WO2019020770A1 - Composés et compositions d'organosilicium - Google Patents

Composés et compositions d'organosilicium Download PDF

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Publication number
WO2019020770A1
WO2019020770A1 PCT/EP2018/070347 EP2018070347W WO2019020770A1 WO 2019020770 A1 WO2019020770 A1 WO 2019020770A1 EP 2018070347 W EP2018070347 W EP 2018070347W WO 2019020770 A1 WO2019020770 A1 WO 2019020770A1
Authority
WO
WIPO (PCT)
Prior art keywords
asphalt
bitumen
propyl
composition
organosilicon compound
Prior art date
Application number
PCT/EP2018/070347
Other languages
English (en)
Inventor
Rafael Ferritto Crespo
Asier GOÑI URTIAGA
Francisco Javier SUÁREZ MARCO
José Miguel MARTÍNEZ MACEDO
Leticia PARRA RODRÍGUEZ
José Javier GARCÍA PARDENILLA
Original Assignee
Ditecpesa, S.A.
Nanoinnova Technologies S.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ditecpesa, S.A., Nanoinnova Technologies S.L. filed Critical Ditecpesa, S.A.
Publication of WO2019020770A1 publication Critical patent/WO2019020770A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/5403—Silicon-containing compounds containing no other elements than carbon or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D195/00—Coating compositions based on bituminous materials, e.g. asphalt, tar, pitch

Definitions

  • 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.
  • 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.
  • 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.
  • the present invention relates to organosilicon compounds of formula I:
  • Ri represents dihydroxypropyl
  • compositions, bitumens and asphalt compositions comprising said organosilicon compounds, and to the use of said asphalt compositions in construction.
  • the present invention provides organosilicon compounds which improve the properties of bitumens and of asphalt compositions comprising said compounds.
  • 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.
  • 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 present invention relates to an organosilicon compound of formula I: R 1 o
  • Ri represents Ci-c, a Iky I substituted by hydroxy or phenyl
  • the organosilicon compound of formula I is not in the form of a salt or a cation.
  • the organosilicon compound of formula I is not cationic.
  • 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.
  • Ri represents dihydroxypropyl or benzyl
  • 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.
  • 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]propyl] (example 4).
  • Another preferred embodiment of the present invention is 9-Octadecenamide, N- [3-[tris(2,3-dihydroxypropyl)silyl]propyl] (example 5).
  • 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
  • a composition comprising at least one of the organosilicon compounds of the first aspect.
  • the composition comprises up to three different compounds of the first aspect.
  • 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.
  • bitumen refers to the organic matter in the form of a black viscous mixture of hydrocarbons obtained mainly from petroleum distillation or naturally.
  • 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
  • asphalt compositions 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.
  • 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.
  • 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).
  • SFCS sideway force coefficient
  • 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.
  • A and (C) for an asphalt composition with no organosiiicon compounds
  • B) and (D) for an asphalt composition comprising an organosiiicon compound of the present invention.
  • 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).
  • organosiiicon compounds of formula (I) were prepared following processes equivalent to those disclosed in the examples below:
  • A is -Si (ORi)a heptadecyl propyl(triglyceryloxy)silyl aminopropyl
  • A is -Si (ORi)a
  • 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-
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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
  • additives / relevant data 1 1 % by weight of ZnO activating glycerin.
  • 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
  • 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)
  • 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.
  • 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.
  • 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.
  • SFCS sideway force coefficient

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne des composés d'organosilicium de formule I ainsi que des compositions, des bitumes et des compositions d'asphalte comprenant lesdits composés d'organosilicium, et l'utilisation desdites compositions d'asphalte en construction.
PCT/EP2018/070347 2017-07-27 2018-07-26 Composés et compositions d'organosilicium WO2019020770A1 (fr)

Applications Claiming Priority (2)

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EP17382501 2017-07-27
EP17382501.9 2017-07-27

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WO2019020770A1 true WO2019020770A1 (fr) 2019-01-31

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024034670A1 (fr) * 2022-08-10 2024-02-15 ダイキン工業株式会社 Article comprenant une couche de traitement de surface

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3861933A (en) 1972-03-09 1975-01-21 Kao Corp Asphalt having high adhesion strength and its preparation
WO2010073261A2 (fr) 2008-12-22 2010-07-01 Ranka, Seema Ajay Compositions asphalte-minéral

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3861933A (en) 1972-03-09 1975-01-21 Kao Corp Asphalt having high adhesion strength and its preparation
WO2010073261A2 (fr) 2008-12-22 2010-07-01 Ranka, Seema Ajay Compositions asphalte-minéral

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHANG CANLIN ET AL: "Influence of UV aging on the rheological properties of bitumen modified with surface organic layered double hydroxides", CONSTRUCTION AND BUILDING MATERIALS, ELSEVIER, NETHERLANDS, vol. 123, 21 July 2016 (2016-07-21), pages 574 - 580, XP029711014, ISSN: 0950-0618, DOI: 10.1016/J.CONBUILDMAT.2016.07.048 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024034670A1 (fr) * 2022-08-10 2024-02-15 ダイキン工業株式会社 Article comprenant une couche de traitement de surface

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