Methods of treating surfaces with ionic organosilicon compositions

ION ORGANOSILICIO COMPOSITIONS TO TREAT SURFACES DESCRIPTION

This invention relates to ionic organosllicon compositions for treating surfaces with methods of waterproofing inorganic surfaces. In further pertussis, the present invention is directed to an inorganic surface treated with an aqueous solution containing an ionic organosllicon compound that would allow a water-repellent film to cover the inorganic surface.

Water resistance is an important issue in many types of construction including masonry and concrete. Water resistance is of the utmost importance since the absorption of moisture and its movement in these types of materials causes or contributes to problems such as expansion, contraction, cracking, staining, mold, reduced resistance to freezing and * defrosting, chemical attack, Corrosion steel reinforcement, and damage to structures from sedimentation. Due to these problems, various techniques have been used to make these surfaces hydrophobic, including treatment of surface structures with water repellent. Water repellent that have been used in the past include oils, waxes, soaps and resins. These water repellents have been applied to Surfaces with brushes, rollers, air spray, or airless spray techniques. One type of water repellent that has been used is organosllicon compounds. It has been found that these compounds in organic solvents are useful for providing water resistance to brick, concrete, stucco, or terrazzo surfaces.

It has been known to use organosillcycles as alkyltrialkoxy compounds to confer water resistance for at least 30 years. Traditionally, the application of these compounds was carried out in flammable solvents such as ethanol, methanol and various liquid hydrocarbons. During application, volatile organic compounds (VOCs) were emitted in excess. Due to these problems, significant efforts were made to formulate a non-flammable composition to confer water resistance to masonry and concrete surfaces. The first approach attempted included several water emulsions containing organosllice compounds. However, these formulations failed to provide water resistance compared to solvent based compositions. In recognition of the deficiencies associated with the formulation of water emulsions, formulations were developed to manufacture water-soluble alkyl-trlalcoxl-sllanos. Formulations of this type use water-soluble quaternary ammonium and amino organosilanes together with alkyltrialkoxy silanes of traditional formulations. The purpose of these formulations was to exploit the soluble organosilanes to solubilize the alqull-trlalcoxl-sllanos that provided this water repellent characteristic.

In addition to water resistance, several types of building materials benefit from treatment with an antmlmlblablane. Anti-mlbranols are chemical compositions that prevent microbial contamination and deterioration of materials. Possibly, the group with the highest prevalence of antimyrobials is the quaternary ammonium compounds. The use of low-level quaternary ammonium sllanos (1% or lower) as antichloroblanins is well known. Due to its antlmlcroblanas qualities, its application is beneficial for a number of surfaces, substrates, instruments and applications.

The compositions disclosed in these patents contain (1) alkyl-alkoxylslanes or slloxanes; (2) a water soluble sllano; and (3) amlnosllane or quaternary ammonium silane. The role of soluble silane, amlnosllane or quaternary ammonium ionic silane in these compositions is to stabilize alqull-alkoxy-sllano, slloxane or other water-insoluble polymers.

The use of water-soluble hydrophobic sllanne has traditionally been preferred as a water repellent in various organic solvents such as alcohols and hydrocarbons due to its superior performance. However, the main limitations of these solvent type compositions include their flammability and inherent toxicity. Although they provide an ecological improvement in relation to solvent-based treatments, the emulsions of existing organoslloxane and water-dispersible organoslloxanes or siloxanes do not resist comparison with solvent-based sllano / slloxane, slloxane or sllanne combinations in terms of stability, depth of penetration and pearling effect of the treated substrate. Additionally, the use of surfactants can cause surface rewetting.

Therefore, the need for an aqueous hypermeablllzaclone treatment capable of providing a water resistance at least as efficient as treatments using solvent-based treatments persists. Accordingly, it is an object of the present invention to provide ionic compositions for treating surfaces with an aqueous solution, where the treated surface exhibits a water resistance at least similar to that provided by solvent-based treatments. Additionally, it is an object of this invention to provide the following three highly desirable requirements for providing long-lasting hydrophobicity in inorganic substrates: (1) application of a safer and environmentally acceptable aqueous solution, (2) hydrophobicity transmission at the molecular level and ( 3) reactivity with a substrate to provide long lasting performance.

BRIEF SUMMARY OF THE INVENTION

This invention is directed to ionic organosilicon compositions for treating inorganic surfaces. Surprisingly, it has been found that the application of water-soluble organosilicon ionic compounds, which until the present invention had only been used in small amounts to solubilize silanes, to inorganic surfaces gives the treated surface an excellent hydrophobic property. The present invention satisfies the aforementioned requirements by applying an aqueous solution comprising an ionic organosilicon compound, having an ionic group, a hydrophobic group and at least one silicon alkoxy group.

The present invention exclusively uses ionic organosilicon compounds as the main component or sole component to confer water repellency by treating surfaces of inorganic substrates. The methods of the present invention comprise the application of all aqueous solutions consisting essentially of at least one ionic organosilicon compound on inorganic surfaces thus conferring water resistance to the surface. Although we do not wish to be subject to the following explanation, we believe that when an aqueous ionic organosilicon solution dries, the molecular packing on the surface is such that the ionic group that allows water solubility is buried deep in the structure after the silane forms chemical bonds with the inorganic surface. Accordingly, after application, the treated surface can be characterized as a long-lasting water repellent coating. Thus, there are differences between what is taught in accordance with the concept of the present invention and what is disclosed in the prior art, as demonstrated in the various patents mentioned and the ones raised above.

US Patent 5209775 related to compositions for making water-repellent surfaces describes a composition that requires each of the following components: (i) an alkyltrialkoxysilane, (ii) a silane coupling agent, (il) an amino resin, and (iv) a quaternary silane ammonium. The above provides a co-hydrolysis product of the alqulltrlmethoxlsílanos and a coupling agent, in combination with amino silanes and an amino resin such as thermosetting resin obtained by combining aldehyde and with a compound containing an amino group. Resins plus amino acids are based on the reaction of formaldehyde with urea or melamine. The two most important primary resins are urea-formaldehyde resins and melamine-formaldehyde resins. Since urea and melamine contain two and three aml groups, and they react polyclunclonally with formaldehyde to form three dimensional crosslinked polymers. In addition, the document describes the use of 0-50% more preferably 25% quaternary ammonium silanes, and therefore the composition of the pre-rolled product that is useful to repel water depends clearly.

US 5300327 refers to an aqueous composition that is an emulsion of water-soluble silicone (siloxane) resins, petroleum and synthetic waxes, alkulltrlmethoxlsllanos.

This uses organofunctional quaternary amino silanes to improve the dispersibility of these water insoluble components.

Roth et al., US N ⁰ 4,835,014, provides a general method for imparting water repellency to absorbent inorganic building materials by contacting at least a first part of the surface of building materials that are water repellent, with at least partially liquid water and subsequently, the application of a solution containing an organosilicon compound and a water immiscible organic solvent to the wet surface of inorganic building materials. US N⁰ 4,835,014 teaches a method for imparting water repellency to inorganic building materials by treating the building materials with solutions containing organosilicon compounds and water immiscible organic solvents. In the present invention, no organic solvent is used. The surprising result of the present invention is that in the application of water-soluble ionic organosilicon compounds to inorganic surfaces, said water-soluble ionic organosilicon compounds provide the inorganic surface treated with excellent hydrophobic property. Then an aqueous composition comprising an ionic organosilicon is applied and allowed to dry, the treated inorganic surface is having a water resistant protective layer chemically bonded to the substrate. JP Patent No. 03-242268, does not provide a composition and a method for Inorganic hardened body surface repair. The purpose of the previous document was to eliminate the need for baking in the coating and adhesion by applying a primer composition having a composition specified in the part to be repaired on the surface of an inorganic hardened body having a layer coating based on silicon alkoxide and then applying a cold setting coating. The composition is different from epoxy compound, organosilicon compound with less than 1 mercapto and less than 2 alkoxy groups, titanic ester and an organic solvent to obtain Primer composition. This has nothing to do with a method of testing an inorganic surface to impart water repellent characteristics. In other words, the present invention is different from the composition and method described in JP.

US 5209775 describes compositions that require each of the following components: (I) an alkyltrialkoxysilane, (ii) a silane coupling agent, (iii) an amine resin, and (v) a quaternary silane ammonium. The patent teaches that these compositions can be used to make water repellent surfaces. This document shows the need and use of water insoluble alkyltrialkoxysilanes with aml resins and a silane coupling agent. In particular, the incorporation of an amine polymer as taught herein in the presently claimed compositions would have a negative impact and change the characteristics of the presently claimed invention. US Patent No. 5,300,327 refers to an aqueous composition which is an emulsion of water-insoluble silicone (siloxane) petroleum resins and synthetic waxes, alkyltrimethoxysilanes. The patent uses organofunctional silanes or quaternary amino to improve the dispersibility of these water insoluble components. However, the present composition only uses only ionic silicon organic compounds as the main or single component to impart water repellency to surface treatment of inorganic substrates. The methods of the present invention involve the application of aqueous solutions of at least one ionic compound to an inorganic surface organosilicon thereby imparting water resistance to the inorganic surface.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will now be described in more detail and some embodiments of the invention will be described but not all. Indeed, these inventions can be embodied in different ways and should not be construed as limited to the embodiments raised here; instead, these embodiments are provided so that the disclosure satisfies the applicable legal requirements.

Compositions for surface treatment suitable for use in the present invention are formed by mixing water and an ionic organosilicon compound. The ionic organosilicon compounds according to the present invention include organosilanes having a formula selection from the group consisting of:

<img file="CU23947B1_D0001.tif" />

R_fl

Ys-a to zk / \ /

R

Ra

Ra

S

<img file="CU23947B1_D0002.tif" />

Yes / / \ / Ya / R

Θ

SOj

Yaa formula:

where in each Y is RO where R is an alkyl radical of one to four carbon atoms, (CH₂CH₂OR)_nOH where n has a value of one to ten, (CH3OCH2CH2O), or (CH₃CH₂OCH₂CH₂OR);

a has a value of zero, one and two;

R 'is a methyl or ethyl radical;

R "is an alkylene group with one to four carbon atoms;

R '”, R” ”and R^v they are alkyl groups containing one to twenty two carbon atoms, where at least one of said groups is greater than eight carbon atoms, 7

CH₂C₆H5, -CH₂CH₂OH, -CH₂OH, and - (CH₂)_XNHC (O) R^SAW where x has a value of two to ten and R^SAW it is a perfluoroalkyl radical having one to twelve carbon atoms;

X is chlorine, bromine, fluorine, iodine, acetate or tosylate and

Z is a positively charged aromatic pyridinium ring of formula C₅H₆N⁺

M is Na, K, or Li or H.

In a preferred embodiment, the organosilicon ionic compounds of the formula:

Ra

R

Yes NT / V

3-a

R '

XR^v wherein R is a methyl or ethyl, a has a value of zero, R "is propylene; R '”is methyl or ethyl; R "" and R^v they are alkyl groups containing from one to twenty two where at least one of said groups is greater than eight carbon atoms and X is chlorine, acetate or tosylate, they can be dissolved in water to form an aqueous solution. Aqueous solutions comprising these ionic organosilicon can be applied to inorganic surfaces to confer water resistance.

Specific examples of said organosilicon ionic compounds are within the spectrum of the present invention and are represented by the formulas (CH₃OR)₃Yes (CH₂)₃N⁺(CH3) 2C18H37Cr (CH3O) 3S¡ (CH2) 3N⁺ (CH3)₂C₁₈H₃₇Br (CH₃OR)₃Yes (CH₂)₃N⁺CH3 (Cl0H21) 2Cr (ΟΗ3Ο) 33ί (ΟΗ2) 3Ν⁺ΟΗ3 (Ο10Η₂₁)₂ΒΓ (CH₃OR)₃Yes (CH₂)₃P⁺(C6H5) 3Cr (CH3O) 3S¡ (CH2) 3P⁺(CsH5)₃Br '(CH₃OR)₃Yes (CH₂)₃N⁺(CH3) 2CH2CsH5Cr (CH2CH3O) 3Si (CH2) 3N⁺ (CH3)₂C₁₈H₃₇Cr (CH₃OR)₃Yes (CH₂)₃N⁺(CH₃)₂(CH₂)₃NHC (O) (CF₂)_andCF₃Cr

In an alternative embodiment, the Ionic compounds corresponding to the formulas chloride (trimethoxysilyl) propylmethylloctadecylammonium, organosilicon chloride of 338 i

ί | ί i

| (trlmethoxysilyl) propylmethylidecylammonium and 3 (trimethoxyl) proplldylmethylhexylchloride chloride are especially suitable for aqueous solutions for application to inorganic surfaces according to the

I present invention. The structures for these ionic organosilicon compounds * are as follows:

<img file="CU23947B1_D0003.tif" />

3- (trimethoxysal) propyl dimethylloctadecyl chloride;

<img file="CU23947B1_D0004.tif" />

3- (trimethoxyl) propylmethyldildecylammonium chloride; and

<img file="CU23947B1_D0005.tif" />

3- (trimethoxyl) propylldimethylhexyl ammonium chloride.

The compositions according to the present invention are made by dissolving an Ionic organosilicon in water. Additionally, more than one organosilicon ionic compound can be dissolved in water to formulate an aqueous composition comprising more than one organosilicon ionic compound. In addition, some compositions according to the present invention may also include known excipients such as, for example, wetting agents, surfactants and antimlcrobial agents. The compositions comply with local and federal state regulations related to volatile organic content (VOC) with the desired application dosage and can be applied to a wide variety of surfaces by any known means including for example by brush, roller, air spray and airless spray techniques. After the application of an aqueous composition comprising an ionic organosllicon and allowing it to dry, a treated surface is obtained comprising a protective water resistant layer bonded to the substrate. Although we do not wish to be subject to the following explanation, it is believed that when dried, the molecular packing on the surface is such that the ionic group that allows water solubility is buried deep inside the structure after the sllano forms bonds surface chemicals. In addition, it is believed that the long chain in the central ionic group prohibits water from reaching the soluble ionic part of the molecule. Accordingly, the present invention also provides treated surfaces comprising a single layer in which the soluble components are protected from water by long chains attached to the soluble component.

Any surface can be transformed with functional groups or reactive sites that will bind with the silanols created by hydrolysis of the silane alkoxy groups in water repellent by treatment with aqueous solutions of the present invention. Accordingly, a surface treated in accordance with the present invention can be characterized as a polycondensate of an ionic organosllice compound. Some suitable surfaces include, for example, heavy and light concrete, masonry products, plaster, concrete blocks, slag bricks, dry pressed bricks, scalicocalcarea bricks, drainage pipes, ceramic tiles, sandstone bricks, plaster, clay , natural stones and rocks, tiles, calcium silicate bricks, cement articles, bricks and slag stones and bricks, stucco, limestone, macadam, marble, grout, mortar, terrazzo, cllnker, pumice, brick, porcelain, adobe, coral, dolomite and asphalt. Non-cement surfaces can be treated with compositions of the present invention including, but not limited to, perlite, cell glass, vermicullta, mica, silica and diatomaceous earth.

In one embodiment, the aqueous ionic organosilicon composition may include at least about 0.1 weight percent of an ionic organosilicon compound. Additionally, some embodiments may include between about 0.1 and about 10 percent by weight of an organosilicon ionic compound while others may comprise between 10 and 99 percent by weight or between about 20 and 60 percent by weight of an organosilicon compound.

Example 1

3- [tri- (2-hydroxyethoxy) silyl] propyldimethyloctadecylammonium chloride

A two-liter, three-mouth flask equipped with a condenser, agitator, thermometer and a distillation head was loaded with 360 grams (six moles) of ethylene glycol. To this solution, 200 grams of -3-chloropropylmethoxysilane are added dropwise at 100 ° C over a period of two hours. A mixture is heated for six hours at 100 ° C during which period 101 grams of material are recovered, mainly boiling methanol below 100 ° C. 460 grams of a mixture of crude product were obtained.

The main component of the raw product mixture was (OHCH₂CH₂OR)₃SiCH₂CH (CH₃) CH₂CI:

Ό

<img file="CU23947B1_D0006.tif" />

3-chloropropyl-tri- (2-hydroxy-ethoxy) silane.

In the same configuration reaction, 265 grams (0.9 mol) of octadecyldimethylamine was added to the crude product solution. This mixture was heated at 120 ° C for 20 hours. After 20 hours, the reaction was completed. The titration of a sample of the product mixture showed that the ionic chlorine concentration was 4.35%. The structure of the main component was (OHCHzCHzObSiCHsCHzCHzNCCHahCiehbCI-:

<img file="CU23947B1_D0007.tif" />

/, Ο | βΗ37 α

θ

Chloride 3- [tr¡- (2-h¡drox¡etox¡) silll] prop¡ld¡met¡loctadec¡lamon¡o.

The ionic chlorine concentration calculated for the product mixture was 4.40%. The product was water soluble in all its proportions.

Example 2

A two-liter three-mouth flask equipped with a condenser, stirrer, thermometer and a distillation head with 636 grams (six moles) of diethylene glycol was charged. To this solution, 200 grams of -3-chloroproplltrlmethoxlslane was added dropwise at 100 ° C over a period of two hours. A mixture was heated for six hours at 125 ° C during which period 101 grams of material were recovered, mainly boiling methanol at less than 100 ° C. 735 grams of a mixture of crude product were obtained.

The main component of the raw product mixture was (OHCH₂CH₂OCH₂CH₂OR)₃S¡CH₂CH (CH₃) CH₂CI:

<img file="CU23947B1_D0008.tif" />

In the same reaction configuration, 265 grams (0.9 mol) of octadeclldlmetlamine was added to the crude product solution. This mixture was heated to

120 ° C for 20 hours. After 20 hours, the reaction was completed. The titration of a sample of the product mixture showed that the ionic chlorine concentration was 2.97%. The structure of the main component was (OHCH2CH₂OCH₂CH2O) 3S¡CH2CH₂CH2N (CH3)₂C₁₈H37CI-:

<img file="CU23947B1_D0009.tif" />

The ionic chlorine concentration calculated for the product mixture was 3.2%. The product was water soluble in all its dimensions.

Example 3

3- (Trimethoxysilyl) -2-methylpropyl dimethylctadecylammonium chloride

A two-liter pressure reactor equipped with an agitator and thermometer with 225 grams of -3-chloro-2-metllpropyl-trimethoxyl (1.1 mol), 295 grams of dlmetlloctadecllamlna (1 , 0 mol) and 100 grams of methanol. A mixture was heated for 30 hours at 120 ° C. After 30 hours the reaction was completed. The titration of a sample of the product mixture showed that the ionic chlorine concentration was 5.62%. The structure of the main component was (CH₃OR)₃SICH₂CH (CH₃) CH₂N (CH₃)2 C₁₈H₃₇CI-:

<img file="CU23947B1_D0010.tif" />

3- \ (trlmetoxlsllll) 2-methylproplldimetlloctadecllamonlo chloride.

The ionic chlorine concentration calculated for the product mixture was 5.71%. The product was water soluble in all its dimensions.

Example 4

3- [tri- (2-hydroxyethoxy) silyl] -2-methylpropyl dimethyl octadecylammonium chloride

A two-liter three-mouth flask equipped with a condenser, stirrer, thermometer and a distillation head with 360 grams (six moles) of ethylene glycol was charged. 212 grams of -3-chloro-2-methylpropyl-trimethoxysilane was added dropwise to the solution at 100 ° C over a period of two hours. A mixture was heated for six hours at 100 ° C during which period 101 grams of material were recovered, mainly boiling methanol at less than 100 ° C. 470 grams of the crude product mixture were obtained. The structure of the main transesterified product was (OHCH₂CH₂OR)₃SICH₂CH (CH₃) CH₂CI;

<img file="CU23947B1_D0011.tif" />

3-Chloro-2-methylpropyl-tri- (2-hydroxyl-ethoxy) sllano.

In the same reaction configuration, 265 grams (0.9 mol) of octadecyldimethylamine was added to the crude product solution. A mixture was heated at 120 ° C for 20 hours. After 20 hours, the reaction was completed. The titration of a sample of the product mixture showed that the ionic chlorine concentration was 4.17%. The structure of the main component was (OHCH₂CH₂OR)₃SiCH₂CH (CH₃) CH₂N (CH₃)₂C₁₈H₃₇CI-:

<img file="CU23947B1_D0012.tif" />

h¡droxietox¡) sllil] 14

The ionic chlorine concentration calculated for the product mixture was 4.32%. The product was water soluble in all its dimensions.

Example 5

A two-liter three-mouth flask equipped with a condenser, stirrer, thermometer and a distillation head with 540 grams (six moles) of ethylene glycol monoethyl ether was charged. To this solution, 200 grams of -3-chloropropyltrimethoxysilane was added dropwise at 100 ° C over a period of two hours. A mixture was heated for six hours at 125 ° C, during which period 101 grams of material were recovered, mainly boiling methanol at less than 100 ° C. 735 grams of a mixture of the crude product were obtained.

The main component of the raw product mixture was (CHgCHzOCHiCHzOJsSiCHzCHíCHajCHzCI:

<img file="CU23947B1_D0013.tif" />

3-Chloropropyltri (2-ethoxyethoxy) slano

In the same reaction configuration, 265 grams (0.9 mol) of octadecyldimethylamine was added to the solution of the crude product. This mixture was heated at 120 ° C for 20 hours. After 20 hours the reaction was completed. The titration of a sample of the product mixture showed that the ionic chlorine concentration was 3.45%. The structure of the main component was (CH₂CH₃OCH2CH₂O) 3S¡CH₂CH₂CH₂N (CH3) 2C₁₈H₃₇CI-:

<img file="CU23947B1_D0014.tif" />

3- [tr¡- (2 ethoxletox¡) s¡l¡l] prop¡ld¡met¡loctadec¡lannonium chloride

The ionic chlorine concentration calculated for the product mixture was 3.52%. The product was water soluble in all its dimensions.

Example 6

Multiple aqueous solutions between 0.1 to 5.0 weight percent of 3- (trimethoxysilyl) propylmethyloctaldecylammonium chloride were prepared by dissolving in drinking water. The treated substrates included a piece of a concrete block, a cement board, plaster for walls and sandstone. These materials were weighed and dried in an oven at 100 ° C until they reached a constant weight. The pieces were then weighed and placed in 1 cm of water for 1 hour, weighed again, and dried in an oven at 100 ° C until a constant weight was reached. At that time, the Individual pieces were weighed, soaked in the water-repellent solution for 20 seconds and then dried and finally weighed again. The treated samples were placed in 1 cm of water for 1 hour and weighed. The percentage of water exclusion for each experiment is provided in Table I, where the percentage of water exclusion was calculated as follows:

(collection of untreated substrate water - collection of treated substrate water) X 100 collection of untreated substrate water Table-I: (%) Exclusion of water with different concentrations

<td></td><td colspan="9">Water exclusion (%)</td>

<td>Concentration</td><td> 0,1</td><td> 0,5</td><td> 1,0</td><td> 1,5</td><td> 2,0</td><td> 2,5</td><td> 3,5</td><td> 5,0</td><td rowspan="5"></td>

<td>Concrete block</td><td> 60</td><td> 68</td><td> 72</td><td> 82</td><td> 87</td><td> 89</td><td> 85</td><td> 82</td>

<td>Cement board</td><td> 59</td><td> 67</td><td> 73</td><td> 88</td><td> 87</td><td> 89</td><td> 88</td><td> 83</td>

<td>Wall plaster</td><td> 70</td><td> 73</td><td> 75</td><td> 82</td><td> 86</td><td> 90</td><td> 89</td><td> 83</td>

<td>Sandstone</td><td> 69</td><td> 76</td><td> 78</td><td> 93</td><td> 93</td><td> 92</td><td> 91</td><td> 91</td>

These results show that solutions of 1.5-3.5 percent by weight provide excellent hydrophobicity for most substrates.

Example 7

Standard M20 block samples were used for testing. Standard size bricks were cut into three equal parts for testing. The sandstone pieces were 7-cm X 6-mm X 7-cm. An untreated control was included for comparison and to calculate water exclusion. The samples were cleaned with a wire and cloth brush. The pieces were weighed and dried in an oven at 100 ° C until they reached a constant weight. Water retention was determined by procedures established in accordance with ASTM D-6489. The pieces were weighed and placed in 1-cm of water for 24 hours, weighed again and dried in an oven at 100 ° C until a constant weight was reached. The pieces were then treated with a water repellent as described in Example 6. After impregnation in 1 cm of water for 24 hours, the pieces were weighed again. Water retention, water absorption percentage (water retention X 100 / weight of the dry piece) and% water exclusion were calculated by:

(control water retention - treated sample water retention) X 100 control water retention

A 2.5 percent by weight solution of 3-chloride (trimethoxysilylpropyldimethylloctadecylammonium chloride was prepared by running water solution. Three samples of each substrate were treated by immersion of the sample for 20 seconds. The samples were allowed to cure for 24 hours. additionally in an oven at 100 ° C. for one hour After the removal of the oven, the samples were allowed to reach room temperature before taking measurements. Water retention was determined using ASTM method D6489. The calculated results of the average of the three samples are summarized in Table-ll

Table-ll Water exclusion based on ASTM D6489

<td>Substratum</td><td>% Water exclusion</td>

<td>Concrete block (M20)</td><td> 89</td>

<td>Brick</td><td> 90</td>

<td>Sandstone</td><td> 85</td>

<td>Cement board</td><td> 80</td>

Example 8

Rilem water penetration hydraulic test (Test 11.4)

A 2.5% solution of 3-chloride (trlmethoxlslllljproplldlmetlloctadecllo) was prepared by dissolving in running water. Three samples of each substrate were treated by immersion of the sample in the aqueous solution for 20 seconds. The samples were allowed to cure for 24 hours. they were further dried in an oven at 100 ° C for one hour.The samples were allowed to reach room temperature before taking measurements. A retention tube was fixed to the surface of the substrate by interposing a strip of putty between the circular edge of the tube and the surface of the masonry material with applied pressure. Water was then added to the opening in the tube until it reached the zero graduation mark. The amount of water absorbed by the substrate in 20 minutes is read from the graduation marks on the tube. Data were provided in Table-lll showing the millimeters (ml) lost in 20 minutes.

Tabla-lll Rilem water penetration hydraulic test (Test 11.4)

<td>Substratum</td><td>Loss of untreated water in 20 minutes ml</td><td>Loss of treated water 2.5 % in 20 minutes ml</td>

<td>Concrete block</td><td> 8,0</td><td> 0,2</td>

<td>(M20)</td><td></td><td></td>

<td>Brick</td><td> 40</td><td> 0,2</td>

<td>Sandstone</td><td> 20</td><td> 0,1</td>

<td>Cement board</td><td> 10</td><td> 0,3</td>

F!

Η ¡i Example 9

Penetration depth

A 2.5% solution of 3 (trimethoxysilyl) propylmethylloctadeclam chloride was prepared by dissolving in water. He

Li treated three samples of each substrate by immersing the sample in the aqueous solution for 20 seconds. The samples were allowed to cure for 24 hours. Then they were dried additionally in an oven at 100 ° C for one hour. The samples were allowed to reach room temperature before taking measurements. Each sample was divided longitudinally using a hammer and chisel. Half of each fractured sample was placed surface down in a dye solution ¹ soluble in water. Only the untreated portion of each sample absorbed the solution and stained. The penetration depth was measured from the surface down to the stained region. The average penetration is provided in Table-IV.

Table-IV Penetration Depth

<td>Substratum</td><td>2.5% treatment</td><td>Time of</td><td>Amount of</td>

<td></td><td>Depth of</td><td>treatment</td><td>Absorption of</td>

<td></td><td>penetration mm</td><td>(seconds)</td><td>solution (%)</td>

<td>Concrete block</td><td> 6</td><td> 20</td><td> 1</td>

<td>(M20)</td><td></td><td></td><td></td>

<td>Brick</td><td> 10</td><td> 20</td><td> 2</td>

<td>Sandstone</td><td> 3</td><td> 20</td><td> 0,3</td>

í

I

Example 10

Capillary absorption test

After conditioning, samples of treated and untreated concrete cubes were taken for further experimentation. The initial weights of all the cubes were recorded. Heavy samples were placed in a container on a porous support made from a package of filter papers. The thickness of the package was about 1 cm. The filter paper package ensures immediate and continuous contact between the water and the surface on which the samples rested only. Flowing water was slowly poured into the container until the paper was completely saturated. The water level was not allowed to exceed the top edge of the package. To reduce the evaporation of water, the vessel was covered with a glass sheet.

To assess the absorption of capillary water, samples were removed from the container after one hour. After cleaning the surface in contact with the water with a damp cloth, each sample was weighed. The results obtained are provided in the

V-table.

V-Table Capillary Absorption

<td>Substratum</td><td>Untreated Amount absorbed water (%)</td><td>Treatment 2.5% Quantity of absorbed water (%)</td>

<td>Concrete block</td><td> 5</td><td> &lt;0,1</td>

<td>(M20)</td><td></td><td></td>

<td>Brick</td><td> 10</td><td> &lt;0,1</td>

II

Example 11

Standard M20 block samples were used for additional testing. An untreated control was included for comparison and to calculate water exclusion. The samples were cleaned with a wire and cloth brush. The pieces were weighed and dried in an oven at 100 ° C until they reached a constant weight. Water absorption was determined by procedures established in accordance with ASTM D-6489. The pieces were weighed and placed in 1 cm of water for 24 hours, weighed again and dried in an oven at 100 ° C until a constant weight was reached. A 2.5% by weight solution of 3 (trimethoxyl) propylmethylidelammonium chloride was prepared by dissolving in running water. Three samples were treated by immersion in the aqueous solution for 20 seconds. The samples were allowed to cure for 24 hours. Then they were further dried in an oven at 100 ° C for one hour. The samples were allowed to reach room temperature before taking measurements. The water absorption, the percentage of water absorption (water absorption X 100 / weight of the dry piece) and% water exclusion were calculated as follows:

(control water absorption - treated sample water absorption) X 100 control water absorption

The average water exclusion calculated for three samples was 87%.

Example 12

Standard M20 block samples were used for further testing. Untreated control was included for comparative purposes and to calculate water exclusion. The samples were cleaned with a wire and cloth brush. The pieces were weighed and dried in an oven at 100 ° C until they reached a constant weight. A 2.5% by weight solution of 3- (trimethoxyl) proplldlmethylhexadecllamonyl chloride was prepared by dissolving in running water. Three samples were treated by immersion in the aqueous solution for 20 seconds. The samples were allowed to cure for 24 hours. Then they were further dried in an oven at 100 ° C for one hour. The samples were allowed to reach room temperature before taking measurements. Water absorption, percentage of water absorption (water absorption X 100 / weight of the dry piece) and% water exclusion were calculated as follows:

(control water absorption - treated sample water absorption) X 100 control water absorption.

Example 13

Standard M20 block samples were used for further testing. Untreated control was included for comparative purposes and to calculate water exclusion. The samples were cleaned with a wire and cloth brush. The pieces were weighed and dried in an oven at 100 ° C until they reached a constant weight. A 2.5% solution by weight was prepared by dissolving the product obtained from example 1, in running water. Three samples were treated by immersion in the aqueous solution for 20 seconds. The samples were allowed to cure for 48 hours. Then they were further dried in an oven at 100 ° C for one hour. The samples were allowed to reach room temperature before taking measurements. Water absorption, the percentage of water absorption (water absorption X 100 / weight of the dry piece) and% water exclusion were calculated as follows:

(control water absorption - treated sample water absorption) X 100 control water absorption.

The average water exclusion calculated for three samples was 91%.

Example 14

Standard M20 block samples were used for further testing. Untreated control was included for comparative purposes and to calculate water exclusion. The samples were cleaned with a wire and cloth brush. The pieces were weighed and dried in an oven at 100 ° C until they reached a constant weight. A 2.5% solution by weight was prepared by dissolving the product obtained from example 2, in running water. Three samples were treated by immersion in the aqueous solution for 20 seconds. The samples were allowed to cure for 5 days. Then they were further dried in an oven at 100 ° C for one hour. The samples were allowed to reach room temperature before taking measurements. The water absorption, the percentage of water absorption (water absorption X 100 / weight of the dry piece) and% water exclusion were calculated as follows:

(control water absorption - treated sample water absorption) X 100 control water absorption.

The average water exclusion calculated for three samples was 81%.

Example 15

Standard M20 block samples were used for further testing. Untreated control was included for comparative purposes and to calculate water exclusion. The samples were cleaned with a wire and cloth brush. The pieces were weighed and dried in an oven at 100 ° C until they reached a constant weight. A 2.5% solution by weight was prepared by dissolving the product obtained from example 4, in running water. Three samples were treated by immersion in the aqueous solution for 20 seconds. The samples were allowed to cure for 48 hours. Then they were further dried in an oven at 100 ° C for one hour. The samples were allowed to reach room temperature before taking measurements. The water absorption, the percentage of water absorption (water absorption X 100 / weight of the dry piece) and the% water exclusion were calculated as follows:

(control water absorption - water absorption of the treated sample) X 100 control water absorption.

The average water exclusion calculated for three samples was 93%.

Example 16

Standard M20 block samples were used for further testing. Untreated control was included for comparative purposes and to calculate water exclusion. The samples were cleaned with a wire and cloth brush. The pieces were weighed and dried in an oven at 100 ° C until they reached a constant weight. A 2.5% solution by weight was prepared by dissolving the product obtained from example 5, in running water. Three samples were treated by immersion in the aqueous solution for 20 seconds. The samples were allowed to cure for 48 hours. Then they were further dried in an oven at 100 ° C for one hour. The samples were allowed to reach room temperature before taking measurements. The water absorption, the percentage of water absorption (water absorption X 100 / weight of the dry piece) and the% water exclusion were calculated as follows:

(control water absorption - treated sample water absorption) X 100 control water absorption.

The average water exclusion calculated for three samples was 93%.

R'Ü I MAR'i

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