Preparation of Novel Aromatic-Aliphatic Poly(ketone ester)s through Condensation of Biomass-Derived Monomers

Article abstract of DOI:10.1002/cctc.201801381

Abstract: Novel unsaturated and saturated monomers with a hydroxyl group and a carboxylic group via aldol condensation reaction of lignin-derived aromatic aldehydes with levulinic acid were prepared through organocatalysis and hydrogenation, respectively.

Full text of DOI:10.1002/cctc.201801381

Accepted Article
Title: Preparation of novel aromatic-aliphatic poly(ketone ester)s
through condensation of biomass-derived monomers
Authors: Haibo Xie, Qin Chen, Tianhua Ren, Yang Chai, Yuanlong
Guo, Ian D. V. Ingram, Michael North, and ZONGBAO ZHAO
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Preparation of novel aromatic-aliphatic poly(ketone ester)s
through condensation of biomass-derived monomers
Qin Chen,[a] Tianhua Ren, [a] Yang Chai, [a] Yuanlong Guo, [a] Ian D. V. Ingram,[b] Michael North,[b] Haibo
Xie*[a] and Zongbao kent Zhao*[c]
Abstract: Novel unsaturated and saturated monomers with a
hydroxyl group and a carboxylic group via aldol condensation reaction
of lignin-derived aromatic aldehydes with levulinic acid were prepared
through organocatalysis and hydrogenation, respectively. The
catalytic process was optimized and the structure of the monomers
were full characterized. The as-prepared monomers were ready for
the subsequent condensation polymerization to achieve a serials of
novel full biobased poly(ester ketone)s. The chemical-physical
properties of the poly(ester ketone)s were evaluated. This provides a
green upgrading strategy to prepare sustainable synthetic polymers
from building blocks available on a large scale using a catalytic
biorefinery approach.
The continuing depletion of fossil resources and increasing
Scheme 1. The choices of aromatic and aliphatic species available from
lignocellulosic biomass for the synthesis of novel aromatic-aliphatic poly(ester
ketone)s.
environmental consciousness stimulate our society to use
renewable biomass feedstocks for energy, chemicals and
materials production, in order to reduce our dependence on fossil
resources.[1] Particularly, in the field of sustainable polymeric
materials obtained from biomass, natural polymers and their
Lignin is one of main components in lignocellulose, and it is
derivatives have been widely used for a variety of applications,
also the most abundant natural aromatic compound on the
many of which play a significant role in our daily lives.[2]
planet.[5] Recent catalytic conversions of lignin produced a broad
Simultaneously, the design and preparation of renewable
library of aromatic compounds, including vanillin, syringaldehyde,
monomers from biomass for polymers through controlled
p-hydroxybenzaldehyde, and creosol.[6] Amongst these, vanillin is
polymerization continues to be one of the most paramount
regarded as a promising bio-based aromatic building-block for
challenges in current polymer research.[3] Lignocellulosic
polymer synthesis and has received much attention. For example,
materials include three primary chemical fractions: (1)
Miller et al. used lignin-based vanillin aldehyde (VA) and acetic
hemicellulose — a polysaccharide predominantly composed of
anhydride to prepare acetyldihydroferulic acid, (3-(3-methoxy-4-
pentoses; (2) cellulose — a glucose polymer; and (3) lignin — a
acetoxyphenyl)propionic acid) which was subjected to
complex polymer of phenylpropane units. The effective
polymerization to yield biorenewable poly(dihydroferulic acid).[7]
implementation of the lignocellulosic biorefinery concept,
This polyester exhibits thermal properties similar to those of
especially via chemical catalytic approach, will produce a portfolio
polyethylene terephthalate (PET), which illustrates the huge
of chemicals which can be potentially upgraded into monomers
potential of lignin-derived monomers for the preparation of
for polymer preparation (Scheme 1). The field of catalytic
aromatic polymers. As an extension of this investigation, a series
conversion of lignocellulosic biomass has been the subject of
of derivatives of VA were prepared using various chemical
several excellent recent reviews.[1c, 4]
strategies for the production of sustainable monomers for not only
polyesters, but also polyurethanes, and epoxy resins with good
performance in thermal and chemical properties being
observed.[8] For example, Wool et al. reported methacrylated
[a]
Dr. Q. Chen, T. Ren, Y. Chai, Y. Guo, Pro. H. Xie
Department of Polymeric Materials & Engineering, College of
Materials & Metallurgy, Guizhou University (China). E-mail:
West Campus, Guizhou University, Huaxi District, Guiyang, P. R.
China, 550025
E-mail: hbxie@gzu.edu.cn
I. D. V. Ingram, M. North
Green Chemistry Centre of Excellence, Department of Chemistry,
University of York
York (UK) YO10 5DD
lignin model compounds including methacrylated guaiacol and
methacrylated eugenol as bio-based reactive diluents for liquid
molding resins. Homopolymers of these methacrylates with glass
transition temperatures similar to those of polystyrene and
poly(methyl methacrylate) were then prepared by bulk
polymerization.[8e] Zhu et al. have also prepared several high-
performing lignin-based polymers.[9] Recently, they synthesized
two novel vanillin-based diepoxides which exhibited similar curing
reactivity to bisphenol A epoxy resin. The cured vanillin-based
epoxides presented excellent flame retardancy and high Tg
together with outstanding mechanical properties.[9c]
[b]
[c]
Pro. Z. Kent Zhao
Dalian Institute of Chemical Physics, CAS
457 Zhongshan Road, Dalian (China).
E-mail: zhaozb@dicp.ac.cn
Supporting information for this article is given via a link at the end of
the document [synthesis and characterization of monomers and
polymers and E-factor calculations].
Another promising pathway to prepare polymeric monomers
from lignocellulosic biomass is the dehydration of cellulose and
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10.1002/cctc.201801381
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hemicellulose into 5-hydroxymethyl-furfural (HMF) and furfural,[10]
and further oxidation of HMF yielding 2,5-diformylfuran[11] and 2,5-
furandicarboxylic acid,[12] which are regarded as promising
alternatives to petroleum-based aromatic monomers for polyester
preparation.[13] Levulinic acid (LA) is a renewable feedstock,
which can be derived both from hemicellulose and cellulose in
lignocellulose via acidic processing.[14] Notably, formic acid is a
sustainable by-product from acidic hydrolysis of carbohydrate
biomass, and can serve as an environmentally friendly hydrogen
donor for catalytic transfer hydrogenation in biomass
upgrading.[15] To the best of our knowledge, levulinic acid has not
previously been used as a flexible precursor for the synthesis of
sustainable aromatic polyesters.
20% yield was obtained under idential conditions. With acetic acid
as the co-catalyst, neither linear secondary amines nor six-
membered cyclic secondary amines including morpholine and
piperidine showed noticeable catalytic activity (Table 1, entries 2-
6).
Table 1. Screening of the catalyst and co-catalyst to prepare unsaturated
monomer[a]
.
Entry
Catalyst
L-Proline
n-Dibutylamine
Diethylamine
Tetramethylguanidine
Morpholine
Co-catalyst
None
AcOH
AcOH
AcOH
AcOH
AcOH
AcOH
HCl
Yield %[b]
1
2
3
4
5
6
7
8
9
20
13
7
1
28
10
42
12
16
21
Piperidine
Pyrrolidine
Pyrrolidine
Pyrrolidine
Although significant progress has been made in the field of
sustainable polyesters, there is still a substantial challenge to
synthesize fully bio-based aromatic-aliphatic polyesters.[16],[17] It is
believed that a short aliphatic component in the main chain will
provide necessary flexibility to aromatic polyesters, thus
increasing their subsequent processability. In many cases, a
petroleum-based chemical was used for the introduction of a
flexible chain into the aromatic polyester, in association with the
use of lignin-derived aromatic or furan compounds.[4b]
Considering the inherent structure characteristics of lignin-derived
aromatic aldehydes and levulinic acid, herein we report a strategy
to prepare monomers with a hydroxyl group and a carboxylic
group via aldol condensation reaction of lignin-derived aromatic
aldehydes with levulinic acid. These structural features offer the
opportunity to prepare polymers using a single monomer instead
of two co-monomers. A series of sustainable aromatic-aliphatic
poly(ester ketone)s are prepared by using conventional bio-based
C2H2O4
F3CCOOH
10
Pyrrolidine
[a] The solution of levulinic acid (16.4 mmol), catalyst (1.64 mmol) and co-
catalyst (1.64 mmol) in 20 mL toluene were added dropwise to vanillin
aldehyde (16.4 mmol) in 40 mL toluene at 40 oC under N2. The mixture was
heated at 100 oC for 2 h and then at 140 oC for 1 h with Dean-Stark water
trap. [b] Isolated yields.
The mechanism of pyrrolidine-acetic acid catalysed aldol
condensations is proposed to proceed through the formation of
an enamine intermediate. The formation of the enamine is the
rate-determining step and largely depends on the nucleophilicity
of the secondary amine.[20] It has been demonstrated that
enamines are formed much more readily by pyrrolidines than by
piperidines and the corresponding pyrrolidine enamines are
known to be more nucleophilic.[21] Our results suggest that the
combination of pyrrolidine and acetic acid could act synergistically
to give high yields, which was supported by the lower yields
obtained when hydrochloric, oxalic or trifluoroacetic acid were
used as the co-catalyst. This result is in accordance with a
previous report which demonstrated that the pyrrolidine-acetic
acid combination was more efficient than other pyrrolidine-acid
combinations in the formation of enamines.[20] The optmized
catalytic system was extended to the aldol condensation reaction
of other lignin derived aromatic aldyhydes with levulinic acid,
including syringaldehyde and para-hydroxybenzaldehyde, giving
3a and 3c in moderate yields of 46% and 36% respectively.
Hydrogenation of arylidene derivatives 3a-c using 10%
palladium on carbon as catalyst in the presence of hydrogen or
formate salts afford mainly compounds 4a-c with satifactory yields
and selectivities (Table S2). Lactone derivatives 5a-c were also
obtained as by-products. The formation of 5a-c can be explained
by further reduction of the carbonyl group to a hydroxyl group,
which reacted with the carboxylic acid to form the lactone. The
lactone derivatives are also potential monomers to prepare
sustainable polymers via ring opening polymerization,[22] but this
was not the main goal in this study.
chemicals
obtainable
from
catalytic
biorefining
of
lignocellulose.[4d]
Scheme 2 illustrates the strategy for the synthesis of the
novel 100% bio-based aromatic-aliphatic poly(ester ketone)s. For
the preparation of unsaturated aromatic monomers 3b, the
influence of various parameters including catalyst structure,
reaction temperature, and catalyst loading were investigated
(Table1 and Table S1). The optimized catalyst was found to be
20 mol% of a combination of pyrrolidine and acetic acid and the
best conditions involved carrying out the aldol condensation
reaction at two different temperatures. Under these conditions,
the α-methyl group of levulinic acid adds to the aldehyde carbon
followed by dehydration to afford the arylidene keto acid
derivatives 3a-c in moderate yields (supporting information). The
1
stereochemistry of the monomers 3a-c were determined by H
NMR spectroscopy, and the results indicate the presence of a
single E-isomer, as the coupling constants relating the two olefinic
protons were in the range of 15-16 Hz.[18] In 13C NMR the chemical
shift at around 199, 175 ppm and 143, 130 ppm are attributed to
the carbonyl and double bond, respectively (supporting
information). Although L-proline is known to be an efficient
bifunctional acid–base organocatalyst for aldol reactions,[19] only
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Scheme 2. General strategy to synthesize fully bio-derived aromatic-aliphatic poly(ester ketone)s.
Table 2. Polymerization and characterization of aromatic-aliphatic poly(ester ketone)s
Entry
1
Monomer
poly(ester ketone)
T (oC)
220
T (h)
12
Cat (1 mol%)
Zn(OAc)2
Yield (%)
52
Mn
PDI
1.8
T50% (oC)[a]
474
W (%)[b]
43.0
Tg (oC)
129
4a
6a
20000
2
3
4
5
6
7
3b
4b
4b’
4b’
4b’
4c
6b’
6b-2
6b-3
6b-4
6b-5
6c
170
170
170
220
220
220
5
Zn(OAc)2
Zn(OAc)2
Zn(OAc)2
Zn(OAc)2
Sb2O3
33
40
49
46
38
43
23000
29000
21000
29000
32000
18000
1.1
1.6
1.8
1.5
1.9
1.8
465
397
407
409
402
464
43.3
32.6
26.4
36.1
37.0
44.5
131
80
81
95
86
12
12
12
24
12
Zn(OAc)2
137
[a] Temperature at which 50% weight loss was observed. [b] Remaining weight at 600 oC.
It is worth noting that formate salts are also good hydrogen
donors for catalytic transfer hydrogenation.[15] As aformentioned,
formic acid is a by-product from the preparation of LA from HMF,
which indicates that a sustainable hydrogenation reagent also
derived from biomass could be used in this synthesis.
via post-functionalization such as Micheal addition, cyclization
and thiol-ene click reaction. In Millers’ study, the direct
polycondensation of dihydroferulic acid only yielded oligomers
under identical conditions, and application of the acetylated ferulic
acid monomer for the polymerization yielded a polyester with
molecular weights comparable to that of commercial PET
(Mn=15000 to 40000).[7] Surprisingly therefore, our results show
that both the unsaturated monomer 3b and saturated monomer
Having established
a strategy for the preparation of
monomers 4a-c, their bulk polycondensation was performed in
the melt (170-220 oC) under dynamic vacuum with 1 mol% of zinc
acetate as catalyst. The evolved water was efficiently removed by
the dynamic vacuum to push the equilibrium toward the polymer.
The structure of poly(ester ketone)s were determined by 1H NMR
and HSQC (Figure S1 to S8). In the 1H NMR spectra of poly(ester
ketone)s (6a, 6c) derived from phenol carboxylic acid monomers
(4a, 4c) showed chemical shift above 8 ppm indicating the
presence of hydroxyl end groups (Figure S1, 2 and S7, 8). The
poly(ester ketone) of 6b-3 obtained from acetylated monomer 4b'
show weak acetyl end group at 2.2 ppm (Figure S5 and S6). The
obtained unsaturated poly(ester ketone)s can be further modified
4b
undergo polycondensation,
yielding corresponding
sustainable poly(ester ketone)s in moderate yields of 33 and 40%
with molecular weights of 23000 (PDI=1.1) and 29000 (PDI=1.6)
(Table 2, entry 2 and 3), respectively. The acetylated monomer
4b' was prepared by using acetic anhydride in the presence of 4-
dimethylaminopyridine in 54% yield. The yield of the poly(ester
ketone) was increased to 49% when the acetylated monomer was
applied under identical conditions, while the molecular weight
slightly decreased to 21000 (Table 2, entry 4). Further increase in
the polycondensation temperature from 170 oC to 220 oC does not
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lead to increases in either poly(ester ketone) yields or molecular
weight. A poly(ester ketone) with molecular weight up to 32000
(PDI=1.9) was achieved when the acetylated monomer was
polymerized in the presence of catalytic antimony(III) oxide. This
indicates that antimony(III) oxide is a superior catalyst to zinc
acetate to achieve a poly(ester ketone) with higher molecular
weight, but at the cost of a slight reduced yield (Table 2, entry 6).
Monomers 4a and 4c were also applied in the polymerization, and
poly(ester ketone)s 6a, 6c with high molecular weight were
obtained under identical conditions (Table 2 entry 1 and 7, Figures
S9 and S15).
seriously limited because its glass transition temperature is rather
low (-6.7 oC) compared to PET and PBT (67 and 38 oC,
respectively). The poly(ester ketone)s possess the same
functional groups but differ in the number of methylene units in
the main chain, which resulted in a decrease in Tg as the number
of methylene units increased. The DSC results imply that although
there are six methylene groups in the flexible chain repeat units
of the as-prepared poly(ester ketone)s, their Tgs are much higher
than that of PHT, and comparable or even higher than those of
PET and PBT (Table S3).
The use of biobased compounds and the new synthetic
strategy to prepare polybutylene terephthalate (PBT) and
polyhexylene terephthalate (PHT) analogues 6a-c is anticipated
to lead to new thermal behaviour of the poly(ester ketone)s, which
is an issue of prime importance for the application of these
polymers as potential thermoplastic materials. Therefore, their
themal properties were evaluated by TGA and DSC and key data
from these measurements are given in Table 2.
The TGA traces of poly(ester ketone)s 6a-c recorded under
a nitrogen atmosphere are depicted in Figure 1. This comparative
plot reveals that all the poly(ester ketone)s show a one-step
degradation pattern, indicating that the presence of a conjugated
double bond (6b’, Table 2 entry 2) and acetyl end group (6b-4,
Table 2 entry 5) did not significantly alter the thermal stability of
the ester linkage. The poly(ester ketone)s exhibited a 50 wt%
weight loss in the range of 395-474 oC indicating comparable
thermal stability to fossil-based polyesters. The structures and
molecular weights of the as-prepared bio- poly(ester ketone) do
influence their thermal properties to some extent. As shown in
Table 2, comparison of saturated and unsaturated poly(ester
ketone)s of similar molecular weight suggests superior thermal
properties for the unsaturated bio-poly(ester ketone) (Table 2
entries 2-4). The unsaturated poly(ester ketone) show higher
residual weight at 600 oC than those saturated poly(ester ketone)
indicating superior thermal stability.
Scheme3: Structural comparison of traditional PHT, 6b and 6b’
110
a: 6a
b: 6b-2
c: 6b-4
d: 6c
100
This can be explained by the synergetic effect of the
introduction of a methoxyl group onto the rigid aromatic benzene
ring and ketones or α,β-unsaturated ketones into the flexible
aliphatic chain in the polymers. The introduction of a methoxyl
group onto the aromatic benzene ring can decrease the symmetry
and increase the free volume of the polymer, thus resulting in a
higher Tg. It is well known that in a linear sp3-carbon chain (e.g. in
PHT) , free rotations around carbon-carbon single bonds can
allow the chains to bend or curl up in various ways, thus resulting
in polymers with low Tg. In carbon-carbon double bonds and
carbon-oxygen double bonds, similar rotations cannot occur, and
the polymeric segmental relaxation is restricted, thus resulting in
a higher Tg (Scheme 3).
90
80
70
60
50
40
30
a
d
c
b
100
200
300
400
500
600
Temperature ( oC)
In addition to their enhanced thermal properties, polyesters
with α,β-unsaturated ketone moieties are anticipated to provide
an important active site for post-polymerization modification via
classic nucleophilic or electrophilic addition reactions, such as the
Michael addition reaction. In this way a library of functional
polyesters may be designed and prepared in the future.[24]
E-factor analysis was employed to evaluate the
environmental impact of our approach and the details are shown
in Tables S4-S15. According to our calculations, the E-factor of
bio-based monomers 4a, 4b and 4c were determined as 7.4, 6.7
Figure 1. TGA traces of newly prepared poly(ester ketone)s.
The semicrystalline aromatic polyester PHT has not achieved
commercial applications, but it still deserves great attention
because its relatively low melting point (144 oC) requires less
severe processing conditions than PET and PBT (mp 255 and 224
oC, respectively).[23] However, PHT is not biodegradable and its
potential utilization in applications above room temperature is
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COMMUNICATION
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bio-based poly(ester ketone)s exhibit comparable thermal
properties to conventional thermosetting materials. As the
obtained functional phenol carboxylic acid monomers can be
further derived to other polymeric monomers, such as bis-epoxy,
which have great potential application in the area of polymers
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modification of the poly(ester ketone)s as well as screening of
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Acknowledgements
This work was supported by the National Natural Science
Foundation of China (NSFC no.21704019 and 21644012).
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Keywords: Vanillin • Levulinic acid • Lignocellulose • Poly(ester
ketone) • Aldol condensation
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10.1002/cctc.201801381
ChemCatChem
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Qin Chen, Tianhua Ren, Yang Chai,
Yuanlong Guo, Ian D. V. Ingram,
Michael North, Haibo Xie*and Zongbao
kent Zhao* Page No. – Page No.
Preparation of novel aromatic-
aliphatic poly(ketone ester)s through
condensation of biomass-derived
monomers
Biobased poly(ester ketone)s were prepared via aldol condensation of aromatic
aldehydes obtainable from lignin with levulinic acid available from cellulose and
hemicellulose via green catalysis and polycondensation.
This article is protected by copyright. All rights reserved.