LACTAME OR AMINO ACID-BASED FATTY AMIDE, AND USE AS AN
ORGANOGELATOR
The invention relates to an amide of specific composition comprising, in its
composition, a lactam or an amino acid in a specific ratio with respect to a diamine, to its
process of preparation and to its use as organogelator or rheology additive in various
applications, such as coating, mastic, sealant, moulding or cosmetic compositions. These
diamides have a performance having a specific behaviour at high temperature, in
particular a behaviour of resistance to running at high temperature, preferably at a
temperature of at least 60°C and more particularly at a temperature of at least 70°C.
This is because the amide additive of the present invention has a high temperature
stability, making possible, at the same time as the activation of said amide at higher
temperatures, its use also in application systems requiring higher temperatures of use. In
particular, the diamide of the invention makes possible activation and temperature stability
and use at a temperature of at least 60°C.
Moreover, the present invention makes possible, by the use of a specific process
practical in its implementation, the fine incorporation of said lactam or amino acid so as to
have a well controlled and fine structure of the diamide, as regards its end (fatty) groups,
so as to have reproducibility and control of the fine structure and consequently of its
rheology performance.
The invention relates first to an amide having a specific composition.
The second subject of the invention is a preparation process with two alternative
modes according to mode A) or according to mode B).
Another subject of the invention is an organogelator, in particular rheology additive,
which comprises or consists of at least one amide according to the invention.
An organic binder composition which comprises an amide of the invention as
organogelator, in particular as rheology additive, the use of said amide for this purpose
and the final products thus obtained are also covered.
Thus, the first subject of the present invention is a fatty amide based on (meaning
capable of being obtained by reaction of):
a) a primary diamine selected from aromatic, cycloaliphatic or linear C2 to C10
aliphatic diamines,
b) a C3 to C12 lactam or amino acid, preferably a C3 to C12 lactam, more preferably a
C4 to C9 lactam and more preferably still a C6 lactam,
c) optionally a second primary diamine differen from said diamine a), preferably
chosen from linear C2 to C10 aliphatic diamines,

d) a hydroxylated fatty, preferably . C18 or C20, monoacid, more.. preferably
12-hydroxystearic acid or 14-hydroxyeicosanoic acid, preferably 12-hydroxystearic
acid,
e) optionally, a nonhydroxylated monoacid chosen from linear C6 to C12, in particular
C6 to C10, aliphatic acids, with the mole ratio e/d of said monoacid e) with respect
to said monoacid d) preferably not exceeding 0.5,
and with the mole ratio b/(a+c) ranging from 0.25 to 3/1, preferably from 0.25 to 2/1 and
more preferentially from 0.35 to 2/1.
Preferably, in the structure of the amide of the present invention, the possible
formation of oligoamide with repeat units derived from the lactam or amino acid b), by
chain extension, is limited to a number of said repeat units not exceeding 3, preferably
being less than 3 and more particular ranging from 1 to 2.
It should be noted that c), in said mole ratio b/(a+c), is considered only in the case
where said diamine c) is present; otherwise, this ratio is reduced to b/a.
According to a specific option of the invention, said fatty amide comprises at least
one diamide carrying, at each end, a fatty group based on monoacid d) which can be
represented by the formula d-b-a-d, d-b-a-b-d, d-a-d and possibly d-c-d, if said diamine c)
is present.
More particularly, when said monoacid e) is present, said amide comprises at least
three diamides which can be represented by the formulae d-b-a-d, d-b-a-b-d, e-b-a-d, e-b-
a-b-d, e-b-a-e, e-b-a-b-e, d-a-d, d-a-e, e-a-e and possibly e-c-e, d-c-d, d-c-e, if said
diamine c) is present.
Mention may be made, as C18 or C20 monoacid d), of 12-hydroxystearic acid
(12-HSA), 9-hydroxystearic acid (9-HSA) and/or 10-hydroxystearic acid (10-HSA) or
14-hydroxyeicosanoic acid (14-HEA) and preferably 12-hydroxystearic acid (12-HSA) and
14-hydroxyeicosanoic acid (14-HEA), 12-hydroxystearic acid (12-HSA) being the most
preferred. Said hydroxylated monoacid may be a mixture of at least two of said monoacids
d) mentioned.
The diamines a) are primary amines. Mention may be made, as examples of linear
aliphatic diamines suitable and preferred for the diamine component a) of said diamide, of
ethylenediamine, propylenediamine, butylenediamine (or tetramethylenediamine),
pentamethylenediamine or hexamethylenediamine and preferably ethylenediamine or
hexamethylenediamine.
Mention may be made, as examples of cycloaliphatic diamines suitable still
according to the component a), of cyclohexane-1,3-diamine, cyclohexane-1,4-diamine and
cyclohexane-1,2-diamine and in particular cyclohexane-1,3-diamine or cyclohexane-

1,4-diamine, isophoronediamine, 1,3-, 1,4- or, 1.,2-bis(aminomethyl)cyclohexane_(derived
from the hydrogenation of m-, p- or o-xylylenediamine respectively), preferably 1,3- or
1,4-bis(aminomethyl)cyclohexane, decahydronaphthalenediamine, bis(4-amino-3-methyl-
cyclohexyl)methane (BMACM) or bis(4-aminocyclohexyl)methane (BACM), or
1-{[4-(aminomethyl)cyclohexyl]oxy}propan-2-amine. The preferred cycloaliphatic diamines
are selected from: cyclohexane-1,3-diamine, cyclohexane-1,4-diamine, 1,3-, 1,4- or
1,2-bis(aminomethyl)cyclohexane, isophoronediamine and
bis(4-aminocyclohexyl)methane.
Mention may be made, as suitable and preferred examples of aromatic diamines
as component a) of said diamide, of xylylenediamines, preferably m- or
p-xylylenediamines, phenylenediamines, preferably m- or p-phenylenediamines, or
toluylenediamines, preferably m- or p-toluylenediamines.
Mention may be made, as examples of suitable linear aliphatic diamines preferred
for the diamine component c) of said diamide, of ethylenediamine, propylenediamine,
butylenediamine (or tetramethylenediamine), pentamethylenediamine, or hexamethylene-
diamine and preferably ethylenediamine or hexamethylenediamine.
The component b) can be a C3 to C12 lactam, that is to say a ring with from 2 to 11
carbon atoms and an amide -CO2NH- group in the ring, where b) can be an equivalent
amino acid, form equivalent to the lactam but of linear instead of cyclic structure. The
component b) is preferably a lactam, in particular a C4 to C9 lactam and more preferably a
C6 lactam, such as caprolactam.
Mention may be made, as examples of monoacids e), of hexanoic, heptanoic,
octanoic, nonanoic, decanoic, undecanoic or dodecanoic (or lauric) acid. The following
acids are preferred: hexanoic acid, octanoic acid, nonanoic acid and decanoic acid.
Preferably, the mole ratio b/(a+c) between diamines a) and optionally c) and the
lactam or amino acid b), in particular lactam b), varies from 0.25 to 2/1 and more
preferentially from 0.35 to 2/1.
According to a specific option, said fatty amide according to the invention has, as
diamine a), a diamine selected from aromatic diamines and more preferentially, in this
case, said diamine a) is an aromatic diamine from: xylylenediamines, preferably m- or
p-xylylenediamines, phenylenediamines, preferably m- or p-phenylenediamines, or
toluylenediamines, preferably m- or p-toluylenediamines. More particularly, said aromatic
diamine a) is a xylylenediamine, preferably m- or p-xylylenediamine and more preferably
m-xylylenediamine. Still in this option and according to a more specific case, said
hydroxylated monoacid d), that, is to say the C18 or C20 hydroxy acid (or hydroxylated
monoacid), is 12-hydroxystearic acid (12-HSA) in the absence of said monoacid e).

According to another alternative option, said monoacid d) (C18 or C20 hydroxy acid) is
12-hydroxystearic acid (12-HSA) in the presence of said monoacid e), preferably e) being
selected from hexanoic acid, octanoic acid, nonanoic acid or decanoic acid.
More particularly, said diamine a) and said diamine c), when c) is present, can
correspond to, or be in the form of, a mixture of diamines composed of an aromatic
diamine a) and of a linear aliphatic diamine c) or to a mixture of a cycloaliphatic diamine a)
and of a linear aliphatic diamine c).
Said amide according to the invention can also be defined as the product that may
be obtained via a process defined according to mode A) or B) comprising the following
successive reaction steps:
- according to mode A):
i) reaction of said diamine a) with said lactam or amino acid b), preferably lactam
b), with formation of a diamine a) modified with b),
ii) reaction of the product of step i) with said monoacid d) in the presence or
absence of said monoacid e) and in the presence or absence of said diamine c), or
- according to mode B):
i') reaction of said monoacid d) or optionally of said monoacid e), if present, with
said lactam or amino acid b), preferably lactam b), with formation of the corresponding
monoacid modified with b),
ii') reaction of said modified monoacid (produced) from step i') with said diamine
a), in the presence or absence of said diamine c) and if said monoacid from said step i') is
said monoacid d), in this case, in the presence or absence of said monoacid e), otherwise,
if said monoacid from said step i') is the monoacid e), in this case, in the presence of said
monoacid d).
According to a specific option of this definition of the amide of the invention
according to mode B), said monoacid e) is present with the successive reaction stages
below:
i') reaction of said monoacid e) with said lactam or amino acid b), preferably lactam
b), with formation of a monoacid e) modified b),
ii') reaction of the said modified monoacid formed at said stage i') with said diamine a)
arid said monoacid d) and in the presence or in the absence of said diamine c).
The second subject of the invention is a corresponding process for the preparation
of the amide as defined above according to the invention which comprises or is carried out
according to at least the mode A) or the mode B) and which comprises the following
successive reaction steps as defined above and recalled below.
The process according to mode A) comprises the following successive steps:

i) reaction of said diamine a) with said lactam or amino acid b), preferably lactam
b), with formation of a diamine a) modified b),
ii) reaction of the product from stage i) with said monoacid d) in the presence or
absence of said monoacid e) and in the presence or absence of said diamine
c).
More specifically, in the said process according to the mode A), said component b)
is a lactam and said reaction with said amine a) is an anionic oligomerization of said
lactam b) using said amine as anionic initiator. This case is particularly valid for a mole
ratio b/(a+c) < 1.
The process according to mode B) comprises the following successive steps:
i') reaction of said monoacid d) or optionally of said monoacid e), if present, with
said lactam or amino acid b), preferably lactam b), with formation of the corresponding
monoacid modified with b),
ii') reaction of said modified monoacid (produced) from step i') with said diamine
a), in the presence or absence of said diamine c) and if said monoacid from said step i') is
said monoacid d), in this case, in the presence or absence of said monoacid e), otherwise,
if said monoacid from said step i') is the monoacid e), in this case, in the presence of said
monoacid d).
According to a first option of this process, according to mode B), said monoacid e)
is present and said process comprises the following successive reaction steps:
i') reaction of said monoacid e) with said lactam or amino acid b), preferably lactam
b), with formation of a monoacid e) modified with b),
ii') reaction of said modified monoacid formed in step i') with said diamine a) and
said monoacid d) and in the presence or absence of said diamine c).
Another subject of the invention is an organogelator, which comprises or consists
of at least one amide as defined above according to the invention or which is obtained by
a process as defined above according to the invention. More particularly, it is in
preactivated form in an organic solvent, preferably in an organic solvent comprising at
least one polar organic solvent.
The invention also covers an organic binder composition, which comprises at least
one amide or an organogelator as are defined above according to the invention.
Preferably, this composition is a coating composition, in particular a paint, varnish,
ink or gel coat composition, a glue or adhesive composition, a stripping, mastic or sealing
composition, a moulding composition or a cosmetic composition.

The invention also covers the use of said amide as organogelator or in particular
as rheology additive in an organic solvent medium and more particularly in coating, glue
or adhesive, stripping agent, mastic or sealant, moulding or cosmetic compositions.
Finally, the invention covers a finished product which comprises at least one amide
as defined according to the invention selected from coatings, mastic or sealant or stripping
agent, moulded part or cosmetic, glue or adhesive seal.
The following examples are presented by way of illustration of the invention and of
its performance, without any limitation of its coverage.


II - Methods and tests used
The formulations are evaluated with two tests: the flow resistance (or resistance to
running) test and an evaluation of the viscosity at different speeds.
Flow resistance test
It is carried out using a running tester (Levelling/Sagging Tester from Sheen
Instruments) which makes it possible to establish the resistance of a coating to running
due to gravity. Manufactured from stainless steel and having a straight blade, this tester
comprises notches of increasing values.
The test consists in depositing different strips of paint of parallel thickness on a
contrast strip using the running tester. The contrast chart is immediately placed in the
vertical position, the thinnest film at the top. The thickness at which the strips meet
indicates the tendency towards running.
Evaluation of the viscosity
It is carried out here using a Brookfield® RV at 25°C (spindle: S 4). The speed of
the spindle is set at 50 RPM (or rpm: rotation per minute) and the viscosity of each paint is
measured after it has stabilized. The operation is repeated for a speed of 20 RPM, 10
RPM, 5 RPM or 1 RPM.
III - Preparation and characterization of the diamides as organogelators and rheology
additives
Synthesis of a meta-(m-)xylylenediamine/caprolactam precondensate according to said
mode A) according to the invention
272 g of m-xylylenediamine (i.e., 2 mol of diamine or 4 equivalents of amine Y-
NH), 226 g of caprolactam (i.e., 2 mol) and 0.8 g of Borchikat® 22 are introduced, under a
nitrogen atmosphere, into a 0.5 litre round-bottomed flask equipped with a thermometer, a
Dean and Stark apparatus, a condenser and a stirrer.
The mixture is heated to 250°C under a stream of nitrogen. The reaction in which
the ring is opened by aminolysis is monitored by observingthe viscosity. After 8 hours,the
viscosity becomes stable and the reaction mixture is cooled to 150°C and then
discharged.
Example. 1: Diamide based qn,anrn-xylylenediamine/caprolactam precondensate and on
hexamethylenediamine

64.4g of m-xylylenediamine/caprolactam precondensate (i.e., .0.25 mol or. 0.5
equivalent of amine, the 0.25 mol of precondensate corresponding at the start to 0.25 mol
of m-XDA which has reacted with 0.25 mol of caprolactam), 63.8 g of
hexamethylenediamine (i.e., 0.25 mol, 0.5 equivalent of amine), and 315.2 g of
12-hydroxystearic acid (1.00 mol, 1.00 equivalent carboxy) are introduced, under a
nitrogen atmosphere, into a 1 litre round-bottomed flask equipped with a thermometer, a
Dean and Stark apparatus, a condenser and a stirrer.
The mixture is heated to 200°C, still under a stream of nitrogen. The water
removed begins to accumulate in the Dean and Stark apparatus from 150°C. The reaction
is monitored by the acid and amine numbers. When the acid and amine values are less
than 10 mg KOH/g, the reaction mixture is cooled to 150°C and then discharged into a
silicone mould. Once cooled to ambient temperature, the product is micronized
mechanically by grinding and sieving in order to obtain a fine and controlled size grading
with a mean size obtained of 7 u.
IV- Evaluation of the rheological performance in a paint formulation
Paint formulations used for the evaluation
1 - Preparation
A millbase formulation is prepared with the proportions of Table 3 in the following
way:
In a disperser bowl (Dispermill® 2075 yellowline, supplier: Erichsen) heated by a
jacket system:
1. Introduction of the epoxy binders and also the dispersant and the defoamer.
The homogenization takes place after 2 minutes at 800 revolutions/minute
(rpm).
2. Introduction of the fillers and pigments and then grinding at 3000
revolutions/minutes for 30 minutes using a 7 cm blade. By virtue of the
jacketed bowl, this stage is cooled with a bath of cold water (20°C).
3. Introduction of the solvents.
2 - Activation
24 hours after the preparation of the millbase, the formulation is again dispersed at
3000 revolutions/minute (rpm) using a 4 cm blade. Each diamide is introduced into the
millbase at.a given activation.temperature (varying from 40°C to 70°C) over 20 minutes at
3000 revolutions/minute.

After the addition of the diluted hardener (Table 4) to the millbase, the paints are
adjusted with a xylene/butanol (1/1) mixture to 0.4 Pa.s (measured on the cone 4 at 25°C
at 2500 s-1 using the JBrookfield® CAP 1000). The proportions between the hardener and
the mixture of solvents are defined in Table 4.
After the adjustment, the paint is mixed at 1500 revolutions/minute for 2 minutes
and then left standing for 30 minutes.

3 - Evaluation of the rheology of the formulations and results
A paint formulation was produced following the proportions of Tables 2 and 3 with
an activation temperature of 60°C according to the protocol set out above.
The resistance to running results (Table 4) and the rheology results (Table 5) show
that the diamide of Example 1 according to the invention has a thixotropic effect on the
formulation once it is activated at 60°C and a good resistance to running.

CLAIMS.
1. Fatty amide, characterized in that it is based on:
a) a primary diamine selected from aromatic, cycloaliphatic or linear C2 to C10
aliphatic diamines,
b) a C3 to C12 lactam or amino acid, preferably a C3 to C12 lactam, more preferably a
C4 to C9 lactam and more preferably still a C6 lactam,
c) optionally, a second primary diamine different from said diamine a), preferably
chosen from linear C2 to C10 aliphatic diamines,
d) a hydroxylated fatty, preferably C18 or C20, monoacid, more preferably
12-hydroxystearic acid or 14-hydroxyeicosanoic acid, preferably 12-hydroxystearic
acid,
e) optionally, a nonhydroxylated monoacid chosen from linear C6 to C12, in particular
C6 to C10, aliphatic acids, the mole ratio e/d of said monoacid e) with respect to
said monoacid d) preferably not exceeding 0.5,
and in that the mole ratio b/(a+c) ranges from 0.25 to 3/1, preferably from 0.25 to 2/1 and
more preferentially from 0.35 to 2/1.
2. Fatty amide according to Claim 1, characterized in that said amide comprises at
least one diamide carrying, at each end, a fatty group based on monoacid d), it being
possible for said diamide to be represented by the formula d-b-a-d, d-b-a-b-d, d-a-d and
possibly d-c-d, if said diamine c) is present.
3. Fatty amide according to Claim 1 or 2, characterized in that said monoacid e) is
present and in that said amide comprises at least three diamides which may be
represented by the formulae d-b-a-d, d-b-a-b-d, e-b-a-d, e-b-a-b-d, e-b-a-e, e-b-a-b-e,
d-a-d, d-a-e, e-a-e and possibly e-c-e, d-c-d, d-c-e, if said diamine c) is present.
4. Fatty amide according to one of Claims 1 to 3, characterized in that said monoacid
d) is 12-hydroxystearic acid.
5. Fatty amide according to one of Claims 1 to 4, characterized in that the mole ratio
b/(a+c) is from 0.25 to 2/1.
6. Fatty amide according to one of Claims 1 to 5, characterized in that said diamine
a) is selected from aromatic diamines.
7. Fatty amide according to Claim 6, characterized in that said amine a) is an
aromatic diamine from: xylylenediamines, preferably m- or p-xylylenediamines,
phenylenediamines, preferably m- or p-phenylenediamines, or toluylenediamines,
preferably m- or p-toluylenediamines.

8. Fatty amide according to Claim 7, characterized in that said diamine is
xylylenediamine, preferably m- or p-xylylenediamine and more preferably m-xylylene-
diamine.
9. Amide according to one of Claims 6 to 8, characterized in that said monoacid d) is
12-hydroxystearic acid in the absence of said monoacid e).
10. Amide according to one of Claims 6 to 8, characterized in that said monoacid d) is
12-hydroxystearic acid in the presence of said monoacid e), preferably selected from
hexanoic acid, octanoic acid, nonanoic acid or decanoic acid.
11. Amide according to one of Claims 1 to 10, characterized in that it is capable of
being obtained by a process, comprising the successive stages below according to mode
A):
i) reaction of said diamine a) with said lactam or amino acid b), preferably lactam b) with
formation of a diamine a) modified by b),
ii) reaction of the product of stage i) with said monoacid d) in the presence or absence of
said monoacid e) and in the presence or absence of said diamine c).
12. Amide according to one of Claims 1 to 10, characterized in that it is capable of
being obtained by a process, comprising the successive stages below according to mode
B):
i') reaction of said monoacid d) or optionally of said monoacid e), if present, with said
lactam or amino acid b), preferably lactam b), with formation of the corresponding
monoacid modified with b),
ii') reaction of said modified monoacid (produced) from step i') with said diamine a), in the
presence or absence of said diamine c) and if said monoacid from said step i') is said
monoacid d), in this case, in the presence or absence of said monoacid e), otherwise, if
said monoacid from said step i') is the monoacid e), in this case, in the presence of said
monoacid d).
13. Amide according to one of Claims 1 to 12, characterized in that said diamine c) is
present.
14. Process for the preparation of an amide as defined according to one of Claims 1 to
10, characterized in that it comprises or is carried out according to at least the mode A)
comprising the successive reaction stages below:
i) reaction of said diamine a) with said lactam or amino acid b), preferably lactam b),
with formation of a.diamine a) modified b),
ii) reaction of the product from stage i) with said monoacid d) in the presence or
absence of said monoacid e) and in the presence or absence of said diamine c).

15. Process according to Claim 14, characterized in that said process according to the
mode A), said component b) is a lactam and in that said reaction with said amine a) is an
anionic oligomerization of said lactam b) using said diamine as anionic initiator.
16. Process for the preparation of an amide as defined according to one of Claims 1 to
10, characterized in that it comprises or is carried out according to at least the mode B)
comprising the successive reaction stages below:
i') reaction of said monoacid d) or optionally of the said monoacid e) if present, with
said lactam or amino acid b), preferably lactam b), with formation of the
corresponding monoacid modified by b),
ii') reaction of said modified monoacid (produced) from step i') with said diamine a), in
the presence or absence of said diamine c) and if said monoacid from said step i')
is said monoacid d), in this case, in the presence or absence of said monoacid e),
otherwise, if said monoacid from said step i') is the monoacid e), in this case, in the
presence of said monoacid d).
17. Process according to Claim 16, characterized in that said monoacid e) is present
with said process comprising the successive reaction stages below:
i') reaction of said monoacid e) with said lactam or amino acid b), preferably lactam
b), with formation of a monoacid e) modified b),
ii') reaction of said modified monoacid formed at stage i') with said diamine a) and
said monoacid d) and in the presence or in the absence of said diamine c).
18. Organogelator, characterized in that it comprises or consists of at least one amide
as defined according to one of Claims 1 to 13 or obtained by a process as defined
according to one of Claims 14 to 17.
19. Organogelator according to Claim 18, characterized in that it is in preactivated
form in an organic solvent, preferably in an organic solvent comprising at least one polar
organic solvent.
20. Organic binder composition, characterized in that it comprises at least one amide
as defined according to one of Claims 1 to 13 or an organogelator as defined according to
Claim 18 or 19.
21 Composition according to Claim 20, characterized in that it is a.coating
composition, in particular a paint, varnish, ink or gel coat composition, a glue or adhesive
composition, a stripping, mastic or sealing composition, a moulding composition or a
cosmetic composition.

22. Use of an amide as defined according to one of Claims 1 to 13 or obtained by. a
process as defined according to Claim 14 to 17, as organogelator, in particular as
rheology additive in an organic solvent medium.
23. Use according to Claim 22, characterized in that it relates to coating, glue or
adhesive, mastic, stripping agent or sealant, moulding or cosmetic compositions.
24. Finished product, characterized in that they comprises at least one amide as
defined according to one of Claims 1 to 13 or obtained by a process as defined according
to one of Claims 14 to 17, said product being selected from coating, mastic, sealant,
stripping agent, moulded part, cosmetic or glue or adhesive seal.