Stable ethylsilicate polymers and method of making the same

Abstract

Ethylsilicate polymers and a method of making, specifically ethylsilicate polymer binders with reduced levels of regulated volatile organic compounds (VOCs) for use in the coatings industry and casting industry, and more specifically to stable, fast cure ethylsilicate polymer binders with low levels of regulated VOCs.

Claims

1. A method of forming a polyethylsilicate composition, wherein said method comprises: adding an ethanol, an acid and a silica source to a reactor; heating the reactor after said adding; adding an ethylsilicate source to the reactor to initiate a hydrolysis reaction; and adding propylene carbonate to the reactor after the hydrolysis reaction, to obtain said polyethylsilicate composition comprising the polyethylsilicate, 18-80% by weight of SiO.sub.2 based on a total weight of the composition, the acid, ethanol, and propylene carbonate in an amount of up to 30% by weight based on the total weight of the composition, and wherein the ethanol and propylene carbonate in combination form less than 70% by weight, based on the total weight of the composition.

2. The method of claim 1, further comprising adding parachlorobenzotrifluoride to the reactor after the hydrolysis reaction.

3. The method of claim 1, further comprising stripping ethanol from the reactor after the hydrolysis reaction.

4. The method of claim 1, wherein said silica source is a colloidal silica sol.

5. The method of claim 1, further comprising adding a propylene carbonate before said adding of the ethylsilicate source.

6. The method of claim 1, further comprising adding a propylene carbonate during said adding of the ethylsilicate source.

7. The method of claim 1, further comprising adding a polyethylsilicate source.

8. A method of forming a polyethylsilicate composition, said method comprising: adding a silica source and a propylene carbonate to a reactor; and adding an ethylsilicate source to the reactor to initiate a hydrolysis reaction, to obtain said polyethylsilicate composition comprising said polyethylsilicate, 18-50% by weight of SiO.sub.2 based on a total weight of the composition, 0 to 60% by weight of an alcohol based on the total weight of the composition, and a positive amount of up to 40% by weight of propylene carbonate based on the total weight of the composition, and wherein the alcohol and propylene carbonate in combination comprise 5-70% by weight, based on the total weight of the composition.

9. The method of claim 8, further comprising adding tert-butylacetate to the reactor after said hydrolysis reaction.

10. The method of claim 8, further comprising adding additional propylene carbonate after said hydrolysis reaction.

11. The method of claim 8, further comprising: adding a mineral acid to the reactor before said hydrolysis reaction; adding a solvent after said hydrolysis reaction, said solvent being selected from the group consisting of propylene carbonate, tert-butylacetate, and parachlorobenzotrifluoride; and adding a polyethylsilicate after said hydrolysis reaction.

12. A method of forming a polyethylsilicate composition said method comprising: adding ethanol, an acid and a silica source, and propylene carbonate to a reactor; heating the reactor after said adding; and hydrolizing the contents of the reactor, to obtain the polyethylsilicate composition comprising polyethylsilicate, 18-80% by weight of SiO.sub.2 based on a total weight of the composition, an acid, ethanol, and propylene carbonate in an amount of up to 30% by weight based on the total weight of the composition, and wherein the ethanol and propylene carbonate in combination form less than 70% by weight, based on the total weight of the composition.

13. The method of claim 12, wherein said hydrolizing the contents of the reactor further comprises adding water to the reactor.

14. The method of claim 12, wherein said silica source is a polyethylsilicate.

15. The method of claim 11, wherein said solvent is tert-butylacetate.

16. The method of claim 11, wherein said solvent is parachlorobenzotrifluoride.

17. The method of claim 11, wherein said solvent is tert-butylacetate and parachlorobenzotrifluoride.

Description

DETAILED DESCRIPTION

(1) The present invention is directed to ethylsilicate polymers and a method of manufacturing ethylsilicate polymers, specifically ethylsilicate polymer binders with reduced levels of regulated volatile organic compounds (VOCs), and more specifically to stable, fast cure ethylsilicate polymer binders with low levels of regulated VOCs.

(2) The reduced regulated VOC ethylsilicate polymer of the present invention is generally formed by substituting a propylene carbonate, oxsol, tertiary butyl acetate, or combination thereof in place of the dipropylene glycol methyl ether or the methyl amyl ketone. Both dipropylene glycol methyl ether or the methyl amyl ketone are commonly used as solvents and are regulated VOCs, and as such, any of such solvents remaining after production in the ethylsilicate polymer product contribute to the calculated amount of regulated VOCs in the ethylsilicate product. Any reduction in the level of regulated VOCs is beneficial to the users, such as value added manufacturers or end users. The present invention has been found to form a high performance, reduced regulated VOC ethylsilicate polymer, with the option for a faster cure with propylene carbonate, oxsol, tertiary butyl acetate, or combination thereof in place of the dipropylene glycol methyl ether or the methyl amyl ketone.

(3) Because prehydrolyzed ethyl polysilicate binders are typically unstable, it has been found that any variation in the manufacturing process or substitution of chemicals creates an unstable product. Therefore, even after substantial effort to create products having non-regulated solvents, which are in the present invention propylene carbonate, oxsol, tertiary butyl acetate or combination thereof, it was found that simple substitution in place of the dipropylene glycol methyl ether or the methyl amyl ketone solvents in the same amounts and using the same process caused reduced performance characteristics or making a product that was completely unusable to customers. In addition, while traditional ethylsilicate polymer binders may be formed with only MAK, or only DPM, the present invention instead uses propylene carbonate as a solvent. In addition, it has been determined that for best performance characteristics that the polypropylene carbonate should be added before hydrolysis to stabilize the reaction during the hydrolysis by preventing undesirable gelation. It is believed that the reaction is stabilized by adding propylene carbonate as a solvent before hydrolysis stabilizes the reaction during the hydrolysis and prevents undesirable gelation during hydrolysis. While additional propylene carbonate may be added after hydrolysis, it has also been found that for the best performance characteristic in high stability for ethylsilicate binders used as primers and other materials, as described below, after hydrolysis a solvent such as oxsol or tertiary butyl acetate, or combination thereof be used, which provides additional stabilization of the material. However, it has been found that for ethylsilicate polymers and binders used in investment casting, tertiary butyl acetate does not perform well and oxsol is too expensive and slow to set up, such that any additional solvent added after hydrolysis is a different low VOC solvent or more propylene carbonate. By using the combination of propylene carbonate before hydrolysis and at least one of oxsol or tertiary butyl acetate after hydrolysis, a stable prehydrolyzed ethyl polysilicate binder with high-performance characteristics and as described below, surprisingly improved drying times may be formed.

(4) As described below in Table 1, the prehydrolyzed ethyl polysilicates from broadly 10-80% by weight. However, in the castings field, binders typically have a broad range of 20-80% by weight, and in the field of primers a broad range of 30%-75%. The preferred ranges for castings is 50-70% by weight prehydrolyzed ethyl polysilicates, and in the primers field 25-80% by weight prehydrolyzed ethyl polysilicates. The product VOCs by weight are 45-80% broadly, with castings field using products having product VOCs with 50-75% by weight, and preferred 55-75%, and in the primers field, products having product VOCs with 50-75% by weight, typically 55-70% by weight and 50-60% by weight. The product may include non-exempt or regulated solvents of Methyl Amyl Ketone (MAK); and 0-25%, preferable 5-20% and more preferably 10-15%; Dipropylene Glycol Methyl Ether (DPM) 0-20%, preferable 5-15%, and more preferably 5-10%, all references by weight percent of the total product. In addition, the above list of MAK, DPM and the like are examples and are not all of the regulated solvents currently used in making ethylsilicate polymers. As all of these are chemicals that are regulated for release of VOCs, the increase in regulated VOCs may be clearly seen. While some binder have been used in the industry with 10-20% by weight VOCs, these binders are very high in SiO.sub.2 content and are very expensive. In addition, the VOCs are regulated VOCs, and these existing low VOC binders have very limited uses with the SiO.sub.2 content. For example, these low VOC binders are not able to be used with refractories, because there is not enough viscosity and therefore does not do well in the castings field or primers field, and they do not have a long shelf life and are hard to blend without gelling, as it is so highly hydrolyzed given the high SiO.sub.2 content. To summarize, they are unstable, gel and are not able to be used in the field, and their primary use is to be a base binder that is diluted with ethanol or other alcohols or regulated solvents before being shipped to the customer for use. Therefore, while these binders exist, they are not useable in the industry as is, and when shipped have a VOC content after dilution that is typically greater 45% by weight.

(5) TABLE-US-00001 TABLE 1 Ranges Broad Narrow Preferred % % % Prehydrolyzed ethyl 20-80 25-45 30-42 polysilicates Wt. % Product VOC Wt % 45-80 50-75 55-75 (Total Non-Exempt Solvents Wt % including ethanol and other alcohols) Specific Gravity  .900-1.200  .940-1.150  .990-1.100 SiO.sub.2 Wt. % 18-50 20-40 25-35 Acidity Wt. % .01-.50 .15-.35 .20-.30 % Hydrolyzed 55-90 60-85 65-80

(6) As described below in Table 2, the resulting prehydrolyzed ethylsilicate product may include by weight percent of the resulting product 20-50%, preferably 25-45% and more preferable 30-42%; ethanol and other alcohols at the time of shipment of 0-60%, preferable 25-50% and more preferably 30-40% by weight of the total product at the time of shipment (for the castings industry 10-60% (due to the high ethanol content or other solvent required when working with refractories), preferably 25-50% and more preferably 30-40% by weight of the product at time of shipment) (for the primers/coatings industry 0-40%, preferably 10-30%, and 15-20% by weight of the product at time of shipment); exempt or non-regulated solvents (VOCs not regulated) which may include Propylene Carbonate (PC) 0-30%, 0-25% typical, preferable 5-15% and more preferably 5-10% by weight of the product at time of shipment; Tert-Butyl Acetate (TBA) 0-30%, 0-25% typical, preferable 5-15% and more preferably 8-15%; Parachlorobenzotriflouride (PCBTF)—also known as Oxsol 100) 0-30%, 0-25% typical, preferable 5-15, and more preferably 8-15%; or at least one of the above, or a combination of at least two of the above, forming a total of exempt or non-regulated solvents of 5-40%, preferable 10-25% and more preferably 16-23% by weight at the time of shipment. In addition, the product at the time of shipment will include 18-50%, preferable 20-40%, and more preferable 25-35% of silica (SiO.sub.2) by weight. Other components of the prehydrolyzed ethyl polysilicate product, as prepared, generally include a mineral or organic acid, and in some binders colloidal silica occurring in 0-20%, preferable 5-15%, and more preferably 7-11% by weight at the time of shipment.

(7) It is expected that a reduction of at least 5-10%, preferably 10-25% and more preferable 20-45% of regulated VOCs will occur in the final prehydrolyzed ethyl polysilicate product of the present invention. In addition, the prevent invention is capable of reducing the regulated or non-exempt VOCs to 0% by weight of the overall product at the time of shipment. However, in the castings industry, the regulated or non-exempt VOCs is expected to have a minimum of 15%, more likely 20% by weight of the final product at the time of shipment, due to casting binders having a higher amount of VOCs in the prior art products, and in addition, some of the non-exempt solvents are not able to be used in the castings industry. For example, TAB is not able to be used in castings industry as it does not have the desired performance characteristics. In addition, the coatings or primers industry has traditionally had lower regulated amounts of allowed VOCs than the castings industry, so the binders used in the castings industry were already improved with lower VOC levels, however due to regulations from governmental industries, it is expected that a greater reduction is required in VOC levels in the future. The present invention may in certain circumstances use regulated or non-exempt solvents, such as MAK, DPM or the like 0-10%, preferably 0-5% and more preferably 0-3% by weight of the product at the time of shipment, to meet certain performance characteristics. However, these binders typically previously had 50% or more of these regulated solvents, and as such, the amount has been reduced by typically a factor of 10 or more, which is a huge reduction in such regulated VOCs.

(8) TABLE-US-00002 TABLE 2 Ranges Broad Narrow Preferred % % % Prehydrolyzed ethyl 20-60  25-45  30-42  polysilicates Wt. % Product VOC Wt % 20-55  30-50  32-40  Specific Gravity .900-1.200 .940-1.150 .990-1.100 SiO.sub.2 Wt. % 18-50  20-40  25-35  Acidity Wt. % .01-.50  .15-.35  .20-.30  % Hydrolyzed 55-90  60-85  65-80  Total Non-Exempt Solvents Wt. % 0-60 0-50 0-40 (including ethanol and other alcohols) Ethanol and other alcohols Wt % 0-60 0-50 0-40 Total Exempt Solvents Wt. % 5-40 10-25  16-23  Reduced VOC Prehydrolyzed ethyl polysilicate Products Propylene Carbonate (PC) 0-30 5-15 5-10 Tert-Butyl Acetate (TBA) 0-30 5-15 8-15 Parachlorobenzotrifluoride (PCBTF) 0-30 5-15 8-15 (Oxsol 100)

(9) A list of examples follows in various tables. These examples have been found to have acceptable performance characteristics, and as identified below, some of the examples were found not to be acceptable. In addition, 2-amino 2-methyl 1-proponal may also be used as a solvent, by itself, or in combination with the other identified solvents. It can be put in before, during or after hydrolysis. Of course, the desired performance characteristics may vary depending on the desired application. For example, the LV4 and LV5 formulations in Tables 18 and 19 are very desirable for use in the casting industry. In comparison, the LV1-LV3 formulations in Tables 3-6 as examples 1-10 and LV3.1 in Tables 18 and 19 are very useful as binders for zinc oxide primers in the coatings industry. The specific example number is provided in the left column of the relevant tables, and specific examples may occur in multiple tables. Table 3 provides exemplary input weights, and Table 4 provides the same information by weight percent. The examples 11 and 21 in the tables is labeled as “standard” because it is a typical industry ethylsilicate polymer binder used with primers. The tables also include references to Silbond HT-28A, Silbond HT-33, Silbond HT-21.5PM, Silbond HT-25, and Silbond HT-30, with information regarding the silicon dioxide levels and product VOC levels, for comparison, as these are existing binders that use DPM, MAK or a combination thereof, and in the event that DPM or MAK is not used, such as in HT-21.5PM, H-25, and HT-30, very high levels of ethanol are used, such as five to eleven times as much ethanol as compared to the HT-28A and HT-33 binders that use DPM and MAK. It should be noted that binders do exist that do not include MAK and DPM, however such binders have very high levels of ethanol, which is a regulated VOC, and as such are not reduced, low level or exempt VOCs binders. Therefore, the invention is not simply directed to the removal of DPM and MAK, but also a binder that uses low levels of ethanol in addition to not use (or using minor amounts) of DPM and MAK.

(10) In Tables 3 and 4, the amount hydrolyzed, the percentage of VOC (by weight percent) and the amount of SiO.sub.2 by weight percent as well as the atmospheric-aged shelf life stability of the product are shown. The same examples are then carried forward into Tables 5 and 6, which provide the final product formulations for the examples that go through the process. It should be noted that Examples 1-5 include no MAK or DPM, while Example 6 includes reduced amounts of MAK and no DPM, which as stated above is regulated for release of VOCs. Examples 7-10 include DPM, which as stated above is regulated for release of VOCs, but no MAK. Example 10 has reduced amounts of DPM and no MAK. Example 11 is an exemplary standard prior art batch input, including full amounts of MAK and DPM. As seen in Tables 3-6, Example 11 includes by weight 50.5% chemicals that are regulated for VOC levels, however the amount of regulated VOC levels may fall as low as 35% in the Examples in Tables 3-6. In the later tables with the LV4 and LV5 formulations or variations thereof, the ethanol amounts in the product may be minimized also creating low VOC binders.

(11) In Tables 3-6, the column headers mean the following: Colloidal Sol means 50% sodium silicate dispersion; Sulfuric Acid means 93% technical grade sulfuric acid; DPM means dipropylene glycol methyl ether (non-exempt solvent); MAK means methyl amyl ketone (non-exempt solvent); PC means propylene carbonate (exempt solvent); PCBTF means parachlorobenzotrifluoride (exempt solvent); TBA means tert-butylacetate (exempt solvent); Hydrolysis means a process used to react ethylsilicates with water; SiO.sub.2 means theoretical silica dioxide content as a percent by weight. As seen in Tables 5 and 6, the final product for all examples included about 31-34% by weight of SiO.sub.2 and was 65.4% hydrolyzed.

(12) TABLE-US-00003 TABLE 3 Low VOC LV-3 Batch Formulations by Weight Composition Dipro- Para- pylene Pro- chloro- Ethyl Glycol Methyl pylene benzo- tert Sili- Col- Sul- Methyl Amyl Car- trifluoride Butyl Atmos- cates loidal furic Ether Ketone bonate (PCBTF) Acetate Hydrol- Product pheric Blend Sol Acid (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO.sub.2 VOC Stability Binder (g) (g) (g (g) (g) (g) (g) (g) % (wt. %) (wt. %) (months) 1 LV-3 PC- 2728.5 537.6 10.6 569.0 65.4 33.56 35.8 3.0 PC 2 LV-3 PC- 2728.5 537.6 10.6 179.8 389.2 65.4 33.56 35.8 3.0 OX 3 LV-3 PC- 2728.5 537.6 10.6 179.8 389.2 65.4 33.56 35.8 3.0 TBA 4 LV-3 tBA- 2728.5 537.6 10.6 359.6 389.2 65.4 32.06 34.2 4.5 double PC 5 LV-3 PC- 2728.5 537.6 10.6 123.8 396.0 65.4 34.43 36.7 2.5 TBA mod. molar 6 LV-3 PC- 2728.5 537.6 10.6 97.3 179.8 291.9 65.4 33.56 38.3 4.5 TBA-MAK 7 LV-3 DPM- 2728.5 537.6 10.6 179.8 389.2 65.4 33.56 40.4 11.5 TBA 8 LV-3 DPM- 2728.5 537.6 10.6 179.8 389.2 65.4 33.56 40.4 7.0 OX 9 LV-3 DPM- 2728.5 537.6 10.6 179.8 389.2 65.4 33.56 40.4 4.5 PC 10 LV-3 PC- 2728.5 537.6 10.6 79.8 279.8 389.2 65.4 31.83 35.9 na TBA-DPM 11 3 Standard 2728.5 537.6 10.6 179.8 389.8 65.4 33.56 50.5 6.0+

(13) TABLE-US-00004 TABLE 4 Low VOC LV-3 Batch Formulations Percent Composition Dipro- Para- pylene Pro- chloro- Ethyl Glycol Methyl pylene benzo- Tertiary Sili- Col- Sul- Methyl Amyl Car- trifluoride Butyl Atmos- cates loidal furic ether Ketone bonate (PCBTF) Acetate Hydrol- SiO.sub.2 Product pheric Blend Sol Acid (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis Wt. VOC Stability Binder (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) % (wt. %) (wt. %) (months) 1 LV-3 PC- 70.96 13.98 0.28 14.80 65.4 33.56 35.8 3.0 PC 2 LV-3 PC- 70.96 13.98 0.28 4.68 10.12 65.4 33.56 35.8 3.0 OX 3 LV-3 PC- 70.96 13.98 0.28 4.68 10.12 65.4 33.56 35.8 3.0 TBA 4 LV-3 tBA- 67.78 13.35 0.26 8.93 9.67 65.4 32.06 34.2 4.5 double PC 5 LV-3 PC- 72.78 14.34 0.28 4.80 7.79 65.4 34.43 36.7 2.5 TBA mod. molar 6 LV-3 PC- 70.96 13.98 0.28 2.53 4.68 7.59 65.4 33.56 38.3 4.5 TBA-MAK 7 LV-3 DPM- 70.96 13.98 0.28 4.68 10.12 65.4 33.56 40.4 11.5 TBA 8 LV-3 DPM- 70.96 13.98 0.28 4.68 10.12 65.4 33.56 40.4 7.0 OX 9 LV-3 DPM- 70.96 13.98 0.28 4.68 10.12 65.4 33.56 40.4 4.5 PC 10 LV-3 PC- 67.28 13.26 0.26 1.97 7.63 9.60 65.4 31.83 35.9 na TBA-DPM 11 3 Standard 70.96 13.98 0.28 4.68 10.12 65.4 33.56 50.5 6.0+

(14) TABLE-US-00005 TABLE 5 Low VOC LV-3 Final Product Formulations by Weight Composition Dipro- Para- pylene Pro- chloro- Glycol Methyl pylene benzotri- Tertiary Poly- Col- Sul- Methyl Amyl Car- fluoride Butyl Atmos- sili- loidal furic Ethanol Ether Ketone bonate (PCBTF) Acetate Hydrol- Product pheric cates Silica Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO.sub.2 VOC Stability Binder (g) (g) (g) (g) (g) (g) (g) (g) (g) % (wt. %) (wt. %) (months) 1 LV-3 PC- 1622.6 268.8 10.6 1374.7 569.0 65.4 33.56 35.7 3.0 PC 2 LV-3 PC- 1622.6 268.8 10.6 1374.7 179.8 389.2 65.4 33.56 35.7 3.0 OX 3 LV-3 PC- 1622.6 268.8 10.6 1374.7 179.8 389.2 65.4 33.56 35.7 3.0 TBA 4 LV-3 tBA- 1622.6 268.8 10.6 1374.7 359.6 389.2 65.4 32.06 34.2 4.5 double PC 5 LV-3 PC- 1622.6 268.8 10.6 1374.7 123.8 396.0 65.4 34.00 36.2 2.5 TBA mod. molar 6 LV-3 PC- 1622.6 268.8 10.6 1374.7 97.3 179.8 291.9 65.4 33.56 38.3 4.5 TBA-MAK 7 LV-3 DPM- 1622.6 268.8 10.6 1374.7 179.8 389.2 65.4 33.56 40.4 11.5 TBA 8 LV-3 DPM- 1622.6 268.8 10.6 1374.7 179.8 389.2 65.4 33.56 40.4 7.0 OX 9 LV-3 DPM- 1622.6 268.8 10.6 1374.7 179.8 389.2 65.4 33.56 40.4 4.5 PC 10 LV-3 PC- 1622.6 268.8 10.6 1374.7 79.8 309.4 389.2 65.4 31.83 35.9 na TBA-DPM 11 3 Standard 1622.6 268.8 10.6 1374.7 179.8 389.2 65.4 33.56 50.5 6.0+

(15) TABLE-US-00006 TABLE 6 Low VOC LV-3 Final Product Formulations Percent Composition Dipro- Para- pylene Pro- chloro- Glycol Methyl pylene benzotri- Tertiary Poly- Col- Sul- Methyl Amyl Car- fluoride Butyl Atmos- sili- loidal furic Ethanol Ether Ketone bonate (PCBTF) Acetate Hydrol- SiO.sub.2 Product pheric cates Silica Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis Wt. VOC Stability Binder (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) % (wt. %) (wt. %) (months) 1 LV-3 PC- 42.19 6.99 0.28 35.75 14.79 65.4 33.56 35.7 3.0 PC 2 LV-3 PC- 42.19 6.99 0.28 35.75 4.68 10.12 65.4 33.56 35.7 3.0 OX 3 LV-3 PC- 42.19 6.99 0.28 35.75 4.68 10.12 65.4 33.56 35.7 3.0 TBA 4 LV-3 tBA- 40.31 6.68 0.26 34.15 8.93 9.67 65.4 32.06 34.2 4.5 double PC 5 LV-3 PC- 42.47 7.08 0.28 36.21 3.26 10.43 65.4 34.00 36.2 2.5 TBA mod. molar 6 LV-3 PC- 42.19 6.99 0.28 35.75 2.53 4.68 7.59 65.4 33.56 38.3 4.5 TBA-MAK 7 LV-3 DPM- 42.19 6.99 0.28 35.75 4.68 10.12 65.4 33.56 40.4 11.5 TBA 8 LV-3 DPM- 42.19 6.99 0.28 35.75 4.68 10.12 65.4 33.56 40.4 7.0 OX 9 LV-3 DPM- 42.19 6.99 0.28 35.75 4.68 10.12 65.4 33.56 40.4 4.5 PC 10 LV-3 PC- 40.02 6.63 0.26 33.90 1.97 7.63 9.60 65.4 31.83 35.9 na TBA-DPM 11 3 Standard 42.19 6.99 0.28 35.75 4.68 10.12 65.4 33.56 50.5 6.0+

(16) As an example of a different amount of hydrolysis and SiO.sub.2, Tables 7-10 are included below. As may be seen from the Tables, the solvents used correlate, such that Example 1 is similar to Example 12, and so on. For ease of reference a prior art Example 21 is included having both DPM and MAK. As may be seen in Tables 7-10, an additional step of stripping off the ethanol and other alcohols occurs, which does not occur with the Examples 1-10 in Tables 3-6. Any inclusion of “na” in the table means that the data is not available, such as a study of the atmospheric stability was not completed or is in process, and should not be taken as meaning not acceptable.

(17) TABLE-US-00007 TABLE 7 Low VOC LV-2 Batch Formulations by Weight Composition Dipro- Para- pylene Pro- chloro- Glycol Methyl pylene benzotri- tert Ethyl Col- Sul- Methyl Amyl Car- fluoride Butyl Stable Sili- loidal furic Ethanol Ether Ketone bonate (PCBTF) Acetate Hydrol- EtOH Product Atmos- cates Sol Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO.sub.2 Strip VOC pheric Binder (g) (g) (g) (g) (g) (g) (g) (g) (g) % (wt. %) (g) (wt. %) (months) 12 LV-2 2xTBA 2093 584.6 7.8 800 515.0 80.7 32.97 1282 37.3 2.5 13 LV-2 2xOX 2093 584.6 7.8 800 515.0 80.7 32.97 1282 37.3 4.5 14 LV-2 2xPC 2093 584.6 7.8 800 515.0 80.7 32.97 1282 37.3 2.5 15 LV-2 PC-TBA 2093 584.6 7.8 800 154.3 360.7 80.7 32.97 1282 37.3 4.0 16 LV-2 PC-OX 2093 584.6 7.8 800 154.3 360.7 80.7 32.97 1282 35.3 4.0 17 LV-2 2xPC- 2093 584.6 7.8 800 308.6 360.7 80.7 31.20 1282 35.3 4.0 TBA 18 LV-2 PC-MAK 2093 548.6 7.8 800 389.2 154.3 80.7 31.80 1282 51.0  9.0+ 19 LV-2 2xPC- 2093 584.6 7.8 800 100.0 308.6 260.7 80.7 31.20 1282 38.7 na TBA-MAK 20 LV-2 2xPC- 2093 584.6 7.8 800 125.0 308.5 360.7 80.7 29.89 1282 38.0 na TBA-DPM 21 2 Standard 2093 584.6 7.8 800 154.3 360.7 80.7 32.97 1282 56.2  6.0+

(18) TABLE-US-00008 TABLE 8 Low VOC LV-2 Batch Formulations Percent Composition Dipro- Para- pylene Pro- chloro- Ethyl Col- Sul- Glycol Methyl pylene benzotri- Tertiary Sili- loidal furic Methyl Amyl Car- fluoride Butyl Hy- Stable cates Sol Acid Ethanol Ether Ketone bonate (PCBTF) Acetate drol- EtOH Product Atmos- (wt. (wt. (wt. (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO.sub.2 Strip VOC pheric Binder %) %) %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) % (wt. %) (g) (wt. %) (months) 12 LV-2 52.32 14.61 0.19 20.00 12.87 80.7 32.97 1282 37.3 2.5 2xTBA 13 LV-2 52.32 14.61 0.19 20.00 12.87 80.7 32.97 1282 37.3 4.5 2xOX 14 LV-2 52.32 14.61 0.19 20.00 12.87 80.7 32.97 1282 37.3 2.5 2xPC 15 LV-2 PC- 52.32 14.61 0.19 20.00 3.86 9.02 80.7 32.97 1282 37.3 4.0 TBA 16 LV-2 PC- 52.32 14.61 0.19 20.00 3.86 9.02 80.7 32.97 1282 37.3 4.0 OX 17 LV-2 50.38 14.07 0.19 19.26 7.43 8.68 80.7 31.20 1282 35.3 4.0 2xPC-TBA 18 LV-2 PC- 51.95 14.51 0.19 19.86 9.66 3.83 80.7 32.63 1282 51.0  9.0+ MAK 19 LV-2 2xPC- 50.38 14.07 0.19 19.26 2.41 7.43 6.27 80.7 31.20 1282 38.7 na TBA-MAK 20 LV-2 2xPC- 48.91 13.66 0.18 18.69 2.92 7.21 8.43 80.7 29.89 1282 38.0 na TBA-DPM 21 2 Standard 52.32 14.61 0.19 20.00 3.86 9.02 80.7 32.97 1282 56.2  6.0+

(19) TABLE-US-00009 TABLE 9 Low VOC LV-2 Final Formulations by Weight Composition Dipro- Para- pylene Pro- chloro- Glycol Methyl pylene benzotri- tert Poly- Col- Sul- Methyl Amyl Car- fluoride Butyl Stable sili- loidal furic Ethanol Ether Ketone bonate (PCBTF) Acetate Hydrol- Product Atmos- cates Silica Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO.sub.2 VOC pheric Binder (g) (g) (g) (g) (g) (g) (g) (g) (g) % (wt. %) (wt. %) (months) 12 LV-2 890.4 292.3 7.8 1012.9 515.0 80.7 32.97 37.3 2.5 2xTBA 13 LV-2 890.4 292.3 7.8 1012.9 515.0 80.7 32.97 37.3 4.5 2xOX 14 LV-2 890.4 292.3 7.8 1012.9 515.0 80.7 32.97 37.3 2.5 2xPC 15 LV-2 PC- 890.4 292.3 7.8 1012.9 154.3 360.7 80.7 32.97 37.3 4.0 TBA 16 LV-2 PC- 890.4 292.3 7.8 1012.9 154.3 360.7 80.7 32.97 37.3 4.0 OX 17 LV-2 890.4 292.3 7.8 1012.9 308.6 360.7 80.7 31.20 35.3 4.0 2xPC-TBA 18 LV-2 PC- 890.4 292.3 7.8 1012.9 389.2 154.3 80.7 32.62 51.0  9.0+ MAK 19 LV-2 2xPC- 890.4 292.3 7.8 1012.9 100.0 308.6 260.7 80.7 31.20 38.7 na TBA-MAK 20 LV-2 2xPC- 890.4 292.3 7.8 1012.9 125.0 308.6 360.7 80.7 29.89 38.0 na TBA-DPM 21 2 Standard 890.4 292.3 7.8 1012.9 154.3 360.7 80.7 32.97 56.2  6.0+

(20) TABLE-US-00010 TABLE 10 Low VOC LV-2 Final Product Formulations Percent Composition Dipro- Para- pylene Pro- chloro- Glycol Methyl pylene benzotri- tert Poly- Col- Sul- Methyl Amyl Car- fluoride Butyl Stable sili- loidal furic Ethanol Ether Ketone bonate (PCBTF) Acetate Hydrol- Product Atmos- cates Silica Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO.sub.2 VOC pheric Binder (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) % (wt. %) (wt. %) (months) 12 LV-2 32.75 10.75 0.29 37.26 18.94 80.7 32.97 37.3 2.5 2xTBA 13 LV-2 32.75 10.75 0.29 37.26 18.94 80.7 32.97 37.3 4.5 2xOX 14 LV-2 32.75 10.75 0.29 37.26 18.94 80.7 32.97 37.3 2.5 2xPC 15 LV-2 PC- 32.75 10.75 0.29 37.26 5.68 13.27 80.7 32.97 37.3 4.0 TBA 16 LV-2 PC- 32.75 10.75 0.29 37.26 5.68 13.27 80.7 32.97 37.3 4.0 OX 17 LV-2 31.00 10.18 0.27 35.26 10.74 12.56 80.7 31.20 35.3 4.0 2xPC-TBA 18 LV-2 PC- 32.41 10.64 0.28 36.87 14.17 5.62 80.7 32.62 51.0 9.0+ MAK 19 LV-2 2xPC- 31.00 10.18 0.27 35.26 3.48 10.74 9.08 80.7 31.20 38.7 na TBA-MAK 20 LV-2 2xPC- 29.70 9.75 0.26 33.79 4.17 10.29 12.03 80.7 29.89 38.0 na TBA-DPM 21 2 Standard 32.75 10.75 0.29 37.26 5.68 13.27 80.7 32.97 56.2 6.0+
As stated above, the ethylsilicate polymer may be a binder used in inorganic zinc rich primers. For an exemplary product using the binder of the present invention, lower regulated VOC levels are achievable, while maintaining desired performance characteristics. As provided below, normal cure primers, which typically means a cure time in excess of twelve hours and more likely closer to twenty-four hours, have various test data regarding the performance characteristics in Table 11 below. Examples 12-17 have been included from Tables 7-10, as well as the control sample of a standard binder not using the present invention, which was Example 21. In addition, new Examples 22-25 are included where Example 22 is similar to Example 13, but the PCBTF (refers to the OX in the chart) is a single, not double amount, Example 23 is similar to Example 14, but includes half of the PC, Example 24 is similar to Example 12, but includes half of the TBA of Example 12, and Example 25 is different form the other examples, as it uses a combination of PCBTF and TBA as replacement solvents. Example 25 has a specific makeup due to the fact no exempt solvent is added to the reaction after hydrolysis and before stripping, the PCBTF and TBA are added after the ethanol strip. As seen in Table 11, Example 21 is the control sample of one exemplary prior binder, as discussed above, and with the exception of the binder in Example 22 (at the top of Table 11), the performance characteristics are similar to the control samples of Example 21 after 48 hours of cure time. The rub test is generally an industry standard solvent resistance rub test, such as ASTM D4752 or NCCA11-18, used to determine the degree of cure of a thin (not baked) film by the coating film resistance to a specified solvent. In the rub test used in Table 11, the solvent is methyl ethyl ketone (MEK) and a cheesecloth is cloaked in MEK and stroked across the surface for a specified stroke distance, rate and pressure. In Table 11, a test standard of fifty double rubs were used for the number of strokes. Similarly, the cross hatch test is a standard test method for measuring adhesion by tape test, where a cross hatch patter is made through an applied film to a substrate and pressure sensitive tape is applied over the area of incisions. The tape is then removed rapidly, such as specified in ASTM D 3359. Similarly, the pencil hardness test is a commonly used industry test similar to a scratch test, where harder and harder pencils are used until the coating is scratched, with the softest pencil lead scratching the surface being the hardness. Therefore, the 6H refers to the hardness of the pencil lead and is the maximum pencil hardness used in the test method.

(21) TABLE-US-00011 TABLE 11 LV-2 Normal Cure Time Paint Trials Low VOC Stable Binders Trial Trial Trial Trial Trial Trial # 2 # 2 # 2 # 1 # 1 # 1 Gel Calc. 50 Rub Pencil Cross 50 Rub Pencil Cross Analysis SiO.sub.2 Time Product MEK Test Hatch MEK Test Hatch Binder Date of Trial Number Page # Wt. % (sec) VOC % (24 hrs) (24 hrs) (24 hrs) (48 hrs) (48 hrs) (48 hrs) 12 LV-2 OX Mar. 6, 2013 158150 B42P31 33.2 209 31.5 13 6H 2-3 13 LV-2 2xOX Apr. 9, 2013 158995 B42P37 32.9 124 37.3 50 6H 4 50 6H 3 23 XHT-28LV- Mar. 20, 2013 158452 B42P35 32.2 67 31.5 48 6H 4-5 PC 14 LV-2 2xPC Apr. 3, 2013 158827 B42P36 33.1 44 37.3 50 6H 3 50 6H 5 24 LV-2 TBA Mar. 20, 2013 158492 B42P35 31.9 68 31.5 50 6H 4 50 6H 4-5 12 LV-2 Apr. 12, 2013 159064 B42P38 33.0 42 37.3 50 H 1-2 2xTBA 16 LV-2 PC-OX Apr. 15, 2013 159146 B42P40 31.7 59 37.3 50 6H 4 50 6H 3-4 17 LV-2 PC-OX Mar. 22, 2013 158495 B44P29 31.9 61 37.3 50 6H 4 50 6H 5 25 LV-2 OX- Mar. 22, 2013 158494 B44P29 32.0 58 37.3 50 6H 4 50 6H 3-4 TBA 15 LV-2 PC- Mar. 22, 2013 158496 B44P29 32.0 60 37.3 50 6H 1-2 TBA 21 Control Mar. 22, 2013 158856 32.8 47 56.2 50 6H 3-4 46 6H 5 # 1 Standard 2 21 Control Mar. 22, 2013 158856 32.8 47 56.2 50 6H 3 # 2-1 Standard 2 21 Control Mar. 22, 2013 158856 32.8 47 56.2 50 6H 3 # 2-2 Standard 2 Pass MEK Rub Test 50 Cross Hatch 3B-5B Pencil Test 4H-6H

(22) Certain of the examples were surprisingly found to have a fast cure time, faster than the control sample. As illustrated in Table 12, the fast cure time binders, Examples 15, 16 and 18, which are also found in Tables 7-10, had similar performance, with Example 15 even at six hours showing what required at least twice as long for the control sample in Example 21. Out-performing the control sample.

(23) TABLE-US-00012 TABLE 12 Fast Cure Paint Trials LV-2 and Standard 2 Solvent Rub Pencil Cross Combination Trial Date Analysis # Test Test Hatch 6 Hour Test Data 18 LV-2 PC/MAK Jan. 17, 2014 5 3H 2B 16 LV-2 PC/OX Jan. 17, 2014 4 4H 2B 15 LV-2 PC/TBA Jan. 17, 2014 50 6H 5B 21 Standard 2 Jan. 17, 2014 163267 9 5H 4B 12 Hour Test Data 18 LV-2 PC/MAK Jan. 17, 2014 33 6H 4B 16 LV-2 PC/OX Jan. 17, 2014 5 5H 3B 15 LV-2 PC/TBA Jan. 17, 2014 50 6H 5B 21 Standard 2 Jan. 17, 2014 163267 50 6H 4B Rub Pencil Cross Trial Date Analysis # Test Test Hatch 8 Hour Test Data Jan. 17, 2014 9 4H 4B Jan. 17, 2014 5 6H 3B Jan. 17, 2014 50 6H 5B Jan. 17, 2014 163267 11 5H 4B 24 Hour Test Data Jan. 18, 2014 50 6H 5B Jan. 18, 2014 24 6H 4B Jan. 18, 2014 50 6H 5B Jan. 18, 2014 163267 50 6H 5B Pass MEK Rub Test 50 Cross Hatch 3B-5B Pencil Test 4H-6H Fast Cure less than 12 hours

(24) Tables 13-17 also show variations of the LV-3 batches, which are provided as Examples 1-10 plus control sample in Example 11 in Tables 3 and 4. The examples are numbered in Tables 13-17 and are sufficient to show that they meet the desired performance characteristics relative to the control sample. In addition, six tests were performed on different runs of the sample examples to provide a wide range of data. The LV-3 batches with PC/TBA samples 3-5 demonstrate fully cured at 6 hours vs 12 and 24 hour fully cured for the Standard 3 control, sample 11.

(25) TABLE-US-00013 TABLE 13 LV-3 Paint Trials Comparison 4 Hour Cure Test Data Solvent Rub Pencil Cross Combination Trial Date Analysis # Test Test Hatch 1 LV-3 PC/PC Sep. 2, 2013 162054 17 4B 2B 1 LV-3 PC/PC Sep. 10, 2013 162054 6 6B 0B 1 LV-3 PC/PC Sep. 30, 2013 162054 3 4B 3B 1 LV-3 PC/PC Oct. 1, 2013 162054 13 4B 3B 1 LV-3 PC/PC Oct. 2, 2013 162054 11  F 3B 1 LV-3 PC/PC Oct. 17, 2013 162054 6 4B 4B 2 LV-3 PC/OX Sep. 2, 2013 162055 34 6H 4B 2 LV-3 PC/OX Sep. 10, 2013 162055 6 2H 4B 2 LV-3 PC/OX Sep. 30, 2013 162055 4 2H 3B 2 LV-3 PC/OX Oct. 1, 2013 162055 19 5H 5B 2 LV-3 PC/OX Oct. 2, 2013 162055 50 6H 5B 2 LV-3 PC/OX Oct. 17, 2013 162055 9 HB 3B 3 LV-3 PC/TBA Sep. 2, 2013 162389 16 5H 4B 3 LV-3 PC/TBA Sep. 10, 2013 162389 26 6H 4B 3 LV-3 PC/TBA Sep. 30, 2013 162389 12 6H 5B 3 LV-3 PC/TBA Oct. 1, 2013 162389 50 6H 5B 3 LV-3 PC/TBA Oct. 2, 2013 162389 24 5H 5B 3 LV-3 PC/TBA Oct. 17, 2013 162389 50 6H 5B 3 LV-3 PC/TBA 4 LV-3 2xPC/TBA 5 LV-3 PC/TBA Inc Acid 11 3 Standard Sep. 2, 2013 160974 32 6H 3B Control 11 3 Standard Sep. 10, 2013 160974 6 2H 2B Control 11 3 Standard Sep. 30, 2013 160974 3 6B 2B Control 11 3 Standard Oct. 1, 2013 160974 11  B 2B Control 11 3 Standard Oct. 2, 2013 160974 20  F 4B Control 11 3 Standard Oct. 17, 2013 160974 4 3B 3B Control 11 3 Standard na na na na na Control

(26) TABLE-US-00014 TABLE 14 LV-3 Paint Trials Comparison 6 Hour Cure Test Data Solvent Rub Pencil Cross Combination Trial Date Analysis # Test Test Hatch 1 LV-3 PC/PC Sep. 2, 2013 162054 50 4H 3B 1 LV-3 PC/PC Sep. 10, 2013 162054 4 4B 2B 1 LV-3 PC/PC Sep. 30, 2013 162054 7 2B 3B 1 LV-3 PC/PC Oct. 1, 2013 162054 12 3H 4B 1 LV-3 PC/PC Oct. 2, 2013 162054 16 6H 5B 1 LV-3 PC/PC Oct. 17, 2013 162054 9 2H 4B 2 LV-3 PC/OX Sep. 2, 2013 162055 34 6H 5B 2 LV-3 PC/OX Sep. 10, 2013 162055 8 5H 4B 2 LV-3 PC/OX Sep. 30, 2013 162055 5 5H 4B 2 LV-3 PC/OX Oct. 1, 2013 162055 32 6H 4B 2 LV-3 PC/OX Oct. 2, 2013 162055 50 6H 5B 2 LV-3 PC/OX Oct. 17, 2013 162055 12  H 5B 3 LV-3 PC/ Sep. 2, 2013 162389 37 6H 4B TBA 3 LV-3 PC/ Sep. 10, 2013 162389 48 6H 4B TBA 3 LV-3 PC/ Sep. 30, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Oct. 1, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Oct. 2, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Oct. 17, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Jan. 17, 2014 164338 50 6H 5B TBA 4 LV-3 Jan. 17, 2014 1300490 27 4H 5B 2xPC/TBA 5 LV-3 PC/ Jan. 17, 2014 1300308 50 6H 5B TBA Inc Acid 11 3 Standard Sep. 2, 2013 160974 42 6H 4B Control 11 3 Standard Sep. 10, 2013 160974 10 6H 5B Control 11 3 Standard Sep. 30, 2013 160974 5 3B 3B Control 11 3 Standard Oct. 1, 2013 160974 39 5H 4B Control 11 3 Standard Oct. 2, 2013 160974 25 4H 5B Control 11 3 Standard Oct. 17, 2013 160974 7 HB 3B Control 11 3 Standard Jan. 17, 2014 131902251 4 2B 1B Control

(27) TABLE-US-00015 TABLE 15 LV-3 Paint Trials Comparison 8 Hour Cure Test Data Solvent Rub Pencil Cross Combination Trial Date Analysis # Test Test Hatch 1 LV-3 PC/PC Sep. 2, 2013 162054 ND ND ND 1 LV-3 PC/PC Sep. 10, 2013 162054 12  B 2B 1 LV-3 PC/PC Sep. 30, 2013 162054  4  B 4B 1 LV-3 PC/PC Oct. 1, 2013 162054 13 2H 4B 1 LV-3 PC/PC Oct. 2, 2013 162054 32 6H 5B 1 LV-3 PC/PC Oct. 17, 2013 162054  5 6H 4B 2 LV-3 PC/OX Sep. 2, 2013 162055 ND ND ND 2 LV-3 PC/OX Sep. 10, 2013 162055 26 5H 5B 2 LV-3 PC/OX Sep. 30, 2013 162055  9 6H 4B 2 LV-3 PC/OX Oct. 1, 2013 162055 41 6H 5B 2 LV-3 PC/OX Oct. 2, 2013 162055 50 6H 5B 2 LV-3 PC/OX Oct. 17, 2013 162055  6 6H 5B 3 LV-3 PC/ Sep. 2, 2013 162389 ND ND ND TBA 3 LV-3 PC/ Sep. 10, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Sep. 30, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Oct. 1, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Oct. 2, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Oct. 17, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Jan. 17, 2014 164338 50 6H 5B TBA 4 LV-3 Jan. 17, 2014 1300490 50 4H 5B 2xPC/TBA 5 LV-3 PC/ Jan. 17, 2014 1300308 50 6H 5B TBA Inc Acid 11 3 Standard Sep. 2, 2013 160974 ND ND ND Control 11 3 Standard Sep. 10, 2013 160974 50 6H 5B Control 11 3 Standard Sep. 30, 2013 160974  5 HB 3B Control 11 3 Standard Oct. 1, 2013 160974 50 6H 4B Control 11 3 Standard Oct. 2, 2013 160974 12 6H 5B Control 11 3 Standard Oct. 17, 2013 160974  8 5H 4B Control 11 3 Standard Jan. 17, 2014 131902251  4 HB 2B Control

(28) TABLE-US-00016 TABLE 16 LV-3 Paint Trials Comparison 12 Hour Cure Test Data Solvent Rub Pencil Cross Combination Trial Date Analysis # Test Test Hatch 1 LV-3 PC/PC Sep. 2, 2013 162054 50 6H 5B 1 LV-3 PC/PC Sep. 10, 2013 162054 7 3H 2B 1 LV-3 PC/PC Sep. 30, 2013 162054 16 6H 4B 1 LV-3 PC/PC Oct. 1, 2013 162054 18 3H 4B 1 LV-3 PC/PC Oct. 2, 2013 162054 40 6H 5B 1 LV-3 PC/PC Oct. 17, 2013 162054 17 6H 4B 2 LV-3 PC/OX Sep. 2, 2013 162055 50 6H 5B 2 LV-3 PC/OX Sep. 10, 2013 162055 19 6H 4B 2 LV-3 PC/OX Sep. 30, 2013 162055 22 4H 4B 2 LV-3 PC/OX Oct. 1, 2013 162055 50 6H 5B 2 LV-3 PC/OX Oct. 2, 2013 162055 50 6H 5B 2 LV-3 PC/OX Oct. 17, 2013 162055 34 6H 5B 3 LV-3 PC/ Sep. 2, 2013 162389 50 6H 4B TBA 3 LV-3 PC/ Sep. 10, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Sep. 30, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Oct. 1, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Oct. 2, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Oct. 17, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Jan. 17, 2014 164338 50 6H 5B TBA 4 LV-3 Jan. 17, 2014 1300490 50 4H 5B 2xPC/TBA 5 LV-3 PC/ Jan. 17, 2014 1300308 50 6H 5B TBA Inc Acid 11 3 Standard Sep. 2, 2013 160974 50 5H 4B Control 11 3 Standard Sep. 10, 2013 160974 50 6H 5B Control 11 3 Standard Sep. 30, 2013 160974 27 6H 4B Control 11 3 Standard Oct. 1, 2013 160974 50 6H 5B Control 11 3 Standard Oct. 2, 2013 160974 50 6H 5B Control 11 3 Standard Oct. 17, 2013 160974 22 6H 4B Control 11 3 Standard Jan. 17, 2014 131902251 23 2H 3B Control

(29) TABLE-US-00017 TABLE 17 LV-3 Paint Trials Comparison 24 Hour Cure Test Data Solvent Rub Pencil Cross Combination Trial Date Analysis # Test Test Hatch 1 LV-3 PC/PC Sep. 2, 2013 162054 50 6H 5B 1 LV-3 PC/PC Sep. 10, 2013 162054 50 6H 5B 1 LV-3 PC/PC Sep. 30, 2013 162054 50 6H 5B 1 LV-3 PC/PC Oct. 1, 2013 162054 50 6H 5B 1 LV-3 PC/PC Oct. 2, 2013 162054 50 6H 5B 1 LV-3 PC/PC Oct. 17, 2013 162054 50 6H 5B 2 LV-3 PC/OX Sep. 2, 2013 162055 50 6H 5B 2 LV-3 PC/OX Sep. 10, 2013 162055 50 6H 5B 2 LV-3 PC/OX Sep. 30, 2013 162055 50 6H 5B 2 LV-3 PC/OX Oct. 1, 2013 162055 50 6H 5B 2 LV-3 PC/OX Oct. 2, 2013 162055 50 6H 5B 2 LV-3 PC/OX Oct. 17, 2013 162055 50 6H 5B 3 LV-3 PC/ Sep. 2, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Sep. 10, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Sep. 30, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Oct. 1, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Oct. 2, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Oct. 2, 2013 162389 50 6H 5B TBA 3 LV-3 PC/ Jan. 18, 2014 164338 50 6H 5B TBA 4 LV-3 Jan. 18, 2014 1300490 50 6H 5B 2xPC/TBA 5 LV-3 PC/ Jan. 18, 2014 1300308 50 6H 5B TBA Inc Acid 11 3 Standard Sep. 2, 2013 160974 50 6H 5B Control 11 3 Standard Sep. 10, 2013 160974 50 6H 5B Control 11 3 Standard Sep. 30, 2013 160974 50 6H 5B Control 11 3 Standard Oct. 1, 2013 160974 50 6H 5B Control 11 3 Standard Oct. 2, 2013 160974 50 6H 5B Control 11 3 Standard Oct. 17, 2013 160974 50 6H 5B Control 11 3 Standard Jan. 17, 2014 131902251 50 6H 4B Control Pass MEK Rub Test 50 Cross Hatch 3B-5B Pencil Test 4H-6H Note: Fast Cure is less than 12 hours Standard cure is 12 to 24 hours

(30) TABLE-US-00018 TABLE 18 Dipro- Para- pylene Pro- chloro- Glycol Methyl pylene benzotri- tert Poly- Col- Sul- Methyl Amyl Car- fluoride Butyl Stable sili- loidal furic Ethanol Ether Ketone bonate (PCBTF) Acetate Hydrol- Product Atmos- cates Silica Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO.sub.2 VOC pheric Binder (g) (g) (g) (g) (g) (g) (g) (g) (g) % (wt. %) (wt. %) (months) LV-4 PC 1043.1 235.4 9.4 2215.1 397 67.6 20.92 56.8 na LV-5 PC 2495.0 0 3.6 1333.7 200 86.0 24.12 52.2 na LV-5 PC 2495.0 0 3.6 666.8 200 86 28.67 43.1 na ½Ethanol LV-3.1 6160.0 1400.0 24.0 5440.0 1500 1500 67.9 30.20 33.9 na (Theoretical)

(31) TABLE-US-00019 TABLE 19 Dipro- Para- pylene Pro- chloro- Glycol Methyl pylene benzotri- tert Poly- Col- Sul- Methyl Amyl Car- fluoride Butyl Stable sili- loidal furic Ethanol Ether Ketone bonate (PCBTF) Acetate Hydrol- Product Atmos- cates Silica Acid (EtOH) (DPM) (MAK) (PC) Oxsol 100 (TBA) ysis SiO.sub.2 VOC pheric Binder (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) % (wt. %) (wt. %) (months) LV-4 PC 26.75 6.04 0.24 56.80 10.18 0.00 67.6 20.92 56.8 na LV-5 PC 43.00 0 0.09 52.18 4.76 0.00 86 24.12 52.2 na LV-5 PC 51.09 0.1 43.15 5.66 28.67 43.1 na ½Ethanol LV-3.1 38.44 8.74 0.15 33.95 9.36 9.36 67.9 30.20 33.9 na (Theoretical)

(32) TABLE-US-00020 TABLE 20 Product Stable SiO.sub.2. VOC Atmospheric Binder .sub.(wt. %) (wt. %) (months) Silbond HT-28A 32.97 56.2 6.0+ Silbond HT-33 33.56 50.5 6.0+ Silbond HT-21.5PM 20.08 74.4 6.0+ Silbond H-25 25.32 54.8 6.0+ Silbond HT-30 30.2 52.7 6.0+

(33) As described above, the ethylsilicate composition in Tables 18 and 19 are specifically configured for the casting industry, although they could be used in the coatings industry, and the LV3.1 is applicable to both industries. The compositions have been found to provide faster set-up times and create a harder ceramic material in the investment casting process. It should be noted that in all the tables, the column identified as Product VOC, is the amount of regulated VOCs, the total VOCs may be higher. In regards to Table 20, these are existing binders made by Silbond, and the amount of regulated VOCs, amount of silica and stability may be seen for comparison. While the casting binders in Tables 18-19 have higher regulated VOCs than some of the other binders, casting binders have always had higher regulated VOCs, and the new compositions are substantially reduced as compared to the prior art.

(34) The procedure for making the binders generally includes charging ethanol and sulfuric acid, if desired colloidal silica sol, heating the reactor, an ethylsilicate is added to the reactor, which is the hydrolysis reaction, additional heat may be applied to the reactor, if desired ethanol is stripped from the reactor, then the reactor is cooled, charge at least one of the exempt solvents and or a non-exempt to the reactor, mix and then package.

(35) More specifically, Example 16 from Tables 7-10 may be formed as follows. First, charge 800.0 g of ethanol and 7.8 g of sulfuric acid in the reactor and mix for 20 minutes. Then Charge 584.6 g of colloidal silica sol to the reactor (colloidal silica sol is 50% sodium silicate dispersion) and heat reactor to 40 degrees C. Meter in slowly 2093 g of ethylsilicates via a dip tube. This is the hydrolysis reaction, which in this formulation produces 1494.9 g of ethanol. Heat to 78 degrees C. and reflux for sixty minutes. If desired, strip ethanol from the reactor, in this example 1282 g of ethanol stripped which is 55% of total ethanol after the hydrolysis. The reactor is then cooled for thirty minutes after which 360.7 g of PCBT (Oxsol 100) is added to the reactor, along with 154.3 g of PC (Propylene Carbonate). The PCBT and PC are mixed in for 30 minutes and the final product is packaged as desired.

(36) In the above example, 1494.9 g of ethanol is produced during hydrolysis.

(37) More specifically, Example 3 from Tables 3-6 may be formed as follows. First, charge 537.6 g of colloidal silica sol to the reactor (colloidal silica sol is 50% sodium silicate dispersion) and 10.6 g of sulfuric acid in the reactor and immediately charge 179.8 g of PC (Propylene Carbonate) to the reactor. Start full cooling on the reactor. Meter in 917.4 g of ethylsilicates via a dip tube. This is the hydrolysis reaction, which in this formulation produces 1374.7 g of ethanol. Add 1313.5 g of ethylsilicates to the reactor. Add 497.6 g of ethylsilicates to the reactor. Allow contents to mix for one hour and adjust reactor temperature to 30-50 degree C. After one hour, add 389.2 g of TBA (tert butyl acetate) is added to the reactor. Mix for 30 minutes and maintain reactor of 30-40 degree C. The final product is packaged as desired. The added ethylsilicates may vary with different polyethylsilicates, and have different amounts of hydrolysis when added.

(38) In the above example, 1374.7 g of ethanol is produced during hydrolysis.

(39) The procedure for making the LV-5 PC, with half the normal Ethanol is as follows. First, charge 666.8 g of ethanol to reactor, add 3.6 g of sulfuric acid to the reactor, add 2495 g of polysilicates to the reactor, and add 200 g of PC (Propylene Carbonate) to the reactor. Heat reactor to 25-45° C., preferably 30-40° C. Hydrolyze into the reactor mixture 167.7 g of water dropwise using an addition funnel. After the water addition is completed, mix for 60 minutes and maintain reactor of 30-40 degree C. After 60 minutes, allow the binder to cure. The final product is packaged as desired. Take a pint sample to the Analytical Lab for analysis. It should be noted for all the above examples, the temperature and times may vary, such as lowering the temperature may just take longer for the method to complete, and increasing the temperature may speed up the method.

(40) While the invention has been described in connection with its preferred embodiments it should be recognized that changes and modifications may be made therein without departing from the scope of appended claims.