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Cellulose-Based Sustainable Polymers: State of
the Art and Future Trends
Marcus Rose, Regina Palkovits*
Introduction
The crude oil-based society, as we know it, is drawn to a
closesincepeakoilwillbereachedinthenearfutureandthe
worldwide consumption of oil-based products is steadily
increasing.Besidestherecyclingofmaterialsfromcrudeoil,
new and in the ideal case renewable resources have to be
opened up to solve the problem. A conceivable optionis the
processing of biomass to obtain novel fuels comparable to
gasoline and diesel for chemical energy storage. Also the
biomass conversion into fine and bulk chemicals for the
replacement of mineral oil-basedproductssuch as themost
polymers is aspired. In 2009, the global plastics production
was about 230 million tonnes including mainly oil-based
polymers.[1] And with an average growth rate of approxi-
mately 9% per year the demand is further increasing. Soon,
the production of oil-based products may be hindered due
to limited sources and risingraw material pricespaving the
way for alternative raw materials based on renewable
feedstocks.
In the past, especially vegetable fats or oils and sugars
found application as renewable resources not least in the
production of biodiesel and bioethanol. These resources,
however, are in competition with the food chain and only
available in limited amounts. In contrast, lignocellulosic
biomass refersto plantbiomasswhichis notin competition
with food supply and worldwide produced in amounts of
170109 tonnes plant material per year.[2]
One of the main components of lignocellulosic biomass
besides ligninand hemicellulose is cellulosewith a fraction
of 3550%.[3] As a renewable resource produced by plants,
algae, and fungi it seems to be an ideal feedstock. Cellulose
itself is a fascinating and versatilebiopolymer that consists
of linear, covalently linked chains ofD-glucose units. These
chains form highly stable networks with a high degree of
Feature Article
Prof. R. Palkovits, M. Rose
Institute for Technical and Macromolecular Chemistry, RWTH
Aachen University, Worringerweg 1, D-52074 Aachen, Germany
E-mail: [email protected]
Prof. R. Palkovits
Max-Planck-Institut fur Kohlenforschung, Kaiser-Wilhelm-Platz 1,
D-45470 Mulheim/Ruhr, Germany
Nowadays, nearly all polymeric materials are produced from crude oil-derived monomers.
With the steadily increasing demand for oil-based products and their decreasing availability in
the near future, one of the main challenges of mankind is the replacement of crude oil as raw
material by renewable resources such as biomass. So far, only a few polymers are available
derived directly from cellulose as a main component of biomass by regeneration. On the other
hand, a significant potential lies in the production of
polymers from cellulose-derived monomers. A huge
variety of different monomers is already available by
convenient catalytic processes. This feature article
focuses on the current status of mono- and resulting
polymers derived either directly from cellulose proces-
sing and regeneration or by catalytic conversion to a
number of monomers for the production of novel poly-
mers and co-polymers.
Macromol. Rapid Commun. 2011, 32, 12991311
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hydrogen bonds in between. An extensive and informative
review on cellulose as biopolymer and sustainable raw
material was published in 2005 by Klemm et al.[4]
describing the structure, properties and chemistry of
cellulose derivatives.
This feature article focuses on established and potentialprocesses for the conversion of cellulose to sustainable
monomers for production of biopolymers highlighting
recent advances in the field as well as future challenges.
Concerning application of cellulose in polymer produc-
tion, cellulose can be converted to regenerated cellulose
without depolymerization but derivatization as in the
viscose process for the production of cellophane and rayon
known for decades. Instead of derivatization, a few
methods such as the Cuoxam and the Lyocell process are
known for physically dissolving and processing of the
cellulose to polymeric products. Alternatively, cellulose can
be catalytically depolymerized to glucose. This C6 mono-
saccharide is the starting material for a huge variety of
compounds that can be obtained by catalytic or biotechno-
logical conversion. A detailed view on this pool of chemicals
is given with regard to (potential) applications as mono-
mers for the production of established but also novel
polymers, while complete value chains for future biorefin-
ery concepts may be found elsewhere.[5]
Regenerated Cellulose
Processing by Cellulose Derivatization
Utilization of cellulose in the form of wood as building
material and energy source, or cotton as raw material for
clothing is as old as civilized mankind itself. The first
chemical utilization of celluloseas a polymericmaterialcan
be dated back to themiddle of thenineteenth century short
after its discovery.[4] Celluloid, a composite of cellulose
nitrate andcamphoras plasticizer, issupposedto be thefirst
thermoplastic material which has been produced on the
industrial scale for decades. Nowadays, in many products
celluloid has been replaced by other polymers due to
improved properties and performance (Figure 1).
Also over 100 years old, but still in use, is the viscose
process for the production of cellophane (films/mem-
branes) and rayon (fibers).[4] Therefore, the cellulose is
alkalized and by addition of CS2 derivatized to cellulose
xanthogenate. This metastable intermediate can be dis-
solvedin anaqueoussodium hydroxidesolution toformthe
so-called viscose. Processing to fibers or films is carried out
in a wet process from which the shaped product is
precipitated and high purity cellulose is regenerated by
removing the substituent. The viscose process suffers from
the disadvantage of the required chemicals such as the CS2and heavy metal compounds for the precipitation process.
These compounds pose a constant ecological threat despite
complex technologies and environmental standards.An alternative method retaining the viscose spinning
technology is the CarbaCell process avoiding hazardous
sulfur-containing compounds for derivatization which is
based on a finish patent from 1979.[6] Instead of the highly
hazardous CS2 as in the viscose process, an aqueous or
organic urea solution is used to convert the native cellulose
into cellulose carbamate, which can be dissolved and
Marcus Rose studied chemistry at the Dresden
University of Technology and prepared his Ph.D.
thesis in the group of Prof. S. Kaskel on the
development and characterization of novel poly-
meric high performance adsorbents and their
processing by electrospinning. A research stay
funded by the DAAD in the group of Prof. G.Yushin (Georgia Institute of Technology in
Atlanta/Georgia, USA) was about the character-
ization of electrochemical energy storage in
carbon-based supercapacitors. Currently, he is
a scientific co-worker in the group of Prof. R.
Palkovits at the RWTH Aachen University devel-
opingnovel heterogeneous catalysts for biomass
conversion.
Regina Palkovits is Associate Professor for
Nanostructured Catalysts at RWTH Aachen.
She studied chemical engineering at the Tech-
nical University Dortmund and carried out her
Ph.D. in the group of Prof. Ferdi Schuth at theMax-Planck-Institut fur Kohlenforschung. After a
research stay in the group of Prof. Bert
Weckhuysen at Utrecht University, she returned
as a group leader to the Max-Planck-Institut fur
Kohlenforschung beforeshe becameProfessor at
RWTH Aachen. Her current research focuses on
thedevelopment of solid catalysts and processes
for the efficient utilization of renewable and
conventional resources.
Figure 1. Conventional methods for utilization of cellulose inpolymer processing.
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processed identically to viscose. An importantadvantageof
the cellulose carbamate is the relatively high stability at
room temperature allowing storage for over a year. Despite
the advantages over the viscose process, the CarbaCell
process has not yet been industrially established due to
certain requirements such as a catalyst, organic solvents,long reaction times, and high temperatures.[4] Recent
studies focused on the use of microwave irradiation as
promising method for the production of cellulose carba-
mate.[7] Due to a well controllable heating process,
conversion of the cellulose is successful within a few
minutes under catalyst-free and solvent-free conditions. In
comparison to alternative methods, the microwave-
assisted process is highly ecological, especially since side
productsandharmfulwasteisavoidedandnorawmaterial
is lost.
In addition to the above mentioned processes, a pool of
other, mainly non-aqueous solvent systems for the
dissolution of cellulose by derivatization has been
described, such as N2O4/dimethylformamide (DMF),
NOSO4H/DMF, (CH3)3SiCl/DMF, (CH2O)x/dimethyl-sulfox-
ide(DMSO),andCCl3COH/dipolar aprotic liquid.[8]Forlarge-
scale application, these methods are more or less out of the
question due to the required hazardous chemicals showing
no significant ecological improvement to the state-of-the-
art processes.
Processing of Dissolved Cellulose
Without Derivatization
Besides the production of regenerated cellulose by deriva-tization,othermethodsareavailablefordirectprocessingof
physically dissolved cellulose (Figure 1). In 1857, Schweizer
published his discovery of the cellulose solubility in an
aqueous ammoniacal solution of copper(II) hydroxide, so
called Schweizers reagent.[9] Tetraaminecopper(II) hydro-
xide [Cu(NH3)4](OH)2 is formed and the cellulose is directly
dissolved by formation of chelate complexes of deproto-
nated cellulosic hydroxyl groups and copper ions.[10]
Despite this complex being a cellulose derivative, this
method is usually counted to the non-derivative processes
for cellulose regeneration since it is a method for direct
dissolution without the need for producing a cellulose
derivative precursor for subsequent dissolution. This
method is known as the Cuoxam process and has been
employed since the beginning of the 20th century for the
production of fibers andfilms (e.g.,Cuprosilk,Cuprophane).
Nowadays, this procedure is only rarely used in a few
countriesanymore since theuse of large amounts of copper
compounds and ammonia pose environmental hazards.
In the last decades much effort has been made for the
development of new methods to dissolve cellulose for
further processing to fibers, films, membranes, etc.[4,8,11]
The CELSOL process requires steam-exploded pulp as
cellulose source, that can be dissolved in aqueous sodium
hydroxide solution for further processing.[4,12] Several
other, more exotic solvent systems have been identified,
such as hydrazine, ammonium rhodanide in liquid
ammonia, SO2/aliphatic amine, DMSO/methylamine, tri-
fluoracetic acid/chlorinated alkanes, solutions of lithiumchloride, or zinc chloride in dimethylacetamide (DMA).[4,8]
Even concentrated phosphoric acid can be used.[13] Due to
high concentrations of cellulose in most of the above
mentioned solvent systems liquid crystalline phases are
formed which can be processed to high-strength cellulose
filaments by spinning. To our knowledge, none of these
processes is used on the industrial scale so far.
Another method developed 30 years ago is the Lyocell
process for the production of regenerated cellulose
fibers using N-methylmorpholine-N-oxide monohydrate
(NMMO) as solvent.[4,14] The clear advantage is the good
solubility of cellulose in NMMO which can be nearly
quantitatively recovered in the process. Additionally, only
small amounts of sodium hydroxide solution and sulfuric
acid are necessary. This renders the Lyocell process a highly
economic and ecological friendly method. In comparison to
thecotton production, the Lyocell process requires not more
chemicals whereas the chemicals in the cotton production
pose a higher environmental hazard. The annual produc-
tionofLyocellfibersespeciallyformanufacturingoftextiles
worldwide is over 100 kt and still increasing.
In recent years, the use of ionic liquids (ILs) for cellulose
processing has gained an enormous interest, especially
since some ILs such as 1-butyl- or 1-allyl-3-methylimida-
zolium chloride (BMIMCl, AMIMCl) are able to completelydissolve cellulose under relatively mild conditions without
additional chemicals.[15] ILsarenon-flammableandpossess
a negligible low vapor pressure which renders them much
better suited for large-scale processes than volatile organic
solvents. Due to their high chemical and thermal stability,
ILs can be used over a wide range of processes and
parameters. Even the recovery of regenerated cellulose
from solution in an IL can be accomplished with water,
ethanol, or comparable environmentally benign solvents.
In a recent study from Righi et al. the cellulose dissolution
by BMIMCl in comparison to the dissolution in NMMO in
the Lyocell process has been analyzed by a life cycle
assessment (LCA).[16] It was shown, that the IL can dissolve
higher amounts of cellulose with a lower time and energy
consumption and that there is a small reduction of the
hazardous compound emission. However, the major
environmental impact is a result of the solvents syntheses.
By highly efficient solvent recycling in the cellulose
regeneration process, also the ILs are promising candidates
in future cellulose processing methods. In line, BASF in
cooperation with ITCF Denkendorf und TITK Rudolstadt
started thedevelopmentof an ionic liquidbased process for
production of viscose. Therein, pulp could be directly
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processed out of the ionic liquid avoiding any derivatiza-
tion.[17]
Cellulose-derived Monomers
Depolymerization of Cellulose
Beside the thermal degradation of lignocellulosic biomass
to pyrolysis products for further conversion similar to
petrochemical processes,[18] or simple combustion to synth-
esis gas and consequent build-up via established procedures,
cellulose can be depolymerized by hydrolysis of the b-1,4-
glycosidic bond to glucose. This reaction opens up a huge
variety of new possibilities to obtain basis chemicals and
potential monomers. The depolymerization can be carried
out enzymatically[19]orcatalystfreeinsupercriticalwater. [20]
Recently,also homogeneous or heterogeneous acidcatalyzed
processes have attracted considerable attention.[3,21]
Figure 2 illustrates selected transformations of cellulose
to novel intermediates which have also been identified by
the Department of Energy (DoE) as potential future bulk
chemicals and provide a high potential to serve as future
feedstocks for the production of polymers.[22] Certainly,
various further transformations are possible and can by far
not be covered in the present review. For comprehensive
overviews with regard to possible transformations and
utilization schemes of lignocellulose, the reader is referred
to several recent reviews.[5,23] Herein, we will mainly focus
on intermediates which found increasingly attention by
academia and chemical industry with regard to theirpotential to serve as substitutes of monomers currently
derived from fossil resources and future feedstocks for the
production of novel polymers.
Possible reactions include the enzymatic or acid cata-
lyzed hydrolysis of cellulose to yield glucose which may be
subsequently converted into ethanol via fermentation.[24]
Further products available via biocatalytic transformationsof glucose include succinic,[25] itaconic,[26] glutamic,
glucaric,[27] and lactic acid,[28] whereat the latter might
also be produced by chemocatalytic means.[29]
Further promising chemocatalytic transformations of
glucose include the hydrogenation to sorbitol,[30] or direct
hydrogenolysis of cellulose to sugar alcohols.[31] Conse-
quently, sorbitol may be dehydrated to sorbitan and
isosorbide or reacted via further hydrogenolysis or hydro-
deoxygenation reactions to yield glycerol and propylene or
ethylene glycol as well as various C1C6 mono-and polyols
and even alkanes.[32] Alternatively, acid catalyzed dehy-
dration of glucose gives access to 5-hydroxymethylfurfural
viadehydration, which maybe rehydrated to levulinicacid.
Comprehensive reviews covering available synthesis pro-
cedures of these compounds can be found elsewhere, [23]
while herein only recent developments will be pinpointed.
Starting from these compounds, a huge variety of products
is available and can by far not be covered in the current
review. Instead, we will focus on compounds which are
exclusivelyavailablebasedoncelluloseandmaygiveriseto
the development of novel polymer materials or substitu-
tion of petrochemical building blocks.[33] Besides, biomass
offers the possibility to derive most of the conventional
petrochemical monomers, e.g., via gasification to syngas
and subsequentreassembly to methanol and hydrocarbonsor via dehydration of ethanol to ethylene. Although such
transformations and products are not in
the closer scope, if applicable we will
highlight recent developments in this
direction.
Glucose Conversion to Ethanol by
Fermentation
Currently, ethanol from renewable
resources is mainly produced by fermen-
tation of sugars derived from sugar
cane or sugar beet with yeast. On a long
run, however, the goal will be the
production of cellulosic ethanol which
will be mainly dependent on the further
development of more efficient and
economic processes for hydrolysis of
cellulose.[34] Additionally, microorgan-
isms are under investigation to convert
even xylose and other pentose contained
in hemicellulose into ethanol.[35] In 2008,
General Motors together with Coskata,
Figure 2. Transformation scheme of cellulose to potential bulk chemical for futurepolymer production (mainly available via bio- (white) or chemocatalytic (light gray)transformations).
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Inc. announced the production of price competitive
cellulosic ethanol with a goal of $0.30 L1. The full-scale
plant capable of producing 50100 million gallons of
ethanol a year (200400 ML a1) is planned to start
operation in 2011.[36]
Based on ethanol, various conventional monomers for
polymer production can be obtained (Figure 3). Although
currently not of industrial relevance, ethanol can be
oxidized to acetic acid via acetaldehyde.[37] Instead, acetic
acid is produced via carbonylation of methanol and to a
smaller extent via bacterial fermentation yielding in total
around 5 Mt a1 of which 65% go into polymer production
in the form of vinylacetate (43%) or celluloseacetate
(25%).[38]
Via dehydration biomass derived ethanol can be con-
verted into ethylene which is currently exclusively
produced in petrochemical industry via steam cracking
and mainly used in the production of polyethylene,
polyethylene oxide, polyvinylchloride and polystyrene. In
2005, ethylene production exceeded 107 milliontonnes and
further market growth is expected.[39] Nevertheless, in the
early 20th century, ethylene was mainly produced by
dehydration of ethanol.[40] Technical implementation was
realized in fluidized bed reactors over solid acid catalysts
suchasactivatedalumina.Insuchvaporphasedehydration
reactions at around 4008C, close to full conversion of
ethanol with around 99.9% selectivity to ethylene could be
reached.[41] This technology might become economic not
only dependent on the market price of oil and bio-ethanol,
but also the growing public interest in polymeric products
derived from renewable feedstocks promotes the develop-
ment. Dow, Braskem which is Brazils largest plastics
producer, and Solvay announced separate projects to build
ethanol-to-ethylene plantsbasedon sugar cane. Lowcost of
sugar cane and an increasing oil price have renewed the
interest in ethanol dehydration. Dow and Braskem will
manufacture green polyethylene while Solvay plans
to use ethylene to supply its polyvinylchloride capacity.
While the projects of Baskem and Solvay with 180 000 and
55 000 t a1, respectively, are on the way, Dow (320 000 t)
announced a delay in construction of their 320 000 t a1
plant.[42]
Another interesting possibility concerns the transforma-tion of ethanol into 1,3-butadiene which finds not only
application in the production of polybutadiene but also for
the production of various copolymers including acryloni-
trile-butadiene-styrene, acrylonitrile-butadiene or styrene-
butadiene. Two possible routes have been reported and are
even used on industrial scale in several parts of the world
including Eastern Europe, China, and India due to lower
capital costs for small scale production of 1,3-butadiene
from ethanol compared to steam cracking.
One process option has been developed by Sergei
Lebedev, transforming ethanol to 1,3-butadiene at 400
450 8C catalyzed by metal oxide catalysts.[43] Although
carried out on an industrial scale to serve the synthetic
rubber industry of the Soviet Unions during and after
WorldWarII,itsuseremainedlimitedtoRussiaandEastern
Europe.
2CH3CH2OH ! CH2 CHCH CH2 2H2OH2
Alternatively, ethanol and acetaldehyde may be con-
verted at 325350 8C. This process has been developed by
the Russian chemist Ivan Ostromoslensky and used in the
United States to produce government rubber during World
War II, while today it is only used in China and India.
CH3CH2OH CH3CHO ! CH2 CH-CH CH2 2H2O
The presented process concepts proceed via dehydration
of ethanol in the gas-phase after separation from water.[44]
However, enzymatic production of ethanol usually yields
lowconcentratedaqueoussolutionofethanol.Thus,adirect
dehydration of ethanol avoiding prior separation from
water would be highly attractive and presents a major
challenge to improve applicability and economics of the
described utilization schemes.
Lactic Acid
Lactic acid is a naturally occurring acid which plays an
important role in themetabolismof most organisms. At the
end of the 18th century it has been isolated from sour milk,
and there have been industrial fermentation processes for
more than a hundred years now. Currently, lactic acid is
commercially produced by fermentation of glucose yield-
ing around 90% calcium lactate, which has to be purified to
obtain pure lactic acid.In commercial processes,lactobacilli
allow the production of both pure enantiomers, while
microbial fermentation usually results in formation of
racemates with 5090% L-lactic acid.[45]
Figure 3. Transformationof ethanol into aceticacid, ethylene,and1,3-butadiene as potential platform chemicals and application inpolymer processing.
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The production of pure lactic acid results in around 1 ton
of CaSO4 per ton of lactic acid which presents the major
drawback of thecurrent commercial process.Consequently,
alternative process options with main focus on improved
purification and separation techniques, e.g., utilizing
desalting and water splitting electrodialysis, are underdebate.[46] Alternative process options, e.g., via heteroge-
neously catalyzed transformation of glucose have found
reasonable attention.[47] Therein, Holm et al. presented the
conversion of mono- and disaccharides into methyl lactite
over lewis acidic zeotypes, such as Sn-Beta, reaching up to
68% yield with sucrose as substrate.[48]
The main challenge, however, is related to the need for
pure enantiomeric lactic acid for production of PLA with
sufficient properties. Consequently, either suitable catalyst
systems allowing for asymmetric synthesis of lactic acid or
efficient technologies for post-synthesis separation of
racemic mixtures have to be developed. Besides, more
sophisticated polymerization technologies could facilitate
direct utilization of racemic mixtures.
Concerning application of lactic acid, it is utilized in food
and cosmetics industry. Nevertheless, the dominant
application area with the largest expected market growth
regards the area of polymer production. Therein, lactic acid
could serve as potential renewable feedstock for the
production of acrylic acid (polyacrylic acid) and propylene
glycol with applications in polyesters, -carbonates, and -
urethanes or even for further transformation to propylene
oxide as feedstock for classical polypropylene oxide
production (Figure 4).[49]
Currently, lactic acid is already intensively used inpolymerization to form polylactide, a biodegradable poly-
mer. PLA is produced by ring opening polymerization of the
dilactide and exhibits similar mechanical properties to
polyethylene terephthalate (PET), but has a significantly
lower maximum service temperature. The monomer is
available from lactic acid by polycondensation up to a
limited molecular weight followed by depolymerization
(Scheme 1).
With regard to polymerization of racemates, an amor-
phous poly-DL-lactide (PDLLA) is obtained. Due to the fact,
thatcrystallinitydependsmostlyonadefinedratioof D-and
L-enantiomers and determines most physical properties,
PDLLA does not exhibit the required properties for most
applications. Polymerizing L-lactide, poly(L-lactide) (PLLA)
can be produced which exhibits high crystallinity (37%), a
glass transition temperature between 60 and 65 8C and a
melting temperature around 175 8C. Via physical blending
withPDLA[poly(D-lactide)], themelting temperature can be
increased by 4050 8C and its heat deflection temperature
can be increased fromca. 60 toup to1908C. PDLA and PLLA
form a stereocomplex with increased crystallinity and
maximum temperature stability for a 50:50 blend. Never-
theless, already 310% PDLA result in a substantial
improvement induced by PDLA acting as nucleating agent
and thereby increasing the overall crystallinity of the
material.[45,50]
Currently, lactic acid is produced with around
250 000 t a1, but estimations foresee a growth up to
15 Mt a1 in 2020.[51] The biodegradable polylactide is
utilized in the production of packaging materials, e.g.,
flexible films, food containers, and carrier bags as well asdisposableproductsincludingbottles, cups,dishes, or trays.
Further areas of application cover fibers and non-wovens
for application as textile fibers, production of hygiene
articles for private and medical use and paper coatings.
Withrespect to commercial applications, NatureWorkswas
the first to launch a commercial production in 2002 with a
capacity of 150 000 t a1 and remained to be the primary
producer of polylactide (PLA) in theUnited Statestillmiddle
of 2010. Meanwhile several other companies entered the
business including PURAC Biomaterials, a Dutch company
and several Chinese manufacturers. At the moment, the
primary producer of PDLLA is PURAC, part of CSM which
recently acquired the remaining 50% of the shares of the
lacticacidproductionfacilityinBlair,Nebraska(US)fromits
joint venture partner Cargill. Also Galactic and Total
Petrochemicals operate a joint-venture, called Futerro
including a PLA pilot plant with 1 500 t a1 in Belgium.
One German company who deals with the production of
PLA is Uhde Inventa-Fischer. Inventa Fischer built a pilot
plant with an annual PLA production of 500 tons in 2010.
Uhde Inventa-Fischer now licensed this technology based
on the pilot plant for facilities of up to 60 000 tons PLA
per year.
Figure 4. Utilization of lactic acid via transformation into acrylicacid, propylene glycol, or propylene oxide and subsequent appli-cation in polymer production or direct polymerization to poly-lactide.
Scheme 1. Preparation of polylactide via dimerization to dilactide
and subsequent ring-opening polymerization to yield polylactide.
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Overall, a significant market growth for both lactic acid
demand and production is expected in the upcoming years.
Although attractive for substitution of PET, further
improvements in polymerization technology as well as
possible catalysts for the efficient enantioselective trans-
formation of glucose into D-and L-lactic acid will be decisiveto further market growth and application areas.
Succinic Acid
Succinic acid presents another potential future building
blockhighlightedby theU.S. Department of Energy(DOE) in
2004 and revisited by Bozell and Petersen recently.[22b] By
fermentation of glucose C4 dicarboxylic acids such as
succinic, fumaric, and malic acid can be obtained. Therein,
especially succinic acid is of great interest as platform
chemical for polymer production.[52]
Nowadays,succinic acid is produced from the C4 fraction
of crude oil via maleic anhydride. But also the biotechno-
logical production by fermentation of cellulose-derived
sugars is a well-established process, especially since
additional CO2 is utilized in this process.[53] Bechthold
et al. classified succinic acid-derived monomers in the four
following groups: (1) acyclic O-containing, (2) acyclic O,N-
containing, (3) cyclic O-containing, and (4) cyclic O,N-
containing.[52] Especially the bifunctional acyclic com-
pounds such as 1,4-butandiol and 1,4-butandiamine in
combination with succinic acid or other dicarboxylic acids
are of interest for the production of polyesters and
polyamides (Figure 5). E.g., the polyamide PA 44 which is
based on succinic acid and 1,4-butanediamine has beendescribed in literature.[52] Additionally, also the commer-
ciallyavailable polymer PA 46 known as Stanyl1 fromDSM
uses 1,4-butanediamine as monomer. Companies such as
Mitsubishi Chemical Corporation and Showa Denko have
developedthepolymersGSPla1, a poly(butylene succinate)
and Bionolle1,apolyesterbasedonethyleneglycoland1,4-
butanediol together with succinic acid or adipic acid.[52]
Bothpolymershavebeenrecentlyintroducedtothemarket.
Therein, thesuccinicacidused forthesepolymersis produced
from biomass by fermentation as mentioned above.
Besides, succinic acid is a potentialplatform chemical for
the production of g-butyrolactone that can be further
converted to 2-pyrrolidone by reaction with ammonia.
2-Pyrrolidone itself is a precursor in the synthesis ofN-vinylpyrrolidone, the monomer of polyvinylpyrrolidone
(PVP), which is obtained by reaction of 2-pyrrolidone
with acetylene in the presence of elemental potassium at
100 8C.[54]
The current market demand of succinic acid is around
15kt witha price ofca.69 Euro kg1.[52] Nevertheless, the
broad field of applications results in an estimated market
potential of several hundred thousand tonnes.[52,55]
Itaconic Acid
Itaconic acid is a C5 unsaturated dicarboxylic acid. It is
produced by fermentation of carbohydrates suchas glucose
by fungi with a current worldwide production of about
15 kt a1.[56] Chemical synthesis is also known, e.g.,
starting from citric acid, but so far it is economically and
ecologically not interesting for large scale production.
Itaconic acid is already utilized as a co-monomer in resins
and in the production of synthetic fibers, e.g., as co-
monomer for styrene-butadiene-acrylonitrile and acrylate
latexes.[56] Dueto itstwo carboxy functionalitiesit ishighly
interesting as monomer for manufacturing new polyesters
or for polyamide production via transformation into
itaconic diamide or 2-methyl-1,4-butanediamine. Besides,
2-methylene-1,4-butanediol is accessible starting fromitaconic acid and offers various possibilities for application
inpolyestersand-amides,e.g.,assubstituteofconventional
diols. Additionally, the methylidene group renders itaconic
acid highly promising as a substituent for crude oil-derived
monomers such as acrylic or methacrylic acid (Figure 6).
Figure 5. Transformations of succinic acid into 1,4-butanediol, 1,4-butanediamine, g-butyrolactone, 2-pyrrolidone, and N-vinylpyr-rolidone as potential monomers for production of polyester, -amides, and polyvinylpyrrolidone.
Figure 6. Itaconic acid as potential cellulose-derived C5 carbonbuilding block for synthesis of novel polymer materials.
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With regard to the properties of potential polymer
products containing such building blocks, little investiga-
tions exist and future studies need certainly to focus on the
impact of these substitutes on mechanical and chemical
properties.[57] Nevertheless, especially the reactive methyl-
idene group in itaconic acid could allow a simple chemicalmodification to deliver tailor-made monomers for certain
applications or even post-polymerization functionaliza-
tion. Concerning commercial applications, the American
start-up Itaconix has received a $1.8 million grant through
the Joint Biomass Research and Development Initiative of
the U.S. Department of Energy and U.S. Department of
Agriculture and offers product lines based on polyitaconic
acid including detergents, materials for water treatments
and super absorbent polymers.[58] Therein, polyitaconic
acid exhibits biodegradability and a superior calcium
binding capacity compared to polyacrylic and polyaspartic
acid which suggests its application in detergent and
antiscaling applications.
Glutamic Acid
Another platform chemical, a C5 building block, which is
also a fermentation product of glucose, is the amino acid
glutamic acid.[22] By reduction and/or hydrogenation it can
be converted to several bifunctional compounds such as
1,5-pentanedicarboxylic acid, 1,5-pentanediol and 2-
amino-1,5-pentandiol (Figure 7). These monomers are
underconsiderationfortheproductionofnovelpolyamides
and polyesters. Glutamic acid can undergo a polymeriza-
tion with itself to poly(glutamic acid) (PGA) which isnaturally produced by bacteria.[59] This polymer is soluble
in water,biodegradable and edible. Thesepropertiesrender
PGA an interesting polymer for applications in medicine,
foods, and pharmaceuticals. Ester derivatives of PGA have
been shown to be well suited for the production of
thermoplastics and can be processed into fibers or
membranes with excellent strength, transparency and
elasticity.[59]
Glucaric Acid
By selective oxidation of the terminal carbon atoms to
carboxy groups by nitric acid, glucose can be converted to
glucaricacid.[22] ItisnotonlyavaluableC 6buildingblockfor
further conversion but it is also under discussion for the
production of hyperbranched polyesters and hydroxylated
nylons (polyhydroxypolyamides) (Figure 8).[60] For indus-
trial scale production of glucaric acid the development of
more efficient and heterogeneous catalyzed processes is
necessary. Abbadi and van Bekkum have investigated the
performance of a commercial Pt/C catalyst in the selective
oxidation of glucose with oxygen showing promising
results.[61] Nevertheless, little investigations concerning
this interesting building block and its derivatives exist and
further investigations are certainly necessary to elucidate
its full potential.
5-Hydroxymethylfurfural and Levulinic Acid
Another interesting classof potential platform chemicalfor
polymer production includes bifunctional derivatives of
furan such as furandicarboxylic acid (FDC), levulinic acid
and even sorbitol-based chemicals. Therein, 5-hydroxy-
methylfurfural (HMF) is a key intermediate in the catalytic
conversion of cellulose to potential monomers based on
furan derivatives.[21a,62] Very recently, Rosatella et al.[63]
published an extensive review on the synthesis and
properties of HMF. It is derived by dehydration of hexoses
such as glucose, fructose, or mannose. Different reaction
pathways have been proposed for this reaction since the
mechanism of the hexose dehydration is not fully clear so
far and may proceed via cyclic or acyclic intermediates.[64]
Nevertheless, the most efficient and selective conversion to
HMF starts from fructose due to its high reactivity and is
generally catalyzed by acids. Liquid Bronsted acids can be
used in homogeneous processes. Alternatively, heteroge-
neouslycatalyzedreactionshavebeendescribedusingsolid
acids such as ion exchange resins and others.[63] Beside
thesemethodsalso heterogeneous gasliquid systemshave
been discussed, in which CO2 is dissolved in an aqueous
solution under the in situ formation of H2CO3. Onthe other
Figure 7. Glutamic acid as monomer forproduction of polyamides,-esters, or polyglutamic acid and starting material for transform-ation into 1,5-pentanedicarboxylic acid (glutaric acid), 1,5-penta-nediol, and 2-amino-1,5-pentanediol.
Figure 8. Glucaric acid as monomer for use in hyperbranchedpolyesters and hydroxylated nylons.
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hand,the reactioncan be also carried outthermally without
a catalyst using sub- or supercritical solvents or solvents
such as dimethylsulfoxide (DMSO) as reaction promoters.
Alternatively, Lewis acids are also able to catalyze the
formation of HMF. The research in this area focuses mainly
on chromium compounds, but also zirconium, titanium,several lanthanides, and other metals are under considera-
tion.[62,63]
In aqueous solutions several by-products are observed
such as difructodianhydrides and humins significantly
reducing the final yields of HMF. Additionally, rehydration
products of HMF such as levulinic and formic acid can be
found. Several attempts have been made to develop non-
aqueous catalytic systems for a more selective conversion
offructosetoHMF.Especiallyionicliquidsareinthefocusof
research as reaction media since they provide outstanding
propertiesforthistypeofreaction. [65] In recent efforts, ionic
liquids have proven useful as solvents in combination with
Bronsted or Lewis acids resulting in nearly quantitative
conversion of fructose to HMF.[65,66] Since HMF cannot be
efficiently removed from an aqueous or ionic liquid phase
by distillation is not favorable due to its high reactivity,
other methods for the product separation have to be
developed. E.g., biphasic systems are under discussion to
continuously extract HMF into an organic phase from
which it can be removed easily.[21a,63]
However, HMF is a versatile platform chemical that can
be catalytically converted to an enormous number of
bifunctional furan derivatives as recently shown in a
comprehensive review by Tong et al.[62] HMF itself is not
sufficiently stable for long term storage.[67]
Thus, a directfurther conversion is intended in recent production
strategies. Target moleculesthat areconsideredas potential
monomers show carboxy, formyl, hydroxyl, amino or
isocyanate functionalities, respectively (Figure 9). The
selectiveoxidationof HMF to 2,5-diformylfuran (DFF)using
classical oxidants such as molecular oxygen or hydrogen
peroxide or direct oxidation to 2,5-furandicarboxylic acid
(FDC) catalyzed e.g., by carbon or alumina-supported
platinum with nearly quantitative yields under mild
conditions (60 8C) is under intense study revealing a high
feasibility of these processes.[62,63] Ribeiro and Schu-
chardt[68]
reported the successful one-pot dehydrationand oxidation of fructose to FDC using a cobalt acetylace-
tonate encapsulated in solgel silica with a fructose
conversion of 72% and a selectivity for FDC of 99%.
Due to very similar properties of the monomers,
especially (FDC) is under discussion as a substituent for
the crude oil-derived terephthalic acid in the production of
polymers like poly(ethylene 2,5-furandicarboxylate) (PEF)
or poly(propylene 2,5-furandicarboxylate) (PPF) in analogy
to polyethylene terephthalate (PET).[67] Even polyamides
with comparable properties like a high strength in aramid
fibers (Kevlar) are conceivable using FDC instead of
terephthalic acid as monomer.[69]
Besides the oxidation of HMF to FDC, it can be converted
to 2,5-bis(hydroxymethyl)furan (BHF) by hydrogenation
withNaBH4 or catalytically by hydrogen over Cu or Pt.[62,63]
Other catalytic active species like Pd/C or Raney nickel
result in additional hydrogenation of thefuran ring to yield
2,5-bis(hydroxymethyl)tetrahydrofuran. BHF as a bifunc-
tional monomer is an important precursor for manufactur-
ing of new polyesters or polyurethane foams by replacing
the respective diol compounds.
Other bifunctional HMF derivatives such as amino or
isocyanate compounds may prove useful as monomers for
novel polyurethanes, polyamides and other polymers
based on monomers with the respective functionalities.E.g., 2,5-bis(aminomethyl)furan can be synthesized from
DFF as reported by El Hajj et al. [70] while 2,5-diisocyana-
tofuran is derived from FDC by reaction with sodium
azide.[71]
The above mentioned side reaction occurring during the
acid catalyzed synthesis of HMF from cellulose and
cellulose-derived sugars by re-hydration of HMF yields
levulinic acid (LA) and one equivalent of formic acid. LA
poses another platform chemical of high importance
(Figure 9). Its production in a one-step reaction directly
from cellulosic biomass is under intense research.[21a,22b]
The importance of LA as a platform chemical for applica-
tions asmonomer canbe shownby thefollowing examples:
The conversion of LA into diphenolic acid has been
investigated using supported heteropoly acids as hetero-
geneous catalysts.[14b,15a] This diphenolicacid is considered
assustainablereplacementforBisphenolAasanadditivein
the production of polycarbonates. The direct utilization of
ketals of LA as monomers for polyurethanes and thermo-
plastics is commercially investigated by the company
Segetis.[15b] Also the acid catalyzed polymerization of LA
with glycerol yields a polymeric material of commercial
interest.[14b] Recently, the conversion of LA to a-angelica
Figure 9. 5-Hydroxymethylfurfural and levulinic acid as potentialbuilding blocks for synthesis of various cellulose-derived mono-mers.
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lactone has been reported using H3PO4 as catalyst.[16,72] By
ring opening polymerization this intermediate can be
transformed into an aliphatic polyester. It is considered a
valuable polymer madefrom renewablesthat is degradable
by light or under acidic/basic conditions.
Interestingly, MaineBioproducts developed the so called
Biofine Process and announced the commercial production
of LA via acid catalyzed dehydration of lignocellulosic
feedstocks in a two-stage process.[73] Therein, pilot plant
studies have already been carried out, opening the way for
commercialization of this technology.
Sorbitol, Sorbitan and Isosorbide and Further Polyols
Besides the presented transformations, cellulose can be
hydrolyzed to release glucose which is consequently
hydrogenated to sorbitol. Alternatively, recent studies
indicate the possibility to convert cellulose directly into
sugar alcohols such as sorbitol via CC and CO bond
cleavage in so called hydrogenolysis reactions over
supported metal catalysts (Figure 10).[74]
Fukuoka and Luo et al. presented the hydrogenolysis of
cellulose over supported Pt, Pd, or Ru catalysts in aqueous
phase at 463 and 518 K, respectively, yielding up to 30% of
sorbitol.[75] Therein, formation of acidic surface sites via
spill-over of hydrogen from the metal onto thesupport was
suggested together with an increased amount of H3O and
OH groups induced by the temperature dependent shift of
the autoprotolysis equilibrium of water. Additionally,
several attempts for controlled hydrogenation in ionic
liquidshavebeenpresented.Therein,Zhuetal. [76] reportthe
conversion of cellulose to hexitols catalyzed by ionic liquid
stabilized ruthenium nanoparticles and a reversible bind-
ingagent. Up to 85%yieldof sorbitol and mannitol could be
obtained.Ignatyevetal.[77]describedthereductivesplitting
of cellulose dissolved in BMimCl. Combining HRuCl-
(CO)(PPh3)3 as molecular catalyst with Pt/C or Ru/C allowed
full conversion of cellulose, but only in combination with
Ru/C up to 74% yield of sorbitol could be reached. While
other combinations mainly provided glucose rather than
sorbitol together with dimers and even 5-hydroxymethyl-
furfural indicating that the hydrogenation reaction pre-
ceded rather slowly under these reaction conditions whencompared to hydrolysis.
Nevertheless, the main challenge for reactions in ionic
liquids refers to the separation of the very polar products
from the ionic liquid. Recently, Moulijn and co-workers
addressed this issue and dissolved cellulose in ZnCl2 in the
presence of Ru/C and hydrogen pressure.[78] Interestingly,
addingCuCl2 or NiCl2 as co-catalystsor working at elevated
reaction temperature allowed not only hydrolyzing cellu-
lose to glucose which is further hydrogenated to sorbitol,
but catalysesthefurther dehydration yieldingisosorbideas
main reaction product. Isosorbide itself is interesting as
product for polymer production, e.g., PEITpolyethylene
isosorbide terephthalate in which some ethylene glycol is
substituted by isosorbide, has already been demonstrated.
Additionally, isosorbide exhibits reduced polarity when
compared to sorbitol and thus facilitates extraction from
the molten salt solution. Alternatively, reactive extraction,
e.g., via formation of isosorbide ethers could be an
interesting approach to allow efficient recovery of the
reaction product.
Moreover, the combined hydrolysis and hydrogenation
of cellulose combining molecular acids and suitable
hydrogenation catalysts in aqueous phase has been
described.[79] While Geboers et al. could optimize the
reaction system towards sorbitol formation reaching up to85% yield of hexitols (15% sorbitan) at 463K, we could
demonstrate the carbon efficient utilization of cellulose at
433 K only combining hydrolysis and hydrogenation with
above 90% yield of sugar alcohols including sorbitol and its
dehydration products, xylitol, erythritol, glycerol, propy-
lene, and ethylene glycol as well as methanol. Therein,
C4C6 sugar alcohols account for the main fraction of
products summing up to around 80% yield.
Future investigations need certainly to focus on insights
concerning the relation between reaction conditions,
catalyst system and product selectivity to allow tailored
synthesis of individual products as this reaction type
allows not only access to sorbitol but further hydrogeno-
lysis can deliver various sugar alcohols. Interestingly,
recentpublicationsevendescribe the direct hydrogenolysis
of cellulose over nickel-modified tungsten supported on
activated carbon as catalysts with remarkable selectivity
to the formation of ethylene glycol.[80] Further investiga-
tions indicated even simple bimetal catalysts to be
suitable for the application although superior yields with
up to 72% ethylene glycol were reached over tungsten
carbide supported on three dimensional mesoporous
carbon.[81]
Figure 10. Conversion of cellulose and glucose, respectively, intosorbitol, xylitol, and erythritol as well as glycerol for polymerproduction or further CC cleavage to yield propylene andethylene glycol as well as glycerol.
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With regard to the mentioned reaction products, sorbitol
is already used in todays chemical industry serving as
dispensing agents and humectants in pharmaceuticals,
cosmetics, and textiles, and for further chemical synthesis
of surfactants and ascorbic acid. Additionally, further
chemical transformations, e.g., via biochemical means toyieldbioethanol, via further dehydrationto obtain sorbitan
and isosorbide or via further hydrogenolysis yielding
various sugaralcohols includingxylitol, erythritol, glycerol,
together with propylene and ethylene glycol, are possible.
Besides, Li and Huber[32] even demonstrated complete
hydrodeoxygenation of sorbitol to alkanes.
Concerning applications of these products in the field of
polymers, especially isosorbide is discussed, as already
mentioned for partial substitute of ethylene glycol in PET
production. The obtained polyethylene isosorbide ter-
ephthalate was reported to exhibit improved mechanical
and thermal properties. Recently,Fenouillot et al. published
a comprehensive review on polymers based on isosorbide,
isomannide, and isoidide.[82] In line, also sorbitan could
potentially be utilized in polyester production. Addition-
ally, isosorbide is discussedas substitute forBisphenol A for
application in epoxy resins and polycarbonates.
Concerning further monomers, especially propylene and
ethylene glycol exhibit high commercial value as they are
already part of the value chain today and the petrochemi-
cally derived version could simply be exchanged by
cellulose based compounds. Additionally, propylene and
ethylene glycol could be dehydrated to deliver propylene
and ethylene for production of biomass derived polyethy-
lene and poly(propylene).Another monomer accessible via hydrogenolysis of
sorbitol, which found increasingly attention not last due
to its increasing availability in the frame of biodiesel
production, presents glycerol.[83] For glycerol itself hardly
any direct application as monomer in polymer production
has been discussed, but further transformations allow
access to acrolein an important intermediate in acrylic acid
production and even the catalytic reaction of glycerol to
lactic acid appears feasible.[84] Therefore, especially propy-
lene and ethylene oxide together with glycerol present
potential compounds to bridge todays value chains and
future biorefinery schemes.
The C4 and C5 sugar alcohols, xylitol and erythritol
together with their dehydration products, have till now
onlybeenminorproductsinhydrogenolysisofcellulosebut
could additionally be obtained via hydrogenoylsis of
hemicellulose and as well be transformed to yield shorter
sugaralcoholsorbeoxidizedtofurtherpotentialmonomers
for polymer production.[85] Consequently, even the pre-
sented transformations can by far not cover the whole
range of monomers available based on cellulose. Instead,
theoverviewintends to highlightrecent trendsin thefields
and pinpoint promising research directions.
Conclusion
With regard to the need of sustainable carbon sources and
an increasing public interest in products based on renew-
able feedstocks, cellulose could serve as a valuable resource
for the direct integration into polymer materials andprovide a variety of classical andalso novel monomers for
integration into polymer production.
Therein, current commercial interest focuses on sub-
stitution of building blocks conventionally derived via
petrochemicalprocessesby biomassbasedcompounds, e.g.,
dehydration of cellulosic bioethanol to yield ethylene.
Additionally, the potential of novel polymers to substitute
classical products is explored, only to mention the
substitution of terephthalic acid with furandicarboxylic
acid in the production of PET equivalent products.
Nevertheless, also novel biomass derived polymer types,
e.g., polyitaconic and polylactic acid, attract increasing
attention and future investigations will certainly pinpoint
various polymers based on novel building blocks which
allow production of biopolymers which cannot only
substituteexisting products but exhibit alternativeproper-
ties and open the possibility for new product lines.
Acknowledgements: We acknowledge financial support by theNanoEnergieTechnikZentrum at University Duisburg-Essen, aninitiative of the state of North Rhine-Westphalia and the EU. Thiswork was performed as part of the Cluster of Excellence Tailor-Made Fuels from Biomass funded by the Excellence Initiative bytheGerman federaland state governments to promote scienceand
research at German universities. Partof the work has been fundedby the Robert Bosch Foundation in the frame of the Robert BoschFellowship for sustainable utilization of renewable naturalresources.
Received: April 7, 2011; Published online: June 10, 2011; DOI:10.1002/marc.201100230
Keywords: biomass; biopolymers; cellulose; monomers; renew-able resources
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