Nylon Intermediates from Bio-Based Levulinic Acid

Article abstract of DOI:10.1002/anie.201812954

Use of ZrO₂/SiO₂ as a solid acid catalyst in the ring-opening of biobased γ-valerolactone with methanol in the gas phase leads to mixtures of methyl 2-, 3-, and 4-pentenoate (MP) in over 95 % selectivity, containing a surprising 81 % of M4P. This process allows the application of a selective hydroformylation to this mixture to convert M4P into methyl 5-formyl-valerate (M5FV) with 90 % selectivity. The other isomers remain unreacted. Reductive amination of M5FV and ring-closure to ?-caprolactam in excellent yield had been reported before. The remaining mixture of 2- and 3-MP was subjected to an isomerising methoxycarbonylation to dimethyl adipate in 91 % yield.

Full text of DOI:10.1002/anie.201812954

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Nylon intermediates from bio-based levulinic acid
Authors: Annemarie Marckwordt, Fatima El Ouahabi, Hadis Amani,
Sergey Tin, Narayana V. Kalevaru, Paul C. J. Kamer,
Sebastian Wohlrab, and Johannes Gerardus de Vries
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201812954
Angew. Chem. 10.1002/ange.201812954
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10.1002/anie.201812954
Angewandte Chemie International Edition
COMMUNICATION
Nylon intermediates from bio-based levulinic acid
Annemarie Marckwordt, Fatima El Ouahabi, Hadis Amani, Sergey Tin, Narayana V. Kalevaru*, Paul C.
J. Kamer, Sebastian Wohlrab and Johannes G. de Vries*
Abstract: Use of ZrO2/SiO2 as solid acid catalyst in the ring-opening
of bio-based -valerolactone with methanol in the gas phase leads to
mixtures of methyl 2-, 3- and 4-pentenoate (MP) in over 95%
selectivity, containing a surprising 81% of M4P. This allows the
application of a selective hydroformylation of this mixture in which
M4P is converted into methyl 5-formyl-valerate (M5FV) with 90%
selectivity and the other isomers remain unreacted. Reductive
amination of M5FV and ring-closure to caprolactam in excellent yield
had been reported before. The remaining mixture of 2- and 3-MP
was subjected to an isomerising methoxycarbonylation to dimethyl
adipate in 91% yield.
The production of Nylon-6 has tremendously increased since its
discovery in 1938 by Paul Schlack at IG-Farben.[1] The polymer
is made by polymerisation of -Caprolactam, which is produced
by several routes, all starting from benzene.[2] In the 1990s,
BASF, DSM and DuPont all worked on synthetic strategies
towards caprolactam starting from methyl 3-pentenoate (M3P)
obtained by palladium-catalysed methoxycarbonylation of the
less expensive butadiene. (Scheme 1).[3] Since M3P has only 5
Scheme 1. Routes to caprolactam from butadiene.
carbon atoms in the chain, a sixth one had to be added via
hydroformylation. This could be done by the isomerising
hydroformylation using catalysts based on rhodium with bulky
high yield to give caprolactam.[8] This route was never
bidentate phosphite ligands that had previously been discovered
by Union Carbide for the conversion of butenes to 1-pentanal.[4]
commercialised as the price of butadiene rose again and hence
the old routes prevailed.
Several patents have appeared claiming similar catalysts for this
reaction[5] and the best selectivity to methyl 5-formyl-valerate
Meanwhile, there is great interest in the production of nylon
(M5FV) remained at 82%.[5c] Selective hydroformylation of
precursors from renewable resources, not only in view of the
dwindling supply of fossil resources, but also because the
methyl 4-pentenoate (M4P) would have been a lot easier as
current production processes for the nylons are associated with
terminal alkenes are more reactive and can be hydroformylated
a rather high carbon footprint.[9] However, it is possible to bring
with very high n/iso selectivity, but the isomerisation of M3P
gives a mixture of isomers containing at best 4% of M4P.[6]
down the carbon footprint tremendously with a renewables-
based process.[10] A good strategy for the conversion of
Distillation of this was cumbersome in view of the very close
renewable resources to chemicals is based on the use of one of
boiling points, which would necessitate the use of extremely high
distillation towers and many recycles and for that reason this
route was not deemed feasible. Nevertheless, DSM developed a
platform chemicals is levulinic acid (LA) as this C5 building block
process that allowed the rhodium-catalysed hydroformylation of
the platform chemicals that were defined in the report made for
the DOE of the United States.[11] One of the most promising
can be made in a single step from lignocellulose by treatment
M4P to M5FV in very high selectivity from a mixture of M3P and
with dilute sulfuric acid at 200°C.[12] In this process the C6-
M4P, which could be obtained more easily with fewer distillation
plates from the isomerization reaction.[7] In this hydroformylation
sugars in the lignocellulose are converted to a 1:1 mixture of
levulinic acid and formic acid with over 50% yield. A process
the M3P remained unreacted. M5FV could be easily separated
was initially developed by Biofine,[13] which however suffered
from unreacted M3P by distillation. The effect of the presence of
from some shortcomings.[14] In the meantime, an improved
M2P in this reaction was never examined. Reductive amination
process was developed by GFBiochemicals.[15] Once LA is
produced on a scale of 100 kTon or more, its price will be lower
than most of the currently produced bulk chemicals.
and ring-closure of the methyl 5-formyl-valerate proceeded in
Several catalytic processes have been reported for the
[a]
A. Marckward, F, El Ouahabi, Dr. H. Amani, Dr. S. Tin, Dr. N. V.
Kalevaru,* Prof. Dr. P. C. J. Kamer, Dr. S. Wohlrab, Prof. Dr.
Johannes G. de Vries*
hydrogenation of LA to -valerolactone (GVL) in excellent
selectivities of over 95%.[16] Best catalysts seem to be those
based on ruthenium on several different carriers. The use of
homogeneous catalysts has also been reported for this
conversion with even higher selectivities.[17]
Furthermore, some processes are known for the conversion
of GVL / methanol (MeOH) to a mixture containing all 5 possible
methyl pentenoates. In this process, the lactone ring-opens to
Leibniz Institut für Katalyse e. V.
Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
E-Mail: Narayana.Kalevaru@catalysis.de
Johannes.devries@catalysis.de
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201812954
Angewandte Chemie International Edition
COMMUNICATION
the unsaturated acid and is esterified at the same time.
Isomerisation of the double bond also takes place. A number of
patents exist on the application of solid acid catalysts.[18] This
results in the formation of mixtures in which the relative amount
of methyl 4-pentenoate (M4P) is usually below 40%. A liquid
as catalysts (Scheme 3). After optimisation of the catalyst
composition, the ZrO2/SiO2 catalyst with a Zr loading of 25wt%
was found to exhibit superior performance compared to other
loadings of Zr. Consequently, we have applied this particular
composition of 25%ZrO2/SiO2 catalyst for the optimisation of the
reaction conditions to enhance the selectivity of the terminally
unsaturated methyl 4-pentenoate along with high space-time-
yields.
The 25%ZrO2/SiO2 catalyst was synthesised by wet
impregnation and characterised by several techniques such as
powder x-ray diffraction (XRD), BET-SA, pore size distribution,
temperature programmed desorption of ammonia (NH3-TPD)
and CHN elemental analysis. The XRD pattern of the
25%ZrO2/SiO2 catalyst revealed the presence of a ZrO2 phase
besides SiO2 (Figure S1). However, the diffraction reflections
were broad due to small crystallite size (<5 nm). The broadness
of the reflections made a clear attribution to either the cubic or
tetragonal phase of ZrO2 difficult. In addition, the presence of a
monoclinic ZrO2 phase could not be excluded. The nitrogen
adsorption-desorption isotherm of the catalyst disclosed the type
IV isotherm which is typical for mesoporous materials (Figure
S2). The mesoporous character of the 25%ZrO2/SiO2 catalyst
with a pore size of 6.7 nm stemmed from the SiO2 support. The
surface area was found to be 286.5 m2/g (Table S1).
phase reactive distillation process has also been reported.[19a]
A
similar procedure using an acidic ionic liquid gave mainly
M3P.[19b] A procedure using basic catalysts in the gas phase is
also known.[20] In this latter process the percentage of M4P is
usually much higher. However, because of the presence of
water that is formed in the reaction, some hydrolysis of the
esters takes place, leading to a rapid deactivation of the basic
catalyst by the formed acid.
Use of the mixture of pentenoate esters in an isomerising
hydroformylation is less attractive because of the presence of
relatively large amounts of M2P. The rhodium-alkyl complex
formed from this compound by insertion of the alkene into the
rhodium hydride complex is relatively stable as a result of the
stabilising action of the ester group thus forming an unproductive
resting state.[21] Additionally this compound leads to the
formation of relatively large amounts of methyl valerate during
the hydroformylation.[3b] For this reason, it would be much more
attractive to apply the second hydroformylation process
developed by DSM. However, this approach will only be
economic if a process can be found in which a mixture of methyl
pentenoates is formed containing at least 80% of methyl 4-
pentenoate based on the use of an acidic catalyst although the
remaining pentenoates can be used for the production of adipic
acid (Scheme 2).
Temperature
programmed
desorption
of
ammonia
measurements revealed that the 25%ZrO2/SiO2 catalyst
possesses weak to moderate acid sites with an ammonia uptake
of 0.26 mmol g-1. In addition, the catalyst contains basic sites as
shown by CO2 desorption (0.17 mmol CO2 g-1) (Figure S3 and
S4).
With this background, we started screening a range of solid
catalysts in the reaction between GVL and methanol to produce
a methyl pentenoate mixture with a high content of M4P (Fig.
S5). The ring-opening of GVL to the MP mixture using methanol
was initially performed as batch process in an autoclave. From
these tests, ZrO2 supported on SiO2 was found to be the most
active catalyst.
Scheme 3. SiO2 supported ZrO2-catalysed gas phase reaction GVL to an
isomeric mixture of methyl pentenoates enriched in methyl 4-pentenoate.
First, the effect of the reaction temperature on the activity and
selectivity was studied. It is obvious from Figure 1a that the
product distribution and the GVL conversion are strongly
dependent on the reaction temperature. The conversion of GVL
is observed to increase from 44% to 85% with increasing
temperature from 255 to 315°C and then levelled-off beyond this
temperature. The total MP selectivity was found to be very high
for all explored temperatures (97 to 99%). At lower temperatures
(255 to 295°C) the desired M4P was the major product while
M2P was a minor product. With the rise in temperature the
selectivity of M2P and M3P is increasing at the expense of M4P.
This is presumably due to increased isomerisation of M4P to
M3P and M2P because the acid sites of the ZrO2/SiO2 catalyst
also enhance the isomerisation reaction. The reaction at 295°C
shows a good balance in terms of reasonably good M4P
selectivity and conversion of GVL.
Scheme 2. Route to two nylon precursors starting from bio-based GVL.
However,
these
batch
processes
suffered
from
reproducibility problems. Thus, subsequent experiments were
performed as gas phase continuous processes using ZrO2/SiO2
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10.1002/anie.201812954
Angewandte Chemie International Edition
COMMUNICATION
100
90
80
70
60
50
40
30
20
10
0
100
90
80
70
60
50
40
30
20
10
0
375
355
100
90
80
70
60
50
40
30
20
10
0
others
335
315
295
275
S M2P
S M3P
S M4P
X GVL
T
2
4
10 21 35 45 59 100 101 107
255
275
295
315
335
1:1
1:3
1:5
1:7
TOS (h)
T (°C)
GVL:MeOH
a.
b.
c.
Figure 1. a) Effect of temperature on the transesterification of GVL to MPs using 25%ZrO2/SiO2 catalyst (p: 1 bar, GVL 8 mmol/h, GVL : MeOH = 1 : 3, N2 as
carrier gas, total flow 4 l/h, GHSV: 1900 h-1). b) Effect of the GVL : MeOH molar ratio on the transesterification of GVL to MPs using 25%ZrO2/SiO2 catalyst (T:
295°C, p: 1 bar, GVL: 8 mmol/h, N2 as carrier gas, total flow 4 l/h, GHSV: 1900 h-1). c) Long-term stability test over 25%ZrO2/SiO2 catalyst (T: 295°C, p: 1 bar,
GVL: 8 mmol/h, GVL : MeOH = 1 : 5; N2 as carrier gas, total flow 4 l/h, GHSV: 1900 h-1).
Next, the influence of the GVL/MeOH molar ratio was
investigated. The GVL/MeOH ratio was varied in the range from
1:1 to 1:7 while the total gas flow was kept constant. At 255°C,
the GVL conversion was only 34% at the 1:1 molar ratio which
increased to 52% at 1:7. Total MP selectivity was found to be
≥97% in all cases. In particular, M4P selectivity improved with
increasing GVL/MeOH ratio from 54% (at 1:1 molar ratio) to 78%
(at 1:5) and then slightly decreased to 74% (at 1:7) (Figure 1b).
In general, the total selectivity of all MP isomers was observed
to be 99% at all GVL/MeOH ratios except for the 1:1 molar ratio
(92%). Thus, the optimal GVL/MeOH molar ratio in terms of M4P
selectivity at a reasonably high conversion of GVL was 1:5.
After optimising the reaction temperature and GVL to MeOH
ratios, the long-term stability of the 25%ZrO2/SiO2 catalyst was
explored under optimised reaction conditions. The idea behind
this long-term test was not only to check the catalyst stability but
also to collect the MPs product mixture over a longer period of
time to allow its use for the hydroformylation reaction to produce
nylon precursors. Figure 1c illustrates that the 25%ZrO2/SiO2
catalyst displayed consistent performance with excellent long-
term stability for a period of ca. 110 h on-stream. The total MP
selectivity remained more or less constant at 99% throughout.
catalyst.[22] However, they tested the catalyst for only 1 h and no
long-term stability was reported. Near the end of the present
long-term test, the reaction temperature was first raised to
315°C and then even to 335°C before being returned to 295°C.
During the whole time, the reaction was continued by dosing the
GVL/MeOH reaction mixture to check the performance of the
catalyst after such long hours of testing. The catalyst displayed
similar behaviour as observed earlier, the rise in temperature led
to an improved GVL conversion while the M4P selectivity
decreased. Amazingly, the total MP selectivity did not drop to a
considerable extent (i.e. varied from 99 to 97% at 335°C). After
returning back to the actual reaction temperature of 295°C again,
the product distribution as well as the GVL conversion closely
resembled to the initial results. This observation proved that the
initial catalyst activity can be restored, if desired, by increasing
the temperature even by only 40°C. Furthermore, this can be
done while the process is running without any need to shut down
the reactor or even stop the reactants dosing. The collected
reaction mixture from the long-term test for a period of ca. 110 h
was then distilled to obtain the pure mixture of MP isomers.
With the mixture of methyl pentenoates, containing 81% of
the terminal pentenoate, 14% of M3P and 5% of M2P in hand
(Table1, entry 0), a selective hydroformylation reaction in the
presence of Rh(CO)2(acac) and phosphine ligands under CO/H2
pressure was performed. The aim of this part of the study is to
selectively convert M4P to the terminal aldehyde M5FV, while
leaving the remaining pentenoate esters untouched (Scheme 4).
Nevertheless, during the first 10 h on-stream,
a
slight
deactivation of the catalyst took place and hence the GVL
conversion decreased from 77% to 65%, which is however
compensated to a certain extent by an increased selectivity to
the target M4P. The deactivation is due to organic deposits as
evidenced by CHN elemental analysis (S4). The amount of
deposits on the spent catalyst after the long-term test was about
2%. The catalyst performance after 10 h on-stream remained
more or less stable at about 65% GVL conversion and 81% M4P
selectivity. Thus the goal of producing a methyl pentenoate
mixture containing >80% methyl 4-pentenoate was successfully
achieved. Furthermore, the space-time-yield (STY) of MPs
amounts to 620 g/kgCat/h of which M4P is 507 g/kgCat/h. To the
best of our knowledge, this is the highest M4P selectivity and
STY reported so far for such a long-term test in a gas phase
continuous mode. Manzer,[20] and more recently Dumesic et al.
also reported very high M4P selectivity from GVL using a basic
Scheme 4. Rhodium-based selective hydroformylation of methyl 4-pentenoate.
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10.1002/anie.201812954
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COMMUNICATION
Thus, the mixture was subjected to a biphasic hydroformylation acidic sites activate the carbonyl function of the lactone for ring-
reaction in water/toluene using 0.3 mol% of Rh(CO)2acac and tri- opening with methanol which is made more nucleophilic by
sulfonated triphenylphosphine (TPPTS) as ligand (L : Rh = 150) interaction with the weakly basic sites. The GVL/MeOH ratio was
at 110°C. M4P was fully converted, achieving 93% selectivity found to play a crucial role in both the product distribution and
towards formylvalerates (both linear M5FV and branched M4FV) the conversion of GVL. The catalyst displayed excellent long-
where the l/b ratio was observed to be 97:3 (Table 1, entry 1). In term stability over a period of ca. 110 h on-stream. Furthermore,
this reaction the amount of M3P increases somewhat, we have shown the possibility of producing M5FV with excellent
presumably
due
to
isomerisation
reactions.
When l/b selectivity via a highly selective hydroformylation of M4P
triphenylphosphine (PPh3) was used as ligand in a single phase leaving the other MP isomers mostly untouched. These
reaction in toluene under the same reaction conditions, full remaining pentenoates were further valorised by an efficient
conversion of M4P with 100% selectivity towards the isomerising methoxycarbonylation which led to the formation of
formylvalerates was obtained. However, the linear aldehyde dimethyl adipate in excellent yield. Once levulinic acid is
M5FV was obtained in only 74% selectivity (Table 1, entry 2). In produced on large scale, this route can easily compete with the
both examples, the formation of small amounts of the current fossil-based route.
hydrogenated product methyl valerate (MV) was also observed,
This is most likely due to hydrogenation of M2P.[3b]
Acknowledgements
Table 1. Hydroformylation of methyl 4-pentenoate[a]
We thank the Leibniz Foundation for the funding of the project:
Composition (mol%)
Selectivity (%)
Agro and Paper Industry Waste to Bulk Chemicals. Levulinic
acid and Furfural as Platform Chemicals (SAW-2016-LIKAT 1
523). We thank Dr. Ralf Jackstell and Mr Rui Sang for support
with the hydroformylation experiments. We thank Dr. Hanan Atia
for the NH3- and CO2-TPD experiments. We thank Dr. Rudy
Parton (GFBiochemicals) and Dr. Michelle Janssen (Innosyn
b.v.) for helpful discussions.
Entry
0
Ligand
-
M4P
81
0
MFV
M3P
14
19
9
M2P
5
MV
0
MFV
l/b
0
-
1[b]
2[c]
TPPTS
PPh3
75
85
1
5
93
97/3
0
1
5
100
74/26
[a] 5.7 Mg of Rh(CO)2acac; 0,022 mmol, 6 mmol M4P, 1 mmol M3P, 0.4 mmol
M2P, T: 110°C, reaction time: 5 h, p: 10 bar H2/CO (1:1) [b] TPPTS: 1,88 g,
3,3 mmol, 150 eq, in toluene and water as biphasic system. [c] PPh3: 0,85 mg,
3,3 mmol, 150 eq. in toluene. Conversions and selectivities were calculated by
NMR and GC using dodecane as an internal standard.
Conflict of interest
The authors declare no conflict of interest.
A facile distillation allowed separation of M5FV from the
remaining pentenoate esters.[23] These were subjected to a
palladium-catalysed isomerising methoxycarbonylation in the
presence of methanol and CO at a pressure of 20 bar (Scheme
5).[24] For this transformation, a catalyst made in situ from
Pd(OAc)2 and 1,2-Bis(di-t-butylphosphinomethyl)benzene (dppx)
was used in order to isomerise the internal alkenes to the
terminal position and form the desired dimethyl adipate.[25] Full
conversion of the pentenoates and the subsequent isolation of
the adipate product in 91% yield was successfully achieved.
Keywords: homogeneous catalysis • heterogeneous catalysis •
-valerolactone • methyl pentenoates • nylon
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In conclusion, we have been able to achieve over 80%
selectivity to the desired M4P from GVL and methanol in a gas
phase process using a 25%ZrO2/SiO2 catalyst. We assume that
this high selectivity to M4P is due to the amphoteric nature of
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10.1002/anie.201812954
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
A. Marckwordt, F. El Ouahabi, Dr. H.
Amani, Dr. S. Tin, Dr. N. V. Kalevaru,*
Prof. Dr. P. C. J. Kamer, Dr. S. Wohlrab,
Prof. Dr. J. G. de Vries*
((Insert TOC Graphic here))
Page No. – Page No.
Nylon intermediates from bio-based
levulinic acid
Bio-based Nylon Use of 25% ZrO2/SiO2 as catalyst allows the gas phase ring-
opening of bio-based -valerolactone with methanol to a mixture of methyl
pentenoates containing 81% of the 4-isomer, which could be selectively
hydroformylated from the mixture to methyl 5-formyl-valerate, an intermediate for
caprolactam. The remaining isomers were converted into dimethyl adipate.
This article is protected by copyright. All rights reserved.