Olefin cross-metathesis as a valuable tool for the preparation of renewable polyesters and polyamides from unsaturated fatty acid esters and carbamates

Article abstract of DOI:10.1039/c4gc00273c

Olefin cross-metathesis of unsaturated fatty acid methyl ester (FAME) derived benzyl carbamates with methyl acrylate is described. The obtained by-product, an α,β-unsaturated ester, was further modified via thia-Michael addition reactions in order to synthesize branched AA-type or AB-type monomers for the preparation of polyesters, which are tuneable by oxidation. Cross-metathesis of fatty acid derived carbamates was used as a novel approach to prepare linear AB-type monomers, which can be used for the preparation of renewable polyamides PA11, PA12 and PA15. The necessary fatty acid carbamates were prepared by applying a catalytic Lossen rearrangement procedure. The presented synthesis strategy has potential for the bio-sourced preparation of monomers for the production of polyamides. All prepared polymers were fully characterized by NMR, SEC, and DSC analyses. Additionally, the Young's modulus of the prepared long-chain polyamide PA15 was determined. This journal is the Partner Organisations 2014.

Full text of DOI:10.1039/c4gc00273c

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ARTICLE
Olefin Cross-Metathesis as a Valuable Tool for the
Preparation of Renewable Polyesters and Polyamides
from Unsaturated Fatty Acid Esters and Carbamates
Cite this: DOI: 10.1039/x0xx00000x
Matthias Winkler and Michael A. R. Meier*
Received 00th January 2012,
Accepted 00th January 2012
Olefin crossꢀmetathesis of unsaturated fatty acid methyl ester (FAMEs) derived benzyl
carbamates with methyl acrylate is described. The obtained byꢀproduct, an α,βꢀunsaturated
ester, was further modified via thiaꢀMichael addition reactions in order to synthesize branched
AAꢀtype or ABꢀtype monomers for the preparation of polyesters, which are tuneable by
oxidation. The crossꢀmetathesis of fatty acid derived carbamates was used as a novel approach
to prepare linear ABꢀtype monomers, which can be used for the preparation of renewable
polyamides PA11, PA12 and PA15. The necessary fatty acid carbamates were prepared
applying a catalytic Lossen rearrangement procedure. The presented synthesis strategy has
potential for the bioꢀsourced preparation of monomers for the production of polyamides. All
prepared polymers were fully characterized by NMR, SEC, and DSC analysis. Additionally,
the Young modulus of the prepared longꢀchain polyamide PA15 was determined.
DOI: 10.1039/x0xx00000x
www.rsc.org/
or erucic acid for SM reactions revealed to be slightly more
challenging since the metathesis equilibrium cannot be shifted
Introduction
Price, availability, and environmental impact are the main
reasons for the chemical industry to move away from fossil
resources. However, the polymer industry is still strongly
depending on the use of petroleum derived monomers. In order
to substitute these monomers, efficient synthetic routes utilizing
renewable resources are needed and of high interest. Moreover,
processes making use of the synthetic potential of nature and
produce little to no waste are highly desirable. Being
recognized as one of the most important and most frequently
used renewable raw materials, plant oils are valuable
alternatives not only for the synthesis of diverse fine chemicals,
but also for polymer chemistry.1,2 Many efficient catalytic
modification reactions of fatty acids or fatty acid methyl esters
(FAMEs) to prepare monomers or monomer precursors have
been developed. Herein, the methoxycarbonylation,3,4 the
by simply removing ethylene as byꢀproduct. However, also
several procedures are known to prepare the oleic or erucic acid
derived diacids via metathesis reactions.19ꢀ21 Furthermore, the
metathesis reaction of FAME with diverse functional
compounds allows the synthesis of functionalized FAMEs.
Herein, the CM of FAMEs with allyl alcohol, allyl chloride,
diethyl maleate or cisꢀbuteneꢀ1,4ꢀdiyl diacetate is well
investigated.22ꢀ25 The above mentioned approaches demonstrate
the versatility of the (crossꢀ)metathesis reaction in order to
synthesize valuable functionalized fatty acid derivatives or fatty
acid based monomers. However, the synthesis of polyamide
monomers using metathesis reactions is barely described. Such
an efficient catalytic synthesis procedure, however, is highly
interesting since polyamides represent a class of highly
valuable engineering plastics. The (cross)ꢀmetathesis of amine
or amide functionalized substrates still remains a great
challenge. Usually, the amine function is protected prior the
metathesis reaction or the metathesis reaction is performed in
acetic media in order to in situ protonate the amine and prevent
catalyst deactivation.26,27 Robinson and coworkers reported the
SM of undecenylamine to prepare the corresponding diamine, a
valuable and renewable AAꢀtype monomer for the preparation
of polyamides. Bruneau et al. reported the crossꢀmetathesis of
10ꢀundecenenitrile or acrylonitrile with methyl 10ꢀundecenoate
or methyl acrylate, respectively.28 The presented tandem
procedure provides a sustainable and very interesting route to
linear amino esters as useful polyamide precursors.
ketonization,5ꢀ7
acetoxylation,8,9
or
enzymatic
transformations10ꢀ12 offer interesting modification possibilities.
Olefin metathesis proofed to be an especially powerful tool in
this context and was used to prepare different monomers from
diverse plant oils in an efficient catalytic manner.1, 13ꢀ15 In 2007,
our group reported on the crossꢀmetathesis of FAMEs and
methyl acrylate.16 All metathesis reactions were performed in
bulk using an excess of the methyl acrylate and the Hoveydaꢀ
Grubbs 2nd generation catalyst. Full conversion of the FAMEs
and a very good crossꢀmetathesis selectivity was obtained using
a catalyst loading of <0.5 mol%. Moreover, the selfꢀmetathesis
(SM) of fatty acids to prepare diesters is described as catalytic
procedure to obtain renewable monomer precursors. In case of
undecenoic acid (a castor oil derivative),17 the selfꢀmetathesis
was used to generate the C20 diacid, an AAꢀtype monomer to
prepare polyesters by polycondensation.18 Employing oleic acid
These findings prompted us to search for novel catalytic
procedures allowing the preparation of fatty acid based amino
esters, which can be used to prepare renewable polyamides.
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Thus, the olefin crossꢀmetathesis of unsaturated fatty acid rearrangement.29 The prepared methyl carbamates can be used
methyl esters (FAMEs) derived carbamates with methyl to synthesize the corresponding amines by simple carbamate
acrylate was investigated for the first time in order to synthesize cleavage under basic conditions. Thus, a crossꢀmetathesis of
renewable polyamides and polyesters. Moreover, utilizing all such carbamates and subsequent carbamate cleavage would
products of the respective metathesis reactions, the crossꢀ enable the synthesis of the desired ABꢀtype monomers as
metathesis byꢀproducts were also converted to valuable illustrated in Figure 1. In order to enable a mild deprotection of
monomers and subsequently polymerized.
the carbamate and hydrogenation of the double bond in one
step, we used fatty acid derived benzyl carbamates as starting
materials for the crossꢀmetathesis reaction with methyl acrylate
(Figure 1). The catalytic Lossen rearrangements were
performed according to our previously reported procedure
utilizing TBD as catalyst, methanol and dibenzyl carbonate.29
Noteworthy, dibenzyl carbonate was synthesized by simple
transꢀesterification of dimethyl carbonate (a renewable and
untoxic reagent), according to the procedure reported from our
group before.30 An advantage of the Lossen rearrangement
performed with dibenzyl carbonate and benzyl alcohol is the
reaction efficiency. Thus, higher yields were obtained as in the
synthesis of the corresponding methyl carbamates.29 Moreover,
the excess of the required alcohol and carbonate was
significantly reduced. On the other hand, the regeneration of the
used benzyl alcohol and dibenzyl carbamate in order to perform
the Lossen rearrangement in a sustainable manner is not as
straightforward. However, the use of a Kugelrohr distillation
apparatus allowed for a simple and efficient recycling of the
benzyl alcohol and dibenzyl carbamate by distillation. It has to
be noted that all Lossen rearrangements were performed with
20 mol% of the TBD catalyst. Interestingly, the reaction can
also be carried out with lower catalyst loadings (5 ꢀ 10 mol%),
though longer reaction times are needed.
Results and discussion
In an earlier publication, we reported on the efficient olefin
crossꢀmetathesis of methyl acrylate and unsaturated fatty acid
methyl esters (FAMEs).16 The crossꢀmetathesis reactions were
performed under solventꢀfree conditions using low catalyst
loadings and selectively provided the corresponding diesters
and an α,β unsaturated ester. The presented catalytic synthesis
procedure offers a sustainable access to polyester precursors.
These findings prompted us to search for a possibility to
perform efficient crossꢀmetathesis reactions of fatty acid based
substrates in order to obtain renewable polyamide precursors.
In principle, instead of employing FAMEs in the crossꢀ
metathesis with methyl acrylate, the use of the corresponding
amine would directly provide the desired amino FAME.
However, crossꢀmetathesis reactions of compounds having an
amine moiety are still quite challenging and usually the amine
function is protected.26 In this context, Bruneau and colleagues
reported the crossꢀmetathesis of 10ꢀundecenenitrile with methyl
acrylate.28 Subsequent hydrogenation of the crossꢀmetathesis
product yielded the desired ABꢀtype monomer as polyamide
precursor. Recently, we reported the synthesis of fatty acid
derived carbamates, which can be obtained in an
environmentally friendly fashion via
a catalytic Lossen
Figure 1: Synthesis of renewable ABꢀtype monomers via Lossen rearrangement, crossꢀmetathesis, and subsequent deprotection.
2 | J. Name., 2012, 00, 1-3
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Figure 2: Comparison of the 1HꢀNMR spectra of the benzyl carbamate 3, the crossꢀmetathesis product 6, and the amino FAME 10.
The crossꢀmetathesis reactions were performed similar to a known varying carbon chain length using TBD or DBU as catalyst. SEC
procedure.16 Thus, all metathesis reactions were performed in bulk analysis of P1, P2 and P3 revealed molecular weights of 14.9 kDa to
using the HovedydaꢀGrubbs second generation catalyst (0.5 mol%) 22.6 kDa and a dispersity of 1.73 to 2.20 (molecular weights were
and an excess of the methyl acrylate. The desired products 4 ꢀ 6 were determined relative to narrow poly(methylmethacrylate) standards,
obtained in good yields (up to 91 %) and were subsequently used for see also SI). The melting points were determined by differential
the preparation of the ωꢀamino FAMEs. In case of the crossꢀ scanning calorimetry (DSC) and ranged from 169 °C to 186 °C
metathesis of benzyl carbamate 3, a white precipitate was formed (Table 1).
after a short reaction time, caused by selfꢀmetathesis, and only rather
low yields (47ꢀ50 %) were obtained. Improved yields of up to 80 % Table 1: Analytic data of the prepared renewable polyamides.
were obtained if the reaction was performed at higher temperatures
(60ꢀ 65 °C, similar to the procedure reported by Slugovc et al. using
ethyl acrylate at a reaction temperature of 75ꢀ80 °C26). Yields of up
to 80 % were also obtained if the reaction was performed on a
smaller scale (1.5 g / 3.4 mmol) under vigorous stirring. As a byꢀ
product, methyl undecꢀ2ꢀenoate 7 is formed, which can be further
derivatized as described below (Figure 3). The hydrogenation of the
double bond and the cleavage of the benzyl carbamate were
performed in one step. First, we used Pd/C as convenient catalyst for
heterogeneous hydrogenations and cleavage of benzyl carbamates.
Although we employed a pressure of 20 bar of hydrogen at a
temperature of 35 °C, the benzyl carbamate was not cleaved after
two days. If the Pearlman’s catalyst (Pd(OH)2/C) was used instead,
the hydrogenation as well as the cleavage of the carbamate was
completed after 16 hours providing the ωꢀamino FAMEs in very
good yields and in high purity without further purification. The
solvent used for the carbamateꢀcleavage/hydrogenation reaction
appeared to be of crucial importance. The desired product was only
obtained in high purity if alcohols, such as methanol or ethanol, were
Polymer
Mn
[kDa]
Ð
Tm
[°C]
Young modulus
[MPa]
P1 (PA11)
P2 (PA12)
P3 (PA15)
PA16 [b]
14.9
22.6
15.2
20.3
2.20
2.13
1.73
1.65
186
182
169
166
1740 [a]
2320 [a]
1480
1550
[a]values are given for commercial nylon 11 (Mn = 31.6 kDa, Ð =
1.53) and nylon 12 (Mn = 38.5 kDa, Ð = 1.46), [b] see literature 31
Compared to commercially available polyamides, the melting points
are in the expected range. For commercially available PA11 and
PA12, melting points of 183 °C and 180°C are reported, which are
similar to the measured melting points of FAME based polyamides
P1 and P2 (Table 1).32 Compared to PA11 and PA12, the amide
frequency of PA15 is lower, and thus the melting point of the fatty
acid derived polyamide P3 (Tm = 169 °C) is lower. If compared to
PA16, having a melting point of 166 °C, the melting point of P3 is
slightly higher due to an increased amide frequency.31
1
used. As an example, the HꢀNMR spectra of the benzyl carbamate
3, the crossꢀmetathesis product 6, and the final amino FAME 10 is
shown in Figure 2, demonstrating the overall successful
transformation of methyl erucate to the desired ABꢀtype monomer.
Subsequently, the prepared amino FAMEs were used in
polycondensation reactions to prepare polyamides (PAs) with a
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Both polymers P3 and PA16 are polyamides having an extended 19.0 kDa and a dispersity of 1.52 ꢀ 1.90. The thermal properties of
aliphatic segment and represent a class of interesting materials.33 the prepared polyesters were studied using DSC, revealing melting
Beside DSC, NMR and SEC analysis, we performed stressꢀstrain points of ꢀ18.6 °C – 15.5 °C.
measurements of the prepared longꢀchain polyamide P3 to determine
the Young modulus and compared the results to commercial PA11
and PA12 (for experimental details of the stressꢀstrain measurements
see SI). The measurements revealed a Young modulus for P3 of
1480 MPa, which is lower than the modulus for the commercial
PA11 and PA12. Apparently, the longer chain polyamides PA15 and
PA16 having a lower amide group frequency have lower Young
modules due to reduced hydrogen bonding. On the other hand, PA11
has a higher amide group frequency, thus having a stronger
hydrogen bond interaction, but its Young modulus is lower than this
of polyamide 12 having a similar molecular weight. Herein, the
slightly longer aliphatic chain segments have a significant impact on
the Young modulus. This effect can be explained by the different
crystallinity of oddꢀ and evenꢀnylons.34 The same effect can be
observed when the PA15 and P16 are compared with each other,
although the difference of the Young moduli is less pronounced.
As byꢀproduct of the crossꢀmetathesis of the fatty acid derived
benzyl carbamates, an α,β unsaturated ester, methyl undecꢀ2ꢀenoate
7 is obtained, which appeared to be an interesting starting material
for further modifications. As known, α,β unsaturated carbonyl
compounds undergo Michael type addition reactions; thus, the use of
7 as a Michael acceptor appears to be an appropriate synthetic
Figure 4: Polymerization of the monomers derived from 7.
strategy to transform the methyl undecꢀ2ꢀenoate to valueꢀadded
As expected, the branched polyesters show low melting points due to
compounds. In order to obtain monomers, we used 2ꢀ
their dangling sideꢀchains. The polymer P6 displayed the highest
mercaptoethanol and methyl thioglycolate as Michaelꢀdonors to
melting point of 15.5 °C, since the employed longꢀchain C15 diol,
obtain monomers 11 or 12, respectively (Figure 3).
derived from methyl erucate, provided increased crystallinity.
Polymer P4 showed a Tg of 8 °C (Table 2).
Table 2: Analytic data of the polyesters and oxidized polyesters
based on monomers 4 ꢀ 7.
Polymer
P4
Mn [kDa]
Ð
Tm [°C]
Tg = 8
ꢀ18.6
15.5
21
17.1
1.52
18.9
1.74
P5
Figure 3: ThiaꢀMichael addition of 2ꢀmercaptoꢀethanol or methyl
thioglycolate to 7.
18.0
1.90
P6
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
P7
ThiaꢀMichael additions performed in bulk and with a small excess of
the thiol (1.2 equivalents) provided the best results. Full conversion
of 7 was achieved after stirring for 5 h at 50 °C using hexylamine
(10 mol%) as catalyst. The obtained monomer 11 was directly used
in polycondensation reactions. Monomer 12 can be used in
polycondensation reactions as well, if an appropriate diol or diamine
is used. Thus, we transformed the obtained diesters from the
metathesis of methyl oleate or ꢀerucate to the corresponding diols 17
and 18 by standard reduction procedures (see supporting
information) and used them as coꢀmonomers (Figure 4). In this way,
we were able to use all products of the respective crossꢀmetathesis
reaction for the synthesis of renewable monomers. In previous work,
1,5,7ꢀtriazabicyclo[4.4.0]decꢀ5ꢀene (TBD) showed very good
performance as organocatalyst for the synthesis of diverse polyesters
and polyamides.35ꢀ37 In the case of monomers 11 and 12, this catalyst
did not work since elimination of the thiol moiety occurred.
However, using tin ethylhexanoate or titanium isopropoxide as
catalyst yielded the desired polyesters without the occurrence of
elimination side reactions (Figure 4). Size exclusion chromatography
(SEC) revealed polymers with a molecular weight of 17.0 –
ꢀ5
P8
25
P9
To modify the thiol containing polyesters (P4 ꢀ P6), we performed
some oxidation reactions with metaꢀchloroperoxybenzoic acid
(mCPBA) in order to convert the sulfur atoms in the backbone of
these polyesters to sulfones (P7 – P9, Figure 5, Table 2). SEC
analysis of the oxidized polymers was not possible, since after the
oxidation the polymers were not soluble in common SEC solvents
(e.g. CHCl3, THF, DMAC, DMF, HFIP, or toluene).
Nevertheless, the slight solubility of the prepared polymers in
1
chloroform allowed for HꢀNMR analysis of the oxidized products,
which revealed the full oxidation of the sulfur, while no degradation
of the polymer was observed (Figure 5). DSC analysis of the
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polymers showed that the melting point of the polyesters increased represented by the Fachagentur Nachwachsende Rohstoffe FNR
due to this oxidation (Table 2).
(FKZ: 22006311) is kindly acknowledged. The authors also
would like to thank Daniel Zimmermann and Helena Hörig
(KIT) for experimental support.
Notes and references
a
Laboratory of Applied Chemistry, Institute of Organic Chemistry,
Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131
Karlsruhe, Germany.
E-mail: m.a.r.meier@kit.edu; http://www.meier-michael.com
Electronic Supplementary Information (ESI) available: Detailed
description of all experimental procedures .See DOI: 10.1039/b000000x/
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Conclusions
The synthesis of plant oil derived renewable polyesters and
polyamides is described. Based on the products obtained by
crossꢀmetathesis of the FAME derived carbamates with methyl
acrylate, diverse monomers were prepared. Methyl undecꢀ2ꢀ
enoate (as byꢀproduct) was utilized in thiaꢀMichael additions to
synthesize an ABꢀ or AAꢀtype monomer. On the other hand, the
obtained diesters from the crossꢀmetathesis were reduced to the
corresponding diols and used for polymerizations with the
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bond was hydrogenated in one step, leading to the amino
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Financial support for this project from the German Federal
Ministry of Food, Agriculture and Consumer Protection,
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6 | J. Name., 2012, 00, 1-3
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