FIELD OF INVENTION

The present invention relates to organosiiicon compounds and to compositions, bitumens and asphalts comprising said organosiiicon compounds. The present invention also relates to the use of said organosiiicon compounds and said compositions and bitumens for improving the adhesion and compaction of asphalts.

BACKGROUND OF THE INVENTION

It is well known that asphalt is a common material used for the preparation of pavement and roofing materials. An extensive variety of compounds have been added to asphalt surfacing compositions in an attempt to render the asphalt water repellent, including organosiiicon compounds.

For many years, organosilanes have been used as a reinforcing agent in bitumen formulations to improve adhesion and wetting of the asphalt aggregate due to the stability of the silicon group. The organosiiicon compounds known and practiced in the art include ethoxy and methoxy functional group attached to the silicon moiety.

WO2010073261 A2 discloses that one disadvantage of using organosilanes is their inability to exhaust and react completely with the surfaces of aggregates if mixed with asphalts. WO2010073261 A2 relates to asphalt and asphalt-mineral compositions including at least one cationic organosiiicon compound intermixed with the asphalt that show improved adherence of asphalt binder to aggregates.

US3861933 relates to an asphalt composition having a high adhesion strength prepared by incorporating to the asphalt a small amount of an aminoalkyl polyalkoxysilane such as trimethoxysilanes and triethoxysilanes.

Therefore, it would be desirable to provide an organosiiicon compound that reacts with bitumen and which is hydrolytically stable, suitable for imparting water repellency, and which allows improved adhesion and compaction. SUMMARY OF THE INVENTION

The present invention relates to organosilicon compounds of formula I:

R,

o

~0- —Si R,

/

(I)

wherein

Ri, represents dihydroxypropyl;

2 represents (i) vinyl, (ii) 1 H-pyrrole-2,5-dione,1 -propyl-N-propylmaleimide-1- propylazoline-2,5-dione or (iii) N-propyl-9-octadecenamide, or salts, solvates or hydrates thereof,

as well as to compositions, bitumens and asphalt compositions comprising said organosilicon compounds, and to the use of said asphalt compositions in construction.

DESCRIPTION OF THE INVENTION

The present invention provides organosilicon compounds which improve the properties of bitumens and of asphalt compositions comprising said compounds. In particular, the asphalt compositions of the present invention have improved chemical properties which make them more resistant to water, to freezing and thawing and to salt, but also have improved mechanical properties such as improved adhesion, cohesion and improved compaction. Thus, the present invention provides improved asphalt compositions for extreme climates but also allows using the asphalt compositions in a faster and better way, allowing the construction of pavements of higher quality.

The inventors of the present invention have surprisingly found that several organosilicon compounds improve the properties of the bitumens and asphalt compositions in an unexpected way. The compositions of the present invention are also stable to ambient humidity. In a first aspect, the present invention relates to an organosilicon compound of formula I: R ₁ o

R _r

^" O- -Si

O

/

R ₁

(I) wherein

Ri , represents Ci-c, a Iky I substituted by hydroxy or phenyl; R2 represents C1-20 a Iky I unsubstituted or substituted by at least one of the following substituents: (i) halogen; (ii) amino; (iii) C2-20 a Iky I unsubstituted or substituted by amino, one or more =0 groups, C1-6 aminoalkyl substituted by C2-6 aminoalkenyl substituted by one ore more substituents selected from =0, aryl or a 5 or 6 membered ring with 1 to 3 heteroatoms selected from N, O and S and optionally substituted with one or two =0 groups; (iv) C2-20 alkenyl or C2-20 aminoalkenyl unsubstituted or substituted by one ore more =0, (v) a 5 or 6 membered ring with 1 to 3 heteroatoms selected from N, O and S and optionally substituted with one or two =0 groups, (vi) amino substituted at the N position by a heteroaryl optionally substituted by at least one substituent selected from halo, C1-20 aminoalkyl and by C1-20 aminoalkyl bound to A, wherein A is Si(Ri ).3, with the proviso that when Ri is benzyl, 2 is not aminopropyl, chloropropyl or vinyl or salts, solvates or hydrates thereof.

In a preferred embodiment of the present invention, the organosilicon compound of formula I is not in the form of a salt or a cation. Preferably, the organosilicon compound of formula I is not cationic. In a preferred embodiment of the first aspect, Ri represents (i) C1-4 alkyl substituted by phenyl or (ii) C1.4 alkyl mono, di or tri substituted by hydroxy I; or salts, solvates or hydrates thereof. In a preferred embodiment of the first aspect, Ri represents dihydroxypropyl or benzyl; and R2 represents (i) C2-6 alkenyl, (ii) C1-6 alkyl substituted by a 5 or 6 membered ring with 1 to 3 heteroatoms selected from N, O and S and optionally substituted with one or two =0 groups or (iii) Ci-e aminoalkyl substituted by C2-20 alkenyl optionally substituted by =0, or salts, solvates or hydrates thereof.

Preferred embodiments of the present invention are the organosilicon compounds of formula (I) listed in table 1. Preferred organosilicon compounds of the invention are the organosilicon compounds of formula (I) listed in table 1 wherein Ri represents dihydroxypropyl. A preferred embodiment of the present invention is the organosilicon compound of formula (I) wherein Ri represents dihydroxypropyl and R2 represents (i) vinyl, (ii) 1 H-pyrrole-2,5-dione,1 -propyl-N-propylmaleimide-1-propylazoline-2,5-dione or (iii) N- propyl-9-octadecenamide, or salts, solvates or hydrates thereof. In this way, a preferred embodiment of the present invention is Glycerol, 1 ,1 ',1 "-[(vinylsilylidyne)trioxy]tri- (example 2). Another preferred embodiment of the present invention is 1 H-Pyrrole-2,5-dione, 1 - [3- [tris(2,3-dihydroxypropyl)silyl]propyl] (example 3). Another preferred embodiment of the present invention is 9-Octadecenaminium,-N-[3-[tris(2,3-dihydroxypropyl)silyl]pro pyl] (example 4). Another preferred embodiment of the present invention is 9-Octadecenamide, N- [3-[tris(2,3-dihydroxypropyl)silyl]propyl] (example 5).

In a preferred embodiment of the fist aspect of the present invention, the compound is in the form of a salt selected from salts prepared from bases or acids including inorganic or organic bases (such as hydroxides or carbonates and amines, basic amino acids, heterocyclic compounds or quaternary ammonium compounds) and inorganic or organic acids (such as hydrochloric acid, sulfuric acid or phosphoric acid and carboxylic acids, hydroxycarboxylic acids, amino acids, phosphonic acids or sulfonic acids). Preferred acids are hydrochloric acid and organic acids such as dodecanesulfonic acid, dodecyl benzene sulfonic acid and 2-(acryloylamino)propane-2-sulfonic acid.

A second aspect of the present invention relates to a composition comprising at least one of the organosilicon compounds of the first aspect. Preferably, the composition comprises up to three different compounds of the first aspect. In a preferred embodiment, all the organosilicon compounds in the composition have Ri representing dihydroxypropyl.

A preferred embodiment of the second aspect is a composition comprising the organosilicon compound of the first aspect wherein Ri represents dihydroxypropyl and R? represents vinyl. Another preferred embodiment of the second aspect is a composition comprising the organosilicon compound of the first aspect wherein Ri represents dihydroxypropyl and R2 represents 1 H-pyrrole-2,5-dione,1 -propyl-N-propylmaleimide-1-propylazoline-2,5-dione. Another preferred embodiment of the second aspect is a composition comprising the organosilicon compound of the first aspect wherein Ri represents dihydroxypropyl and R2 represents N-propyl-9-octadecenamide. A preferred composition is the one comprising the compounds of examples 2, 3 and 5.

A third aspect of the present invention relates to a bitumen comprising the compound of the first aspect or the composition of the second aspect. As disclosed herein, the term "bitumen ^" refers to the organic matter in the form of a black viscous mixture of hydrocarbons obtained mainly from petroleum distillation or naturally. In a preferred embodiment of the third aspect, the amount of organosilicon compound of the first aspect or mix of organosilicon compounds of the first aspect ranges from 0.001 to 1 % w/w, preferably from 0.01 to 0.25 % w/w, more preferably from 0.03 to 0.15 % w/w in respect of the total weight of the bitumen. A fourth aspect of the present invention relates to an asphalt composition comprising the compound of the first aspect or the composition of the second aspect or the bitumen of the third aspect, and aggregate particles. Asphalt compositions comprise bitumen and aggregate particles. Aggregate particles in asphalt compositions are commonly aggregates which typically include dolomite, granites, river-bed crushed gravel, sandstone, limestone, basalt and other inorganic stones. The present invention has been tested as shown in the examples with different types of aggregates and no impact of the aggregates origin or nature could be appreciated.

The asphalt compositions of the present invention exhibit improved properties due to the interaction of the organosilicon compound or compounds of the present invention with the bitumen components as well as with the aggregates components. These compounds improve the cohesion of the bitumen and the aggregates therefore improving both the chemical and the mechanical properties of the asphalt.

In a fifth aspect, the present invention relates to the use of the bitumen of the third aspect or the asphalt of the fourth aspect in construction, preferably in paving, more preferably in road paving. Other uses of the bitumen of the third aspect or the asphalt of the fourth aspect are in roofing, soundproofing, pipe coating, cable coatings, paints, water proofing or ink production. When the bitumen or the asphalt of the invention are used for road paving, the road shows a sideway force coefficient (SFCS): SCRIM(r) according to UNE 41201 :2010 IN of at least 10 % higher, preferably 15 % higher, more preferably 20 % higher than the average for an road paved with an asphalt composition not comprising the bitumen or the asphalt of the invention (see example 1 1 and table 8). DESCRIPTION OF THE DRAWINGS

Figure 1 . Pictures of the results of the adhesion test using the standard practice for effect of water on bituminous-coated aggregate using boiling water as described in ASTM standard D3625/D3625M (A) and (C) for an asphalt composition with no organosiiicon compounds and (B) and (D) for an asphalt composition comprising an organosiiicon compound of the present invention. For pictures C and D, the test was performed with 4 % w/w NaCI.

Figure 2. A. Picture of the cylindrical specimens before the test. B and C. Pictures of the results of the particle loss test using the standard practice described in standard UNE EN 12697-17 for an asphalt composition with no organosiiicon compounds (smaller specimens) and for an asphalt composition comprising an organosiiicon compound of the present invention (bigger specimens).

Figure 3. Densities in t/m ³ reached after three passes of the compactor machine for a control asphalt (left column) and for an asphalt composition of the invention (right column).

EXAMPLES

The following examples illustrate the advantages of the compounds of the present invention for improving the properties of bitumens and asphalt compositions.

Example 1 : Organosiiicon compounds

The following organosiiicon compounds of formula (I) were prepared following processes equivalent to those disclosed in the examples below:

Table 1 . Organosiiicon compounds

Compound Ri

1 benzyl

hexadecyl

2 dihydroxypropyl

hexadecyl

3 dihydroxypropyl

aminopropyl benzyl

heptadecyl aminopropyl

dihydroxypropyl

heptadecyl aminopropyl

dihydroxypropyl

vinyl dihydroxypropyl

chloropropyl

A

dihydroxypropyl f

wherein A is -Si (ORi)a heptadecyl propyl(triglyceryloxy)silyl aminopropyl

dihydroxypropyl allylaminopropyl

O

dihydroxypropyl

1 H-Pyrrole-2,5-dione,1-propyl-N-Propylmaleimide 1- propylazoline-2,5-dione 0

dihydroxypropyl

3-phenyl-N-[2-(propylamino)ethyl]prop-2-enamide

dihydroxypropyl cT

heptadecanamide N-propyl

dihydroxypropyl

wherein A is -Si (ORi)a

4-N-(triglyceryloxy)siiyi propyi-6-N-propyi-2-N-octadecyl-

1 ,3,5-triazine-2,4,6-triamine

dihydroxypropyl

6-chloro-2-N-heptadecyl-4-N-propyl-1 ,3,5-triazine-2,4- diamine 15 dihydroxypropyl

heptadec-9-enyl aminopropyl

0

16 dihydroxypropyl

9-octadecenamide N-propyl

Salts of the compounds of table 1 were also prepared. Particularly, chloride salts as well as salts of organic acids such as dodecane sulfonate salts, dodecyl benzene sulfonate salts, 2-(acryloylamino)propane-2-sulfonate salts were prepared. Example 2: Synthesis of Glycerol, 1 , 1 ', 1 "-[(vinylsilylidyne)trioxy]tri-

In a 500 mL round bottom flask equipped with a condenser circulating cool water, thermometer and a distillation head was added 0.1 mol (15.27 mL) of trimethoxy(vinyl)silane (CAS 2768-01-7); 0.6 mol (44 mL) of glycerol (CAS 56-81 -5) and a catalytic amount p- Toluenesulfonic acid monohydrate (CAS 6192-52-5 ) (19 mg). The mixture was heated at 100 °C under magnetic agitation and low pressure was applied (400 Torr) for the distillation and condensation of the methanol generated during the reaction. After approximately 2 hours at low pressure the reaction mixture did not see further evolution of methanol, the mixture was cooled and the resulting composition was directly used in the bitumen modification step.

Example 3: Synthesis of 1 H-Pyrrole-2,5-dione, 1- [3-[tris(2,3-dihydroxypropyl)silyl]propyl]-

In a 500 ml_ round bottom flask were 0.1 mol (23.36 mL) of (3-aminopropyl)triethoxysilane (CAS 919-30-2) and maleic anhydride (CAS 108-31-6) 0.1 mol (9.80 g) were added neat at room temperature. The mixture was keep at r.t. under a bath of water during 15 minutes.

Then, the mixture was placed at 130 °C during 2 hours. Then I equip the round bottom flask with a condenser circulating cool water, thermometer and a distillation head. Glycerol 0.6 mol (44 mL) (CAS 56-81-5) and a catalytic amount p-toluenesulfonic acid monohydrate (CAS 6192-52-5) (19 mg) were added. The mixture was heated at 130 C under magnetic agitation and low pressure was applied (400 Torr) for the distillation and condensation of the ethanol generated during the reaction.

After approximately 2 hours at low pressure the reaction mixture did not see further evolution of ethanol, the mixture was cooled and the resulting composition was directly used in the bitumen modification step.

Example 4: Synthesis of 9-Octadecenaminium,-/V-[3-[tris(2,3-dihydroxypropyl)silyl]pr opyl]

In a 500 mL round bottom flask equipped with a condenser circulating cool water, thermometer and a distillation head was added 0.1 mol (18.45 mL) of (3- chloropropyl)trimethoxysilane (CAS 2530-85-2); 0.6 mol (44 mL) of glycerol (CAS 56-81-5) and a catalytic amount p-toluenesulfonic acid monohydrate (CAS 6192-52-5) (19 mg). The mixture was heated at 1 10 C under magnetic agitation and low pressure was applied (400 Torr) for the distillation and condensation of the methanol generated during the reaction.

After approximately 1 hour at low pressure the reaction mixture did not see further evolution of methanol.

Oleylamine, technical 70 % (CAS 1 12-90-3) 0.1 mol (42.77 mL) were added and a catalytic amount (20 mg) of INa were placed in the reaction mixture. The reaction was kept at 1 10 °C during 2 hours under magnetic agitation. Then, the mixture was cooled and the resulting composition was directly used in the bitumen modification step.

Example 5: Synthesis of 9-Octadecenamide, N- [3-[tris(2,3-dihydroxypropyl)silyl]propyl]-

In a 500 mL round bottom flask were 0.1 mol (23.36 mL) of (3-aminopropyl)triethoxysilane (CAS 919-30-2) and oleic acid, technical 90% (CAS 1 12-80-1 ) 0.1 mol (35 mL) were added neat at room temperature. Then, the mixture was placed at 130 C during 2 hours. Then the round bottom flask is equipped with a condenser circulating cool water, thermometer and a distillation head. Glycerol 0.6 mol (44 mL) (CAS 56-81 -5) and a catalytic amount p- toluenesulfonic acid monohydrate (CAS 6192-52-5) (19 mg) were added. The mixture was heated at 130 C under magnetic agitation and low pressure was applied (400 Torr) for the distillation and condensation of the ethanol generated during the reaction.

After approximately 1 hour at low pressure the reaction mixture did not see further evolution of ethanol, the mixture was cooled and the resulting composition was directly used in the bitumen modification step. Example 6: Adhesion tests

Asphalt compositions comprising bitumens comprising the organosilicon compounds of example 1 as well as their salts were tested for adhesion using the standard practice for effect of water on bituminous-coated aggregate using boiling water as described in ASTM standard D3625/D3625M. As illustrated in table 2 and figure 1 , the asphalt compositions comprising bitumens comprising the organosilicon compound of the present invention show improved adhesion. This improved adhesion makes the asphalt compositions of the invention much more resistant to the salt treatments that are applied in winter to avoid the formation of ice on the roads, as shown in figures 1 C and D. Table 2. Results of the observation of the behaviour in the adhesion test of compositions comprising no organosilicon compound or comprising 0.05 % w/w of organosilicon compound in respect of the total weight of the bitumen composition.

-: under 50 % asphalt coating remained on the aggregate surface.

+: over 75 % asphalt coating remained on the aggregate surface.

++: over 95 % asphalt coating remained on the aggregate surface. +++: apparently all the asphalt coating remained on the aggregate surface.

Example 7: Water sensitivity

Bitumens comprising the organosilicon compounds of example 1 or their salts were tested for water sensitivity following standard UNE EN 12697-12 in asphalt compositions comprising aggregates of siliceous and lime origin.

Table 3. Results of the water sensitivity test for control asphalt composition (no organosilicon compound).

Test tubes before immersion

Fracture type Indirect

Bulk Tensile

Height clear pull (T) tensile

Test tubes density strength

(mm) deformed (D) strength

(SSD) (N)

combined ( C) (MPa)

1 68.1 2,397.6 30,665 clear pull (T) 2.823

2 68.6 2,399.6 33,318 clear pull (T) 3.045

3 68.3 2,412.9 30,265 clear pull (T) 2.779

Average 68.327 2,403.367 31 ,416.000 2.882

Test tubes after immersion

Fracture type Indirect

Bulk Tensile

Height clear pull (T) tensile

Test tubes density strength

(mm) deformed (D) strength

(SSD) (N)

combined ( C) (MPa)

4 68.6 2,406.1 29,785 clear pull (T) 2.722

5 68.8 2,407.6 32,368 clear pull (T) 2.952

6 69.0 2,410.6 29,784 clear pull (T) 2.706

Average 68.783 2,408.100 30,645.667 2.793

Indirect tensile strength ratio ITSR (%) = 96.9 %

Table 4. Results of the water sensitivity test for asphalt compositions comprising bitumens comprising compound 5 in 0.05 % w/w of organosilicon compound in respect of the total weight of the bitumen composition.

Indirect tensile strength ratio ITSR (%) The water sensitivity test revealed that the asphalt compositions comprising bitumen comprising compound 5 have improved properties, with a difference in the ITSR of 8.4 %. This shows that the addition of the compound of the invention to asphalt compositions increases the resistance of the pavement and the life time against adverse factors such as water.

The same test was performed in equivalent conditions with compounds 6, 10 and 16 and mixes thereof. In all cases, the asphalt compositions comprising bitumens comprising one or more organosiiicon compounds of the invention showed improved resistance of the pavement and the life time against adverse factors such as water. Example 8: compaction

The densities in t/m ³ were analysed for control asphalt compositions and for asphalt compositions comprising a bitumen comprising a mix of compounds 6 + 10 + 16 in a total amount of 0.05 % w/w of organosiiicon compound mix in respect of the total weight of the bitumen composition. The compaction assays were done measuring the densities using the Bomag Asphalt Manager software, where the optimum compaction density is measured and taken as "white" in the calibration, for comparing the densities that are reached during compaction. On the other hand, the number of passes of the compactor machine needed to achieve the expected density are counted. The density is measured after each pass. For asphalt compositions comprising bitumens comprising the compounds of the invention, a smaller number of passes was required to reach the expected density. In this manner, the quality and time of compaction are improved, since overcompaction due to an excess of passes of the road roller is avoided.

The graph in figure 3 shows that the asphalt compositions of the invention (right column, comprising a bitumen comprising 0.05 % w/w of compound 10 in respect of the total weight of the bitumen) reaches a higher density than the asphalt composition with no organosiiicon compounds (left column) after 3 passes of the compactor machine.

Example 9: cohesion

Bitumens modified with SBS polymer (4 % w/w in respect of the total weight of the bitumen) with and without the organosiiicon compounds of example 1 or their salts were tested for particle loss following standard UNE EN 12697-17 in asphalt compositions comprising aggregates of siliceous and lime origin. Table 5. Particle loss in a control asphalt composition and in an asphalt composition comprising bitumens comprising 0.05 % w/w of compound 10 in respect of the total weight of the bitumen composition.

The results of the cohesion test can be appreciated in figure 2, where the smaller specimens correspond to control asphalt compositions, which loose 64.9 % mass in average, while the asphalt compositions of the invention only loose 34.9 % mass in average.

These results show hat the asphalt compositions of the invention have a longer life, since they show higher resistance to traffic efforts. Example 10: comparative example

Bitumens comprising the organosilicon compounds of example 1 or their salts were tested for water sensitivity following standard UNE EN 12697-12 in asphalt compositions comprising aggregates of siliceous and lime origin and were compared to asphalt compositions with a commercial bitumen which does not comprise the organosilicon compounds.

Table 6. Comparative examples from Oil of the

Bitumen PG-3 specifications company invention

Maximum density (metric ton/m ³ ) 2.617 2.618 N.A.

Bulk Density dim. (metric ton/m ³ ) 2.146 2.130 N.A.

Spaces in the mix (%) 18.0 18.6 > 12 < 18

Spaces in Aggregates (%) 27.8 28.4 N.A.

Filled spaces (%) 35.4 34.4 N.A.

Particle loss (%) 5.7 3.9 < 20

Water Sensitivity (%) ITSR 87.1 100.1 > 90

Permanent Deformation (mm) WTS 0.052 0.029 < 0.07

Binder runoff (%) 0.15 N.A. Table 6 shows that the asphalt comprising the bitumen of the present invention shows less particle loss (3.9 % vs. 5.7 %), and much better adhesion, with ITSR of 100.1 % vs. 87.1 %. Also, the asphalts of the present invention show an excellent value of permanent deformation (0.029 mm vs. 0.15 mm). Example 1 1 : process for the preparation of the organosilicon compounds and compositions

It has been found that the excess glycerin can be reduced without affecting the effectiveness of the aggregate-bitumen adhesion until with 3 equivalents of glycerin for each starting organosilane molecule exchanged is sufficient for the reaction to be completed. On the other hand, the amount of polyethylene dimethyl ether has been optimized so that on the one hand it provides the appropriate viscosity and helps the dispersion of the product in the bitumen. The optimum ratio found is 200 ml. per mole of starting silane.

Table 7. Optimization of the formulation for the boiling test without / with SBS

Compound Synthesis and composition

Compound 6 Excess glycerin = 3 equivalents

Starting silane = triacetoxy silane

Solvent = PEG-Dimethyl ether MW 240 Solvent ratio per 0.1 mol silane = 70 ml_ Other additives / relevant data = no

Compound 6 Excess glycerin = 3 equivalents

Starting silane = triacetoxy silane

Solvent = solvent-free

Solvent ratio per 0.1 mol silane = 0

Other additives / relevant data = 1 1 % by weight of ZnO activating glycerin.

Compound 6 Excess glycerin = 3 equivalents

Starting silane = triacetoxy silane

Solvent = PEG-Dimethyl ether MW 240 Solvent ratio per 0.1 mol silane = 35 ml_ Other additives / relevant data = octadecyl dimethyl amine to reduce the smell of acetic acid.

Compound 6 Excess glycerin = 3 equivalents

Starting silane = trimethoxy silane

Solvent = PEG-Dimethyl ether MW 240 Solvent ratio per 0.1 mol silane = 35 mL Other additives / relevant data = no

Compound 15 Excess glycerin = 3 equivalents

Starting silane = trimethoxy silane

Solvent = PEG-Dimethyl ether MW 240 Solvent ratio per 0.1 mol silane = 35 ml. Other additives / relevant data = no

Compound 16 Excess glycerin = 3 equivalents

Starting silane = triethoxy silane KH 550 Solvent = PEG-Dimethyl ether MW 240 Solvent ratio per 0.1 mol silane = 20 ml_ Other additives / relevant data = no

Compound 16 Excess glycerin = 2 equivalents

Starting silane = trimethoxy silane KH 550 Solvent = PEG-Dimethyl ether MW 240 Solvent ratio per 0.1 mol silane = 20 ml_ Other additives / relevant data = no

Example 1 1 : test of the asphalt of the invention

Asphalt comprising 0.05 weight % of a mixture of organosilicon compounds 6, 10 and 16 (with respect to bitumen). Validation of bitumen developed on site

The effectiveness of the bitumen of the invention has been validated in the section of the work: Autovia A-2 between P.K. 232.8 to 340.0 in Spain. The choice of this section is due to the fact that it requires continuous winter treatments with salt application.

Work formula used in the test section: the following working formula has been used in the established test section of the A-2 dual carriageway between P.K. 232.8 to 340.0, in order to assess its effectiveness: Hot bituminous mixture type BBTM 1 1 B PMB 45/80-65 (porphyry aggregate, calcium hydroxide filler, PMB 45/80-65 with organosilicon compounds of the invention)

Determination of the adhesiveness of the working formula used. Contrast tests: The analysis of the determination of the adhesiveness of the working formula was carried out, that is, the effect of water on loose asphalt mixtures, according to I.N.V.F-757-07 / ASTM D 3625-96. The adhesiveness of conventional bitumens and bitumens was compared with the addition of the compounds of the invention.

In view of the results of the analysis of the determination of adhesiveness (effect of water on loose asphalt mixtures, according to I.N.V.F-757-07 / ASTM D 3625-96), we can speak of a good adhesive behaviour.

Water sensitivity test according to UNE-EN 12697-12: The sensitivity to water is the ease with bituminous mixtures to progressively degrade their mechanical properties due to the action of water -both in the liquid state and in the form of water vapor- causing:

Stripping: loss of adhesiveness in the interface between bitumen and aggregate. - Lack of cohesion of the mastic (set consisting of bitumen and filler).

This loss of adhesiveness and / or cohesion is usually manifested by one of the following forms: detachment of the binder film from the surface of the aggregate without evident breakage; displacement of the bitumen as a consequence of the penetration of water through the cracks present in the same, spontaneous emulsification, pressure in the pores and production of aggregate surfaces without binder due to unwinding phenomena caused by chemical and electrostatic reactions between water and the aggregates.

The sensitivity to the action of water is evaluated according to the method EN 12697-12, in which the relationship between the indirect tensile strength of specimens subjected to a process of immersion in water and that of specimens maintained in the air (ITSR, indirect tensile strength ratio). This parameter is equivalent to the conserved resistance obtained by applying the immersion-compression test.

The results of a usual asphalt mixture, PMB 45/80-65, subjected to a process of immersion in water and maintained in air are shown:

- ITSd = 1305.7 / ITSw = 1236.37 / ITSR ratio (%) = 94.6 And an asphalt mixture with nanomaterials also subjected to a process of immersion in water and maintained in air, PMB 45/80-65 with organosilicon compounds of the invention:

- ITSd = 1641.6 / ITSw = 1524.4 / ITSR ratio (%) = 92.9

An analysis of the results has been carried out and it has been determined that there is a significant increase of the ITSd and the ITSw, in particular, has increased by 25.7% and 23.3% respectively in the asphalt mixture with nanomaterials (PMB 45/80-65 with organosilicon compounds of the invention).

On the other hand, there is a small variation in the ITSR between the usual asphalt mixture and the asphalt mixture with nanomaterials, although it is not a very significant variation. Specifically, it has decreased by 1.8% in the asphalt mixture that presents nanomaterials (PMB 45/80-65 with organosilicon compounds of the invention). Tests on the test section and compliance with the PG-3 requirements. In these tests it is verified that the tested mixture fulfils all the requirements established in the standard PG- 03.

As a summary, it was concluded that the improvement of properties of the new asphalt mixture would be summarized in the following points:

High resistance to crack reflection and high resistance to fatigue; result of the use of last generation polymers incorporated by chemical means to bitumen and the chemical union provided by the nanomaterials used.

Approximately 10 times increase in salt attack resistance; given the covalent chemical bond that makes it more difficult for bitumen to move from the surface of the aggregate and this can be attacked.

Sensitivity to water; thanks to the chemical union, the highest values that could be expected in this property are achieved.

Less formation of ruts; given the chemical bond that makes the flow of bitumen more difficult in the mixture at high temperatures.

Lengthening the useful life period, improving waterproofing; with respect to useful life will be greater consequence of the improvement in fatigue and with respect to waterproofing will be an equivalent factor that is a function of the granuiometric dosage of the asphalt mixture and the bitumen content.

- Lower economic cost and environmental improvement; thanks to the lengthening of the life of the firm, it is not necessary to reinforce pavements in the terms that are normally needed. The life cycle analysis of these road surfaces presents much higher values, significantly delaying the need for firm reinforcement.

The asphalt mixes with the bitumen of the invention have sideway force coefficient (SFCS): SCRIM(r) (according to UNE 41201 :2010 IN) 21 % better than the usual ones (without the compounds of the invention), in the tests carried out on the Madrid-Barcelona highway between km 240 and 340 presenting values between 77 and 78 against an average of measurements of 64. This is because the high adhesion of the bitumen of the invention delays the loss of fine aggregates allowing the asphalt pavement to maintain a greater microtexture that results in a greater SFC. This observed property of a better SFC is very important as it increases the safety of the drivers by maintaining more time the tyre pavement adhesion of the vehicles. The results in table 8 show that the asphalt mixes with the bitumens of the invention have higher SFC values and therefore improve the tyre pavement adhesion and this results in an improvement in road safety for drivers. Table 8. Sideway force coefficients(SFCS): SCRI M(r) . Comparative examples.

*** with the organosilicon compounds of the invention as disclosed in example 1 1 .