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

Abstract

The present invention relates to coolants 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), based on alkylene glycols or derivatives thereof, which comprise 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 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; and at least one of the following compounds of formulae (VI) and/or (VII): ##STR00005## wherein R.sup.2 is an organic radical having from 8 to 22 carbon atoms, R.sup.3 is an organic radical having from 6 to 10 carbon atoms, n is a positive integer from 10 to 60, p and q are each, independently of one another, a positive integer from 1 to 40, and each X.sub.i for i=1 to n, 1 to p and 1 to q 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—.

2. The coolant composition according to claim 1, comprising at least one compound of formula (VI), wherein the structural element R.sup.2—O— in formula (VI) is derived from alcohols selected from the group consisting of octyl alcohol (capryl alcohol), nonyl alcohol (pelargonyl alcohol), decyl alcohol (capric alcohol), undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol, tetradecyl alcohol (myristyl alcohol), pentadecyl alcohol, hexadecyl alcohol (cetyl alcohol, palmityl alcohol), heptadecyl alcohol, octadecyl alcohol (stearyl alcohol), oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenoyl alcohol, nonadecyl alcohol, eicosyl alcohol (arachyl alcohol) and mixtures thereof.

3. The coolant composition according to claim 1, comprising at least one compound of formula (VI), wherein the structural element R.sup.2—O— in formula (VI) is derived from alcohols selected from the group consisting of 2-ethylhexanol, 2-propylheptanol, tridecanol isomer mixtures and heptadecanol isomer mixtures.

4. The coolant composition according to claim 1, comprising at least one compound of formula (VI), wherein the structural element R.sup.2—O— in formula (VI) is derived alkoxylated caster oils.

5. The coolant composition according to claim 1, comprising at least one compound of formula (VII), wherein the structural element R.sup.3—N< in formula (VII) is derived from amines selected from the group consisting of n-hexylamine, 2-methylpentylamine, n-heptylamine, 2-heptylamine, isoheptylamine, 1-methylhexylamine, n-octylamine, 2-ethylhexylamine, 2-aminooctane, 6-methyl-2-heptylamine, n-nonylamine, isononylamine, n-decylamine and 2-propylheptylamine and mixtures thereof.

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

7. The coolant composition according to claim 1, wherein the coolant composition comprises at least one compound of formula (VI) and n in formula (VI) is from 18 to 60, and/or wherein the coolant composition comprises at least one compound of formula (VII) and p and q in formula (VII) are each 1.

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

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

10. 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 of the compounds of formulae (VI) and/or (VII); and wherein the sum of all components (a) to (e) is 100% by weight.

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

12. The coolant composition according to claim 1, further comprising a compound of formula (V): ##STR00006## 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.2—O—.

13. The coolant composition according to claim 12, wherein the structural element R.sup.1—COO— in the formula (V) is derived from acids 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].

14. The coolant composition according to claim 13, wherein the structural element R.sup.1—COO— in the formula (V) originates from fatty acid mixtures originating from the 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.

15. The coolant composition according to claim 12, 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 a combined amount of the compound of formula (V) and the at least one compound of formulae (VI) and/or (VII); and wherein the sum of all components (a) to (e) is 100% by weight.

16. The coolant composition according to claim 1, comprising at least one compound of formula (VII).

17. The coolant composition according to claim 1, comprising at least one compound of formula (VII), wherein R.sup.3 is an alkyl or alkenyl radical having from 6 to 10 carbon atoms.

18. The coolant composition according to claim 1, comprising at least one compound of formula (VII), wherein R.sup.3 is an alkyl radical having from 7 to 9 carbon atoms.

19. The coolant composition according to claim 1, wherein X.sub.i is —CH.sub.2—CH.sub.2—O— and p and q are independently of one another a positive integer from 1 to 30.

20. The coolant composition according to claim 1, comprising at least one compound of formula (VII), wherein the compound of formula (VII) is selected from the group consisting of two-fold ethoxylated n-octylamine, eight-fold ethoxylated n-octylamine, twenty-fold ethoxylated n-octylamine, forty-fold ethoxylated n-octylamine, eight-fold ethoxylated n-hexylamine, twenty-fold ethoxylated n-hexylamine, and forty-fold ethoxylated n-hexylamine.

21. The coolant composition according to claim 1, comprising at least one compound of formula (VII), wherein the compound of formula (VII) is selected from the group consisting of two-fold ethoxylated n-octylamine, eight-fold ethoxylated n-octylamine, twenty-fold ethoxylated n-octylamine, and forty-fold ethoxylated n-octylamine.

22. The coolant composition according to claim 1, comprising at least one compound of formula (VII), wherein the compound of formula (VII) is two-fold ethoxylated n-octylamine.

23. 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 which have 2 or 3 heteroatoms 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, and at least one of the following compounds of formulae (VI) and/or (VII): ##STR00007## wherein R.sup.2 is an organic radical having from 8 to 22 carbon atoms, R.sup.3 is an organic radical having from 6 to 10 carbon atoms, n is a positive integer from 10 to 60, p and q are each, independently of one another, a positive integer from 1 to 40, and each X.sub.i for i=1 to n, 1 to p and 1 to q 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(CHs).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—.

24. The method according to claim 23, wherein the antifreeze concentrate comprises at least one compound of formula (VII).

25. The method according to claim 23, wherein the antifreeze concentrate comprises at least one compound of formula (VII), and wherein R.sup.3 is an alkyl or alkenyl radical having from 6 to 10 carbon atoms.

26. The method according to claim 23, wherein the antifreeze concentrate comprises at least one compound of formula (VII), and wherein R.sup.3 is an alkyl radical having from 7 to 9 carbon atoms.

27. The method according to claim 23, wherein X.sub.i is —CH.sub.2—CH.sub.2—O— and p and q are independently of one another a positive integer from 1 to 30.

28. The method according to claim 23, wherein the antifreeze concentrate comprises at least one compound of formula (VII), and wherein the compound of formula (VII) is selected from the group consisting of two-fold ethoxylated n-octylamine, eight-fold ethoxylated n-octylamine, twenty-fold ethoxylated n-octylamine, forty-fold ethoxylated n-octylammne, eight-fold ethoxylated n-hexylamine, twenty-fold ethoxylated n-hexylamine, and forty-fold ethoxylated n-hexylamine.

29. The method according to claim 23, wherein the antifreeze concentrate comprises at least one compound of formula (VII), and wherein the compound of formula (VII) is selected from the group consisting of two-fold ethoxylated n-octylamine, eight-fold ethoxylated n-octylamine, twenty-fold ethoxylated n-octylamine, and forty-fold ethoxylated n-octylamine.

30. The method according to claim 23, wherein the antifreeze concentrate comprises at least one compound of formula (VII), and wherein the compound of formula (VII) is two-fold ethoxylated n-octylamine.

31. A method, comprising reducing nonferrous metal corrosion using 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 which have 2 or 3 heteroatoms 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 of the following compounds of formulae (VI) and/or (VII): ##STR00008## wherein R.sup.2 is an organic radical having from 8 to 22 carbon atoms, R.sup.3 is an organic radical having from 6 to 10 carbon atoms, n is a positive integer from 10 to 60, p and q are each, independently of one another, a positive integer from 1 to 40, and each X.sub.i for i=1 to n, 1 to p and 1 to q 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 Fluid Fluid Fluid Fluid Fluid Fluid Starting materials 1 2 3 4 5 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

(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 Fluid Fluid Fluid Fluid Fluid 1 2 3 4 5 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 Fluid Fluid Fluid Fluid Fluid 1 2 3 4 5 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

(10) Compositions of Further Test Fluids

(11) TABLE-US-00004 Fluid Fluid Fluid Fluid Fluid Fluid Fluid 13 Starting materials 7 8 9 10 11 12 (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 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

(12) 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):

(13) 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

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

(15) 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

(16) Compositions of Further Test Fluids with Tolutriazole as Corrosion Inhibitor

(17) 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 —

(18) 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):

(19) 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

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

(21) 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

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

(23) 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 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 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 — — —

(24) TABLE-US-00011 TABLE 2 Fluid Fluid Fluid Fluid Fluid Fluid Fluid Starting materials 41 42 43 44 45 46 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 0.25

(25) 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

(26) 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

(27) TABLE-US-00014 TABLE 5 Fluid Fluid Fluid Fluid Fluid Fluid Starting materials 71 72 73 74 75 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 — —

(28) TABLE-US-00015 TABLE 6 Fluid Fluid Fluid Fluid Fluid Fluid Starting materials 81 82 83 84 85 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 — —

(29) TABLE-US-00016 TABLE 7 Fluid Fluid Fluid Fluid Fluid Fluid Starting materials 91 92 93 94 95 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 — —

(30) TABLE-US-00017 TABLE 8 Fluid Fluid Fluid Fluid Fluid Fluid Starting materials 101 102 103 104 105 106 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 Dimethoxydimethylsilane 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 — —

(31) 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 100 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 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-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 100 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 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

(33) TABLE-US-00020 TABLE 11 Fluid Fluid Fluid Fluid Fluid Fluid Starting materials 131 132 133 134 135 136 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 — —

(34) 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

(35) 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 — — —

(36) 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 — — —

(37) 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 — — —

(38) 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 — — —

(39) 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 — — —

(40) 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 — — —

(41) 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 — — —

(42) 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 — — —

(43) 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 — — —

(44) 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 — — —

(45) TABLE-US-00032 TABLE 23 Fluid Fluid 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