European Polymer Journal 49 (2013) 1146–1150

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European Polymer Journal

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Editorial items

Recent advances in bio-based polymers and composites

Preface to the BiPoCo 2012 Special Section

The increasing environmental awareness of the society resources for the chemical industry, if appropriate and
has become an important factor in recent decades affecting cost-effective techniques can be developed for their
legislation, commerce and industry as well as research and extraction, characterization and conversion. Biomass, how-
development to a great extent [1–7]. This tendency has ever, generally consist of a very complex mixture of organ-
also been recognized by the European Community, which ic compounds, the separation of which is a rather
supports numerous projects in order to promote innova- challenging task. It is also very difficult to define and main-
tive solutions leading to a sustainable economy. Three tain constant composition and quality of the raw materials,
such projects of the Seventh Framework Programme with because several environmental factors affect these charac-
overlapping scopes, Biostruct [8], Forbioplast [9] and Woo- teristics, e.g. species of the source, geographical region, cli-
dy [10], focused on the valorization of forest-derived re- mate, weather, etc. In some cases, even describing the
sources for the production of various bio-based products, exact chemical structure of natural macromolecules
including polymers, additives, and composites with natu- proved to be difficult; one of the most abundant biopoly-
ral reinforcements. The leaders of these projects decided mers, lignin is an excellent example. However, a profound
to join forces to organize a conference in order to create knowledge of the structure of lignin and other complex
a possibility to disseminate their results as well as to in- natural compounds is a crucial requirement for their suc-
crease the efficiency of their research and development cessful valorization.
by exchanging ideas with leading experts in the field. The ability of natural systems to fulfill a certain func-
The International Conference on Bio-based Polymers and tion, on the other hand, lies in their complexity, thus vir-
Composites (BiPoCo 2012) was organized for the first time gin, extracted natural compounds can rarely be applied
in Siófok, Hungary, between May 27th and 31th, 2012, without modification. Lignin, for instance, represents a
with 234 registered participants delivering more than 90 renewable source of aromatic compounds being able to
oral and 110 poster presentations. Scientific and techno- provide a wide range of chemicals. In their feature article,
logical lectures focused on the theory and practice of bio- Lange et al. [12] give a state-of-the-art review of the struc-
polymers, renewable-based monomers, fillers and tural aspects of lignin including its isolation, characteriza-
additives as well as sustainable polymer blends and com- tion and modification, focusing on the oxidative upgrade of
posites with possible application in packaging, agriculture, this polymer. The authors emphasize that the variable
automotive or biomedicine. In the following sections we complex structure of lignin (see Fig. 1) requires the devel-
provide a short overview of the main research areas and opment of modification strategies aimed at controlling and
presentations related to the event, and by doing so, con- tailoring its multi-functionality, i.e. selective oxidation,
tinue the line set by Filip Du Prez, Jean-Marie Raquez reactive groups protection and functionalization. The reac-
and Philippe Dubois as Editors of the recent Biobased Poly- tive free hydroxyl groups of lignin make this material an
mers and Related Materials special issue of the European ideal structural base for the synthesis of complex poly-
Polymer Journal [11]. Below we introduce to the reader meric systems, e.g. polyurethanes (PU), as Cinelli et al. sug-
the BiPoCo 2012 Special Section containing four feature gest [13]. In their paper, the authors report the production
articles and several research papers. of partially renewable-based PU soft foams with possible
applications in the packaging and automotive industries.
1. Natural building blocks Other natural phenolic compounds can also provide
important complex building blocks, among which the sig-
Nature offers an extremely wide range of macromole- nificance of tannins should be emphasized, because of
cules and small molecular weight compounds in abun- their abundance in nature. Gallic acid (Fig. 1), one of the
dance. Quite a few of these materials might be valuable main components of hydrolyzable tannins, can be used

0014-3057/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
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 Editorial items / European Polymer Journal 49 (2013) 1146–1150 1147

as a renewable monomer for thermosetting applications. important condition for the development of suitable stabi-
Aouf et al. [14] describe the production of a bio-based lizer packages.
epoxy resin using a novel glycidyl derivative of gallic acid, Besides natural phenolic compounds, triglycerides, the
which demonstrates the feasibility of formulating epoxy main constituents of plant oils, also represent a major po-
thermosets based completely on a natural phenolic tential alternative feedstock for the polymer industry
compound. [17,18]. They are available in large quantities at low price,
Synthetic phenolic antioxidants are widely applied as while their chemical modification might lead to a large
stabilizers for polyolefins and many other polymers to pro- variety of monomers [19] and polymers [20,21]. Although
tect them during processing and application. The possible in many cases plant oils do not require extensive modifica-
effect of the reaction products of these compounds on tion before their application, a wide range of techniques
the environment as well as on human health, however, are available for the synthesis of valuable, bio-based deriv-
raised several questions recently, thus their substitution atives. For their renewability and interesting properties, a
with environmentally friendly alternatives would be growing interest can be observed in the use of triglycerides
highly desirable. Several natural antioxidants, and many and fatty acids as precursors of monomers for various
phenolic compounds among them, might be ideal candi- polymers, e.g. thermosets [22] and elastomeric compounds
dates for this purpose [15,16]. The effect of one of such [23]. Hydroxylated plant oils are of high importance in
materials, curcumin (Fig. 1), on the melt stability of poly- polyurethane production, as they might replace conven-
ethylene was investigated for the first time by Tátraaljai tional fossil-based polyols [24,25]. Since a wide range of
et al. [16]. The authors found in their study that curcumin neat or modified triglycerides can be used for this purpose,
is more efficient than the synthetic antioxidant applied describing the correlation between their chemical struc-
routinely in practice, while they also suggested a possible ture and the macroscopic properties of the resulting poly-
stabilizing mechanism, the knowledge of which is an mer is of large importance. Fridrihsone et al. [25] studied

Fig. 1. Natural phenolic compounds (a) lignin model compounds [12], (b) gallic acid [14], and (c) curcumin [16].
1148 Editorial items / European Polymer Journal 49 (2013) 1146–1150

the impact of molecular weight between cross-links, ure- blend consisting of starch, polycaprolactone and chitosan
thane group concentration and dangling chain concentra- was studied by Alix et al. [31], in order to obtain an active
tion on structure, physical, mechanical and thermal food packaging material with water scavenging effect. The
properties of PU networks. lack of a plasticizer in the blend decreases the risk of
migration of low molecular weight compounds into the
2. Biopolymers and their modification product, while chitosan acts as antimicrobial agent
increasing shelf-life.
The generally accepted definition of biopolymers covers Biopolymers can also be modified by the incorporation
polymers that are bio-based, biodegradable or both [26]. of fillers and reinforcements, thus providing various bio-
The substitution of conventional raw materials with composites. Although conventional, mineral fillers might
renewable feedstocks and the application of biodegradable also be applied [32], most studies focus on the potential
and compostable plastics can be advantageous in many use of natural lignocellulosic fibers, i.e. wood flour, sisal,
areas. Nevertheless, besides their obvious benefits, these flax, etc. into both conventional and biopolymers [6]. These
materials also possess several drawbacks. The abundance biocomposite materials predominantly find applications in
of natural polymers results in low price, but their proper- the building and automotive industry. Recently, environ-
ties do not come even close to those of commodity plastics. mental concerns lead to a considerable spread of renew-
While synthetic biopolymers, i.e. polymers based on able-based and biodegradable matrices, many of these
renewable monomers are more expensive, their properties based on plant oils, e.g. epoxy, alkydic and polyurethane
are also often inferior compared to fossil-based alterna- thermosets, as well as PU elastomers, as Mosiewicki and
tives, or at least do not correspond to the expectations of Aranguren [33] emphasize in their feature article. The
converters or users. As a consequence, biopolymers gener- authors review the effect of different particles, synthetic
ally are not applied without modification. In their feature and natural fibers as well as nanosized inclusions in tri-
article, Imre and Pukánszky [27] give an overview of the glycerides based polymeric systems. Lignocellulosic rein-
various physical (plasticizing, blending [28], composite forcements might present a viable alternative to glass
preparation) and chemical (copolymerization [29], grafting fibers applied traditionally, while biopolymer systems con-
[30]) modification approaches, focusing on structure (the taining particles with one or more dimensions in the nano-
typical morphology of bi-component polymer blends can meter scale, i.e. bio-nanocomposites, form a special class of
be observed in Fig. 2), interfacial interactions, macroscopic materials possessing a range of unique characteristics with
properties and compatibilization in biopolymer-based respect to gas and water vapor permeability, thermal sta-
blends. Since the structure of bio-based and biodegradable bility, fire resistance, mechanical and optical properties,
polymers generally favors their chemical modification, etc. The characteristics of biopolymers can be altered using
special emphasis was placed on reactive compatibilization either natural nanofibers (cellulose nanofibers and nano-
techniques and reactive processing. The application of bio- whiskers) [34], as in the case of a bacterial cellulose rein-
polymer blends is reviewed in the paper including ad- forced chitosan film shown in Fig. 3 [35,36], or inorganic
vanced biomedical applications as well as other nanofillers (silica, layered silicates) [37], providing differ-
commercial areas. ent combinations of properties [38]. In order to achieve
Various applications require considerably differing nanoscale dispersion, i.e. intercalated or exfoliated struc-
properties; bio-based grades are mostly used in automo- ture resulting in superior properties, nanoclays must be
tive and electronics, while biodegradability is particularly modified with suitable organic compounds in order to pro-
advantageous in agriculture and packaging. A biopolymer mote the separation of the silicate layers. Fernández et al.
[39] compare the effect of different surface modification

Fig. 2. Morphology of a poly(lactic acid)/poly(butylene adipate-co-tere-

phtalate) (PBAT) blend (10 v/v% PBAT, fracture surface, SEM, 2500 Fig. 3. Morphology of a chitosan film reinforced with bacterial cellulose
magnification). nanofibers (5 v/v% nanofibers, SEM, 10,000 magnification) [35,36].
 Editorial items / European Polymer Journal 49 (2013) 1146–1150 1149

strategies on the properties of poly(lactic acid) nanocom- 4. Conclusions

posites using various characterization techniques. A mix-
ture of intercalated and exfoliated structure was In the near future the role of both renewable-based
confirmed in all cases. materials and biodegradability is expected to grow in the
polymer industry, thus scientific research and develop-
3. Advanced biomedical applications ment must pay more attention to these areas. With the
articles collected in the BiPoCo 2012 Special Section of
Bio-based and biodegradable polymeric materials are the European Polymer Journal, we offer an overview of re-
applied in many fields ranging from packaging and agri- cent developments in the field of biopolymer science to the
culture to applications with higher added value, i.e. elec- reader, with an outlook for future developments. The inter-
tronics and automotive. Various advanced biomaterials est in the materials discussed in this contribution, the suc-
are also being used in increasing quantities in biomedical cess of BiPoCo 2012 related to them, and the very positive
applications [40]. One of the main functions of these response of the participants encouraged our group to orga-
materials is to bridge the interface between artificial nize the second conference with an extended scope includ-
and biological systems, i.e. they must be biocompatible. ing advanced biomaterials. BiPoCo 2014 will take place in
Biodegradability is also favorable in most cases, but a Visegrád, Hungary, from August 24 to 28 in 2014.
long list of other important and specific requirements
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