J Polym Res (2010) 17:837–845
DOI 10.1007/s10965-009-9375-7
ORIGINAL PAPER
Silicone-modified cellulose. Crosslinking of the cellulose
acetate with 1,1,3,3-tetramethyldisiloxane by Pt-catalyzed
dehydrogenative coupling
George Stiubianu & Maria Cazacu & Alina Nicolescu &
Viorica Hamciuc & Stelian Vlad
Received: 17 August 2009 / Accepted: 1 December 2009 / Published online: 18 December 2009
# Springer Science+Business Media B.V. 2009
Abstract Cellulose acetate was reacted with different
amounts of 1,1,3,3-tetramethyldisiloxane in presence of
Karstedt’s catalyst, in solution, by using dry acetone as a
solvent. A dehydrocoupling reaction between Si-H and
C-OH groups with H2 evolving and the formation of Si-O-C
bond occured, as proved by FTIR and NMR spectra, having
as a result the crosslinking of cellulose derivative. A model
reaction was followed online by 1H NMR spectroscopy.
Morphological changes as a result of the siloxane coupling to
the cellulose derivative were emphasized by Environmental
Scanning Electron Microscopy (ESEM). The surface (water
contact angle and water vapor sorption capacities) and
mechanical properties (breaking strength, breaking strain
and Young modulus) of the networks processed as films
were investigated and the results were correlated with the
reactants ratios.
Keywords Siloxane-modified cellulose . Siloxane .
Cellulose . Surface properties
Introduction
Cellulose crosslinking is a very important process for
practical applications because crosslinking markedly
improves the wet performance (wet modulus of elasticity,
dimensional stability, and creep properties) of cellulose-
G. Stiubianu (*) : M. Cazacu : A. Nicolescu : V. Hamciuc :
S. Vlad
“Petru Poni” Institute of Macromolecular Chemistry,
Aleea Gr. Ghica Voda 41A,
700487 Iasi, Romania
e-mail: george.stiubianu@icmpp.ro
based materials [1]. Crosslinks limit the swelling of the
cellulose derivatives and protect the preexisting hydrogen
bonds against the water disrupting and dissolving action
[2]. Due to the polar nature, the cellulose response to
cross-linking is different towards the rubbery polymers
[3].
The most commonly used crosslinking systems for
cellulose are based on N-methylol chemistry. These
systems confer, beside many desirable mechanical stable
properties, strength loss and the potential to release
formaldehyde, a known human carcinogen [1]. Therefore,
such a procedure is now abandoned and it is actively
seeking for formaldehyde-free crosslinking methods. Other
chemical systems that do not contain formaldehyde, e.g.
polycarboxylic acids, or methods of forming ionic cross-
links have also been reported [1, 2, 4, 5].
In this paper we approached the crosslinking of
cellulose, namely its derivative, cellulose acetate, with a
siloxane, 1,1,3,3-tetramethyldisiloxane, as crosslinking
agent in presence of a Platinum-based catalyst. The cross-
linking of cellulose with polysiloxanes has already been
reported [6]. We chose the cellulose acetate (CA) due to its
good solubility. In addition, this is one of the most
important and low cost derivatives that show neutral
properties, capacity to form films having good optical
clarity, high modulus and adequate flexural and tensile
strengths. These features are, among others, responsible for
the broad applications of this polymer in areas such as
pharmacology, electronics, wastewater treatment, liquid
chromatography, textile, plastic, and food industries, etc.
[7, 8]. Due to the reactants and conditions used, a
dehydrocoupling reaction occurred between Si-H and
C-OH groups, also named as O-silylation (silylation of the
oxygen atom) [9].
838 G. Stiubianu et al.

Table 1 Some spectral and compositional data for the prepared Karstedt’s catalyst, Pt2{[(CH2 =CH)Me2Si]2O}3 (Platinum-
crosslinked samples
Divinyltetramethyldisiloxane complex in xylene, 2.1–2.4%
Sample Feed molar ratio, CAa/DH IR absorption intensity ratio of Platinum), supplied by ABCR.
the relevant bands Acetone CHIMOPAR (Romania) was freshly distiled
from NaH just before using.
A803/A1218 A857/A803
CH3Si/νC-O Si-O-C/CH3Si
Equipments
CR 1.0/0.0 – –
CS1 1.3/1.0 0.387 0.663 Fourier transform infrared (FT-IR) spectra were obtained on
CS2 1.0/1.5 0.708 0.640 a Bruker Vertex 70 FT-IR analyzer. Analyses were
CS3 1.0/3.0 0.821 0.650 performed on the films in reflectance mode (ATR), in the
600–4000 cm−1 range, at room temperature with 2 cm−1
a
The structural unit was considered resolution and accumulation of 32 scans.
The NMR spectra have been recorded on a Bruker Avance
Experimental III 400 MHz spectrometer, equipped with a 5 mm multinu-
clear, inverse detection z-gradient probehead. Acetone—d6
Materials was used as a solvent.
Microscopic investigations were performed on an Envi-
Cellulose acetate, C6H7,5O2,5(OCOCH3)2,5, CA, supplied ronmental Scanning Electron Microscope (ESEM) type
by Fluka, with the characteristics: DS=2,5; d420 =0,996; Quanta 2000 operating at 510 kV with backscattered
purity >99%. electrons in low vacuum mode. As far as the ESEM
1,1,3,3-Tetramethyldisiloxane, DH, supplied by ABCR investigation was concerned, freeze drying technique was
GmbH & Co KG (Germany), b.p. 70–71°C, d420 =0.76, applied, the drying effect on the film morphology in
purity 97%, was used as such. swollen state being thus leveled off.

Fig. 1 Photo images of the

prepared films
Silicone-modified cellulose
Tensile strength tests were performed at room tempera-
ture using an Instron Single Column Systems tensile testing
machine (model 3345) equipped with a 5kN load cell and
activated grips, which prevented slippage of the sample
before break. The used cross-head speed was 50 mm/min.
Specimens for tensile measurements were cut out from the
thick films using a V cutter. At least five identical dumbbell
shaped specimens for each sample were tested, and their
average mechanical properties are reported. The reported
errors are the subsequent standard deviations.
Dynamic contact angles (DCA) and contact angle
hysteresis were measured by using a KSV Sigma 700
tensiometer system—a modular high performance computer
controlled surface tension/contact angle meter. Water was
used as measure liquid. The DCA runs were performed on
rectangular films. The average values of three measure-
ments were taken into consideration.
The measurements for dynamic vapour sorption and
sorption hysterezis were performed with an IGASorp
Dynamic Vapour Sorption apparatus, with the character-
Fig. 2 Comparative FTIR spectra for reactants and crosslinked products: a DH; b CA; c CS1; d CS2; e CS3; f CS3 after treatment with CH3COOH
839
istics: minimum gas pressure: 2 bar; resolution of 0.1 μg for
100 mg and with sample containers made out of stainless
steel micron size mesh where the samples were dried with a
flow of pure nitrogen (>99.9%).
Procedure
In a well-dried two-neck round flask having attached a reflux
condenser and nitrogen adduction, CA was solved in freshly
dried acetone to form a 3%-wt solution cellulose acetate in
acetone. DH was added in different ratios towards CA under
stirring to this solution, according to Table 1. Karstedt’s
catalyst (0.15 μl/mmol Si-H groups) was added and the
mixture was stirred first 3 h at room temperature and then
was poured in a Petri dish, which was partially covered and
overnight left for slow solvent evaporation. Films easily
detachable from the glass surface were formed in all cases.
A reaction between reactants, cellulose acetate and 1,1,3,3-
tetramethyldisiloxane taken in 1:1.1 molar ratio was con-
ducted directly in 1H-NMR analysis tube. The modification
840 G. Stiubianu et al.

of the reaction mixture spectrum as a result of the catalyst
adding as well as after 24 h of reaction at room temperature
was followed in order to identify the reaction pathways.
Hydrogen dosage was performed by using an adapted
procedure according to reference [10], using a custom-made
flat bottom glass bottle with a round back end beak. The
molar ratio between the two reactants was identical with that
used for the sample CS2 (CA/DH=1.0/1.5). Thus, 1,1,3,3-
tetramethyldisiloxane was inserted in the beak (0,037 g;
0.276 mmol) and the cellulose acetate (0,0497; 0.186 mmol)
solution in acetone together with the Karstedt catalyst
(0,0001 ml) was introduced on the flat bottom of the bottle.
By spinning the bottle along its transversal axis the reagents
are brought into contact with one another and the reaction
begins. The volume of gaseous hydrogen eliminated from the
reaction is measured as the volume displaced in a water
column [10]. The evolved hydrogen as a measure of the
completion of this reaction was calculated with the formula:
Hð%Þ ¼ V 273 ðP  pÞ 100; 8=760 T a 22; 414
where: H (%)—percentage of hydrogen relative to the amount
of reagent; V—volume of hydrogen released (mililiters);
P—atmospheric pressure (mm Hg); p—saturation vapour
pressure of water vapours, in presence of water, at the ambient
temperature (mm Hg); T—absolute temperature at the time of
reaction (K); a—milligrams of reagent(s) which release
hydrogen; 22,414—volume of one mole of gas at standard
conditions (liters).
The degradability test
A film piece was introduced in an acid medium created by
adding a drop of CH3COOH in 3 ml water and kept in such
a medium for 4 h. Afterwards, the film was washed with
water at neutral pH and dried.
Results and discussion
We attempted to crosslink the cellulose by using a siloxane
having Si-H telechelic groups as a crosslinking agent. A
derivative, cellulose acetate having a substitution degree,
SD=2.5, was chosen due to its good solubility. The reaction
occurred in dried acetone in presence of platinum catalyst.

OCOCH3 OCOCH3
OCOCH3 OH
O O HO
CH3OCO
O O
CH3OCO O CH3OCO O
OH O OCOCH3 O
OH OCOCH3
+
CH3 CH3
H O H
Si Si

CH3 CH3

Karstedt catalyst H2

OCOCH3 O OCOCH3 O OCOCH3 OCOCH3 O OCOCH3

O CH3OCO O CH3OCO O CH3OCO O CH3OCO
O O O O
O O O O
CH3OCO O CH3OCO O HO O CH3OCO OCOCH3 O
O OH OCOCH3 O OCOCH3 OH O
H3 C
CH3 Si
CH3
Si Si CH3
H3 C
H3C O
O O
CH3 H3 C
Si Si n
CH3 CH3
Si H3C
H3 C
O
O H3 C
Si
CH3
n CH3
Si OH
H3 C

O OCOCH3 OH OH O OCOCH3 OH
OCOCH3
CH3OCO O CH3OCO O CH3OCO O CH3OCO O
O O O O
O O O O
O CH3OCO O CH3OCO O CH3OCO O CH3OCO
O OCOCH3 O OCOCH3 OCOCH3 O OCOCH3
O

Scheme 1 Model reaction scheme for the crosslinking of cellulose acetate with siloxane
Silicone-modified cellulose 841

Different ratios between the two components were used does not participate in the reaction. Actually, in these
according to Table 1. conditions there is not a hydrosilylation reaction which
The aspect of the crosslinked cellulose acetate processed takes place but a dehydrocoupling one. In the presence of
as films can be seen in the photos in Fig. 1. Platinum catalyst, hydrogen is eliminated between the
By analysing the FTIR spectra (Fig. 2) of the starting siloxane Si-H groups and C-OH groups from cellulose.
compounds and those of the reaction products we can see The development of the reaction on this path is supported
the next: the 1737 cm−1 peak assigned to −O-C=O group by the experimental observations according to which gas
from cellulose acetate remains unmodified both as bubbles are being produced during the mixing of the
intensity and as position thus leading to the conclusion it reagents in the presence of catalyst as well as by the
Fig. 3 The 1H-NMR spectra of
cellulose acetate and 1,1,3,3-
tetramethyldisiloxane : a initial
mixture; b in the presence of
Karstedt’s catalyst, and c after
24 h from the addition of Kar-
stedt’s catalyst
842
literature data according to which the reaction takes place
indeed in this way [11]. In the spectra of all products there
can be noticed the dissapearence of the 2100 cm−1 band
assigned to Si-H bond. Instead, there are present other
absorption bands characteristic for the siloxane compo-
nent: 2962 cm−1 (C-H from Si-CH3), 1262 and 803 cm−1
(Si-CH3). The Si-O-Si as well as new formed Si-O-C
bands are superimposed with the C-O-C from cellulose in
the range 1030–1090 cm−1. However, a band assigned to
Si-O-C bond can be identified as a shoulder at 857 cm−1
[12] (Fig. 2). Such a band is not visible in reactant’s
spectra. This band disappears by treating the film with
acid according to procedure described in the experimental
part. The insert in Fig. 2 emphasizes this modification of
the FTIR spectrum. The intensities ratio corresponding to
newly created Si-O-C bond (857 cm−1) and Si-CH3
(803 cm−1) from the siloxane can be considered as a
measure of the crosslinking. The crosslinking degrees of
the three samples expressed by the values of this index are
close although the siloxane addition in the initial reaction
mixture rises from CA/DH=1.3/1 in CS1 to 1.0/3.0 molar
ratio in CS3 (Table 1). This can be explained by the fact
that only part of the siloxane crosslinks the cellulose
acetate, the rest being involved in other reactions. Thus,
the hydrolysis of DH in the presence of water traces
forming Si-OH groups can not be excluded. Otherwise, in
FTIR spectra there is a band assigned to OH groups at
about 3400 cm−1 (3456 cm−1 in the case of sample CS3).
The Pt-catalyzed condensation of Si-H with Si-OH groups
Fig. 4 The H-C HMBC spec-
trum of the reaction mixture,
spectral widths −0.5–6 ppm
(for proton) and −10–82 ppm
(for carbon)
G. Stiubianu et al.
leading to the siloxane chain extension by Si-O-Si bonds
is also possible. However, in IR spectra this can not be
seen due to the bands overlapping.
Based on the above mentioned results, we made a model
reaction, according to Scheme 1.
The reaction occurrence was followed by 1H NMR direct
in the analysis tube by using CA/DH=1:1.1 feed molar
ratio. In the 1H-NMR spectrum of the initial reaction
mixture (Fig. 3a), the most upfield shifted group of signals
(δ 0.0–0.12 ppm) was assigned to the methyl protons from
the (CH3)2SiO moiety, this indicating the presence of other
species besides disiloxane (i.e., trisiloxane, tetrasiloxane,
n-siloxane, the average value of n being about 0.4). The
signal corresponding to the methyl protons from (CH3)2SiH
moiety appears as a doublet, at δ 0.19 ppm, being split due
to the proton-proton coupling with the proton from the
neighbouring SiH group. The remaining protons from
1,1,3,3-tetramethyldisiloxane, those from SiH groups, give
rise to a heptet at δ 4.70 ppm. The protons from cellulose
acetate give rise to a group of sharp signals at δ 1.92–
2.09 ppm (methyl protons from the acetate groups) and
unresolved broad signals in the range δ 3.05–5.10 ppm (the
protons from the glucose ring) as was proved using H-H
COSY and H-C HMQC NMR spectra in concordance with
the model from the ref. [13–15].
By adding Karstedt’s catalyst quick modification of the
spectrum occurs (Fig. 3b). Besides peaks belonging to the
catalyst (at δ 0.09–0.35, 1.05–1.23, 2.04–2.43, 2.60–2.66,
6.95–7.29 ppm) identified by prior analysis, a modification
Silicone-modified cellulose
in the reactants spectra is evident. The most representative
consists in the Si-H peak intensity reduction.
As it can be noticed from Fig. 3c, after 24 h from the
addition of Karstedt’s catalyst, the intensities of the signals
corresponding to the protons from the SiH (δ 4.70 ppm) and
(CH3)2SiH (δ 0.19 ppm) groups decrease, whereas the
intensities of the signals corresponding to the protons from
(CH3)2SiO moieties (δ 0.0–0.12 ppm) increase, supporting
the formation of new (CH3)2SiO groups. Moreover, new
signals appear in the 1H-NMR spectrum. Based on H-C
HMQC and H-C HMBC spectra, we were able to assign
these signals as belonging to the protons from SiOH group
(δ 5.12 ppm) and from CH2 group of cellulose (δ 4.12 ppm),
involved in the Si-O-C formation.
In Fig. 4 the H-C HMBC spectrum is presented. On the
F2 axis the proton spectrum is represented, whereas on the
F1 axis the internal projection of proton-carbon long range
correlations is represented.
In this spectrum, a correlation peak appears between the
methyl protons from (CH3)2SiO group (δ 0.078 ppm) and
the 6CH2 carbon (δ 63.8 ppm) from the glucose ring,
proving the formation of Si-O-C link.
The formation of (CH3)2SiOH is supported through the
correlation peak between the protons from δ 5.12 ppm and
the methyl carbons, belonging to (CH3)2SiO group, from
δ −0.47 ppm.
The hydrogen evolving in the reaction was measured by
the method described in the experimental procedure. H2
amount measured after 250 min of room temperature
reaction was 0.14 g H2/100 g reaction mixture.
The target properties of the cellulose derivative, which
are expected to be in principal modified by crosslinking
with siloxane are surface properties. This interest is
motivated by the fact that high moisture sorption capacity
of the cellulose and its derivatives can lead to the instability
of some parameters as well as the normal difficulties of
dimensional changes [16].
Water vapour sorption capacity as well as water contact
angles were evaluated on the prepared samples and
Table 2 The water dynamic contact angles
Sample Water dynamic angles Hysteresis Hc
θ aa θrb
CR 74.8 46.8 28.0
CS1 87.8 47.3 40.6
CS2 83.4 59.2 24.3
CS3 82.9 62.0 20.9
a
Advancing (maximum) contact angle
b
Receding (minimum) contact angle
c
Hysteresis H=θa - θr
843
Fig. 5 Rapid water vapor sorption isotherms
compared with the values obtained on cellulose acetate
film considered as a model.
Contact angle, θ, is commonly used as the most direct
quantitative measure of the wetting of a solid by a liquid.
The tensiometric method was used for measuring water
dynamic contact angles, by the Wilhelmy plate technique.
Values obtained for advancing and receding contact angles
both for model and hybrid samples are presented in Table 2.
The difference between the maximum advancing and
minimum receding contact angle values known as contact
angle hysteresis has also been calculated, which is a
measure of the surface heterogeneity and roughness.
As expected, the water contact angle increases as a result
of the siloxane involving by crosslinking.
Water vapor uptake capacity for the sample at 25°C in
the relative humidity range RH 0–90% was investigated by
using the IGAsorp equipment. The vapor pressure was
increased in 10% humidity steps, each having a pre-
established equilibrium time between 70 and 80 min
(minimum time and time out, respectively). The cycle was
ended by decreasing the vapor pressure in steps to obtain
also the desorption isotherms. The drying of the samples
before sorption measurements was carried out at 25ºC in
flowing nitrogen (250 ml/min) until the weight of the
sample was in equilibrium at RH <1%. The sorption/
desorption isotherms for the hybrid samples (CS1-CS3) in
comparison with those for a pure cellulose acetate film (CR)
are presented in Fig. 5. The obtained values for the total water
vapor sorption capacity are summarized in Table 3.
Table 3 Maximum water vapor sorption values
Sample Total water sorption, % wt. (d.b) at RH=90%, T=25°C
CR 11.5
CS1 9.6
CS2 6.9
CS3 7.5
844
Fig. 6 ESEM images of the
water swollen and subsequently
lyophilised films
By siloxane insertion, the water sorption capacity of the
cellulose acetate decreases from 11.5%wt to 6.9%wt in the
case of the sample CS2 (Table 3). The slightly unexpected
variation in the trend of the sorption capacity value as well
as for the water contact angle for the samples CS2 and CS3
can be explained by the phase separation. Cellulose and
siloxane derivatives are incompatible materials due to the
high difference between their polarities. By chemical
crosslinking they are forced to co-exist in a common
Fig. 7 Stress-strain curves for the crosslinked samples as compared
with cellulose acetate model ones
G. Stiubianu et al.
structure. The reduced length of the siloxane sequence used
as crosslinking bridge (a single Si-O-Si) should reduce the
phase separation probability. However, when the siloxane
addition in the reaction mixture is higher, as in the case of
the sample CS3, a macroscopic phase separation occurs
affecting the sample’s uniformity. This is due to the
increasing siloxane chain length as a result of Si-H
hydrolysis and subsequently self-condensation as was
emphasized by NMR spectra.
Fig. 8 Breaking strength, breaking strain and modulus for the crosslinked
samples CS1-CS3 as compared with the reference sample CR
Silicone-modified cellulose
Information about the morphology of the films in swollen
state in water is provided by ESEM images shown in Fig. 6.
As can be seen, the morphology of the crosslinked films
differs from that of the cellulose acetate and modifies with
the used reactants ratio and implicitly with the composition
of the resulted network, the crosslinking degrees appreci-
ated on the basis of FTIR absorbance’s A857 (Si-O-C)/A801
(CH3Si) ratio, being closely enough for the three samples.
Sample CS3 shows the largest pores. This can be due to the
high phase separation induced by the presence of the higher
siloxane content.
By siloxane insertion, the mechanical properties of the
resulted materials were worsened (Fig. 7). Thus, both
breaking strength and modulus decrease with siloxane
content increases. Instead, by crosslinking of the cellulose
with siloxane a slight increase of breaking strain can be
noticed, this being more significant in the case of the
sample CS1 (Fig. 8). This is induced by the high flexibility
of the siloxane bond.
Conclusions
Cellulose-siloxane crosslinked structures were prepared by
the Pt-catalysed dehydrocoupling reaction. Besides cross-
linking with the formation of Si-O-C bond, the hydrolysis of
Si-H followed or not by self-condensation reactions with
siloxane chain extension also occur. The presence of the
siloxane leads to the modification of the surface properties of
the cellulose acetate. Both the wettability, expressed as water
contact angle, as well as water vapour sorption capacity
decreases as siloxane content increases. However, there is a
threshold after which these properties do not significantly
change but the phase separation at the macroscopic level
appears with undesired effects. From the physical appearance
845
point of view, the samples became opaque as the siloxane
content increases. The siloxane presence also induces
modifications in the mechanical properties.
Acknowledgments The financial support provided by the Romanian
Ministry of Education and Research under grants: PN II-PC 31-079/
14.09.2007. The authors thank Ms. Florica Doroftei for taking the
ESEM micrographs.
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