U.S. patent application number 12/523838 was filed with the patent office on 2010-08-05 for bituminous composition with thermoreversible properties.
This patent application is currently assigned to TOTAL RAFFINAGE MARKETING. Invention is credited to Laurent Bouteille, Benjamin Isare, Laurence Lapalu, Regis Vincent.
Application Number | 20100192804 12/523838 |
Document ID | / |
Family ID | 38349525 |
Filed Date | 2010-08-05 |
United States Patent
Application |
20100192804 |
Kind Code |
A1 |
Lapalu; Laurence ; et
al. |
August 5, 2010 |
BITUMINOUS COMPOSITION WITH THERMOREVERSIBLE PROPERTIES
Abstract
The invention relates to a bituminous composition that comprises
a major portion of at least one bitumen and a minor portion of at
least one chemical additive, said additive being an organogelling
agent that generates a network of hydrogen bonds between the
organogelling molecules constituting the same, and trapping the
bitumen phase up to a maximum temperature T.sub.R of between 40 and
120.degree. C. The invention also relates to the use of these
bitumen compositions in the field of road applications,
particularly in the production of road binders, as well as in
industrial applications. The invention also relates to a method for
preparing these bituminous compositions.
Inventors: |
Lapalu; Laurence;
(Villeurbanne, FR) ; Vincent; Regis; (Grigny,
FR) ; Bouteille; Laurent; (Bourg La Reine, FR)
; Isare; Benjamin; (Frevillers, FR) |
Correspondence
Address: |
HARNESS, DICKEY & PIERCE, P.L.C.
P.O. BOX 828
BLOOMFIELD HILLS
MI
48303
US
|
Assignee: |
TOTAL RAFFINAGE MARKETING
Puteaux
FR
|
Family ID: |
38349525 |
Appl. No.: |
12/523838 |
Filed: |
January 18, 2008 |
PCT Filed: |
January 18, 2008 |
PCT NO: |
PCT/FR08/00066 |
371 Date: |
April 13, 2010 |
Current U.S.
Class: |
106/277 ;
106/273.1; 106/284.4 |
Current CPC
Class: |
C09D 195/00 20130101;
C08K 5/092 20130101; C08K 5/0008 20130101; C08K 5/0008 20130101;
C08L 95/00 20130101; C08L 95/00 20130101; C08L 95/00 20130101; C08L
2666/66 20130101 |
Class at
Publication: |
106/277 ;
106/284.4; 106/273.1 |
International
Class: |
C08L 95/00 20060101
C08L095/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 23, 2007 |
FR |
07 00441 |
Jul 19, 2007 |
FR |
07 05225 |
Claims
1. A bituminous composition comprising a major proportion of at
least one bitumen and a minor proportion of at least one chemical
additive, the additive being an organogelator creating a network of
hydrogen bonds between organogelling molecules which have a molar
mass of less than or equal to 2000 gmol.sup.-1, said organogelator
comprising at least one hydrogen bond donor D, at least one
hydrogen bond acceptor A and at least one compatibilizer C in the
bitumen, said compatibilizer C comprising a group chosen from: at
least one linear hydrocarbon chain comprising at least 4 carbon
atoms, or at least one aliphatic ring of 3 to 8 atoms, or at least
one condensed polycyclic system which is aliphatic, or partly
aromatic or also wholly aromatic, each ring comprising 5 or 6
atoms, alone or in a mixture.
2. The composition according to claim 1, wherein the donor D
comprises a heteroatom bearing a hydrogen chosen from nitrogen N,
oxygen O and/or sulphur S.
3. The composition according to claim 1, wherein the donor D is
chosen from the alcohol, thiol, phenol, primary amine, secondary
amine, quaternary ammonium, amide, urea, hydrazine, carboxylic
acid, oxime, hydrazone, imine groups and combinations thereof.
4. The composition according to claim 1, wherein the acceptor A
comprises a heteroatom bearing electronic doublets chosen from
oxygen O, sulphur S, nitrogen N and/or phosphorus P.
5. The composition according to claim 1, wherein the acceptor A is
chosen from the C.dbd.O, S.dbd.O, N.dbd.O or P.dbd.O groups and the
linear or cyclic hydrocarbon groups containing in their hydrocarbon
chain a heteroatom of oxygen O, sulphur S, nitrogen N or phosphorus
P.
6. The composition according to claim 1, wherein the acceptor A is
chosen from the alcohol, phenol, amide, ester, urea, hydrazine,
acid, ketone, aldehyde, lactone, lactame, anhydride, imide,
sulphoxide, sulphone, sulphonate, sulphate, sulphite, sulphonic
acid, sulphide, ether, phosphine, phosphite, phosphonate,
phosphate, nitrite or nitrate groups and combinations thereof.
7. The composition according to claim 1, wherein the organogelator
comprises organogelling molecules of identical chemical
structure.
8. The composition according to claim 1, wherein the organogelator
comprises at least one unit of general formula (I):
R--(NH).sub.nCONH--(X).sub.m--NHCO(NH).sub.n--R', the R and R'
groups, identical or different, contain a linear, branched or
cyclic, saturated or unsaturated hydrocarbon chain, comprising 1 to
22 carbon atoms, optionally substituted, and optionally comprising
heteroatoms, rings and/or heterocycles; the X group contains a
linear, cyclic or branched, saturated or unsaturated hydrocarbon
chain, comprising 1 to 22 carbon atoms, optionally substituted, and
optionally comprising heteroatoms, rings and/or heterocycles; n and
m are integers having a value of 0 or 1 independently of each
other.
9. The composition according to claim 8, wherein the organogelator
comprises a hydrazide unit when n and m have a value of 0.
10. The composition according to claim 8, wherein the organogelator
comprises two amide units when n has a value of 0 and m has a value
of 1.
11. The composition according to claim 8, wherein the organogelator
comprises two urea units when n and m have a value of 1.
12. The composition according to claim 8, wherein the R and/or R'
group comprises an aliphatic hydrocarbon chain of 4 to 22 carbon
atoms, in particular chosen from the C.sub.4H.sub.9,
C.sub.5H.sub.11, C.sub.9H.sub.19, C.sub.11H.sub.23,
C.sub.12H.sub.25, C.sub.17H.sub.35, C.sub.18H.sub.37,
C.sub.21H.sub.43, C.sub.22H.sub.45 groups.
13. The composition according to claim 8, wherein the X group
comprises an aliphatic hydrocarbon chain of 1 to 2 carbon
atoms.
14. The composition according to claim 8, wherein the X group
comprises two rings of 6 carbon atoms linked by a CH.sub.2 group,
these rings being aliphatic or aromatic.
15. The composition according to claim 1, wherein the organogelator
comprises at least one unit of general formula (II):
(R--NHCO).sub.x--Z--(NHCO--R').sub.y R and R', identical or
different, contain a linear, branched or cyclic, saturated or
unsaturated hydrocarbon chain comprising 1 to 22 carbon atoms,
optionally substituted, and optionally comprising heteroatoms,
rings and/or heterocycles, Z represents a tri-functionalized group
chosen from the following groups: ##STR00021## x and y are
different integers with a value varying from 0 to 3 and such that
x+y=3.
16. The composition according to claim 1, wherein the organogelator
comprises at least one sorbitol derivative (III).
17. The composition according to claim 16, wherein the sorbitol
derivative is a product of the reaction between an aldehyde and
D-sorbitol.
18. The composition according to claim 17, wherein the
organogelator is 1,3:2,4-Di-O-benzylidene-D-sorbitol.
19. The composition according to claim 1, wherein the organogelator
comprises at least one unit of general formula (IV):
R''--(COOH).sub.z with R'' a linear or branched, saturated or
unsaturated chain comprising 4 to 68 carbon atoms, preferably 4 to
54 carbon atoms, more preferentially 4 to 36 carbon atoms and z an
integer varying from 2 to 4.
20. The composition according to claim 19, wherein the
organogelator is a diacid of general formula
HOOC--C.sub.wH.sub.2w--COOH with w an integer varying from 4 to 22,
preferably 4 to 12 where z=2 and R''=C.sub.wH.sub.2w.
21. The composition according to claim 20, wherein the
organogelator is a diacid chosen from the following diacids: adipic
acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,
undecanedioic acid, 1,2-dodecanedioic acid or tetradecanedioic
acid.
22. The composition according to claim 1, wherein the organogelator
comprises at least one unit of general formula (V): ##STR00022##
the Y and Y' groups represent independently of each other, an atom
or group chosen from: H, --(CH.sub.2)q-CH.sub.3,
--(CH.sub.2)q-NH.sub.2, --(CH.sub.2)q-OH, --(CH.sub.2)q-COOH or
##STR00023## with q an integer varying from 2 to 18, preferably 2
to 10, preferably 2 to 4 and p an integer greater than or equal to
2, preferably having a value of 2 or 3.
23. The composition according to claim 22, wherein the
organogelator has the formula: ##STR00024##
24. The composition according to claim 1, wherein the organogelator
comprises at least one unit of general formula (VI):
R--NH--CO--CO--NH--R' with R and R', identical or different, which
represent a linear, branched or cyclic, saturated or unsaturated
hydrocarbon chain, comprising 1 to 22 carbon atoms, optionally
substituted, and optionally comprising heteroatoms, rings and/or
heterocycles.
25. The composition according to claim 1, wherein the organogelator
(VII) comprises at least 2 organogelling molecules of different
chemical structure, all of the three units A, D and C being found
in the organogelator.
26. The composition according to claim 25, wherein the
organogelator comprises an amine derivative and a carboxylic acid
derivative.
27. The composition according to claim 25, wherein the
organogelator comprises an aminopyrimidine derivative and a
barbituric acid derivative.
28. The composition according to claim 25, wherein the
organogelator comprises a sulphosuccinate derivative and a phenol
derivative.
29. The composition according to claim 1, wherein the organogelling
molecules have a molar mass of less than or equal to 1000
gmol.sup.-1.
30. The composition according to claim 1, wherein the organogelator
is present at 0.1 to 5% by mass with respect to the bitumen.
31. The composition according to claim 1, wherein the bitumen also
comprises at least one polymer and/or one flux.
32. The composition according to claim 1, wherein the bitumen is
chosen from the atmospheric distillation residues, the vacuum
distillation residues, visbroken residues, blown residues, their
mixtures and combinations thereof.
33. A use of a bituminous composition according to claim 1, further
comprising manufacturing a bituminous binder, in particular an
anhydrous binder, a bituminous emulsion, a polymer bitumen or a
fluxed bitumen.
34. The use of a bituminous composition according to claim 33 in a
mixture with aggregates for manufacturing a surface dressing, a hot
mix, a cold mix, a cold-cast mix, a gravel emulsion or a wearing
course.
35. The use of a bituminous composition according to claim 33 for
manufacturing a sealing membrane, a membrane or an impregnation
layer.
36. A method for obtaining a bituminous composition according to
claim 1, wherein the organogelator is introduced when hot at
temperatures varying from 140 to 180.degree. C., either into the
bitumen alone, into the bitumen modified or not modified by
polymers, into the bitumen in the form of bituminous binder or into
the bitumen when the latter is in the form of anhydrous binder,
bituminous mix, or surface dressing, or during the manufacture of
said bitumens, binders or dressings.
37. The method according to claim 36 for obtaining a bituminous
composition which is hard at the temperatures of use without
increasing its viscosity when hot.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a National Phase Entry of International
Application No. PCT/FR2008/000066, filed on Jan. 18, 2008, which
claims priority to French Patent Application No. 07 05225, filed on
Jul. 19, 2007 and French Patent Application No. 07 00441, filed on
Jan. 23, 2007, all of which are incorporated by reference
herein.
TECHNICAL FIELD
[0002] The present invention belongs to the field of the bitumens.
More specifically, it relates to bituminous compositions comprising
an organogelator type additive, the bituminous compositions having
thermoreversible viscosity and hardness characteristics. The
invention also relates to the use of these bituminous compositions
in the fields of highway applications, in particular in the
manufacture of road binders, and in the fields of industrial
applications. The invention also relates to the method for
preparing these bituminous compositions.
TECHNICAL CONTEXT
[0003] The use of bitumen in the manufacture of materials for
highway and industrial applications has been known for a long time:
bitumen is the main hydrocarbon binder used in the field of road
construction or civil engineering. To be able to be used as a
binder in these different applications, the bitumen must have
certain physico-chemical properties. One of the most important
properties is the hardness of the bitumen; the latter must be high
enough at the temperatures of use to avoid the formation of ruts
caused by traffic. Another very important characteristic is the
viscosity of the bitumen; the bitumen must be sufficiently fluid at
the lowest possible application temperatures. The use of a
bituminous binder therefore requires a combination of both the
hardness of the bitumen at the temperatures of use and a low
viscosity when hot.
PRIOR ART
[0004] The bitumens are generally obtained from residues
originating from atmospheric and/or vacuum distillation of crude
oil, but also after elimination of the light fractions of the
native bitumens, asphalts or bituminous sands. In order to adjust
the hardness of a bitumen, it is possible to redistill them at very
high temperatures or at lower pressure in order to eliminate the
light fractions. In fact the more the bitumen is constituted by
heavy fractions, the greater its hardness. This technique is not
always sufficiently efficient and the heavy fractions are never
completely free of light fractions.
[0005] Another means for hardening a bitumen is to blow it. Blown
bitumens are manufactured in a blowing unit, by passing a flow of
air and/or oxygen through an original bitumen. This operation can
be carried out in the presence of an oxidation catalyst, for
example phosphoric acid. Generally, the blowing is carried out at
high temperatures, of the order of 200 to 300.degree. C., for
relatively long periods of time typically comprised between 30
minutes and 2 hours, continuously or in batches. This blowing
method has a certain number of drawbacks. Firstly, blown bitumens
are more susceptible to ageing than the original bitumens.
Moreover, the manufacture of blown bitumen requires a blowing
installation especially provided for this purpose. One of the major
drawbacks of blown bitumens is their viscosity at a given
temperature which is greater than that of the original bitumen.
Another drawback linked to this high viscosity is the need to heat
the blown bitumen to an application temperature greater than that
of a non-blown bitumen of the same type, which increases energy
expenditure and requires the use of additional protection for the
operators.
[0006] Another means for hardening a bitumen is to add polymers to
it. The Applicant company was one of the first to develop and
patent the use of bituminous compositions containing polymers
(FR2376188, FR7818534, EP0799280, EP0690892). These polymers make
it possible in particular to improve the cohesion of the binder, to
improve the elastic properties of the binder, to increase the
plasticity range of the bitumen, to increase the resistance to
deformation and also to increase the hardness of the bitumen by
reducing its penetrability. At the temperatures of use, these
characteristics are therefore clearly improved. However when hot
the addition of polymers to the bituminous composition generally
leads to an increase in the viscosity of the bituminous
composition. To be able to be applied to the carriageway, the
bituminous binder with added polymers must therefore be heated to
an application temperature greater than that of a bituminous binder
of equivalent type without polymers. In order to use these polymer
bitumens, the same drawbacks are noted as those noted for blown
bitumens. The applicant company, in the Patent Application
FR2889198, has claimed a chemical blowing method which involves
introducing a hardening additive into a bitumen, this additive
increasing the hardness of the bitumen at the temperatures of use
and limiting the increase in the viscosity when hot.
BRIEF DESCRIPTION OF THE INVENTION
[0007] Continuing its work, the applicant company has sought other
compounds making it possible to harden the bitumens at the
temperatures of use without increasing their viscosity when hot.
The applicant company has developed novel bituminous compositions
having the characteristics of bitumens hardened by adding polymers
at the temperatures of use and not having the characteristics of
bitumens with added polymers when hot.
[0008] For this purpose, the invention refers to bituminous
compositions comprising a major proportion of at least one bitumen
and a minor proportion of at least one chemical additive, said
chemical additive being an organogelator creating a network of
hydrogen bonds between organogelling molecules which have a molar
mass of less than or equal to 2000 gmol.sup.-1, said organogelator
comprising at least one hydrogen bond donor D, at least one
hydrogen bond acceptor A and at least one compatibilizer C in the
bitumen, said compatibilizer C comprising a group chosen from:
[0009] at least one linear hydrocarbon chain comprising at least 4
carbon atoms, or [0010] at least one aliphatic ring of 3 to 8
atoms, or [0011] at least one condensed polycyclic system, which is
aliphatic or partly aromatic or also wholly aromatic, each ring
comprising 5 or 6 atoms, alone or in a mixture.
[0012] Preferably, the donor D comprises a heteroatom bearing a
hydrogen chosen from nitrogen N, oxygen O and/or sulphur S.
Preferably, the donor D is chosen from the alcohol, thiol, phenol,
primary amine, secondary amine, quaternary ammonium, amide, urea,
hydrazine, carboxylic acid, oxime, hydrazone, imine groups and
combinations thereof. Preferably, the acceptor A comprises a
heteroatom bearing electronic doublets chosen from oxygen O,
sulphur S, nitrogen N and/or phosphorus P. Preferably, the acceptor
A is chosen from the C.dbd.O, S.dbd.O, N.dbd.O or P.dbd.O groups
and the linear or cyclic hydrocarbon groups containing in their
hydrocarbon chain a heteroatom of oxygen O, sulphur S, nitrogen N
or phosphorus P. Preferably, the acceptor A is chosen from the
alcohol, phenol, amide, ester, urea, hydrazine, acid, ketone,
aldehyde, lactone, lactame, anhydride, imide, sulphoxide, sulphone,
sulphonate, sulphate, sulphite, sulphonic acid, sulphide, ether,
phosphine, phosphites, phosphonate, phosphate, nitrite or nitrate
groups and combinations thereof.
[0013] According to an embodiment, the organogelator excludes the
compounds of alkyl amido-imidazolidine and alkyl amido-imidazoline
type. According to an embodiment, the organogelator, comprises
organogelling molecules of identical chemical structure. According
to an embodiment, the organogelator comprises at least one unit of
general formula (I):
R--(NH).sub.nCONH--(X).sub.m--NHCO(NH).sub.n--R',
[0014] the R and R' groups, identical or different, contain a
linear, branched or cyclic, saturated or unsaturated hydrocarbon
chain, comprising 1 to 22 carbon atoms, optionally substituted, and
optionally comprising heteroatoms, rings and/or heterocycles;
[0015] the X group contains a linear, cyclic or branched, saturated
or unsaturated hydrocarbon chain, comprising 1 to 22 carbon atoms,
optionally substituted, and optionally comprising heteroatoms,
rings and/or heterocycles;
[0016] n and m are integers having a value of 0 or 1 independently
of each other.
[0017] Preferably, the organogelator comprises a hydrazide unit
when n and m have a value of 0. Preferably, the organogelator
comprises two amide units when n has a value of 0 and m has a value
of 1. Preferably, the organogelator comprises two urea units when n
and m have a value of 1.
[0018] According to an embodiment, the R and/or R' group comprises
an aliphatic hydrocarbon chain of 4 to 22 carbon atoms, in
particular, chosen from the C.sub.4H.sub.9, C.sub.5H.sub.11,
C.sub.9H.sub.19, C.sub.11H.sub.23, C.sub.12H.sub.25,
C.sub.17H.sub.35, C.sub.18H.sub.37, C.sub.21H.sub.43,
C.sub.22H.sub.45 groups. The X group comprises an aliphatic
hydrocarbon chain of 1 to 2 carbon atoms. The X group comprises two
rings of 6 carbon atoms linked by a CH.sub.2 group, these rings
being aliphatic or aromatic.
[0019] According to an embodiment, the organogelator comprises at
least one unit of general formula (II):
(R--NHCO).sub.x--Z--(NHCO--R').sub.y
[0020] R and R', identical or different, contain a linear, branched
or cyclic, saturated or unsaturated hydrocarbon chain comprising 1
to 22 carbon atoms, optionally substituted, and optionally
comprising heteroatoms, rings and/or heterocycles,
[0021] Z represents a tri-functionalized group chosen from the
following groups:
##STR00001##
[0022] x and y are different integers with a value varying from 0
to 3 and such that x+y=3.
[0023] According to an embodiment, the organogelator (III)
comprises at least one sorbitol derivative. The sorbitol derivative
is a product of the reaction between an aldehyde and D-sorbitol.
Preferably, the organogelator is
1,3:2,4-Di-O-benzylidene-D-sorbitol.
[0024] According to an embodiment, the organogelator comprises at
least one unit of general formula (IV): R''--(COOH).sub.z
with R'' a linear or branched, saturated or unsaturated chain
comprising 4 to 68 carbon atoms, preferably 4 to 54 carbon atoms,
more preferentially 4 to 36 carbon atoms and z an integer varying
from 2 to 4.
[0025] Preferably, the organogelator is a diacid of general formula
HOOC--C.sub.wH.sub.2w--COOH with w an integer varying from 4 to 22,
preferably from 4 to 12 where z=2 and R''=C.sub.wH.sub.2w.
Preferably, the organogelator is a diacid chosen from the following
diacids: adipic acid, pimelic acid, suberic acid, azelaic acid,
sebacic acid, undecanedioic acid, acid 1,2-dodecanedioic or
tetradecanedioic acid.
[0026] According to an embodiment, the organogelator comprises at
least one unit of general formula (V):
##STR00002##
[0027] the Y and Y' groups represent independently of each other,
an atom or group chosen from: H, --(CH.sub.2)q-CH.sub.3,
--(CH.sub.2)q-NH.sub.2, --(CH.sub.2)q-OH, --(CH.sub.2)q-COOH or
##STR00003##
[0028] with q an integer varying from 2 to 18, preferably from 2 to
10, preferably from 2 to 4 and p an integer greater than or equal
to 2, preferably having a value of 2 or 3.
[0029] Preferably, the organogelator has the formula:
##STR00004##
[0030] According to an embodiment, the organogelator comprises at
least one unit of general formula (VI): R--NH--CO--CO--NH--R'
with R and R', identical or different, which represent a linear,
branched or cyclic, saturated or unsaturated hydrocarbon chain,
comprising 1 to 22 carbon atoms, optionally substituted, and
optionally comprising heteroatoms, rings and/or heterocycles.
[0031] According to an embodiment, the organogelator (VII)
comprises at least 2 organogelling molecules of different chemical
structure, all of the three units A, D and C being found in the
organogelator. Preferably, the organogelator comprises an amine
derivative and a carboxylic acid derivative. Preferably, the
organogelator comprises an aminopyrimidine derivative and a
barbituric acid derivative. Preferably, the organogelator comprises
a sulphosuccinate derivative and a phenol derivative.
[0032] According to an embodiment, the organogelling molecules have
a molar mass of less than or equal to 1000 gmol.sup.-1. According
to an embodiment, the organogelator is present from 0.1 to 5% by
mass with respect to the bitumen. According to an embodiment, the
bitumen also comprises at least one polymer and/or flux.
Preferably, the bitumen is chosen from the atmospheric distillation
residues, vacuum distillation residues, visbroken residues, blown
residues, mixtures and combinations thereof.
[0033] The invention also relates to the use of these bituminous
compositions in order to produce bituminous binders, in particular
anhydrous binders, bituminous emulsions, polymer bitumens or fluxed
bitumens. These bituminous binders then being able to be combined
with aggregates in order to provide surface dressings, hot mixes,
cold mixes, cold-cast mixes, gravel emulsions or wearing courses.
The applications of the bituminous compositions according to the
invention being able to be used in highway applications or
industrial applications such as sealing membranes, membranes or
impregnation layers.
[0034] The invention finally relates to a method for obtaining a
bituminous composition which is hard at the temperatures of use
without increasing its viscosity when hot, during which the
organogelator can equally well be introduced at a temperature
between 140 and 180.degree. C. into the bitumen alone, or during
manufacture, into the polymer bitumen, in the bitumen in the form
of bituminous binder or into the bitumen when the latter is in the
form of an anhydrous binder, in the form of a coated material or a
surface dressing. The advantage of the present invention is
obtaining bituminous compositions suitable for each envisaged use
regardless of the hardness of the bitumen used. Thus the production
of a hard bituminous composition depends neither on the nature of
the crude oil used, nor on the quantity of light fractions
contained in the bitumens used.
DETAILED DESCRIPTION OF THE INVENTION
[0035] By organogelator within the meaning of the invention, is
meant a combination of several so-called organogelling molecules of
identical or different chemical structure. In the bitumen, these
organogelling molecules are capable of establishing physical
interactions with each other leading to auto-aggregation with
formation of a 3D supra-molecular network which is responsible for
the gelling of the bitumen. The close packing of the organogelling
molecules results in the formation of a network of fibrils,
immobilizing the molecules in the bitumen.
[0036] At the temperatures of use, ranging from 10 to 60.degree.
C., the organogelling molecules bind to each other non-covalently,
in particular by hydrogen bonds. These hydrogen bonds disappear
when the bitumen is heated to a high temperature. Thus at the
temperatures of use, the organogelator constituted by a large
number of organogelling molecules can be compared to a
"supramolecular" polymer and gives the thus-modified bitumen the
properties of a standard bitumen/polymer composition, in particular
with regard to hardness. At the temperatures of use, the gelling
due to the aggregation of the organogelling molecules, causes a
thickening of the bituminous medium, leading to an increase in the
hardness. The bitumen no longer flows under its own weight, its
hardness at the temperatures of use is increased with respect to
the original bitumen alone with no organogelling additives. When
the bituminous composition is heated, the interactions stabilizing
the organogelator disappear, and the bitumen recovers the
properties of a bitumen with no additives, the viscosity of the
bituminous composition when hot returns to that of the original
bitumen.
[0037] The physical interactions between organogelling molecules
are varied and include in particular hydrogen bond type
interactions between a hydrogen bond donor D and a hydrogen bond
acceptor A, .pi. interactions between unsaturated rings, dipolar
interactions and combinations thereof. The organogelling molecules
can establish a single or several types of interactions with
neighbouring molecules. The establishment of one or other of these
interactions is promoted by the architecture of the organogelling
molecules. Within the framework of the invention, the
organogelator, constituted by several organogelling molecules,
comprises several groups capable of establishing hydrogen bonds. In
order to establish these hydrogen bonds, the organogelator
comprises at least one hydrogen bond acceptor A, at least one
hydrogen bond donor D.
[0038] In order to be able to gel and harden the bitumen, the
organogelator must be soluble in the bitumen when hot. The main
chemical constituents of bitumen are asphaltenes and maltenes.
Asphaltenes are compounds, in particular heterocyclic, constituted
by a number of polycondensed aromatic rings and naphthene rings.
The maltenes are mainly constituted by long paraffin chains. As a
result, the organogelator according to the invention comprises at
least one chemical group C making the organogelator compatible with
the chemical compounds of the bitumen. This compatibilizer C can
comprise, alone or in a mixture, a group chosen from: at least one
long hydrocarbon chain compatible with the maltene fraction of the
bitumen, or at least one aliphatic ring of 3 to 8 atoms, or at
least one condensed polycyclic system, which is aliphatic or partly
aromatic or wholly aromatic, compatible with the asphaltene
fraction of the bitumen, each ring comprising 5 or 6 atoms.
[0039] According to a preferred embodiment of the invention, the
organogelator comprises as a result at least one hydrogen bond
donor D, at least one hydrogen bond acceptor A in order to be able
to form hydrogen bonds between organogelling molecules and at least
one compatibilizer C in the bitumen comprising at least one linear
hydrocarbon chain of at least 4 carbon atoms. This linear
hydrocarbon chain therefore comprises at least 4 covalently bound,
preferably adjacent carbon atoms. The compatibilizer C makes it
possible both to increase the solubility of the organogelator in
the bitumen but also to reinforce the interactions between
organogelling molecules.
[0040] According to another preferred embodiment of the invention,
the organogelator comprises at least one hydrogen bond donor D, at
least one hydrogen bond acceptor A in order to be able to form
hydrogen bonds between organogelling molecules and at least one
compatibilizer C in the bitumen comprising at least one aliphatic
ring of 3 to 8 atoms. According to another preferred embodiment of
the invention, the organogelator comprises at least one hydrogen
bond donor D, at least one hydrogen bond acceptor A in order to be
able to form hydrogen bonds between organogelling molecules and at
least one compatibilizer C in the bitumen comprising at least one
condensed polycyclic system, which is aliphatic or partly aromatic
or wholly aromatic, each ring comprising 5 or 6 atoms. These
polycyclic systems by virtue of their structure provide
compatibility with the asphaltene fraction of the bitumen.
[0041] According to a preferred embodiment of the invention, the
hydrogen bond donor D comprises a heteroatom bearing a hydrogen
chosen from nitrogen N, oxygen O and/or sulphur S. According to a
preferred embodiment of the invention, the hydrogen bond acceptor A
comprises a heteroatom bearing electronic doublets chosen from
oxygen O, sulphur S, nitrogen N and/or phosphorus P. Thus, the
donor D can be chosen from the alcohol, thiol, phenol, primary
amine, secondary amine, quaternary ammonium, amide, urea,
hydrazine, carboxylic acid, oxime, hydrazone, imine groups and
combinations thereof.
[0042] The acceptor A can be chosen from the C.dbd.O, S.dbd.O,
P.dbd.O or N.dbd.O groups and the linear or cyclic hydrocarbon
groups containing in their hydrocarbon chain a heteroatom of oxygen
O, sulphur S, nitrogen N or phosphorus P. Preferably, the acceptor
A is chosen from the alcohol, phenol, amide, ester, urea,
hydrazine, carboxylic acid, ketone, aldehyde, lactone, lactame,
anhydride, imide, sulphoxide, sulphone, sulphonate, sulphate,
sulphite, sulphonic acid, sulphide, ether, phosphine, phosphite,
phosphonate, phosphate, nitrate or nitrite groups and combinations
thereof.
[0043] According to the invention, the organogelator can contain
organogelling molecules all having the same chemical structure. The
three units A, D and C are present in each organogelling molecule
so that a gel can be formed in the bitumen phase. The
organogelators which can be used in the invention are in particular
those described in the article by P. Terech and R. G. Weiss "Low
molecular mass gelators of organic liquids and the properties of
their gels" (Chem. Rev. 1997, 97, 3133-3159).
[0044] More especially, the organogelator according to the
invention can contain organogelling molecules of formula (I)
below:
R--(NH).sub.nCONH--(X).sub.m--NHCO(NH).sub.n--R' (I)
[0045] in which:
[0046] R and R', identical or different, contain a linear, cyclic
or branched, saturated or unsaturated hydrocarbon chain, comprising
1 to 22 carbon atoms, optionally substituted and optionally
comprising heteroatoms, rings and/or heterocycles;
[0047] X contains a linear, cyclic or branched, saturated or
unsaturated hydrocarbon chain, comprising 1 to 22 carbon atoms,
optionally substituted and optionally comprising heteroatoms, rings
and/or heterocycles;
[0048] n and m are integers having independently of each other a
value of 0 or 1.
[0049] In a variant of the invention, the integer m has a value of
0. In this particular case, the R--(NH).sub.nCONH and
NHCO(NH).sub.n--R' groups are covalently bound by a CONH--NHCO
hydrazide bond. In this case, the R group or the R' group or both,
constitute the compatibilizer C. The R group or the R' group then
comprises a group chosen from at least one hydrocarbon chain of at
least 4 carbon atoms, at least one aliphatic ring of 3 to 8 atoms,
at least one condensed polycyclic system which is aliphatic,
partially aromatic or wholly aromatic, each ring comprising 5 or 6
atoms, alone or in a mixture. Preferably, R and R', identical or
different, are saturated linear hydrocarbon chains comprising 4 to
22 carbon atoms. Among the preferred saturated linear hydrocarbon
chains, there can be mentioned the C.sub.4H.sub.9, C.sub.5H.sub.11,
C.sub.9H.sub.19, C.sub.11H.sub.23, C.sub.12H.sub.25,
C.sub.17H.sub.35, C.sub.18H.sub.37, C.sub.21H.sub.43,
C.sub.22H.sub.45 groups.
[0050] In another variant of the invention, the integer m has a
value of 1. In this case, the R group, the R' group and/or the X
group constitute the compatibilizer C. The R group, the R' group
and/or the X group, then comprises a group chosen from at least one
hydrocarbon chain of at least 4 carbon atoms, at least one
aliphatic ring of 3 to 8 atoms, at least one condensed polycyclic
system which is aliphatic, partially aromatic or wholly aromatic,
each ring comprising 5 or 6 atoms, alone or in a mixture.
[0051] Preferably, the X group represents a saturated linear
hydrocarbon chain comprising 1 to 22 carbon atoms. Preferably, the
X group is chosen from the C.sub.2H.sub.4, C.sub.3H.sub.6
groups.
The X group can also be a cyclohexyl group or a phenyl group, the
R--(NH).sub.nCONH-- and NHCO(NH).sub.n--R'-- radicals can then be
in ortho, meta or para position. Moreover, they can be in cis or
trans position with respect to one another. Moreover, when the X
radical is cyclic, this ring can be substituted by groups other
than the two main R--(NH).sub.nCONH-- and --NHCO(NH).sub.n--R'
groups.
[0052] The X group can also comprise two or more condensed or
non-condensed aliphatic and/or aromatic rings. Thus, according to a
preferred variant of the invention, the X group is a group
comprising two aliphatic rings linked by an optionally substituted
CH.sub.2 group such as for example:
##STR00005##
According to another variant of the invention, the X group is a
group comprising two aromatic rings linked by an optionally
substituted CH.sub.2 group such as for example:
##STR00006##
[0053] Among the preferred organogelators according to the
invention, there can be mentioned the hydrazide derivatives
corresponding to the following formulae:
C.sub.5H.sub.11--CONH--NHCO--C.sub.5H.sub.11
C.sub.9H.sub.19--CONH--NHCO--C.sub.9H.sub.19
C.sub.11H.sub.23--CONH--NHCO--C.sub.11H.sub.23
C.sub.17H.sub.35--CONH--NHCO--C.sub.17H.sub.35
C.sub.21H.sub.43--CONH--NHCO--C.sub.21H.sub.43
There the diamides can also be mentioned, of which a preferred
diamide is N,N'-ethylenedi(stearamide),
C.sub.17H.sub.35--CONH--CH.sub.2--CH.sub.2--NHCO--C.sub.17H.sub.35.
Other preferred compounds are ureide derivatives, of which one
particular urea, 4,4'-bis(dodecylaminocarbonylamino)diphenylmethane
has the formula:
C.sub.12H.sub.25--NHCONH--C.sub.6H.sub.4--CH.sub.2--C.sub.6H.sub.4--NHCO-
NH--C.sub.12H.sub.25.
[0054] Still according to the invention the organogelator can
contain organogelling molecules of formula (II) below:
(R--NH--CO).sub.x--Z--(NH--CO--R').sub.y (II)
[0055] in which:
[0056] R and R', identical or different, contain a linear, branched
or cyclic, saturated or unsaturated hydrocarbon chain comprising 1
to 22 carbon atoms, optionally substituted, and optionally
comprising heteroatoms, rings and/or heterocycles;
[0057] Z represents a tri-functionalized group chosen from the
following groups:
##STR00007##
[0058] x and y are different integers with a value varying from 0
to 3 and such that x+y=3.
[0059] Among the preferred compounds corresponding to formula (II),
there can be mentioned, when x is equal to 0 and Z represents
Z.sub.2, N2, N4, N6-tridecylmelamine having the following formula
with R' representing the C.sub.9H.sub.19 group:
##STR00008##
[0060] Other preferred compounds corresponding to formula (II), are
such that x is equal to 0, Z represents Z.sub.2 and R' represents a
linear, saturated hydrocarbon chain of 1 to 22 carbon atoms,
preferably 2 to 18 carbon atoms, preferably 5 to 12 carbon atoms.
Other preferred compounds corresponding to formula (II), are such
that y is equal to 0 and Z represents Z.sub.1, the compounds then
have the formula:
##STR00009##
[0061] with R chosen from the following groups alone or
mixtures
##STR00010##
Other preferred compounds corresponding to formula (U), are such
that y is equal to 0, Z represents Z.sub.1 and R represents a
linear, saturated hydrocarbon chain of 1 to 22 carbon atoms,
preferably 8 to 12 carbon atoms.
[0062] Still according to the invention, the organogelator
comprises sorbitol derivatives (III) and in particular,
1,3:2,4-Di-O-benzylidene-D-sorbitol. By sorbitol derivative is
meant any reaction product obtained from sorbitol. In particular,
any reaction product obtained by reacting an aldehyde with
sorbitol. By this condensation reaction, sorbitol acetals, which
are sorbitol derivatives, are obtained.
1,3:2,4-Di-O-benzylidene-D-sorbitol is obtained by reacting 1 mole
of D-sorbitol and 2 moles of benzaldehyde and has the formula:
##STR00011##
[0063] The sorbitol derivatives can thus be all aldehyde
condensation products, in particular aromatics with sorbitol.
Sorbitol derivatives will then be obtained with the general
formula:
##STR00012##
Where Ar.sub.1 and Ar.sub.2 are optionally substituted aromatic
rings.
[0064] Among the sorbitol derivatives, apart from
1,3:2,4-Di-O-benzylidene-D-sorbitol there can be found for example
1,3:2,4:5,6-tri-O-benzylidene-D-sorbitol,
2,4-mono-O-benzylidene-D-sorbitol, 1,3:2,4-bis(p-methylbenzylidene)
sorbitol, 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol,
1,3:2,4-bis(p-ethylbenzylidene) sorbitol,
1,3:2,4-bis(p-propylbenzylidene) sorbitol,
1,3:2,4-bis(p-butylbenzylidene) sorbitol,
1,3:2,4-bis(p-ethoxylbenzylidene) sorbitol,
1,3:2,4-bis(p-chlorobenzylidene) sorbitol,
1,3:2,4-bis(p-bromobenzylidene) sorbitol,
1,3:2,4-Di-O-methylbenzylidene-D-sorbitol,
1,3:2,4-Di-O-dimethylbenzylidene-D-sorbitol,
1,3:2,4-Di-O-(4-methylbenzylidene)-D-sorbitol,
1,3:2,4-Di-O-(4,3-dimethylbenzylidene)-D-sorbitol. Instead of
sorbitol, the use of any other polyalcohol such as for example,
xylitol, mannitol and/or ribitol could be envisaged.
[0065] Still according to the invention, other organogelators
contain organogelling molecules of general formula (IV), with R'' a
linear or branched, saturated or unsaturated chain comprising 4 to
68 carbon atoms, preferably 4 to 54 carbon atoms, more
preferentially 4 to 36 carbon atoms and z an integer varying from 2
to 4: R''--(COOH).sub.z (IV). The organogelators corresponding to
formula (IV) can be diacids (z=2), triacids (z=3) or tetracids
(z=4). The preferred organogelators are diacids with z=2.
Similarly, the R'' group is preferably a saturated linear chain of
formula C.sub.wH.sub.2w with w an integer varying from 4 to 22,
preferably from 4 to 12. Preferably, the diacids have the general
formula HOOC--C.sub.wH.sub.2w--COOH with w an integer varying from
4 to 22, preferably from 4 to 12 and where z=2 and
R''=C.sub.wH.sub.2w.
[0066] The preferred diacids are the following:
[0067] adipic acid or 1,6-hexanedioic acid with w=4
[0068] pimelic acid or 1,7-heptanedioic acid with w=5
[0069] suberic acid or 1,8-octanedioic acid with w=6
[0070] azelaic acid or 1,9-nonanedioic acid with w=7
[0071] sebacic acid or 1,10-decanedioic acid with w=8
[0072] undecanedioic acid with w=9
[0073] 1,2-dodecanedioic acid with w=10
[0074] tetradecanedioic acid with w=12
[0075] The diacids can also be diacid dimers of unsaturated fatty
acid(s) i.e. dimers formed from at least one unsaturated fatty
acid, for example from a single unsaturated fatty acid or from two
different unsaturated fatty acids. The diacid dimers of unsaturated
fatty acid(s) are in a standard fashion obtained by intermolecular
dimerization reaction of at least one unsaturated fatty acid (Diels
Aider reaction for example). Preferably, a single type of
unsaturated fatty acid is dimerized. They are derived in particular
from the dimerization of an unsaturated fatty acid, in particular
C.sub.8 to C.sub.34, in particular C.sub.12 to C.sub.22, in
particular C.sub.10 to C.sub.20, and more particularly C.sub.18. A
preferred fatty acid dimer is obtained by dimerization of linoleic
acid, the latter then being able to be partially or totally
hydrogenated. Another preferred fatty acid dimer has the formula
HOOC--(CH.sub.2).sub.7--CH.dbd.CH--(CH.sub.2).sub.7--COOH. Another
preferred fatty acid dimer is obtained by dimerization of methyl
linoleate. In the same way, it is possible to find fatty acid
triacids and fatty acid tetracids, obtained respectively by
trimerization and tetramerization of at least one fatty acid.
[0076] Other organogelators contain organogelling molecules of
general formula (V) below:
##STR00013##
[0077] The Y and Y' groups represent independently of each other,
an atom or group chosen from: H, --(CH.sub.2)q-CH.sub.3,
--(CH.sub.2)q-NH.sub.2, --(CH.sub.2)q-OH, --(CH.sub.2)q-COOH or
##STR00014##
with q an integer varying from 2 to 18, preferably 2 to 10,
preferably 2 to 4 and p an integer greater than or equal to 2,
preferably having a value of 2 or 3.
[0078] Among the preferred organogelators corresponding to formula
(V), there can be mentioned the following compounds:
##STR00015##
[0079] Still according to the invention, other organogelators
contain organogelling molecules of general formula (VI)
R--NH--CO--CO--NH--R', with R and R', identical or different, which
represent a linear, branched or cyclic, saturated or unsaturated
hydrocarbon chain comprising 1 to 22 carbon atoms, optionally
substituted, and optionally comprising heteroatoms, rings and/or
heterocycles. Preferably, R and R', identical or different,
represent a linear, saturated hydrocarbon chain comprising 1 to 22
carbon atoms, preferably 8 to 12 carbon atoms.
[0080] Still according to the invention the organogelator can also
contain organogelling molecules which do not all have the same
chemical structure. Thus according to the invention, the
organogelator (VII) can contain at least two types of organogelling
molecules having a different chemical structure. When there are two
types of organogelling molecules, the three units A, D and C are
found throughout the organogelator constituted by organogelling
molecules of different chemical structure, but distributed
differently over these two types of organogelling molecules. Thus
if a type T.sub.1 of organogelling molecules and a second type
T.sub.2 are considered, T.sub.1 can contain the units A and C and
T.sub.2 the unit D. It is also possible to have the combination D+C
in a first type T.sub.1 of organogelling molecules and A in a
second type T.sub.2 of organogelling molecules. It is also possible
to envisage a first type T.sub.1 having the three units A, D, C and
a second type T.sub.2 also having the three units A, C, D but based
on a different chemical structure. The three units not being of the
same chemical nature or not distributed in the same way over
T.sub.1 and T.sub.2.
[0081] Among these organogelators (VII) comprising two types of
organogelling molecules, there can be mentioned the combinations of
the derivatives chosen from the amine derivatives, aminopyrimidine
derivatives or phenol derivatives combined with molecules chosen
from the carboxylic acid derivatives, barbituric acid derivatives
or sulphosuccinate derivatives. Preferably, there can be mentioned
the combinations:
[0082] of amine derivatives combined with carboxylic acid
derivatives,
[0083] of aminopyrimidine derivatives combined with barbituric acid
derivatives,
[0084] of phenol derivatives combined with sulphosuccinate
derivatives.
Among these combinations there can be mentioned in particular the
combination of 5-octyl-2,4,6-triammopyrimidine and
5,5-dioctylbarbituric acid or the combination of
5-octyl-2,4,6-triaminopyrimidine and barbituric acid.
[0085] There can also be mentioned the combinations of 2-naphthol
or tannic acid or lauryl gallate with the sodium salts of dioctyl
sulphosuccinate or dihexyl sulphosuccinate. The scope of the
invention will not be exceeded by combining several different
molecules such as those previously mentioned and in particular the
molecules described in formulae (I), (II), (III), (IV), (V), (VI)
and (VII). According to a preferred embodiment of the invention the
organogelling molecules have a molar mass less than or equal to
2000 gmol.sup.-1 and preferably less than or equal to 1000
gmol.sup.-1.
[0086] The rupture temperature T.sub.R at which the network of
hydrogen bonds disappears is a function of the number and strength
of the bonds created within the organogelator and is consequently a
function of the chemical structure of the organogelling molecules
and the concentration of the organogelator in the bitumen. The
rupture temperature T.sub.R is according to the invention comprised
between 40.degree. C. and 120.degree. C. These temperatures were
determined experimentally by measuring the ring and ball softening
temperature as defined in the standard NF EN 1427. It was possible
to correlate these rupture temperatures with the disappearance of
the hydrogen bonds by means of infrared spectroscopy which made it
possible to monitor the development of the intensity of the
absorption bands corresponding to the hydrogen bonds present in the
organogelator at the different test temperatures.
[0087] The bituminous compositions according to the invention are
constituted by a major proportion of bitumen and a minor proportion
of organogelator. The organogelator represents 0.1 to 5.0% by
weight with respect to the weight of bitumen. A quantity of less
than 0.1% by weight of organogelator could be insufficient to
obtain a bituminous composition according to the invention, as the
organogelling molecules would be too far away from each other to
bind together; whereas a quantity greater than 5.0% by weight of
organogelator may not be necessary, as the organogelator acts at a
low dose. According to a preferred implementation, the
organogelator represents 0.5 to 3% by weight with respect to the
weight of bitumen, and better still, 1 to 2% by weight with respect
to the weight of bitumen.
[0088] The bituminous compositions according to the invention can
contain bitumens of different origins. There can be mentioned
firstly the bitumens of natural origin, those contained in deposits
of natural bitumen, natural asphalt or bituminous sands. The
bitumens according to the invention are also the bitumens
originating from the refining of crude oil. The bitumens originate
from the atmospheric and/or vacuum distillation of oil. These
bitumens being able to be optionally blown, visbroken and/or
de-asphalted. The bitumens can be bitumens of hard or soft grade.
The different bitumens obtained by the refining processes can be
combined with each other in order to obtain the best technical
compromise.
[0089] The bitumens used can also be bitumens fluxed by adding
volatile solvents, fluxes of oil origin, carbochemical fluxes
and/or fluxes of vegetable origin. The bitumens used can also be
special bitumens such as the bitumens modified by the addition of
polymers. By way of examples of polymers for bitumen, there can be
mentioned elastomers such as the copolymers SB, SBS, SIS, SBS*,
SBR, EPDM, polychloroprene, polynorbonene and optionally
polyolefins such as polyethylenes PE, PEHD, polypropylene PP,
plastomers such as EVA, EMA, copolymers of olefins and unsaturated
carboxylic esters EBA, elastomeric polyolefin copolymers,
polybutene-type polyolefins, copolymers of ethylene and acrylic,
methacrylic acid or maleic anhydride esters, copolymers and
terpolymers of ethylene and glycidyl methacrylate,
ethylene-propylene copolymers, rubbers, polyisobutylenes, SEBSs,
ABSs.
[0090] Other additives can also be added to a bitumen base
according to the invention. These are for example vulcanization
agents and/or cross-linking agents capable of reacting with a
polymer, when an elastomer and/or a plastomer, which can be
functionalized and/or can comprise reactive sites, is involved.
Among the vulcanization agents there can be mentioned those which
are based on sulphur and its derivatives, used to cross-link an
elastomer at levels of 0.01% to 30% with respect to the weight of
elastomer.
[0091] Among the cross-linking agents there can be mentioned
cationic cross-linking agents such as mono- or polyacids, or
carboxylic anhydrides, carboxylic acid esters, sulphonic,
sulphuric, phosphoric acids, even acid chlorides, phenols, at
levels of 0.01% to 30% with respect to the polymer. These agents
are capable of reacting with the elastomer and/or the
functionalized plastomer. They can be used to complement or replace
vulcanization agents.
[0092] Various uses of the bituminous compositions obtained
according to the invention are envisaged, in particular for the
preparation of a bituminous binder, which can in turn be used for
preparing a combination with aggregates, in particular road
aggregates. Another aspect of the invention is the use of a
bituminous composition in various industrial applications, in
particular for preparing a sealing membrane, membrane or
impregnation layer. With regard to highway applications, the
invention relates in particular to bituminous mixes as materials
for the construction and maintenance of road foundations and their
surfacing, as well as for carrying out all road works. Thus, the
invention relates for example to surface dressings, hot mixes, cold
mixes, cold-cast mixes, gravel emulsions, base, binder, bonding and
wearing courses, and other combinations of a bituminous binder and
highway aggregate having particular properties such as anti-rutting
courses, draining mixes, or asphalts (mixture of a bituminous
binder and sand-type aggregates). With regard to the industrial
applications of the bituminous compositions, the following can be
mentioned: the manufacture of sealing membranes, anti-noise
membranes, insulating membranes, surface coatings, carpet tiles,
impregnation layers, etc.
[0093] The invention also relates to a method for obtaining a
bituminous composition which is hard at the temperatures of use
without increasing its viscosity when hot. The organogelator can
equally well be introduced into the bitumen alone, or during
manufacture, into the polymer bitumen, into the bituminous binder,
into the binder in the anhydrous form or in the form of a
bituminous mix, but always when hot to temperatures varying from
140 to 180.degree. C. The mixtures can then be stirred at these
temperatures until solubilization of the organogelator in the
bitumen, the polymer bitumen, the bituminous binder, the binder in
the anhydrous form or in the form of a bituminous mix.
EXAMPLES
[0094] The invention is illustrated by the following non-limitative
examples. The rheological and mechanical characteristics of the
bitumens or of the bitumen-organogelator compositions to which
reference is made in these examples are measured as indicated in
Table 1. Moreover, the Brookfield viscosity is expressed in mPas.
The viscosity is measured using a Brookfield CAP 2000+ viscometer.
It is measured at 140 and 160.degree. C. and at a speed of rotation
of 300 rpm. The measurement is read after 30 seconds for each
temperature.
TABLE-US-00001 TABLE 1 Measurement Property Abbreviation Unit
standard Needle penetrability at 25.degree. C. P.sub.25 1/10 mm NF
EN 1426 Ring and ball softening point RBSP .degree. C. NF EN 1427
Brookfield viscosity -- Mpa s Cf. examples
Example 1
Preparation of a Bitumen/Organogelator Composition of Formula
(I)
[0095] This first example relates to bitumen+organogelator
compositions of general formula (I) according to the invention.
Five types of organogelling molecules have been used in this
example, at different concentrations. Their chemical structures are
as follows:
C.sub.5H.sub.11--CONH--NHCO--C.sub.5H.sub.11 (1)
C.sub.9H.sub.19--CONH--NHCO--C.sub.9H.sub.19 (2)
C.sub.11H.sub.23--CONH--NHCO--C.sub.11H.sub.23 (3)
C.sub.17H.sub.35--CONH--CH.sub.2--CH.sub.2--NHCO--C.sub.17H.sub.35
(4)
C.sub.12H.sub.25--NHCONH--C.sub.6H.sub.4--CH.sub.2--C.sub.6H.sub.4--NHCO-
NH--C.sub.12H.sub.25 (5)
[0096] The preparations are produced at 160-170.degree. C., in a
reactor with stirring. The control bitumen C.sub.1 is introduced
into the reactor first. Then, the organogelator is added. The
mixtures are stirred for approximately 60 minutes. Their final
appearance is homogeneous. The mixtures are cooled down to ambient
temperature. The control bitumen C.sub.1 is a direct distillation
bitumen of grade 70-100 the characteristics of which correspond to
the standard NF EN 12591.
TABLE-US-00002 TABLE 2 Nature of the Organogelator Compositions
organogelator concentration C.sub.1 (control) -- 0% C.sub.2 (1) 1%
C.sub.3 (1) 2% C.sub.4 (1) 3% C.sub.5 (2) 2% C.sub.6 (2) 3% C.sub.7
(3) 2% C.sub.8 (3) 3% C.sub.9 (3) 4% C.sub.10 (4) 2% C.sub.11 (4)
3% C.sub.12 (5) 3%
[0097] Determination of the Rupture Temperature T.sub.R by Infrared
Spectroscopy
[0098] In order to carry out the measurements, a drop is taken from
the preheated and applied to a KBr pellet, then the KBr pellet is
scraped onto a glass slide in order to obtain a relatively
translucid "film". The IR device used is a Nicolet Avatar 320
spectrometer, the temperature controller is a (P/N21525) from
Specac. At different temperatures, the evolution of the absorption
bands of the groups involved in the hydrogen bonds is
monitored.
[0099] For the particular C.sub.6 composition, the spectra of FIG.
1 are obtained.
[0100] The more the temperature increases, the lower the intensity
of the band around 3200 cm.sup.-1 of the bound NHs. Taking the
intensity of the bound NH band as a function of temperature, the
graph of FIG. 2 is obtained which gives us the rupture temperature
T.sub.R=105.degree. C. of the composition C.sub.6.
[0101] For the C.sub.4 composition, the rupture temperature T.sub.R
obtained is 85.degree. C.
[0102] For the C.sub.8 composition, the rupture temperature T.sub.R
obtained is 105.degree. C.
[0103] These rupture temperatures are also determined by measuring
the ring and ball softening temperature. The results are reported
in Table 3 below:
[0104] Determination of the Physical Properties of the
Bitumen+Organogelator Compositions
TABLE-US-00003 TABLE 3 Ring and ball softening Pfeiffer Com-
Penetrability point index Viscosity Viscosity positions P.sub.25
(RBSP) PI at 140.degree. C. at 160.degree. C. C.sub.1 76 46.6 -1.0
267 165 (control) C.sub.2 62 48.4 -1.1 261 160 C.sub.3 51 70.8 3.0
255 158 C.sub.4 46 86.4 4.9 250 155 C.sub.5 55 81.4 4.8 242 153
C.sub.6 52 105.2 7.4 228 148 C.sub.7 55 80.6 4.7 240 151 C.sub.8 50
102.6 6.9 232 147 C.sub.9 47 111.0 7.5 224 145 C.sub.10 58 91.0 6.1
225 145 C.sub.11 55 96.5 6.5 203 144 C.sub.12 69 52.2 0.14 298
173
[0105] The needle penetrability, measured at 25.degree. C., is
expressed in 1/10 mm.
[0106] The ring and ball softening point is expressed in .degree.
C.
[0107] The Pfeiffer penetration index PI is defined by the
following calculation formula:
IP = 1952 - 500 .times. log ( P 25 ) - 20 .times. RBSP 50 .times.
log ( P 25 ) - RBSP - 120 ##EQU00001##
[0108] The viscosity, measured at 160.degree. C., is expressed in
mPas.sup.-1.
[0109] As shown by the results in Table 3, the correlation between
the softening temperatures and the temperature of the disappearance
of the IR bands corresponding to the hydrogen bonds for the
examples C.sub.6 and C.sub.4 is established as the rupture
temperatures are virtually identical to the softening
temperatures.
[0110] Moreover, whatever the organogelator used, its action is
equivalent. It is characterized by a reduction in the penetrability
P.sub.25, an increase in the ring and ball temperature and an
increase in the Pfeiffer index. This reflects a greater hardness
and consistency of the bitumen bases with the different
organogelators added.
[0111] Similarly, the higher the organogelator concentration, the
greater the hardness and consistency of the bitumen. A greater
network of hydrogen bonds increases the hardness of the bitumen at
the temperatures of use.
[0112] Finally, the viscosities at a given temperature of the
bitumen alone and the bitumen with additives are equivalent. The
addition of organogelator makes it possible to harden the
bituminous composition without increasing the viscosity of the
bituminous composition when hot.
Example 2
Preparation of a Bitumen/Organogelator Composition with
Organogelling Molecules of a Different Nature (VII)
[0113] The compositions are prepared in the same way as in example
1. The organogelator concentration is 3%. The organogelator (for
example C.sub.13 or C.sub.14) is constituted by a first type
T.sub.1 of organogelling molecules (A.sub.1) and by a second type
T.sub.2 of organogelling molecules (B.sub.1 or B.sub.2). The molar
ratio of the two types T.sub.1 and T.sub.2 is 1 to 1.
[0114] Aminopyrimidine+barbituric acid
##STR00016##
[0115] The composition C.sub.13 comprises an aminopyrimidine
derivative A.sub.1, 5-octyl-2,4,6-triaminopyrimidine and a
barbituric acid derivative B.sub.1, 5,5-dioctylbarbituric acid. The
C.sub.14 composition comprises an aminopyrimidine derivative
A.sub.1, 5-octyl-2,4,6-triaminopyrimidine and barbituric acid
B.sub.2.
TABLE-US-00004 TABLE 4 Ring and ball softening Com- Penetrability
point Pfeiffer Viscosity Viscosity positions P.sub.25 (RBSP) index
PI at 140.degree. C. at 160.degree. C. C.sub.1 76 47.5 -0.8 267 165
C.sub.13 59 52.0 -0.31 276 168 C.sub.14 61 52.5 -0.11 311 186
[0116] Phenol+sulphosuccinate
[0117] The C.sub.15 composition comprises the sodium salt of
dioctyl sulphosuccinate and tannic acid. The C.sub.16 composition
comprises the sodium salt of dihexyl sulphosuccinate and tannic
acid. The C.sub.17 composition comprises the sodium salt of dihexyl
sulphosuccinate and lauryl gallate. The C.sub.18 composition
comprises the sodium salt of dihexyl sulphosuccinate and
2-naphthol.
TABLE-US-00005 TABLE 5 Ring and ball softening Com- Penetrability
point Pfeiffer Viscosity Viscosity positions P.sub.25 (RBSP) index
PI at 140.degree. C. at 160.degree. C. C.sub.1 76 47.5 -0.8 267 165
C.sub.15 71 52.2 0.2 277 163 C.sub.16 60 52.8 -0.08 253 144
C.sub.17 70 50.8 -0.17 268 164 C.sub.18 68 51.4 -0.09 267 164
Conclusions identical to those of example 1 can be drawn.
Example 3
Preparation of a Bitumen/Organogelator Composition with a Sorbitol
Derivative (III) 1,3:2,4-Di-O-benzylidene-D-sorbitol (DBS) As
Organogelator
[0118] The compositions are prepared in the same way as in example
1. The organogelator is used at different concentrations.
TABLE-US-00006 TABLE 6 Organogelator Compositions concentration
C.sub.1 (control) 0% C.sub.19 3% C.sub.20 1% C.sub.21 0.66%
C.sub.22 0.33% C.sub.23 0.1%
[0119] The results obtained are recorded in Table 7 below:
TABLE-US-00007 TABLE 7 Ring and ball softening Com- Penetrability
point Pfeiffer Viscosity Viscosity positions P.sub.25 (RBSP) index
PI at 140.degree. C. at 160.degree. C. C.sub.1 (control) 76 46.6
-1.0 267 165 C.sub.19 36 161 10 310 125 C.sub.20 39 143.5 9.31 314
118 C.sub.21 46 131.5 8.95 298 115 C.sub.22 55 94 6.28 257 113
C.sub.23 74 47.8 -0.82 253 111
[0120] It is noted that the addition of DBS makes it possible to
significantly increase the ring and ball temperature of the
compositions even at low DBS concentrations (see for example
C.sub.22). The penetrability also reduces with the addition of DBS.
The viscosities at 140.degree. C. and 160.degree. C. of the
compositions with additives are equivalent to those of the bitumen
alone.
Example 4
Preparation of a Bitumen/Organogelator Composition of Formula
(IV)
[0121] The compositions are prepared in the same way as in example
1. The different organogelators in Table 8 are used.
TABLE-US-00008 TABLE 8 Nature of the Organogelator Compositions
organogelator concentration C.sub.1 (control) -- 0% C.sub.24
HOOC--(CH.sub.2).sub.4--COOH 3% C.sub.25
HOOC--(CH.sub.2).sub.5--COOH 3% C.sub.26
HOOC--(CH.sub.2).sub.6--COOH 3% C.sub.27
HOOC--(CH.sub.2).sub.7--COOH 3% C.sub.28
HOOC--(CH.sub.2).sub.8--COOH 3% C.sub.29
HOOC--(CH.sub.2).sub.9--COOH 3% C.sub.30
HOOC--(CH.sub.2).sub.10--COOH 3% C.sub.31
HOOC--(CH.sub.2).sub.12--COOH 3%
TABLE-US-00009 TABLE 9 Ring and ball softening Com- Penetrability
point Pfeiffer Viscosity Viscosity positions P.sub.25 (RBSP) index
PI at 140.degree. C. at 160.degree. C. C.sub.1 (control) 76 46.6
-1.0 267 165 C.sub.24 52 68.8 2.73 280 114 C.sub.25 57 64.4 2.21
250 108 C.sub.26 55 77.5 4.23 242 104 C.sub.27 37 103.6 6.22 223
100 C.sub.28 39 104.8 6.46 225 97 C.sub.29 35 106.3 6.34 220 97
C.sub.30 29 110.5 6.28 217 95 C.sub.31 28 110 6.16 217 96
[0122] With the diacids, the viscosities of the compositions are
equivalent and even less than that of the bitumen alone. At ambient
temperature, the compositions according to the invention are
clearly harder than the bitumen alone. When hot, the compositions
according to the invention have a ring and ball temperature clearly
higher than that of the bitumen alone.
Example 5
Preparation of a Bitumen/Organogelator Composition with a Sorbitol
Derivative (III), 1,3:2,4-bis-(p-methylbenzylidene)-sorbitol (MDBS)
as Organogelator
[0123] The compositions are prepared in the same way as in example
1. MDBS at different concentrations (Table 10) is used.
1,3:2,4-Di-O-(4,3-methylbenzylidene)-D-sorbitol (MDBS) has the
formula:
TABLE-US-00010 TABLE 10 ##STR00017## Compositions Organogelator
concentration C.sub.1 (control) 0% C.sub.32 3% C.sub.33 1% C.sub.34
0.66% C.sub.35 0.5%
[0124] The results obtained are recorded in Table 11 below:
TABLE-US-00011 TABLE 11 Ring and ball softening Com- Penetrability
point Pfeiffer Viscosity Viscosity positions P.sub.25 (RBSP) index
PI at 140.degree. C. at 160.degree. C. C.sub.1 (control) 76 46.6
-1.0 267 165 C.sub.32 63 57 1.0 -- -- C.sub.33 50 85 4.97 301 130
C.sub.34 48 95 6.9502 286 124 C.sub.35 52 85 5.08 291 126
[0125] It is noted that the addition of MDBS makes it possible to
increase the ring and ball temperature of the compositions. The
penetrability also reduces with the addition of the MDBS. The
viscosities at 140.degree. C. and 160.degree. C. of the
compositions with additives are equivalent to those of the bitumen
alone.
Example 6
Preparation of a Bitumen/Organogelator Composition of Formula
(II)
[0126] The compositions are prepared in the same way as in example
1. Four organogelators corresponding to formula (II) are used:
[0127] Irgaclear XT386 sold by Ciba (y equal to 0, Z being the
Z.sub.1 group), at the following concentrations (Table 12):
TABLE-US-00012 [0127] TABLE 12 Organogelator Compositions
concentration C.sub.1 (control) 0% C.sub.36 3% C.sub.37 1% C.sub.38
0.66%
[0128] a compound of formula:
[0128] ##STR00018## [0129] With y equal to 0, Z being the Z group;
and R the C.sub.12H.sub.25 group, at a concentration of 3% by mass
(C.sub.39). [0130] a compound of formula:
[0130] ##STR00019## [0131] With x equal to 0, Z being the Z.sub.2
group and R' the C.sub.2H.sub.5 group, at a concentration of 3% by
mass (C.sub.40). [0132] a compound of formula:
[0132] ##STR00020## [0133] With x equal to 0, Z being the Z.sub.2
group and R' the C.sub.5H.sub.11 group, at a concentration of 3% by
mass (C.sub.41).
[0134] The results are recorded in Table 13 below:
TABLE-US-00013 TABLE 13 Ring and ball softening Pfeiffer Viscosity
Com- Penetrability point index at Viscosity positions P.sub.25
(RBSP) PI 140.degree. C. at 160.degree. C. C.sub.1 (control) 76
46.6 -1.0 267 165 C.sub.36 57 55.0 -0.29 -- -- C.sub.37 66 52.5
0.09 310 137 C.sub.38 72 48.8 -0.62 288 128 C.sub.39 52 95 6.23 279
103 C.sub.40 68 48.8 -0.77 292 131 C.sub.41 72 48.5 -0.70 282
114
[0135] With the organogelators of formula (II), the viscosities of
the compositions are equivalent and even less than that of the
bitumen alone. At ambient temperature, the compositions according
to the invention are harder than the bitumen alone. When hot, the
compositions according to the invention have a ring and ball
temperature higher than those of the bitumen alone.
Example 7
Preparation of a Bitumen/Organogelator Composition of Formula
(VI)
[0136] The compositions are prepared in the same way as in example
1. Two organogelators corresponding to formula (VI) are used:
[0137] C.sub.12H.sub.25--NH--CO--CO--NH--C.sub.12H.sub.25
(concentration 2%, C.sub.42)
[0138] C.sub.8H.sub.17--NH--CO--CO--NH--C.sub.8H.sub.17
(concentration 3%, C.sub.43)
TABLE-US-00014 TABLE 14 Ring and ball softening Pfeiffer Viscosity
Viscosity Com- Penetrability point index at at positions P.sub.25
(RBSP) PI 140.degree. C. 160.degree. C. C.sub.1 (control) 76 46.6
-1.0 267 165 C.sub.42 74 50 -0.22 204 92 C.sub.43 62 50 -0.69 237
107
GENERAL CONCLUSION
[0139] The bitumen is hardened at the temperatures of use by the
organogelator constituted by the same organogelling molecule or by
two molecules of different chemical nature; the viscosity when hot
not being increased relative to that of the bitumen with no
additives.
* * * * *