AMINO ACID PREPARATION METHOD COMPRISING A STEP OF
HYDROFORMYLATION OF AN UNSATURATED FATTY NITRILE
The work which led to this invention received financial support from the
5 European Union in the context of Framework Program 7 (FP712007-2013) under
project No. 241718 EUROBIOREF.
Field of the invention:
The present invention relates to a novel process for synthesizing
10 o-aminoalkanoic acids which can be used in the polymer industry, in particular
polyamides, said process comprising a step of hydroformylation of an unsaturated fatty
nitrile.
The term "unsaturated fatty nitrile" is intended to mean any compound of formula (I):
RI-CH=CH-[(CH2),-CH=CH],-(CH2),CN in which R1 is H or an alkyl radical comprising
15 from 1 to 11 carbon atoms, comprising, where appropriate, a hydroxyl function, and q,
m and r are integer indices such that q = 0 or 1, 0 5 m S 2 and 4 5 r 5 13, and mixtures
thereof. At the current time, it is known how to produce these unsaturated fatty nitrile
compounds from unsaturated fatty acid or ester compounds, or from saturated
compounds comprising a hydroxyl function, which may be both of fossil origin and of
20 renewable origin.
For the purposes of the invention, the term "to-aminoalkanoic acids", hereinafter
"a-amino acids" or simply "amino acids", is in fact intended to mean any long-chain
w-amino acid, i.e. in which the chain comprises at least 8 carbon atoms.
Indeed, the polyamides targeted by the present invention are technical polyamides, i.e.
25 performance polyamides, high performance polyamides, or even very high
performance polyamides, produced from monomers comprising at least 8 carbon
atoms, preferably at least 10 carbon atoms, as opposed to the "commodity"
polyamides, such as "nylon 6 , the marketed amounts (volumes) of which are much
higher and the costs of which are much lower than those of the technical polyamides.
30
Prior art:
The polyamide industry uses an entire range of monomers formed from
diamines and diacids, from lactams, and especially from w-amino acids. The latter are
defined by the length of the methylene chain (-CH,), separating two amide functions
35 -CO-NH-. These monomers are generally produced by chemical synthesis using as the
starting materials C, to C, olefins, cycloalkanes or benzene, which are hydrocarbons
derived from fossil sources. For example, C2 olefins are used to produce the C9 amino
acid used in nonanoic acid; Cq olefins are used to produce hexamethylenediamine;
laurolactam and caprolactam are produced from cycloalkanes; adipic acid, nylon 6 and
5 nylon 6,6 are produced from benzene.
With regard to the preparation of polyamides from unsaturated nitrile
' compounds, patent US 7 026 473 describes the hydroxycarbonylation or the
methoxycarbonylation of a pentenenitrile to give 5-cyanovaleric acid or ester (6 C
atoms), in the presence of CO (carbon monoxide) and respectively of water or of
10 alcohol. Only the methoxycarbonylation with methanol is in fact exemplified. By means
of reduction, the 5-cyanovaleric acid (ester) forms 6-aminocaproic acid (ester), which in
turn gives E-caprolactam by cyclization (this is the monomer of nylon-6). The process
described in said document has several drawbacks. The methoxycarbonylation step is
slow and costly in terms of catalysts. The conversion is not full and requires lengthy
15 reaction times. Furthermore, many co-products are formed, in particular branched
products, which must be separated from the linear product that it is desired to produce.
Said document does not relate to a process comprising a hydroformylation step, nor to
the production of amino acids having a carbon number at least equal to 8. The process
described uses nitrile compounds with a short chain, 5 carbons, to produce 6-carbon
20 products with chemical properties very different than those sought by the present
invention. Moreover, said document does not relate to the production of biobased
amino acids.
Patent document WO 97133854 describes a process for producing terminal
aldehyde by hydroformylation of an alkene, such as hexene, butadiene, methyl
25 3-pentenoate or 3-pentenenitrile. Said document shows that it is much more difficult to
obtain a linear aldehyde (low proportion of linears obtained) from a nitrile (3-pentenenitrile)
than from an ester. Furthermore, in the case of hydroformylation, a high
proportion (21%, 16.3%) of reduced product (valeronitrile), i.e. no longer containing
aldehyde, is obtained from nitrile of the prior art because of the hydrogenation of the
30 double bond by the catalyst. In addition, the obtaining of linear products in the prior art
occurs to the detriment of the conversion. Once again, said document does not relate
to the production of amino acids having a carbon number at least equal to 8. The
process described uses nitrile compoilnds with a short chain, 5 carbons, to produce 6-
carbon products with chemical properties very different than those sought by the
present invention. Moreover, said document does not relate to the production of
biobased amino acids.
Current developments with regard to the environment are resulting in the use of
natural starting materials originating from a renewable source being favored in the
5 fields of energy and chemistry. Only a few monomers are produced at the current time
from biobased starting materials, such as castor oil, which makes it possible to produce
polyamide 11 sold under the tradename ~ i l s a ne~ru; cic oil which makes it possible to
produce polyamide 13/13, or else lesquerolic oil which makes it possible to produce
polyamide 13.
10 Typically, the process for producing 11-aminoundecanoic acid comprises the following
steps:
1) alcoholysis (methanolysis) of castor oil to give methyl ricinoleate (MR),
2) cracking (pyrolysis) of the MR,
3) distillation so as to recover methyl undecylenate,
15 4) hydrolysis of the methyl undecylenate to give undecylenic acid,
5) hydrobromination so as to obtain I I-bromoundecanoic acid,
6) ammonolysis with an ammoniacal aqueous solution so as to give ll-aminoundecanoic
acid.
The polycondensation of the 11-aminoundecanoic acid, by hydrolytic polymerization in
20 the presence of phosphoric acid as catalyst, subsequently makes it possible to obtain
polyamide 11.
The process for synthesizing 11-aminoundecanoic acid, carried out industrially for
several decades, is satisfactory by and large. However, it has a certain number of
drawbacks. The first drawback is that the implementation thereof is in practice subject
25 to access to a single specific starting material, castor oil. Furthermore, the castor bean
contains a toxin: ricin, which is extremely toxic. The second drawback is linked to
certain reagents used, ammonia and bromine in particular, which require expensive
storage and use precautions, and need investment in specific units for separating and
recycling the ammonium bromide formed. The third drawback is linked to the co-
30 products obtained via the process: glycerol but also numerous by-products that need to
be exploited separately, such as heptanaldehyde, esterol: mixture of uncracked fatty
acid esters.
Document US 6 307 108 (see in particular column 9, lines 25-58) describes the
production of methyl 12-aminododecanoate from methyl undecylenate (MU), derived
35 from castor oil. The process comprises a step of hydroformylation of the MU so as to
form the C12 aldehyde ester, and then a step of reductive amination so as to produce
the C,Z amino ester. In order to be able to produce the corresponding amino acid, this
process makes it necessary to carry out an additional step of hydrolysis of the amino
ester under conditions which have the drawback of leading to its direct
5 polycondensation to "polyamide", the chain growth of which is limited by the presence
of the ester groups.
The objective of the present invention is therefore to find a novel process for
direct synthesis of w-amino acids, involving other starting materials and reagents,
which avoids the formation of by-products, which minimizes the number of steps, and
10 which does not have the abovementioned drawbacks.
The objective of the present invention is also to find a novel process for
synthesizing the whole range of long-chain w-amino acids, which is simple to
implement, and which as much as possible uses renewable starting materials, which
are preferably widely accessible.
15 The expression "renewable starting materials which are widely accessible" is
intended to mean those which are readily available, for example derived from plants
which are already grown andlor easy to grow, in an amount compatible with industrial
production, and inexpensive.
In this "bio" approach, the applicant 'has already described several processes
20 for synthesizing o-amino acids from unsaturated fatty nitriles of renewable origin.
Patent documents W0 20101055273, FRI 1.55174, FRI 1.56526 and FRI 1.57542
describe, in particular, the steps for synthesis of an 01-amino acid from an unsaturated
fatty nitrile by oxidative cleavage or by cross metathesis with an acrylate resulting in a
nitrile acid, and then the hydrogenation thereof to give an amino acid. These processes
25 comprise a metathesis using catalysts and starting co-materials which are relatively
expensive, such as acrylonitrile or methyl acrylate. In particular, the ruthenium ligands
used to catalyze the metathesis are very specific and constitute most of the costs of the
catalyst. Furthermore, on all the carbons of the amino acid formed by means of these
processes, at least 2 carbons are not biobased if the methyl acrylate or the acrylonitrile
30 are not themselves biobased, improvement thereof still being sought, the objektive
being to produce amino acids which aim to be 100% renewable. Moreover, in
document WO 20101055273 in particular, the process comprises a controlled
ozonolysis, which amounts to removing a carbon from the carbon chain, whereas, on
the contrary, in the case of the synthesis of specialty polyamides, the aim is to increase
35 the length of the carbon chain of the monomers produced. Furthermore, the metathesis
process in the abovementioned documents results not in an amino acid, but in an
amino ester when the starting materials are, for example, a fatty ester and acrylonitrile,
or alternatively a fatty nitrile and methyl acrylate. In order to produce a conventional
polyamide, the amino ester must be reconverted beforehand into an amino acid, which
5 requires an additional very complex step to hydrolyze an ester function under hot
conditions, without initiating the polymerization of the amino ester.
The objective of the present invention is therefore also to find a novel process
using catalysts, in particular ligands, and co-materials which are simpler and less
expensive, and make it possible to increase the content of material of renewable origin
lo of the amino acids.
The applicant has now found a novel synthesis process involving a step of
hydroformylation of an unsaturated fatty nitrile, with hydrogen (Hz) and carbon
monoxide (CO), and not comprising the abovementioned drawbacks.
15 Detailed description of the invention:
In the present description, it is specified that, when reference is made to ranges,
expressions of the type "ranging from ... to" or "containing/comprising from ... to"
include the limits of the range. Conversely, expressions of the type "between ... and ..."
exclude the limits of the range.
20 Unless otherwise mentioned, the percentages expressed are molar percentages.
Unless otherwise mentioned, the parameters to which reference is made are measured
at atmospheric pressure.
A subject of the present invention is therefore a process for synthesizing an o-amino
25 acid compound of formula HOOC-R'-CH2NH2,
where R' is an alkyl radical comprising from 6 to 15 carbon atoms or an alkylene radical
comprising from 6 to 15 carbon atoms and from 0 to 2 unsaturations,
comprising:
1) a step of hydroformylation of an unsaturated fatty nitrile chosen from the compounds
30 of formula: R1-(3H=CH-[(CH2)q-CH=CH],-(CHz)&N
where Rt is H (a hydrogen) or an alkyl radical comprising from 1 to 11 carbon atoms
comprising, where appropriate, a hydroxyl function, it being possible for the C=C
double bond(s) to be in the cis or trans conformation, q, m and r are integer indices
suchthatq=Oor1,Ormr2and4~rr13,
35 and mixtures'thereof,
by reacting said nitrile with carbon monoxide and dihydrogen
so as to obtain at least one fatty nitrile aldehyde of formula:
HOC-R-CN,
2) a step of oxidation in the presence of dioxygen (molecular oxygen), during which the
5 nitrile aldehyde obtained in step 1 is converted into fatty nitrile acid of formula:
HOOC-R-CN,
3) a reduction step during which the nitrile acid obtained in step 2 is converted into an
w-amino acid of formula:
HOOC-R'-CHZNH~.
lo The novel process of the invention, in which a step of hydroformylation of an
unsaturated fatty nitrile, followed by a step of oxidation of the resulting aldehyde to give
an acid, and then by a step of reduction of the nitrile function to give an amine function,
is carried out, results in the direct synthesis of amino acids.
Advantageously, the process according to the invention also comprises a step of
I5 catalytic cross metathesis with an alkene chosen from ethylene, propylene, but-I-ene
and but-2-ene, preferably ethylene, propylene and but-I-ene, preferably ethylene or
but-I-ene, carried out on the fatty nitrile before step 1) so as to produce an omegaunsaturated
fatty nitrile corresponding to the formula:
R,-CH=CH-(CH2),CN, where R2 is H or an alkyl radical comprising from 1 to 3 carbon
20 atoms, preferably corresponding to the formula CH2=CH-(CH2),-CN, i.e. preferably
when R2 is H.
When R2 is an alkyl radical, during the hydroformylation, the double bond can be
brought back to the terminal position, before the addition of the CO, and can therefore
result in a linear amino acid, which explains why the various abovementioned alkenes
25 can be used in the process of the invention. This step of catalytic cross metathesis with
an alkene is conventionally carried out under the same conditions as those described,
for example, in patent application WO 20101055273 on page 9, lines 12 to 18.
The starting unsaturated fatty nitrile used in the process according to the invention is
generally obtained from unsaturated (or hydroxylated) fatty acid or ester compounds by
30 nitrilation (ammoniation) of at least one acid or ester function of these compounds
which can be derived from starting materials of fossil origin or of renewable origin.
The unsaturated fatty acid or ester compounds can be obtained, for example,
according to the process described by patent document US 4 510 331. The latter
describes in particular the production of 7-octenoic acid, by isomerization of 2,7-
35 octadien-1-01 to give 7-octen-I-al, and then oxidation of the latter to give an acid. The
2,7-octadien-1-01 is produced industrially by reaction ("telomerization") of butadiene
with water in the presence of a palladium catalyst according to the process described in
patent documents GB 2074156A and DE 3112213. This type of process uses starting
materials of fossil origin.
5 Alternatively, the unsaturated fatty nitriles are produced from unsaturated fatty acids or
esters of renewable origin, derived from natural oils. These processes developed
recently by Arkema are described in particular in patent documents: WO 20101055273,
FRI 1.55174, FRI 1.56526 and FRI 1.57542.
For the purposes of the invention, the term "unsaturated fatty nitrile" is preferably
10 intended to mean those obtained at least partially from unsaturated natural fatty acids.
Advantageously, the process according to the invention therefore comprises a step of
producing said fatty nitrile from an unsaturated fatty acid or ester of natural origin of
formula: (Rf-CH=CH-[(CH2),-CH=CH],-(CH2)r-COO-),-G in which p is an integer index
such that 1 5 p 5 3, and G is H (a hydrogen), an alkyl radical having from 1 to 11
15 carbon atoms or a radical comprising 2 or 3 carbon atoms bearing I or 2 hydroxyl
function@), it being possible for the C=C double bond(s) to be in the cis or trans
conformation, said production comprising:
- the ammoniation (action which consists in introducing ammonia into a product) of the
carbonyl function of the unsaturated fatty acid (or ester) of natural origin, to give a
20 nitrile function.
The reaction scheme for the synthesis of nitriles from acids, by amrnoniation (or
nitrilation, the two terms being used without distinction), well known to those skilled in
the art, can be summarized in the following way.
R-COOH + NH3 -t [R-COO-NH4+] -t [R-CONHz] + Hz0 4 RCN + Hz0
25 This scheme applies just as much to natural fatty acids (esters) as it does to
w-unsaturated fatty acids. The process can be carried out batchwise in the liquid or gas
phase or continuously in the gas phase. The reaction is carried out at a high
temperature above 250°C and in the presence of a catalyst which is generally a metal
oxide and most commonly zinc oxide. The continuous removal of the water formed
30. while in addition entraining the ammonia which has not reacted enables rapid
completion of the reaction.
Liquid-phase ammoniation is very suitable for long fatty chains (comprising at least 10
carbon atoms). However, when operating with shorter chain lengths, gas-phase
ammoniation may become more appropriate. It is also known practice, from GB
641 955, to carly out the ammoniation using urea or cyanuric acid as agent. Any other
source of ammonia may also be used.
According to one particular embodiment, the unsaturated fatty nitrile used according to
the invention is produced from natural unsaturated long-chain fatty acids. The term
5 "natural long-chain fatty acid" is intended to mean an acid derived from a plant
background or from an animal background, including algae and other microorganisms,
and which is therefore renewable, comprising from 6 to 24 carbon atoms, with
preferably at least 7 (if the final amino acid has at least 8 C) carbon atoms, preferably
at least 8 carbon atoms, preferably at least 10 carbon atoms, and preferably at least 14
10 carbon atoms per molecule. These various acids are derived from vegetable oils
extracted from various plants, such as sunflower, rapeseed, camelina, the castor oil
plant, lesquerella, olive, soya, the palm tree, coriander, celery, dill, carrot, fennel or
Limnanthes alba (meadowfoam). They are also derived from the terrestrial or marine
animal world, and, in the latter case, equally in the form of fish, mammals and algae. It
15 is generally a question of fats originating from ruminants, from fish such as cod, or from
tnarine mammals such as whales or dolphins.
As unsaturated fatty acid suitable more particularly for implementing the invention,
mention may be made of: petroselenic acid (cis-6-octadecenoic acid), its derivative
6-heptenoic acid obtained by ethenolysis (cross metathesis with ethylene), a-linolenic
20 acid (6,9,12-octadecatrienoic acid), it being possible for these acids to be obtained
from coriander for example; cis-8-eicosenoic acid, cis-5,8,11,14-eicosatrienoic acid
(arachidonic acid), ricinoleic acid which gives, after dehydration, conjugated 8,lOoctadecadienoic
acid; caproleic (cis-9-decenoic) acid, palmitoleic (cis-9-hexadecenoic)
acid, myristoleic (cis-9-tetradecenoic) acid, oleic (cis-9-octadecenoic) acid, 9-decenoic
25 acid obtained by ethenolysis of an oleic acid for example, elaidic (trans-9-
octadecenoic) acid, ricinoleic (12-hydroxy-cis-9-octadecenoic) acid, gadoleic (cis-9-
eicosenoic) acid, linoleic (9,12-octadecadienoic) acid, rumenic (9,ll-octadecadienoic)
acid, conjugated linoleic (9,ll-octadecadienoic) acid, it being possible for these acids
to be obtained from sunflower, rapeseed, the castor oil plant, olive, soya, the palm tree,
30 flax, avocado, sea buckthorn, coriander, celery, dill, carrot, fennel, Limnanthes
(meadowfoam); 10,12 conjugated linoleic acid (10,12-octadecadienoic acid),
10-undecylenic acid obtained by thermal cracking of the methyl ester of ricinoleic acid
for example; vaccenic (cis-I I-octadecenoic) acid, gondoic (cis-I I-eicosenoic) acid,
lesquerolic (14-hydroxy-cis-11-eicosenoic) acid, cetoleic (cis-11-docosenoic) acid,
35 - which can be obtained from Lesquerella oil (lesquerolic), from Camelina sativa oil
(gondoic), from the oil of a plant of the family Sapindaceae, from fish fat, from oils of
microalgae (cetoleic), by dehydration of 12-hydroxystearic acid itself obtained by
hydrogenation of ricinoleic acid (vaccenic acid and its trans equivalent), conjugated
linoleic acid (9,ll-octadecadienoic acid), obtained for example by dehydration of
5 ricinoleic acid; (cis or trans) 12-octadecenoic acid obtained for example by dehydration
of 12-hydroxystearic acid (abbreviated as 12HSA), itself obtained by hydrogenation of
ricinoleic acid, 10,12 conjugated linoleic acid (10,12-octadecadienoic acid),
12-tridecenoic acid obtained by thermal cracking of the (in particular methyl) ester of
lesquerolic acid; erucic (cis-13-docosenoic) acid and brassidic (trans-13-docosenoic)
10 acid which can for example be obtained from erucic rapeseed, from Honesty or from
sea kale (sea cabbage); (cis or trans) 13-eicosenoic acid obtained by dehydration of
14-hydroxyeicosanoic acid, itself obtained by hydrogenation of lesquerolic acid, (cis or
trans) 14-eicosenoic acid obtained by dehydration of 14-hydroxyeicosanoic acid
(abbreviated as 14HEA), itself obtained by hydrogenation of lesquerolic acid (the
15 dehydration can be carried out on both sides of the OH), ne~onic(c is-15-tetracosoic)
acid which can be obtained from Malania oleifera and from Honesty (Lunaria annua
also known as Pope's coin or moneyplant); or mixtures thereof. It is also possible to
dispense with the step of dehydration of the acids 12HSA and 14HEA by carrying out
the conversion to nitrile directly on these saturated and hydroxylated fatty acids, as
20 described in the patent document having the filing number FRI 1.56526. An advantage
of this solution is that the hydrogenation of ricinoleic acid in a mixture with the other
fatty acids of castor oil results in a mixture no longer containing as majority species
only 12HSA, stearic acid and palmitic acid. The dehydration following (or
simultaneously with) the conversion into nitrile results in a very clean nitrile containing
25 more than 85% of monounsaturated nitrile. The same is true with 14HEA, as described
in patent document FRI 1.56526.
Among the abovementioned unsaturated fatty acids, preference is given to those which
are the most abundantly available, and in particular fatty acids unsaturated in the 6-9 or
6-10 position, the numbering being from the acid group. The use of nitriles and of fatty
30 acids comprising from 10 to 24 carbon atoms, and preferably those comprising 10
carbons or 11 carbons with an unsaturation in the omega or o position, i.e. at the end
of the chain with respect to the acid group, is in fact preferred. Preference is given, for
example, to fatty acids containing 18 carbons comprising an unsaturation in the 6-9 or
10 position with respect to the nitrile or acid group, i.e. in the w-9 or 8 position,
35 respectively, which by ethenolysis will result in o-unsaturated acids, and also ricinoleic
acid which, by thermal cracking of its methyl ester, gives the methyl ester of
undecylenic acid.
The fatty acids mentioned above can be isolated by any of the techniques well known
to those skilled in the art: molecular distillation, including short path distillation,
5 crystallization, liquid-liquid extraction, complexation with urea, including extraction with
supercritical C02, andlor any combination of these techniques.
According to one particular embodiment of the process of the invention, the
unsaturated fatty nitrile is obtained from a fatty acid ester, it being possible for the latter
to be advantageously chosen from the esters of the abovementioned fatty acids, in
10 particular their methyl esters. The routes for obtaining a fatty nitrile from a fatty acid
ester are, for example, described in document WO 20101089512.
According to another embodiment, the unsaturated fatty nitrile is obtained from a
hydroxy fatty acid, such as 12HSA and 14HEA. More generally, the hydroxy fatty acid
can advantageously be chosen from those described in the patent application having
15 the filing number FRI 1.56526.
Alternatively, the unsaturated fatty nitrile is obtained from a triglyceride, it being
possible for the latter to be advantageously chosen from: a vegetable oil comprising a
mixture of unsaturated fatty acid triglycerides, such as sunflower oil, rapeseed oil,
castor oil, lesquerella oil, camelina oil, olive oil, soya bean oil, palm oil, Sapindaceae
20 (soapberry) oil, in particular avocado oil, sea buckthorn oil, coriander oil, celery oil, dill
oil, carrot oil, fennel oil, mango oil, Limnanthes alba (meadowfoam) oil, and mixtures
thereof; microalgae; animal fats.
According to another embodiment, the unsaturated fatty nitrile is obtained from a plant
wax, for example jojoba wax.
25 Advantageously, the process according to the invention also comprises, before the
ammoniation step described above:
- either a catalytic cross metathesis with ethylene (or other C2 to C4 light alpha-olefin)
carried out on the unsaturated fatty acid (or ester or triglyceride) of natural origin,
- or a pyrolysis of the unsaturated fatty acid or ester of natural origin, followed by
30 distillation (then optionally hydrolysis to give an acid in the case of the ester),
so as to produce an omega-unsaturated fatty acid (or ester) of formula:
CH2=CH-(CH2)rCOOR2, R2 being H or a C1-C4 alkyl radical,
and such that, after the ammoniation step carried out on this omega-unsaturated fatty
acid (or ester), an omega-unsaturated fatty nitrile of formula:
35 CH2=CH-(CH2),-CN is obiained.
The obtaining of such an unsaturated fatty nitrile from an unsaturated fatty acidlester is
in particular described in patent application W0 2010105527, in particular in the
paragraphs describing the "first stage" of the process which is the subject of said
document: i.e. on page 5, lines 12 to 32, on page 7, lines 17 to 26, on page 8, lines 1 to
5 9, on page 10, line 29 to page 11, line 19.
According to one particular embodiment of the process of the invention, use is made of
an w-unsaturated nitrile of formula CH2=CH-(CH,),-CN obtained by conversion of an
unsaturated fatty acidlester in two successive steps (the order being unimportant):
ethenolysis (cross metathesis with ethylene) and ammoniation, as described in
lo document WO 20101055273. According to another variant of the process, hydroxylated
fatty acids are used as starting material, such as ricinoleic acid and lesquerolic acid
which correspond to the general formula R1-CH=CH-(CH,),-COOH with R, equal to
CH,-(CH2)5CHOH-CH2- and p equal, respectively, to 7 and 9. The acid in its methyl
ester form is subjected to a pyrolysis resulting in an w-unsaturated ester of formula
15 CH2=CH-(CH,)p+l-COOCH3 which is converted by ammoniation, directly or via the acid,
into an w-unsaturated nitrile, According to yet another embodiment, the unsaturated
fatty nitrile is produced as described in document FR11.55174, by ammoniation of a
compound of fatty acid, ester or glyceride type, resulting in the corresponding
unsaturated nitrile. According to one particular embodiment of the process of the
20 invention, the hydrogenation of unsaturated hydroxylated fatty acids comprising at least
18 carbon atoms per molecule, resulting in saturated hydroxylated fatty acids, followed
by the dehydration thereof, resulting in monounsaturated fatty acids, are carried out as
in the process of document FR11.56526, with, in addition, either an intermediate step
of nitrilation of the acid function of the monounsaturated fatty acid, resulting in an
25 unsaturated nitrile, or an intermediate step of nitrilation of the acid function of the
saturated hydroxylated fatty acid resulting from the hydrogenation step with
concomitant dehydration, resulting in an unsaturated fatty nitrile. Particular conditions
for obtaining unsaturated fatty nitriles are described in document FR11.57542,
comprising the nitrilation of an w-unsaturated acidlester of formula CH2=CH-(CH2),-
30 COOR in which n is 7 or 8 and R is either H or an alkyl radical comprising 1 to 4 carbon
atoms, by reacting ammonia in a reactor operating continuously in the gas phase or in
the mixed liquid-gas phase, in the presence of a solid catalyst.
Whether it is a question of metathesis on the fatty nitrile or else on the unsaturated acid
(or fatty ester), the cross metathesis reaction with an alkene, such as ethylene,
35 implemented in certain variants of the process of the invention, is caried out at a
temperature of between 20 and 100°C at a pressure of 1 to 30 bar, in the presence of a
conventional metathesis catalyst, for example of ruthenium type. The reaction time is
chosen according to the reagents used and so as to be as close as possible to the
equilibrium of the reaction. The reaction is carried out under an alkene pressure
5 The pyrolysis reaction implemented in one variant of the process of the invention is
preferably carried out on the ester form of the fatty acid concerned, generally the
methyl ester. The reaction is carried out at high temperature, of between 400 and
750°C and preferably between 500 and 600aC, in the presence of overheated water
vapor.
lo Preferably, the starting acid is a hydroxylated acid, and it is preferably ricinoleic acid or
lesquerolic acid, ricinoleic acid being preferred since it results in 12-aminododecanoic
acid according to the process of the invention.
According to one preferred embodiment, the process according to the invention
consists of a process for synthesizing an w-amino acid compound of formula
15 HOOC-(CH2)w2-CH2NH2,
from a monounsaturated fatty nitrile compound of formula
CHz=CH-(CH2)rCN
comprising the following steps:
- the hydroformylation of the unsaturated nitrile compound so as to obtain a nitrile-
20 aldehyde compound of formula HOC-(CH,),-CN, then
- the oxidation of the nitrile-aldehyde compound so as to obtain the corresponding
nitrile-acid compound of formula
HOOC-(CH2),2-CN, and
- the reduction of the nitrile-acid compound to give an w-amino acid of formula
25 HOOC-(CHz),+z-CHzNH2.
1) HYDROFORMYLATION
Hydroformylation, also known as 0x0 process, is a synthesis route for producing
aldehydes from alkenes that was discovered in 1938 by Otto Roelen from Ruhrchemie.
30 The basib reaction is the following:
R-CH =C:H2+CO+H,sR-C2H.,-CHO+ R-CH(CHC))-CN,
This process is widely used industrially to produce aldehydes in a range of C3-C19,
Butanal is, moreover, the main product synthesized by this reaction, with approximately
75% of total production using hydroformylation as synthesis route. The
35 hydroformylation step according to the process of the invention uses the methods and
devices that are well known and already used by conventional hydroformylation
processes. All the usual methods for adding and mixing the reagents and the
components of a catalyst or catalysts, like the usual separation techniques for the
conventional hydroformylation reaction, can therefore be used for this step of the
5 process of the invention. The hydroformylation step according to the process of the
invention has the advantage of being able to be used directly in the numerous devices
that exist. This would not be the case with methoxycarbonylation nor with
hydroxycarbonylation, for example.
Advantageously, the hydroformylation step is catalyzed in the presence of a catalyst
10 system comprising:
- at least one metal of groups V to XI of the periodic table of elements, selected for its
activity for converting the unsaturated nitrile, preferably at least one metal of group VIII,
preferably at least one metal chosen from rhodium, palladium, cobalt and ruthenium,
and mixtures thereof; and
15 - at least one bidentate ligand selected for the selectivity of the hydroformylation
reaction in favor of the linear aldehyde, preferably at least one chelating diphosphine,
or a monodentate ligand of monophosphine or monophosphite type.
The [ligand]l[metal] molar ratio is advantageously included in the range of from 60:l to
I:
97%) and
also good yields in terms of linear aldehyde. The examples below describe tests of
15 undecenenitrile hydroformylation catalyzed by the Rh-biphephos system.
General ~rocedure:
The hydroformylation reactions were carried out in 30 ml stainless steel autoclaves.
Under the typical conditions, a solution, in toluene (IQml), of Rh(acac)(CO)* (from
0.001 to 0.0001 mmol), phosphine (from 0.002 to 0.02 mmol) and undecenenitrile
20 (5.0 mmol) is mixed in a Schlenk tube under an inert argon atmosphere so as to form a
homogeneous solution. After stirring at ambient temperature for 1 hour, this solution is
introduced, via a pipe, into the autoclave preconditioned under an inert atmosphere.
The reactor is sealed, flushed several times with a COIH, mixture (1:1), then
pressurized at 20 bar of this CO/H2 mixture at ambient temperature, and then heated to
25 the desired temperature using a waterbath or an oil bath. During the reaction, several
samples are taken in order to monitor the conversion. After an appropriate reaction
time, the autoclave is brought back to ambient temperature and then to atmospheric
pressure. The mixture is collected and then analyzed by NMR.
Table 3: Effect of femperature during the undecenenitrile h v d r o f o r m ~ l a t i o n ' ~ ~
Temp C O ~ V . [ ~ ~ Internal Sel. (%)Ib1
Entry
PC) (yo) alkenes (%) 2 3
1 80 52 20 99 1
2 100 75 20 99 1
3 120 88 22 99 1
4 140 94 26 99 1
[undecenenitrile] = 5.0 mmol, [undecene~~itrile]I[Rb=] 20 000, [biphephos]/[Rl~] = 20,
toluene = 10 rill, P = 20 bar COIH, ($:I), 4 h.
lbl Cot~version of the nitrile I selectivity I % of internal alkenc and 2 and 3 detereiined by 'H
5 NlMR and GLC analyses.
%of internal alkeae, residual or formed during the reaction.
The previous examples show that the Rh-biphephos system is very active and
selective in undecenenitrile hydroformylation (table 3). In a temperature range of 80-
10 120"C, good conversions (52-94% of 20 000 equiv) were obtained in 4 h, and also
excellent selectivities ranging up to 99%.
In order to overcome the possible problem of isomerization leading to the formation of
internal alkenes, other experiments are carried out while increasing the reaction time,
since, after total conversion of the substrate, the catalyst can isomerize the internal
15 alkenes to terminal alkene and hydroformylize the latter to linear aldehyde (table 4).
Example of table 4, entrv 4: Hvdroformvlation of I ,lo-undecenenitrile (Rh-biphephosl
with SlRh = 20 000 and URh = 20 and recvclina of the catalyst:
A solution, in toluene, of Rh(acac)(CO)~ (0.65 mg, 0.0025 mmol), biphephos (4 mg,
20 0.005 mmol) and undecenenitrile (826 mg, 5.0 mmol) is prepared in a Schlenk tube
under an inert argon atmosphere so as to form a homogeneous solution which is
stirred at ambient temperature for 1 h. The biphephoslrhodium molar ratio is 20:l and
the substratekhodium molar ratio is 20 000:l. The solution is introduced, via a pipe,
into a 30 ml autoclave preconditioned under an inert atmosphere. The reactor is
25 sealed, flushed several times with a CO/H2 gas mixture (1:1), then pressurized with
20 bar of CO/H2 (I:?) at ambient temperature, and then heated to 120°C. After 4 h,
67% of the undecenenitrile has been consumed. After 24 h, the medium is brought
back to ambient temperature and to atmospheric pressure. The mixture is collected
and analyzed by NMR. The analysis shows that the reaction is.complete and that there
30 remains an internal olefin proportion of 13%, while 87% of products formed correspond
to branched (1%) and linear (99%) aldehydes. If the reaction is allowed to continue, the
internal alkenes will be isomerized and hydroformylized.
Thus, after 48 h of reaction, there then remains only a 5% proportion of internal olefins,
while 95% of products formed correspond to branched (1%) and linear (99%)
5 aldehydes.
Once the reaction has finished, recycling by distillation is carried out, under an inert
atmosphere, using a Kugelrohr ("ball oven") distillation system at a temperature of
180°C and a pressure of 1 mbar. The hydroformylation products obtained in a first
fraction are stable and no trace of residual catalyst or ligand was detected after NMR
10 analysis ('H and 3 ' ~ ) .T he catalyst contained at the bottom of the column was reused
for a second run. For this, the catalyst is reintroduced into the Schlenk tube with 10 ml
of toluene, a new amount of biphephos (0.0005 mmol, 5equiv) and 5 mmol of 1,lOundecenenitrile.
The solution is again introduced, via a pipe, into a 30 ml autoclave
preconditioned under an inert atmosphere. The reactor is sealed, flushed several times
15 with a COIH, gas mixture (?:I), then pressurized with 20 bar of COIH2 (1:l) at ambient
temperature, and then heated to 120°C. After 48 h, the medium is then brought back to
ambient temperature and to atmospheric pressure. The mixture is collected and
analyzed by NMR. The analysis shows that the reaction is complete and that there
remains a 2% proportion of internal olefin, while 98% of products formed correspond to
20 branched (2%) and linear (98%) aldehydes. This recycling can be carried out on
several cycles without loss of selectivity.
Example of table 4, entry 7: Hydroformylation of 1.10-undecenenitrile (Rh-biphephos)
with SlRh = 50 000 and URh = 20:
25 A solution, in toluene (0.65 mg, 0.0025 mmol), of Rh(a~ac)(CO)b~i,p hephos (2.0 mg,
0.0025 mmol) and undecenenitrile (826 mg, 5.0 mmol) is prepared in a Schlenk tube
under an inert argon atmosphere so as to form a homogeneous solution which is
stirred at ambient temperature for 1 h. The biphephoslrhodium molar ratio is 10:l and
the substratelrhodium molar ratio is 20000:l. The solution is introduced, via a pipe,
30 ' into a 30 ml autoclave preconditioned under an inert atmosphere. The reactor is
sealed, flushed several times with a COIH2 gas mixture (1:1), then pressurized with
20 bar of CO/H2 (1:l) at ambient temperature, and then heated to 120°C. After 48 h,
the medium is brought back to ambient temperature and to atmospheric pressure. The
mixture is collected and analyzed by NMR. The analysis shows that the reaction is
3; complete and that there remains an 18% proportion of internal olefin, while 82% of
products formed correspond to branched (2%) and linear (98%) aldehydes. If the
reaction is allowed to continue, the internal alkenes will be isomerized and
hydroformylized.
m 4
Biphephos Time Conv. Internal sel. (%) ['I
Entry [S]/[Rh]
(h)
alkenes
(equiv) Internal
(Oh) Ic1 n-2 is03 4 aldehydes
5 la] [undecenenitrile] = 5.0 mmol, [undecenenitrile]/[Rh] = 20 000, [biphephos]/[Rh] =
20, toluene = 10 ml, P = 20 bar COIH, ($:I), 4 h.
Ib1 Conversion of the nitrilelselectivity/% of internal alkene and 2 and 3 determined by
'H NMR and GLC analyses.
['I % of internal alkene, residual or formed duiing the reaction. nd = not detected.
10
The Rh-biphephos catalyst can also be recycled by distilling the solvent and the
organic products (aldehydes, residual internal alkenes) with a Kugelrohr ("ball oven")
system, at 180°C under a dynamic vacuum of 1 mbar. The solid residue (still with a
small amount of organic products) thus recovered can then be reused on several
5 cycles without substantial loss of selectivity, after having occasionally added fresh
ligand between two cycles so as to prevent a modification of the active species in
catalysis. This procedure is first carried out using an SIRh ratio of 20 000 and an LlRh
ratio of 10 (table 5). Thus, very good selectivities were obtained on 4 cycles and the
isomerizationlhydroformylation of the internal alkenes appears to be just as efficient
lo since there was no accumulation of these internal alkenes.
Table 5. Hvdrofomvlation of undecenenitrile during 4 cvcles["'
biphephos
Time Conv. Internal sel. (%)PI
~ n t r y ' ~ ' Cycle alkenes
added (eq) rC) (h) (%)Ib1 (%) "I fso- internal
17-2 3 aldehydes
1 I 120 24 95 11 99 1 0
la' [undecenenitrile] = 10 mmol, [undecenenitrile]l[Rh] = 20 000, [biphephos]/[Rh] =
10, toluene = 5 ml, P = 20 bar CO/H2 (1:l).
15 lb'C~nver~ioonf the nitrilelselectivity/% of internal alkene and 2 and 3 determined by
'H NMR and GLC analyses.
% of internal alkene, residual or formed during the reaction. nd = not detected.
Iq The catalyst is recycled under an inert atmosphere, 5 equiv of biphephos were added,
toluene = 5 mi, P = 20 bar COIH2 (?:I).
20 IeT1h e catalyst is recycled under an inert atmosphere, and reused without addition of ligand,
toluene = 5 ml. P = 20 bar COIH, (1 :I).
These results prove that it is easy, according to the process of the invention, to recycle
this catalyst via the distillation route. Other tests are carried out while increasing the
25 SlRh ratio to 100 000 with a higher LlRh ratio (initially 20). Table 6 shows that this
procedure operates without any great reduction in activity; the productivity is very good
since it reaches close to 200 000 on two cycles (the first + the recycling), while using
only 25 equivalents of biphephos.
Examples of table 6, entries 1 and 2: Hvdroformylation of 1.10-undecenenitrile (Rh-
5 biphephos) with SlRh = 100 000 and URh = 20; and recvclinn of the catalyst:
A solution, in toluene (0.026 mg, 0.0001 mmol), of Rh(aca~)(CO)b~ip, hephos (1.6 mg,
0.002 mmol) and undecenenitrile (1.65 g, 10.0 mmol) is prepared in a Schlenk tube
under an inert argon atmosphere so as to form a homogeneous solution which is
stirred at ambient temperature for 1 h. The biphephoslrhodium molar ratio is 20:l and
10 the substratelrhodium molar ratio is 100 000:l. The solution is introduced, via a pipe,
into a 30 ml autoclave preconditioned under an inert atmosphere. The reactor is
sealed, flushed several times with a CO/H2 gas mixture (I:$), then pressurized with
20 bar of COIH, (1:l) at ambient temperature, and then heated to 120°C. After 48 h,
85% of the undecenenitrile has been consumed. The temperature is then adjusted to
15 130°C, over the course of a further 48 h reaction time, and the medium is brought back
to ambient temperature and to atmospheric pressure. The mixture is collected and
analyzed by NMR. The analysis shows that the reaction is complete and that there
remains a 9% proportion of internal olefin, while 91% of products formed correspond to
branched (2%) and linear (98%) aldehydes.
20 Once the reaction has finished, recycling by distillation is carried out, under an inert
atmosphere, using a Kugelrohr distillation system at a temperature of 180°C and a
dynamic vacuum of 1 mbar. The hydroformylation products obtained in a first fraction
are stable and no trace of residual catalyst or ligand is detected after NMR analysis ('H
and 3'P). The catalyst contained at the bottom of the column is reused for a second
25 run. For this, the catalyst is reintroduced into the Schlenk tube with 10 ml of toluene, a
fresh amount of biphephos (0.5 Jmol, 5 equiv) and 10 mmol of 1,lO-undecenenitrile.
The solution is again introduced, via a pipe, into a 30 ml autoclave preconditioned
under an inert atmosphere. The reactor is sealed, flushed several times with a COIH2
gas mixture (1:1), then pressurized with 20 bar of COlH2 (1:l) at ambient temperature,
30 and then heated to 120°C. After 48 h, 72% of the undecenenitrile is consumed. The
temperature is then adjusted to 130"C, over the course of a further 48 h reaction time,
and the medium is brought back to ambient temperature and to atmospheric pressure.
The mixture is collected and analyzed by NMR. The analysis shows that the reaction is
complete and that there remains an 11% proportion of internal olefins, while 89% of the
35 products formed correspond to branched (2%) and linear (98%) aldehydes.
Table 6. Hvdroformvlation of undecenenitrile on 2 cvcles at hiah S/Rh ratio@
Biphephos Time ~ o n v . inte%rn al Sel. (%)[bl
EntryEa1 Cycle
added (eq)
TrC) (h)
(%)'I alkenestcl n-2 iso-3 ss-pdt
a Cvcle 120 48 85 23 99 1
la[]u ndecenenitrile] = 10 mmol, [undecenenitrile]/[Rh] = 100 000, [biphephos]l[Rh] =
20, toluene = 10 ml, P = 20 bar CO/H2 (1:l).
5 Ib'Conversion of the nitrilelselectivityl% of internal alkene determined by 'H NMR and
GLC analyses. '" 1 of internal alkene, residual or formed during the reaction.
Id' The catalyst is recycled under an inert atmosphere, 5 equiv of biphephos were added.
toluene = 10 mi, P = 20 bar CO/H2 (I:?).
10 Comparative example with methyl 10-undecenoate
Other tests are carried out in order to compare the performance levels of the
Rh-biphephos system on undecenenitrile and methyl 10-undecenoate (table 7). The
tests are carried out with methyl undecenoate which was distilled beforehand. In the
light of the results (in particular when comparing entry 4 of table 7 with entry 1 of table
15 6), it appears that the Rh-biphephos system is less selective and less active with
respect to methyl 10-undecenoate than with the fatty nitrile.
Example of table 7, entry 4: Hvdroformvlation of methvl 10-undecenoate (Rhbiohephos)
with SlRh = 100 000 and LlRh = 20:
20 This test is carried out under the same conditions as those described above in the
example of table 6, with the 1,lO-undecenenitrile being replaced with methyl 10-
undecenoate. There is no recycling of the catalyst in this case. Afler 48 h, 68% of the
methyl 10-undecenoate has been consumed. A sample is collected and analyzed by
NMR. The analysis shows that there remains a 45% proportion of internal olefin, while
25 23% of products formed correspond to branched (15%) and linear (85%) aldehydes.
Table 7. H~droformylationo f methyl 10-undecenoafeI aJ
T Time Conv. inte%rn al Sel. (%)[bl
Entry SlRh URh rC) (h) (')'b' alkenes[cl n-2 iso-3 ss-pdt
4 100 000 20 120 48 68 45 85 12 3
la' distilled methyl 10-undecenenitrile = 5.0 mmol, toluene = 10 ml, P = 20 bar COIH2
(I:<).
5 Ib1 Conversion of the methyl 10-undecenoatelselectivityl% of internal alkene
determined by 'H NMR and GLC analyses. '" 1 of internal alkene, residual or formed during the reaction.
When all is said and done, the process according to the invention has numerous
10 advantages compared with the existing processes. It is simple to implement. It does not
require any particular equipment and can be implemented in existing industrial devices,
which makes it possible to initiate marketing, even with small tonnages in terms of
production capacity. It also does not require expensive starting materials or expensive
catalysts. The process according to the invention is versatile since it makes it possible
15 to use a wide range of starting materials; it is not linked to one oil in particular.
Contrary to the prior art processes which necessarily use a metathesis step, and result
in an amino ester when the starting materials are, for example, a fatty ester and
acrylonitrile, or a fatty nitrile and methyl acrylate, an amino acid is obtained according
to the process of the invention. Furthermore, the number of carbons of non-renewable
20 origin of the amino acid obtained according to the process of the invention is zero, or is
limited to 1 when the syngas (CO) used during the hydroformylation is not produced
from biomass.
CLAIMS
1- A process for synthesizing an o-amino acid compound of formula
HOOC-R'-CH2NH2, where R' is an alkyl radical comprising from 6 to 15 carbon
atoms or an alkylene radical comprising from 6 to 15 carbon atoms and from 0 to 2
unsaturations,
comprising:
I ) a step of hydroformylation of an unsaturated fatty nitrile chosen from the compounds
10 of formula:
RI-CH=CH-[(CH~)~-CH=CH],-(CH~)&N
where RI is H or an alkyl radical comprising from 1 to 11 carbon atoms
comprising, where appropriate, a hydroxyl function,
q, m and r are integer indices such that q = 0 or I , 0 S m 5 2 and 4 S r 5 13, and
15 mixtures thereof,
by reacting said nitrile with carbon monoxide and dihydrogen so as to obtain at
least one fatty nitrile aldehyde of formula:
HOC-R'-CN,
2) a step of oxidation in the presence of dioxygen, during which the nitrile-aldehyde
20 obtained in step 3 is converted into a fatty nitrile-acid of formula:
HOOC-R'-CN,
3) a reduction step during which the nitrile-acid obtained in step 2J is converted into an
01-amino acid of formula:
HOOC-R'-CH2NH2.
2- The process as claimed in claim 1, also coniprising a step of catalytic cross
metathesis with an alkene chosen from ethylene, propylene, but-I-ene and but-2-ene,
carried out on the fatty nitrile before step 1) so as to produce an omega-unsaturated
fatty nitrile corresponding to the formula R2-CH=CH-(CH2)iCN where R, is H or an
30 alkyl radical comprising from 1 to 3 carbon atoms.
3- The process as claimed in claim 1, also comprising a step of producing said
fatty nitrile from an unsaturated fatty acid or ester of natural origin of formula:
(R1-CH=CH-[(CH2),-CH=CH]m-(CH2)&OO-),-G, where
p is an integer index such that 1 5 p r 3,
G is H, an alkyl radical having from 1 to 11 carbon atoms or a radical comprising
2 or 3 carbon atoms bearing 1 or 2 hydroxyl function(s),
said production comprising the ammoniation of the carbonyl function of the unsaturated
fatty acid or ester of natural origin to give a nitrile function.
5
4- The process as claimed in claim 3, also comprising, before ammoniation:
- either a catalytic cross metathesis with ethylene carried out on the unsaturated fatty
acid or ester of natural origin,
- or a pyrolysis of the unsaturated fatty acid or ester of natural origin, followed by
lo distillation, then optionally hydrolysis to give an acid in the case of the ester,
so as to produce an omega-unsaturated fatty acid or ester of formula:
CH2=CH-(CH2),COOR2, R2 being H or a C2-C4 alkyl radical,
and such that, after the ammoniation step carried out on this omega-unsaturated fatty
acid or ester, an omega-unsaturated fatty nitrile of formula CH2=CH-(CH2),CN is
15 obtained.
5- The process as claimed in claim 3 or 4, wherein the unsaturated fatty acid (or
ester) of natural origin is a hydroxylated acid (or ester), preferably ricinoleic acid (or
ester) or lesquerolic acid (or ester), more preferably ricinoleic acid.
20
6- The process as claimed in claim 1, for synthesizing an o-amino acid
compound of formula
HOOC-(CHZ)~+~-CH~NHZ,
from a monounsaturated fatty nitrile compound of formula
25 CHz=CH-(CH2)rCN
comprising:
- the hydroformylation of the nitrile compound so as to obtain a nitrile aldehyde
compound of formula HOC-(CH2),2-CN, then
- the oxidation of the nitrile aldehyde compound so as to obtain the corresponding
' 30 nitrile acid compound of formula HOOC-(CH2),2-CN, and
-the reduction of the nitrile acid compound to give an m-amino acid of formula
HOOC-(CH2)c+z-CH2NHz.
7- The process as claimed in any one of the preceding claims, wherein the
35 hydroformylation is catalyzed in the presence of a system comprising:
150°C, preferably from 100 to 140°C, preferably from 120 to 140°C, preferably at a
temperature approximately equal to 140°C.
15- The process as claimed in any one of the preceding claims, wherein the
5 hydroformylation is carried out for a period of time ranging from 2 to 24 hours,
preferably from 2 to 6 hours.
16- The process as claimed in any one of the preceding claims, wherein the
hydroformylation is carried out at a partial COIH, pressure included in the range of from
10 5 to 50 bar, preferably from 10 to 40 bar, preferably from 10 to 30 bar, preferably at
20 bar of COIH,, and according to a CO:H, ratio included in the range of from 1:3 to
3:l.
17- The process as claimed in any one of the preceding claims, wherein the
15 [Substrate]/[Metal] ratio is included in the range of from 5000 to 500 000, preferably
from 5000 to 400 000, preferably from 5000 to 300 000, preferably from 5000 to
200 000, preferably from 5000 to 150 000.
18- The process as claimed in any one of the preceding claims, wherein the
20 oxidation step is carried out by sparging dioxygen or a dioxygen-containing gas mixture
in the product resulting from the hydroformylation, optionally in the presence of the
hydroformylation catalyst.
19- The process as claimed in one of the preceding claims, wherein the oxidation
25 step is carried out without the addition of solvent andlor without the addition of
dioxygen activation catalyst.
20- The process as claimed in one of the preceding claims, wherein the oxidation
step is carried out at a partial dioxygen pressure ranging from 1 bar to 50 bar, in
30 particular from 1 bar to 20 bar, preferably from 1 to 5 bar.
21- The process as claimed in one of the preceding claims, wherein the dioxygen
is continuously injected into the reaction medium by bubbling, preferably in the form of
an air or oxygen stream, preferably injected in excess with respect to the stoichiometry
35 of the oxidation reaction.
22- The process as claimed in one of the preceding claims, wherein the molar
ratio of the dioxygen relative to the product resillting from the hydroformylation step is
included in the range of from 3:2 to 100:2.
5
23- The process as claimed in one of the preceding claims, wherein the oxidation
is carried otrt at a telnperatlrre included in the range of from 0% to 100"C, preferably
from 20°C to 10O0C, in particular from 30°C to 90"C, preferably from 40°C to 80°C,
optionally in 2 consecutive increasing stationary temperature phases.
24- The process as claimed in any one of the preceding claims, also comprising
a step of synthesis of polyalnide by polymerization using the w-antino acid obtained in
step 3.
15 25- The process as claimed in any one of claims 7 to 24, wherein the
hydroformylation step comprises the recycling of the hydroformylation catalyst system,
optionally supplemented by a provision of new catalyst and/or ligand during a
subsequent hydroformylation cycle.
: .>
20 26- The process as claimed in claim 25, wherein the recycled catalyst system is
obtained by at least partial evaporation of solvent andlor of nitrile-aldehyde andlor of
~rnreactedre agent.