from 0.05 to 5% by weight of the at least one compound of formula (V); and wherein a sum of all components (a) to (e) is 100% by weight.

18. A method, comprising: reducing nonferrous metal corrosion by operating a cooling system with a coolant composition having a conductivity of not more than 50 μS/cm in a fuel cell and/or battery, the coolant composition comprising at least one antifreeze concentrate comprising: at least one alkylene glycol or derivative thereof, one or more five-membered heterocyclic compounds, which are azole derivatives, and which have 2 or 3 heteroatoms selected from the group consisting of nitrogen and sulfur, and comprise no or at most one sulfur atom and can bear an aromatic or saturated six-membered fused-on ring, ion free water, and at least one compound of formula (V): ##STR00009## wherein R.sup.1 is an organic radical having from 7 to 21 carbon atoms, n is a positive integer from 10 to 60, and each X.sub.i for i=1 to n is selected independently from the group consisting of —CH.sub.2—CH.sub.2—O—, —CH.sub.2—CH(CH.sub.3)—O—, —CH(CH.sub.3)—CH.sub.2—O—, —CH.sub.2—C(CH.sub.3).sub.2—O—, —C(CH.sub.3).sub.2—CH.sub.2—O—, —CH.sub.2—CH(C.sub.2H.sub.5)—O—, —CH(C.sub.2H.sub.5)—CH.sub.2—O—, —CH(CH.sub.3)—CH(CH.sub.3)—O—, —CH.sub.2—CH.sub.2—CH.sub.2—O—, and —CH.sub.2—CH.sub.2—CH.sub.2—CH.sub.2O—.

19. A method, comprising: reducing foam formation in a coolant composition by formulating a coolant composition with at least one compound of formula (V); ##STR00010## wherein R.sup.1 is an organic radical having from 7 to 21 carbon atoms, n is a positive integer from 10 to 60, and each X.sub.i for i=1 to n is selected independently from the group consisting of —CH.sub.2—CH.sub.2—O—, —CH.sub.2—CH(CH.sub.3)—O—, —CH(CH.sub.3)—CH.sub.2—O—, —CH.sub.2—C(CH.sub.3).sub.2—O—, —C(CH.sub.3).sub.2—CH.sub.2—O—, —CH.sub.2—CH(C.sub.2H.sub.5)—O—, —CH(C.sub.2H.sub.5)—CH.sub.2—O—, —CH(CH.sub.3)—CH(CH.sub.3)—O—, —CH.sub.2—CH.sub.2—CH.sub.2—O—, and —CH.sub.2—CH.sub.2—CH.sub.2—CH.sub.2O—.

Description

EXAMPLES

(1) The invention is illustrated in the following examples, but without it being restricted thereto.

(2) The test solutions were tested in accordance with the test method ASTM D1384 with the modification that the aqueous dilution with ASTM water to 33% of volume, which is usual in accordance with ASTM D1384, is omitted. Instead, the test fluid (about 50% strength by volume solution with distilled water) was tested without further dilution since a battery coolant has to have a low electrical conductivity of about 20 μS/cm, but ASTM D1384 water has a high electrical conductivity (caused by the corrosion accelerators in the form of various cations and anions).

(3) Compositions of the Test Fluids

(4) TABLE-US-00001 Starting materials Fluid 1 Fluid 2 Fluid 3 Fluid 4 Fluid 5 Fluid 6 Monoethylene glycol 50.0 50.0 50.0 50.0 50.0 50.0 Water 49.8 49.8 49.8 49.8 49.8 49.8 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 To this were added Castor oil ethoxylate 0.25 0.2 (hydrogenated) with 60 EO Caprylamine ethoxylate 0.03 0.03 0.047 0.042 0.038 0.037 with 2 EO Castor oil ethoxylate with 0.2 0.2 40 EO Castor oil ethoxylate with 0.05 0.2 20 EO EO: Ethylene oxide units

(5) The comparison of the base composition composed of monoethylene glycol, water, benzotriazole and tetraethoxysilane without further additives led to very severe corrosion on iron materials within a few hours, associated with an increase in the electrical conductivity to values of greater than 1000 μS/cm.

(6) On the other hand, when the additives were present, the following physical data were obtained in accordance with ASTM D1384 (without aqueous dilution with ASTM water to 33% by volume):

(7) TABLE-US-00002 Fluid 1 Fluid 2 Fluid 3 Fluid 4 Fluid 5 Fluid 6 pH, before test 7.5 7.48 7.00 7.00 7.00 7.00 pH, after test 6.9 6.8 7.44 7.32 7.11 7.04 Alkali reserve of ml of  0.49 0.18 0.39 0.36 0.38 0.35 HCl 0.1 mol/l before test Alkali reserve of ml of 0.1 0.08 0.26 0.27 0.10 0.20 HCl 0.1 mol/l after test Conductivity in μS/cm n.b. 19.5 28.2 25.9 24.0 23.1 before test Conductivity in μS/cm 23.5  24.5 30.8 29.2 27.0 27.1 after test

(8) The following degrees of corrosion were determined in accordance with ASTM D1384 (specific change in mass with corrosion blank mg/cm.sup.2)

(9) TABLE-US-00003 Fluid 1 Fluid 2 Fluid 3 Fluid 4 Fluid 5 Fluid 6 Copper F—CU −0.04 0.06 −0.03 −0.03 −0.10 −0.10 Soft solder L - PbSn30 BASF −0.34 −0.19 −0.10 −0.20 −0.11 −0.11 Brass Ms - 63 −0.13 0.06 −0.10 −0.09 −0.17 −0.17 Steel H - II −0.02 0.02 0.00 0.01 −0.01 −0.01 Grey cast iron GG - 25 −0.56 0.03 −0.33 0.02 0.01 0.01 Cast aluminum G - AlSi6Cu4 0.06 0.11 −0.06 0.05 0.05 0.04
Compositions of Further Test Fluids

(10) TABLE-US-00004 Starting Fluid 13 materials Fluid 7 Fluid 8 Fluid 9 Fluid 10 Fluid 11 Fluid 12 (Comparison) Monoethylene 50.0 50.0 50.0 50.0 50.0 50.0 50.0 glycol Water 49.8 49.8 49.8 49.8 49.8 49.8 49.8 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added Compound 1* 0.25 — — 0.2 — — — Compound 2** 0.03 0.03 0.04 0.042 0.038 0.037 — Compound 3*** — 0.2 — — 0.2 — — Compound 4**** — 0.05 — — — 0.2 — *Compound 1: commercial, on statistical average 60-fold ethoxylated octadecanoic acid **Compound 2: commercial, double ethoxylated n-octylamine ***Compound 3: commercial, on statistical average 40-fold ethoxylated octadecanoic acid ****Compound 4: commercial, on statistical average 20-fold ethoxylated C.sub.18-carboxylic acid, mixture of saturated and unsaturated carboxylic acids

(11) When the additives were present the following physical data were obtained in accordance with ASTM 01384 (without aqueous dilution with ASTM water to 33% by volume):

(12) TABLE-US-00005 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 13 7 8 9 10 11 12 (Comparison) pH, before test 6.57 6.61 6.86 6.87 6.82 6.86 4.85 pH, after test 6.11 6.05 6.45 6.35 6.26 6.19 3.76 Alkali reserve of ml of HCl 0.25 0.25 0.23 0.29 0.22 0.26 0 0.1 mol/l before test Alkali reserve of ml of HCl 0 0.13 0.23 0.23 0.15 0.10 0 0.1 mol/l after test Conductivity in μS/cm 21.5 22.0 27.8 26.2 22.9 22.9 0.8 before test Conductivity in μS/cm 23.9 22.2 31.5 28.8 26.8 25.6 23.6 after test

(13) The following degrees of corrosion were determined in accordance with ASTM D1384 (specific change in mass without corrosion blank mg/cm.sup.2)

(14) TABLE-US-00006 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 13 7 8 9 10 11 12 (Comparison) Copper F—CU −0.05 −0.05 −0.05 −0.07 −0.06 −0.07 −0.06 Soft solder L - −0.18 −0.12 −0.12 −0.16 −0.14 −0.06 −0.49 PbSn30 BASF Brass Ms - 63 −0.06 −0.09 −0.06 −0.10 −0.09 −0.09 −0.15 Steel H - II +0.01 ±0.00 −0.01 −0.01 −0.02 ±0.00 −4.16 Grey cast iron −0.04 +0.03 −0.08 +0.02 +0.04 +0.05 −6.18 GG - 25 Cast aluminum +0.09 +0.06 +0.04 +0.11 +0.12 +0.05 +0.20 G - AlSi6Cu4

(15) Compositions of further test fluids with tolutriazole as corrosion inhibitor

(16) TABLE-US-00007 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 20 Starting materials 14 15 16 17 18 19 (Comparison) Monoethylene glycol 50.0 50.0 50.0 50.0 50.0 50.0 50.0 Water 49.8 49.8 49.8 49.8 49.8 49.8 49.8 Tolutriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added Compound 1 0.25 — — 0.2 — — — Compound 2 0.03 0.03 0.04 0.042 0.038 0.037 — Compound 3 — 0.2 — — 0.2 — — Compound 4 — 0.05 — — — 0.2 —

(17) When the additives were present, the following physical data were obtained in accordance with ASTM 01384 (without aqueous dilution with ASTM water to 33% by volume):

(18) TABLE-US-00008 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 20 14 15 16 17 18 19 (Comparison) pH, before test 6.93 6.99 7.18 7.19 7.08 7.07 4.45 pH, after test 6.04 6.62 6.97 6.73 6.76 6.65 3.76 Alkali reserve of ml of 0.24 0.23 0.27 0.26 0.20 0.25 0 HCl 0.1 mol/l before test Alkali reserve of ml of 0.05 0.09 0.21 0.15 0.09 0.08 0 HCl 0.1 mol/l after test Conductivity in μS/cm 17.8 19.0 23.5 23.0 20.8 20.2 0.8 before test Conductivity in μS/cm 23.2 20.7 28.5 30.9 22.9 23.9 21.1 after test

(19) The following degrees of corrosion were determined in accordance with ASTM 01384 (specific change in mass without corrosion blank mg/cm.sup.2)

(20) TABLE-US-00009 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 20 14 15 16 17 18 19 (Comparison) Copper F—CU −0.07 −0.05 −0.07 −0.05 −0.07 −0.07 −0.04 Soft solder L - −0.29 −0.06 −0.09 −0.28 −0.11 −0.05 −0.22 PbSn30 BASF Brass Ms - 63 −0.08 −0.09 −0.07 −0.09 −0.10 −0.12 −0.05 Steel H - II −0.03 −0.01 −0.02 ±0.00 ±0.00 +0.02 −4.02 Grey cast iron −0.15 +0.03 −0.24 −0.93 +0.02 +0.04 −7.12 GG - 25 Cast aluminum +0.05 +0.09 +0.08 +0.08 +0.04 +0.05 +0.13 G - AlSi6Cu4

(21) Further test fluids are listed in Tables 1 to 23.

(22) TABLE-US-00010 TABLE 1 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 37 Starting materials 31 32 33 34 35 36 (Comparison) 1,2-Propylene 50 50 50 50 50 50 50 glycol Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilene 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added Compound 2 0.03 0.03 0.04 0.042 0.038 0.037 — Compound 4 — 0.05 — — — 0.2 — Compound 3 — 0.2 — — 0.2 — — Compound 1 0.25 — — 0.2 — — —

(23) TABLE-US-00011 TABLE 2 Starting materials Fluid 41 Fluid 42 Fluid 43 Fluid 44 Fluid 45 Fluid 46 Fluid 47 1,2-Propylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Triethoxymethylsilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 8-fold ethoxylated 0.3 octylamine 20-fold ethoxylated 0.3 octylamine 40-fold ethoxylated 0.3 octylamine 60-fold ethoxylated 0.3 octylamine 8-fold ethoxylated 0.3 hexylamine 20-fold ethoxylated 0.3 hexylamine 40-fold ethoxylated 0.3 hexylamine Compound 4 0.25 0.25 0.25 0.25 0.25 0.25 025

(24) TABLE-US-00012 TABLE 3 Fluid Fluid Fluid Fluid Fluid Fluid Fluid Starting materials 51 52 53 54 55 56 57 1,2-Propylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Triethoxymethylsilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 8-fold ethoxylated 0.3 octylamine 20-fold ethoxylated 0.3 octylamine 40-fold ethoxylated 0.3 octylamine 60-fold ethoxylated 0.3 octylamine 8-fold ethoxylated 0.3 hexylamine 20-fold ethoxylated 0.3 hexylamine 40-fold ethoxylated 0.3 hexylamine Compound 3 0.25 0.25 0.25 0.25 0.25 0.25 0.25

(25) TABLE-US-00013 TABLE 4 Fluid Fluid Fluid Fluid Fluid Fluid Fluid Starting materials 61 62 63 64 65 66 67 1,2-Propylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Triethoxymethylsilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 8-fold ethoxylated 0.3 octylamine 20-fold ethoxylated 0.3 octylamine 40-fold ethoxylated 0.3 octylamine 60-fold ethoxylated 0.3 octylamine 8-fold ethoxylated 0.3 hexylamine 20-fold ethoxylated 0.3 hexylamine 40-fold ethoxylated 0.3 hexylamine Compound 1 0.25 0.25 0.25 0.25 0.25 0.25 0.25

(26) TABLE-US-00014 TABLE 5 Starting materials Fluid 71 Fluid 72 Fluid 73 Fluid 74 Fluid 75 Fluid 76 1,2-Propylene glycol 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 Diethoxydimethylsilane 0.1 0.1 0.1 0.1 0.1 0.1 To this were added Compound 2 0.03 0.03 0.04 0.042 0.038 0.037 Compound 4 — 0.05 — — — 0.2 Compound 3 — 0.2 — — 0.2 — Compound 1 0.25 — — 0.2 — —

(27) TABLE-US-00015 TABLE 6 Starting materials Fluid 81 Fluid 82 Fluid 83 Fluid 84 Fluid 85 Fluid 86 1,2-Propylene glycol 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 Ethoxytrimethylsilane 0.1 0.1 0.1 0.1 0.1 0.1 To this were added Compound 2 0.03 0.03 0.04 0.042 0.038 0.037 Compound 4 — 0.05 — — — 0.2 Compound 3 — 0.2 — — 0.2 — Compound 1 0.25 — — 0.2 — —

(28) TABLE-US-00016 TABLE 7 Starting materials Fluid 91 Fluid 92 Fluid 93 Fluid 94 Fluid 95 Fluid 96 1,2-Propylene glycol 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 Tetramethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 To this were added Compound 2 0.03 0.03 0.04 0.042 0.038 0.037 Compound 4 — 0.05 — — — 0.2 Compound 3 — 0.2 — — 0.2 — Compound 1 0.25 — — 0.2 — —

(29) TABLE-US-00017 TABLE 8 Starting materials Fluid 101 Fluid 102 Fluid 103 Fluid 104 Fluid 105 Fluid 106 1,2-Propylene glycol 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 Dimethoxydimethylane 0.1 0.1 0.1 0.1 0.1 0.1 To this were added Compound 2 0.03 0.03 0.04 0.042 0.038 0.037 Compound 4 — 0.05 — — — 0.2 Compound 3 — 0.2 — — 0.2 — Compound 1 0.25 — — 0.2 — —

(30) TABLE-US-00018 TABLE 9 Fluid Fluid Fluid Fluid Fluid Fluid Fluid Fluid 118 Starting materials 111 112 113 114 115 116 117 (Comparison) Diethylene glycol 50 50 50 50 50 50 50 50 Water to to to to to to to to 100 100 100 100 100 100 100 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Triethoxymethylsilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 8-fold ethoxylated 0.3 octylamine 20-fold ethoxylated 0.3 octylamine 40-fold ethoxylated 0.3 octylamine 60-fold ethoxylated 0.3 octylamine 8-fold ethoxylated 0.3 hexylamine 20-fold ethoxylated 0.3 hexylamine 40-fold ethoxylated 0.3 hexylamine Compound 3 0.25 0.25 0.25 0.25 0.25 0.25 0.25

(31) TABLE-US-00019 TABLE 10 Fluid Fluid Fluid Fluid Fluid Fluid Fluid Fluid 128 Starting materials 121 122 123 124 125 126 127 (Comparison) Triethylene glycol 50 50 50 50 50 50 50 50 Water to to to to to to to to 100 100 100 100 100 100 100 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Triethoxymethylsilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 8-fold ethoxylated 0.3 octylamine 20-fold ethoxylated 0.3 octylamine 40-fold ethoxylated 0.3 octylamine 60-fold ethoxylated 0.3 octylamine 8-fold ethoxylated 0.3 hexylamine 20-fold ethoxylated 0.3 hexylamine 40-fold ethoxylated 0.3 hexylamine Compound 3 0.25 0.25 0.25 0.25 0.25 0.25 0.25

(32) TABLE-US-00020 TABLE 11 Starting materials Fluid 131 Fluid 132 Fluid 133 Fluid 134 Fluid 135 Fluid 136 1,2-Propylene glycol 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 Tolutriazole 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 To this were added Compound 2 0.03 0.03 0.04 0.042 0.038 0.037 Compound 4 — 0.05 — — — 0.2 Compound 3 — 0.2 — — 0.2 — Compound 1 0.25 — — 0.2 — —

(33) TABLE-US-00021 TABLE 12 Fluid Fluid Fluid Fluid Fluid Fluid Fluid Starting materials 141 142 143 144 145 146 147 1,2-Propylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Tolutriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Triethoxymethylsilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 8-fold ethoxylated 0.3 octylamine 20-fold ethoxylated 0.3 octylamine 40-fold ethoxylated 0.3 octylamine 60-fold ethoxylated 0.3 octylamine 8-fold ethoxylated 0.3 hexylamine 20-fold ethoxylated 0.3 hexylamine 40-fold ethoxylated 0.3 hexylamine Compound 3 0.25 0.25 0.25 0.25 0.25 0.25 0.25

(34) TABLE-US-00022 TABLE 13 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 157 Starting materials 151 152 153 154 155 156 (Comparison) Monoethylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 8-fold ethoxylated 0.03 0.03 0.04 0.042 0.038 0.037 — octylamine Compound 4 — 0.05 — — — 0.2 — Compound 3 — 0.2 — — 0.2 — — Compound 1 0.25 — — 0.2 — — —

(35) TABLE-US-00023 TABLE 14 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 167 Starting materials 161 162 163 164 165 166 (Comparison) Monoethylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 20-fold ethoxylated 0.03 0.03 0.04 0.042 0.038 0.037 — octylamine Compound 4 — 0.05 — — — 0.2 — Compound 3 — 0.2 — — 0.2 — — Compound 1 0.25 — — 0.2 — — —

(36) TABLE-US-00024 TABLE 15 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 177 Starting materials 171 172 173 174 175 176 (Comparison) Monoethylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 40-fold ethoxylated 0.03 0.03 0.04 0.042 0.038 0.037 — octylamine Compound 4 — 0.05 — — — 0.2 — Compound 3 — 0.2 — — 0.2 — — Compound 1 0.25 — — 0.2 — — —

(37) TABLE-US-00025 TABLE 16 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 187 Starting materials 181 182 183 184 185 186 (Comparison) Monoethylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 60-fold ethoxylated 0.03 0.03 0.04 0.042 0.038 0.037 — octylamine Compound 4 — 0.05 — — — 0.2 — Compound 3 — 0.2 — — 0.2 — — Compound 1 0.25 — — 0.2 — — —

(38) TABLE-US-00026 TABLE 17 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 197 Starting materials 191 192 193 194 195 196 (Comparison) Monoethylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 8-fold ethoxylated 0.03 0.03 0.04 0.042 0.038 0.037 — hexylamine Compound 4 — 0.05 — — — 0.2 — Compound 3 — 0.2 — — 0.2 — — Compound 1 0.25 — — 0.2 — — —

(39) TABLE-US-00027 TABLE 18 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 207 Starting materials 201 202 203 204 205 206 (Comparison) Monoethylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 20-fold ethoxylated 0.03 0.03 0.04 0.042 0.038 0.037 — hexylamine Compound 4 — 0.05 — — — 0.2 — Compound 3 — 0.2 — — 0.2 — — Compound 1 0.25 — — 0.2 — — —

(40) TABLE-US-00028 TABLE 19 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 217 Starting materials 211 212 213 214 215 216 (Comparison) Monoethylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 40-fold ethoxylated 0.03 0.03 0.04 0.042 0.038 0.037 — hexylamine Compound 4 — 0.05 — — — 0.2 — Compound 3 — 0.2 — — 0.2 — — Compound 1 0.25 — — 0.2 — — —

(41) TABLE-US-00029 TABLE 20 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 227 Starting materials 221 222 223 224 225 226 (Comparison) Monoethylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 60-fold ethoxylated 0.03 0.03 0.04 0.042 0.038 0.037 — hexylamine Compound 4 — 0.05 — — — 0.2 — Compound 3 — 0.2 — — 0.2 — — Compound 1 0.25 — — 0.2 — — —

(42) TABLE-US-00030 TABLE 21 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 237 Starting materials 231 232 233 234 235 236 (Comparison) Monoethylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 20-fold ethoxylated 0.03 0.03 0.04 0.042 0.038 0.037 — n-octanol Compound 4 — 0.05 — — — 0.2 — Compound 3 — 0.2 — — 0.2 — — Compound 1 0.25 — — 0.2 — — —

(43) TABLE-US-00031 TABLE 22 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 247 Starting materials 241 242 243 244 245 246 (Comparison) Monoethylene glycol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tetraethoxysilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 40-fold ethoxylated 0.03 0.03 0.04 0.042 0.038 0.037 — n-octanol Compound 4 — 0.05 — — — 0.2 — Compound 3 — 0.2 — — 0.2 — — Compound 1 0.25 — — 0.2 — — —

(44) TABLE-US-00032 TABLE 23 Fluid Fiuid Fluid Fluid Fluid Fluid Fluid Starting materials 251 252 253 254 255 256 257 Glycerol 50 50 50 50 50 50 50 Water to 100 to 100 to 100 to 100 to 100 to 100 to 100 Benzotriazole 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Triethoxymethylsilane 0.1 0.1 0.1 0.1 0.1 0.1 0.1 To this were added 8-fold ethoxylated 0.3 octylamine 20-fold ethoxylated 0.3 octylamine 40-fold ethoxylated 0.3 octylamine 60-fold ethoxylated 0.3 octylamine 8-fold ethoxylated 0.3 hexylamine 20-fold ethoxylated 0.3 hexylamine 40-fold ethoxylated 0.3 hexylamine Compound 4 0.25 0.25 0.25 0.25 0.25 0.25 0.25