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Chemical modification of cellulose in order to increase the wettability and

adhesion in composites

Article  in  Afinidad -Barcelona- · September 2004

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AFINIDAD REVISTA DE QUÍMICA TEÓRICA Y APLICADA
EDITADA POR LA ASOCIACIÓN DE QUÍMICOS E INGENIEROS
DEL INSTITUTO QUÍMICO DE SARRIÁ

Chemical Modification of Cellulose in Order

to Increase the Wettability and Adhesion
in Composites
M. Gou , F. Corrales , F. Vilaseca *, M.F. Llop , P. Mutjé .
1 1 1,2 1 1

1
LEPAMAP Group, Department of Chemical Engineering, University of Girona, Girona 17071 (Spain).
2
Department of Materials, Queen Mary University of London, London E1 4NS (UK).

Modificación química de celulosa a fin de mejorar la mojabilidad y la adhesión en materiales compuestos.

Modificació química de cel·lulosa a fi de millorar la mullabilitat i l’adhesió en materials compòsits.

Recibido: 3-IX-2004

Afinidad (2004), 61 (513), 393-395

 Chemical Modification of Cellulose in Order
to Increase the Wettability and Adhesion
in Composites
M. Gou , F. Corrales , F. Vilaseca *, M.F. Llop , P. Mutjé .
1 1 1,2 1 1

1
LEPAMAP Group, Department of Chemical Engineering, University of Girona, Girona 17071 (Spain).
2
Department of Materials, Queen Mary University of London, London E1 4NS (UK).

Modificación química de celulosa a fin de mejorar la mojabilidad y la adhesión en materiales compuestos.

Modificació química de cel·lulosa a fi de millorar la mullabilitat i l’adhesió en materials compòsits.

Recibido: 3-IX-2004

RESUMEN
Se ha propuesto un proceso en dos etapas que trans-
forma el carácter hidrofílico de la superficie de substra-
tos celulósicos en hidrofóbico. En una primera etapa se
modificó químicamente la celulosa con anhídrido meta-
crílico y posteriormente se recubrió con poliestireno
mediante un proceso de co-polimerización. Aunque ya
en la primera etapa se obtuvo una celulosa modificada
con carácter superficial hidrofóbico, el proceso de poli-
merización incremento el comportamiento hidrofóbico.
Palabras clave: Substrato celulósico. Agente de acopla-
miento. Recubrimiento con poliestireno. Modificación
superficial. Mojabilidad.
RESUM
S’ha proposat un procés en dues etapes que transforma
el caràcter hidrofílic de la superfície dels substrats
cel·lulòsics en hidrofòbic. En una primera etapa es va
modificar químicament la cel·lulosa amb anhídrid meta-
crílic i posteriorment es va recobrir amb poliestirè mit-
jançant un procés de co-polimerització. Tot i que ja en
la primera etapa es va obtenir una cel·lulosa modificada
amb caràcter superficial hidrofòbic, el procés de poli-
merització va incrementar el comportament hidrofòbic.
Mots clau: Substrat cel·lulòsic. Agent d’acoblament.
Recobriment amb poliestirè. Modificació superficial.
Mullabilitat.

SUMMARY
A two steps process has been proposed to turn the
hydrophilic character of surface cellulosic substrates for
hydrophobic. Initially pure cellulose has been chemically
modified with methacrylic anhydride and subsequently
coated with polysterene by co-polymerisation process.
Although the first step yielded modified cellulose with
hydrophobic surface character, the polymerisation pro- * To whom correspondence should be addressed at
cess increased that hydrophobic behaviour. f.vilaseca@qmul.ac.uk, Department of Materials,
Key words: Cellulosic substrate. Coupling agent. Queen Mary University of London, Mile End Road
Polystyrene coating. Surface modification. Wettability. E1 4NS, London

393
INTRODUCTION
In the last decades, polymers have replaced many of the
conventional metals/materials in many applications
because of their advantages in ease processing, in bet-
ter productivity, and possible cost reduction. Moreover,
properties of polymers may be modified using fillers and
(1)
fibres to suit high strength / high modulus requirements .
Composites reinforced with glass and carbon fibres have
found applications in many fields, but their non-recy-
clability becomes a significant disadvantage at the end
(2, 3, 4)
of their lifetime . Unlike the traditional engineering
fibres, natural fibres derived from annual plants show
several advantages like recyclability, availability, com-
parative cost lower, lightweight and acceptable strength
values. Nevertheless, the hydrophilic nature of natural
fibres adversely affects the adhesion to hydrophobic
polymeric matrices and it may cause lose of strength in
the final composite. To improve the compatibility bet-
ween biofibres and polymeric matrices, many surface
modifications such as dewaxing, delignification, blea-
ching, acetylating, or chemical grafting have been pro-
(1, 2, 3, 5)
posed . Furthermore, coupling agents such as sila-
nes, titanates, zirconates, triazine compounds or alkyl
(6, 7)
halide reagents have been used to modify the surfa-
ce properties and to enhance performance. The aim of
this work is to study the surface modification of cellulo-
sic substrates with a bi-functional reagent able to react
with hydroxyl groups of cellulose and with an olefinic
monomer as well. In a first step, chemical modification
of the substrate with the coupling agent, which should
turn the surface cellulose partially hydrophobic, has been
done. In a second step, covalent linkages between the
modified cellulose and the olefinic monomer (co-poly-
merisation) were looked for the cellulose surface as coa-
(3)
ting . Then, it was expected to obtain modified cellulo-
se with poor water affinity and better wettability for the
(8)
matrix . Several methods confirmed a decrease in the
hydrophilic nature of surface cellulose after this method.
Even if the co-polymerisation of polystyrene onto the
modified cellulose were not very extensive, it neverthe-
less contributed to increase the hydrophobic behaviour
of cellulosic materials.
Figure 1. (a) FTIR spectrum of pure methacrylic anhydri-
de (AMA). (b) FTIR spectrum of pure cellulose (AV) and
modified cellulose with methacrylic anhydride (AVAMA).
394
MATERIALS AND METHODS
Different cellulosic substrates were used such as microcrys-
talline cellulose (Avicel®‚ pH 101 powder) supplied by Fluka
(Barcelona, Spain), tracing sheets of vegetal paper from
Guarro Casas SA (Campdevànol, Spain), and Whatman®‚
filter paper supplied by Touron S.A. (Girona, Spain).
Methacrylic anhydride (AMA) from Aldrich Chemical Co.
with high-purity commercial product was used as coupling
agent. Pyridine from Panreac SA was used as reaction
media. The solvent was thoroughly dried over activated
0.4 nm sieves for a week. Styrene (PS) from Aldrich
Chemical Co. was used as monomer in the polymerisation
reaction whereas α,α'-azoisobutironitrile (AIBN) from Fluka
SA was applied as initiator.
The vegetal paper and the filter paper were cut in order to
obtain specimens of one per three centimetres. All cellu-
losic materials were vacuum dried at 90 ºC for 24 hours
before being placed in the flask for chemical modification.
Then, the cellulosic substrates were suspended in the dry
solvent while 2.8 ml of the coupling agent per gram of subs-
trate was slowly added under magnetic stirring in a dry
nitrogen atmosphere. The solvent/substrate ratio tested
were 40 ml per gram of cellulosic substrate. The reaction
was maintained for 24 hours at boiling conditions. Then,
the liquid phase was drained through a sintered glass fil-
ter and the solid was washed several times with the dry
solvent, to remove residual reagent. The modified cellulo-
sic substrate were dried under vacuum at 90 ºC for 24 hours,
and kept for the ensuing characterisation and for the poly-
merisation reaction. The styrene monomer was pre-trea-
ted with 1M caustic soda to extract 4-ter-butyl catecol used
as stabiliser. The extracted styrene was dried over CaH2
for 24 hours and then kept over activated 0.4 nm sieves.
Thus, one gram of the modified cellulose substrate was
covered with styrene (30 ml) and AIBN (2% by weight of
styrene) for the polymerisation reaction. The polymerisa-
tion was carried out at 70 °C for 24 hours. In order to eli-
minate the ungrafted species, the modified cellulosic subs-
trates were submitted to 2-days soxhlet extractions in
CH2Cl2. The residual solids were also dried in vacuum at
90 ºC for 24 hours and stored thereafter under nitrogen
before characterisation.
Figure 2. (a) FTIR spectrum of polystyrene (PS). (b) FTIR
spectrum of modified cellulose with methacrylic anhydri-
de (AVAM) and modified-polymerised cellulose (AVAMPS).
 Chemical modifications were followed by Fourier trans-
form infrared spectroscopy (FTIR) obtained from KBr pellets
by means of a Galaxy series FTIR 5000 from Matson. The
spectrometer was used in the transmission mode with a
–1 –1
resolution of 2 cm in the range of 4000 – 400 cm . In addi-
tion, inverse gas chromatography (IGC), contact angle and
enzymatic degradation were also applied to evaluate the
surface energy and the acid/base ratio, the hydrophobic
surface behaviour, and the accessibility of cellulose fibre,
respectively. For the enzymatic assay, samples were intro-
duced in a buffer solution (pH = 4.8) of 2.14 g/l of
Trichoderma deesei at 50 °C for 25 days and the weight
reduction of the cellulosic part was measured.
RESULTS AND DISCUSION
The reaction of pure cellulose (Avicel ® ) with anhydride met-
hacrylic yielded the expected surface modified cellulose
shown in Figure 1. The characteristic ester group was
–1
detected in modified cellulose spectrum at 1723 cm indi-
cating the occurrence of the condensation reaction. In the
second reaction, the mass polymerisation over modified
cellulose, FTIR spectra of Figure 2, were obtained. In spi-
te of there being no relevant differences between modi-
fied cellulose spectra after and before polymerisation, a
–1
short moving of ester absorption peak to 1736 cm was
noticed, due to the conjugated double bond disappearing
during polymerisation. Moreover, the small absorption
–1
bands at 754 and 702 cm were characteristic of the pre-
sence of hydrogen aromatic moiety in the modified-poly-
merised cellulose.
In order to evaluate the surface properties of the modified
and modified-polymerised cellulose, other complementary
techniques were applied. Values of the surface energy and
acid/base ratios were obtained by inverse gas chromato-
graphy. The surface energy of pure cellulose was found to
be γ s = 41.6 mJ/m2, close to the theoretical value (γ s = 40
d d
2
mJ/m ) for pure cellulose, while the surface energy of modi-
2
fied-polymerised cellulose was 29.5 mJ/m , very similar to
d 2
the polystyrene theoretical value (γ s = 29 mJ/m ), sugges-
ting that the cellulose surface was coated in the polyme-
risation process. Furthermore, the acid/basic character
fallen down from 4.5 for pure cellulose to 1.8 after the modi-
fication and polymerisation reactions.
Furthermore, the same modification and modification-poly-
merisation were applied over sheet cellulosic substrates.
The wettability of sheet cellulosic substrates (filter and
vegetal papers) was measured by the contact angle met-
hod using water as solvent. When filter paper was used,
the water-drop placed on the substrate rapidly penetrated
and the contact angle was undetectable, even though, the
contact angle was 107 ± 3º for the modified cellulosic subs-
trates and 120 ± 3º for the modified and subsequently poly-
merised cellulosic substrates. A high contact angle implies
a strong hydrophobic character and this increases with the
modification and subsequent polymerisation processes.
For vegetal paper, the unmodified samples gave a contact
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angle of 50 ± 2º, which increased to 83 ± 4º and 113 ± 3º
for modified and modified-polymerised substrates res-
pectively.
Finally, enzymatic degradation of pure and modified-poly-
merised substrates was measured to evaluate the easy
access of cellulose fibres after modification process. Once
the enzymatic reaction was realised, the weight reduc-
tion of cellulose was over 95 % for pure cellulosic subs-
trates while it was lower than 15 % for the modified-poly-
merised one, indicating the effectiveness of the applied
coating, which extremely decreased the accessibility of
modified and polymerised cellulosic surface for the micro-
organisms.
CONCLUSIONS
A good hydrophobizing process has been proposed to
improve the wettability of cellulosic reinforcements with
polymeric matrices. The coupling agent used methacrylic
anhydride, has condensed with hydroxyl groups of cellu-
losic substrates and has copolymerised with styrene mono-
mer, which has coated the surface of modified cellulosic
material. The characterisation methods applied has pro-
ved the increasing in hydrophobic properties of treated
surfaces of cellulosic material, which may contribute to
better compatibility and adhesion between biofibres and
polymeric matrices.
ACKNOWLEDGEMENT
The authors acknowledge the financial support by the
University of Girona in the program "Research Plan 1999".
The authors are grateful to Prof. A. Gandini from E.F.P.
(Institut National Polytechnique de Grenoble), France for
the contribution to results and discussion.
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