Professional Documents
Culture Documents
Materiaux Polyme`res, Ecole Francaise de Papeterie et des Industries Graphiques (INPG), BP 65, 38402 St. Martin dHe`res, France
modied at their surface in order to become more com- homoOPO generated by anionic transfer from the
patible with the polymeric matrix. growing OPO grafts formed on the macromolecular
substrate.
Polymer electrolytes The modied chitosan chains now bore some unre-
acted OH and NH groups and short PO grafts termin-
2
Previous work on this topic concentrated on the use of ated by more accessible hydroxy functions. They were
cellulosic derivatives as lm-forming precursors for reacted with mixtures of OPO and OEO mono- and
polymer electrolytes.6,7 Our long-standing interest in di-isocyanates to prepare the lm-forming networks
these materials8 had allowed us to achieve very satisfac- possessing loose oligoether branches with the following
tory mechanical and electrochemical properties, but typical structure :
they required a specic improvement in terms of the
possibility of preparing lms as thin as possible, prefer-
ably in the few micrometre range. In fact, the manufac-
ture of solid-state batteries, sensors or electrochromic
devices requires the use of very thin lms. Cellulose
ethers, appropriately modied by oligoethylene oxide
(OEO) and propylene oxide (OPO) branches and cross-
links, gave an adequate solution to that problem6,7 and
this positive result suggested that perhaps even better
performances could be attained using other lm-
forming polysaccharides. Chitin and chitosan seemed
the obvious candidates for this task, and work was
therefore initiated on these widely-accessible polymers
produced by numerous crustaceans in the form of their
outer skin or carapace.
Cellulose and its common derivatives still bearing
hydroxy groups react with isocyanates, albeit slowly in
the case of insoluble materials, and thus branched and
crosslinked structures could be prepared using oligo-
ether mono- and di-isocyanates6,7 synthesized in our
laboratory by an original route. When chitosans with The introduction of lithium salts of strong Brnsted
variable extents of amino groups were treated with acids into these fully-amorphous solvating networks
phenyl isocyanate under heterogeneous conditions, little produced polymer electrolytes with good ionic conduc-
reaction could be induced, even with long treatments in tivities and mechanical properties. Their thorough
highly polar media. Only the surface of the poly- physicochemical characterization, aimed at establishing
saccharide particles were attacked with no further pen- the feasability of using thin lms in devices such as
etration of this otherwise strong reagent.9 Thus, solid-state batteries, sensors, electrochromic panels and
although OEO and OPO isocyanates reacted readily supercapacitors, is presently under way.
with the OH and NH groups of D-glucosamine,10
2
the chitosan model monomeric structure, the very Reinforcing cellulosic fibres
pronounced cohesive energy of chitosans10 hindered the
access of any isocyanate within their supramolecular This new research interest is the result of a collabo-
assemblies. ration with colleagues who specialize in the study of the
This unforeseen problem spurred a dierent approach mechanical properties of polymeric composites. The use
to the preparation of these new polymer electrolytes, of cellulosic bres as reinforcing elements in composite
namely oxipropylation of chitosans. This reaction materials with polymeric matrices has witnessed a very
had received very little previous attention and was important surge of activity involving numerous labor-
therefore investigated in detail in our laboratory.11 Dry atories and industrial concerns.12 Moreover, the ubiqui-
chitosan particles were mixed with propylene oxide in tous nature of this natural resource is well reected by
the presence of KOH, and the resulting suspensions the fact that publications on this topic have been
heated to 8090C in a stainless steel reactor with appearing from a large number of countries. The variety
vigorous stirring. When the pressure dropped to atmo- of natural and regenerated types of cellulosic bres avail-
spheric level, the product was recovered and character- able (bre length, lignin content, degree of crystallinity,
ized. In this way practically all the chitosan could be mechanical properties, etc.) gives a wide range of pos-
converted into a viscous liquid by choosing the appro- sibilities in terms of the nature and application of the
priate initial proportions of the reagents and catalyst. corresponding composites.
The other product of these reactions was always some The problems related to the elaboration of compos-
ites in which a polymeric matrix is associated with cel- The results of this investigation are particu-
lulosic bres have to do with ensuring a good larly encouraging, not only because all the attemp-
compatibility between these components and, if pos- ted chemical modications were successful, but,
sible, providing a high adhesive quality to their inter- more importantly, because, with the polymeric
face. When glass bres are used in these types of reagents, a good improvement of the mechanical
materials, specic reactions are carried out at the properties of composites with styrenic matrices was
surface of the glass in order to achieve these two aims. obtained.14
A similar approach was taken in our laboratory by The satisfactory outcome of this study has promp-
adapting it to the specic context of cellulosic bres. ted its pursuit according to a dierent strategy which
This investigation was conducted with several dierent consists of appending polymerizable functions onto
types of bres so that the characterization of the modi- the cellulosic bres, e.g. by the reaction of styrenic
ed surface could be as complete as possible. Thus for isocyanates or acrylic anhydrides. The resulting
example, (i) pure tracing paper was used as a substrate materials are then introduced into a monomer and
with the aim of measuring contact angles before and the ensuing polymerization thus involves the latter
after the specic chemical treatment of its surface ; (ii) a and also the reactive unsaturations on the bres. In
semicrystalline cellulosic powder was the best starting other words, the matrix is prepared in situ and becomes
substrate for inverse gas chromatography, and (iii) long linked covalently to the reinforcing elements of the
regenerated bres played the best role for the prep- resulting composite.15
aration and mechanical testing of composites.
A number of reagents were selected for studying the
chemical alteration of the surface of the cellulosic bres.
Some of them were commercially available (such as LIGNINS AS MACROMONOMERS
alkenyl succinic anhydride (ASA) and styrenemaleic
anhydride copolymers) whereas others were synthesized After a thorough study of the synthesis of polyester net-
in our laboratory, (the above-mentioned OPO and OEO works based on the condensation of both aliphatic and
monoisocyanates and a set of copolymers of styrene phenolic OH groups from dierent types of lignin with
with 3-isopropenyl-a,a@-dimethylbenzyl isocyanate difunctional acidic reagents,16h18 our attention has
(TMI).13 Thus, two distinct types of reactions were been switched more recently towards the preparation of
envisaged on the supercial OH groups, their esteri- other materials based on urethane and oxirane chem-
cation or their transformation into urethane moieties. istry.
The main aim, however, was to modify the surface The possibility of modifying the surface and solu-
energy of the cellulose using either small or large reac- bility characteristics of lignins by treating them with
tive molecules :14 on the one hand, oligoether iso- monofunctional isocyanates, revealed that the attach-
cyanates provided fairly large grafts but a modest ment of relatively short hairs possessing hydrophilic
reduction in polarity (from OH groups to ether properties, e.g. oligomeric ethylene oxide chains, did
functions) ; on the other hand, ASA coupling gave rise indeed provide a means of modifying quite drastically
to a more drastic switch to a non-polar character, but those properties, even when only about one half of
with shorter chains. The most radical modication in the available OH groups were involved. These
this context was achieved with the NCO- and materials showed a marked solubility in water and
anhydride-bearing styrenic copolymers with which long displayed glass transition temperatures which
branching was associated with a thorough reduction of decreased as the extent of grafting increased and
the surface energy to an entirely dispersive character. went from about 60C for pristine lignin to
The simplied representation of the intermolecular [60C with 80% substitution.19 This study was
assembly between the cellulosic surface and a styrene- accompanied by a meticulous investigation of model
TMI copolymer is given below. reactions involving both phenolic and benzylic
structures simulating the aromatic units in lignin, and
CH wOwCH wCH wNCO, representing the mono-
3 2 2
meric version of the oligomeric isocyanate used as
hair.20
In the same vein, the use of oligoether diisocyanates
produced networks which gave a swelling behaviour
and T values reecting the hydrophilicity and segmen-
g
tal mobility of the bridging chains. Various gels were
prepared by changing the relative proportion of oligo-
diisocyanate with respect to the total OH groups borne
by the lignin core molecules.19
A schematic visualization of these two types of
Yes
These compounds were used as reagents with various
aromatic amines to synthesize Schi bases which might
display liquid crystal behaviour. It is well known that Yes
furanic derivatives with substituents at C2C5 do not give
rise to mesogenic structures, even when the aspect ratio
seems correct, because the bond angle resulting from that No
substitution pattern is too small and the molecular
structure is therefore distorted with respect to a rod-like No
shape.28 Thus, among the numerous combinations
explored, only a few gave rise to mesophases.29 Exam-
ples of these, compared with some failures, are shown in
Table 1. These results29 conrmed that the 2,5-disubstitu- tion reaction and the resulting polymers (containing
ted thiophene heterocycle is better able to generate meso- variable extents of chromophores) were found to give
genic structures than the furanic counterpart because of gels very eectively by near-UV irradiation. Among the
a wider C2C5 connecting angle.28 It is important to numerous conjugated dimers tested, some contained
underline that these considerations based on molecular pyridine moieties which introduced the possibility of a
morphologies do not apply to polymeric structures in hydrophilic character through quaternization :
which additional structural features can produce the
desired liquid crystal behaviour, as with aromatic-
furanic polyamides30 or cellulosic derivatives.31
The other interesting property of these oligomers and
polymers, whether furanic, thiophenic or mixed, is their
photosensitivity. Various dimeric models were sub-
mitted to a detailed photophysical and photochemical
study.32 In dilute solution, intramolecular cistrans
isomerization dominates and the thermodynamic mix-
tures of isomers is obtained upon steady irradiation Polymers based on the Diels Alder reaction
with j [ 300 nm :
The furan heterocycle is among the most classical struc-
tures capable of responding to the DielsAlder (DA)
cycloaddition because of its pronounced dienic charac-
ter. Thus, its condensation with typical dienophiles such
In concentrated solutions and in the solid state, as maleic anhydride or mono- and bis-maleimides are
cyclodimerization is the only relevant photoevent which textbook examples. However, two obstacles can arise in
occurs, often with high regiospecicity. Thus, for this context, namely the presence of electronegative sub-
example, the simple furanic dimeric aldehyde gives a stituents such as carbonyl groups (furfural does not
single cyclobutane derivative : undergo the DA reaction) and/or steric hindrance
induced by bulky substituents. The application of the
DA reaction to furanic polymers can be envisaged
according to dierent modes. Recent work in our labor-
atory provides a source of examples for some of these
approaches.
various model reactions were rst investigated, before This tactical trick worked quite well and it was possible
turning to actual polymers. The latter materials to show that the polyadducts underwent the retroDA
included : (i) structures with furan rings in each unit, e.g. reaction to almost 100% conversion. Indeed the recov-
furanic polyurethanes with the heterocycle in various ered polymers gave spectra and degrees of poly-
conformations with respect to the polymer backbone merization (DPs) identical to those of the original
(pendant, 2,5 or 3,4 enchainment) ; (ii) structures derived materials used for the original DA reaction, and the
from the copolymerization of a conventional monomer only other product arising from this process was the
with dierent percentages of a furanic comonomer, e.g. DA adduct of 2-methylfuran with the maleimide.
methyl methacrylate and 2-furfuryl methacrylate ; (iii) These encouraging results prompted the pursuit of the
structures arising from the chemical insertion of varying investigation by turning to the use of bismaleimides. With
proportions of furan moieties as substituents in a con- all the furanic polymers and copolymers prepared in
ventional polymer or copolymer, e.g. the acetalization various studies, the crosslinking was veried and found
of PVA with furfural. to be highly eective.34,35 Again, the styrenic copoly-
In a preliminary study,34,35 dierent furanic polymers mers shown above were employed for more detailed
and copolymers, including all the types of structures tests, including reversibility at high temperature. With
described above, were treated with monomaleimides to gelled materials arising from copolymers bearing 510%
establish a relationship between the furanic ring posi- of furan moieties (i.e. with low crosslinking densities
tion in the macromolecular chain and its reactivity in after the DA reaction with the bisdienophile), the retro-
the DA cycloaddition, and also to study the extent of DA, carried out again with an excess of 2-methylfuran,
thermal reversibility of the adducts. Within the rst dominated and regenerated the original linear macro-
context, it was shown that pendant furan rings joined to molecular structures, as veried by spectroscopic, elemen-
the macromolecule through the C2 position are the tal and DP analyses. With crosslinked materials prepared
most reactive, as is indeed expected on steric grounds. from the bismaleimide and the copolymer containing
As for the second point, the following styrenic random 50% of furan comonomers, only part of the recovered
copolymers were studied in detail using dierent com- product was soluble, suggesting that some (minor) side
positions :35 reactions, such as aromatization of the adducts and/
or polymerization through the imide unsaturations,
hindered the completion of the retroDA process.
The implications of this study are that it should be
entirely possible to elaborate crosslinked structures
arising from the DA reaction which can be readily
returned to their linear (thermoplastic) origin by
heating. The application of this procedure to recyclable
In order to avoid the recyclization of the regenerated tyres seems attractive.
furan moieties upon cooling, via the DA reaction with
the concomitant maleimide liberated by heating, an Polycondensation by successive DA steps. One way to
excess of 2-methylfuran was added to the system. Its build linear polymers by the application of the DA
role was obviously to trap the vast majority of the cycloaddition consists of taking two complementary
maleimide molecules by the DA cycloaddition occurring monomers, one bearing two furanic end-groups (A-A)
as the mixture was cooled down. and the other two dienophilic functions (B-B). This
approach has been recently tackled in our laboratory.35
Before studying the actual polycondensation, the syn-
theses of model compounds were examined in terms of
yields and structures as a function of the specic nature
of the reagents. Having established the feasability of
dimers and trimers, the following combination was
chosen as a rst system of linear polycondensation :
The major difficulty encountered in this investigation occurrence of both reactions, but obviously does not
was the early precipitation of the product, even in sol- anticipate either chromophore formation or branching.
vents of high polarity. In other words, although the The numerous studies devoted to the understanding of
premises of success are not questioned, the DPs of the these questions concentrated on structural analyses of
polymers are rather low because of the difficulty of the products and failed to get to the heart of the matter.
keeping the reactions homogeneous. Work is in The synthesis and reactions of model compounds simu-
progress to improve the situation, and also to change lating the expected oligomers and the use of various
the structure of the polycondensates by converting the monomeric species, homologous to FA, but in which ad
adducts into aromatic moieties. This irreversible modi- hoc substitutions were introduced, opened the way to a
cation should provide materials with good thermal sta- thorough insight into the origin of the side reactions
bility. giving rise to the anomalous features.36
The other way to build a polycondensate by the DA The mechanism leading to the progressive colour-
reaction is to call upon a single monomer containing ation of the polymers is now clear. As shown in the set
both complementary groups (A-B). The rst clear-cut of reactions below, a series of hydride ion/proton losses
example of this alternative approach is the recent introduces conjugated unsaturations in the backbone of
synthesis35 of the rst furanic maleimide possessing the the polyfurfuryl structure and gives rise concomitantly
very simple structure to methyl end-groups. The resulting chromophores are
thus made up of a regular alternation of 2,5-furanic and
2,5-dihydrofuranic heterocycles joined by unsaturated
methine moieties. The number and length of these
This crystalline compound melts at 92C and gives a sequences increases with the reaction time, giving rise to
sharp exotherm around 170C indicating its poly- the characteristic phenomenology of both colour deep-
merization. Together with some homologues bearing ening and bathochromic shift in the visible spectra of
substituents either on the furan ring or on the malei- the polymerizing solutions. Note that these events can
mide unsaturation, and with structures involving other occur only if the oligomers formed by the linear con-
spacers between the two reactive ends, this monomer densation reactions possess labile hydrogen atoms on
represents the starting point of a new strategy in the the aliphatic carbon joining the furan rings. Indeed, 1,1-
exploitation of the DA reaction for the synthesis of dimethylFA gives colourless linear oligomers with a
polymers from furanic derivatives. Again it is planned predominant head-to-tail 2,5-structure and occasional
to submit the resulting polycondensates to specic head-to-head units, but no traces of conjugated moi-
chemical modications involving their adduct moieties. eties.36
rings (dienophiles). The second approach seemed more few years on lithographic materials, i.e. highly viscous
credible because it would explain more convincingly the mixtures. Among the topics which are relevant to this
fact that these systems tend to move suddenly from broad approach, the use of various diluents derived
linear oligomers to crosslinked materials, as suggested from the biomass to replace the petroleum-based deriv-
by the fact that branched structures have never been atives deserves special attention. Such a study involves
isolated, despite the numerous investigations in which modication of the natural triglycerides by tran-
intermediate compounds were identied. sesterication leading to single-chain fatty acid alkyl
The detailed knowledge of these perturbing mecha- esters39 and their use in new LIV.39,40 A thorough
nisms is particularly relevant to future applications of research eort consisting of a comparison of the rheolo-
the FA-based polymers both in terms of the possibility gical and surface energy properties of standard com-
of synthesizing the ideal structure (if it is stable) and in positions with those in which the vegetable oil(s) take a
view of exploiting certain specic properties of the con- growing role, has allowed the formulation of viable inks
jugated sequences, e.g. electronic conduction, if they can and varnishes capable of being used in various domains
be optimized with or without the intervention of cross- of printing technology.
linking. The parameters which must be optimized through
Interestingly, no study has been published on the this substitution are, on the one hand, the viscoelastic
behaviour of 2-thiophene methanol under similar condi- response of the material and, on the other, its dynamic
tions. Our recent investigation on this subject37 indi- adhesive character commonly measured as tack value.
cates that the dominant condensation is now the Moreover, in the case of standard oset, the capacity of
head-to-head reaction between the primary OH groups ink or varnish to emulsify the aqueous fountain solution
to give the stable ether is another indispensible property which must be
retained when replacing the mineral diluent by the
modied vegetable oil. This latter aspect requires a
careful characterization of surface and interfacial ener-
without appreciable oligomerization through the C5 gies. Finally, the actual printing implies a very fast
position. spreading of the viscous liquid onto the substrate ; in
order to simulate this process, an original instrument
was developed in our laboratory to measure dynamic
USE OF VEGETABLE OILS IN PRINTING contact angles and spreading areas.41
INKS AND VARNISHES
(iii) zero or one CxC unsaturation along the chains. A went through a maximum for a calculated [OH]/
closer inspection of this suberin by GC/mass [NCO] ratio of unity.
spectrometry43 revealed that it was in fact made up of As for the use of suberin as a non-reactive additive,
two distinct fractions, one consisting of C16C24 mol- its role in improving certain properties of inks and var-
ecules (M B 350), of which the following three were the nishes was tested using various commercial and experi-
n
most abundant : mental all-vegetable compositions (see above). Suberin
does not dissolve in these formulations and can there-
fore be envisaged to migrate to the surface of the drying
ink or varnish and improve optical and tribological fea-
tures through its partial crystallization.
This work is presently in full progress in both direc-
tions.
CONCLUSIONS
and another with an average molecular weight about The dierent examples outlined in this short review give
three times higher. a modest idea of the enormous potential of the biomass
The whole extracted product, hereafter called as a source of interesting polymeric materials for a wide
suberin, is the object of an ongoing study in our labor- range of applications. As already emphasized elsewhere,
atory aimed at dierent chemical and physical uses, as it is regrettable that only a relatively modest number of
summarized below. laboratories are engaged in this type of research, com-
The chemical exploitation of suberin was initiated by pared with the vast activity devoted to petroleum-based
using it as a macromonomer suited for the elaboration polymers. However, as witnessed by this special issue,
of polycondensates, given the presence of not only OH the motivation of using renewable resources for the
groups in its structure, but also of carboxylic moieties elaboration of new polymers is increasing steadily and
which can be hydrolysed to COOH or employed as we hope that some of the topics described here will
such in polytransesterication reactions. The rst study stimulate further involvement outside our laboratory.
conducted in this context called upon the synthesis of
polyurethanes. In order to gain a sound criterion of the
reactivity of suberin towards isocyanates, model reac-
tions preceded the actual polymerizations. REFERENCES
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