Open Journal of Polymer Chemistry, 2012, 2, 144-151

http://dx.doi.org/10.4236/ojpchem.2012.24019 Published Online November 2012 (http://www.SciRP.org/journal/ojpchem)

Synthesis and Characterization of a New Cellulose

Acetate-Propionate Gel: Crosslinking Density
Determination
Patrícia Allue Dantas, Vagner Roberto Botaro*
Departamento de Física Química, e Matemática, Universidade Federal de São Carlos, Campus Sorocaba,
Rodovia João Leme dos Santos, (SP-264) Km 110, Bairro do Itinga, Sorocaba, São Paulo, Brasil
Email: *[email protected]

Received September 1, 2012; revised October 5, 2012; accepted October 16, 2012

ABSTRACT
Crosslinking is one of the most commonly reactions used to improve the physical properties of cellulose derivatives.
Cellulose Acetate Propionate (CAP) is a commercial ester obtained as a cellulose derivative and it can be used as basis
for the synthesis of crosslinked chains as described in this work. Typical used crosslinkers are di-functional compounds,
such as dianhydrides or diisocyanate. The formation of polymeric 3D structures as described in this work occurs typi-
cally by the reaction of the linear chains bearing free OH groups with crosslinking agents such as dianhydrides. These
reactions are used to make a very absorbent material, typically a gel. The syntheses were performed in homogeneous
medium with acetate propionate in a very dry atmosphere by employing PMDA (Pyromellitic Dianhydride) and BTDA
(3,3’, 4,4’ Benzophenone Tetracarboxylated Dianhydride) as crosslinking agents in a reflux system. TGA analysis has
shown the different thermal stability of the gels when compared with CAP. Typical TGA curves have demonstrated the
lower stability of the crosslinked chains when compared to CAP as consequence of esther linkages formed in the gels
structures. The Mc, which is the value for the molar mass between crosslinkings points in 3D structure, was determined
according to Flory-Rehner theory. This important parameter has demonstrated greater reactivity of PMDA in compari-
son with the BTDA in the reactions conditions’ employed in this work.

Keywords: Gel; Flory-Rehner; Crosslinking; Cellulose Acetate Propionate; TGA

1. Introduction There are several cellulose derivatives as for example

esters, but only three have commercial importance: cel-
Chemical modifications of conventional organic poly-
lulose acetate (CA); a mixed Cellulose ester of Acetate
mers are important techniques to explore new materials
and Propionate (CAP) and a mixed of cellulose acetate
having prospects of improved properties [1,2]. In many
and butyrate (CAB) [5]. CAP is a commercial ester ob-
of the cases cited in the literature, the crosslinking reac-
tions are used to improve the properties of polysaccha- tained from modification of cellulose and it can be used
rides, forming three-dimensional polymeric networks to synthesis of network chains, as described in this work.
that swell rapidly, absorbing a large amount of water [3]. The formation of esters occurs when the non modified
On account of this, a great demand for research, are be- hydroxyl groups of the cellulose chains are replaced by
ing conducted seeking the introduction and the develop- acyl groups. Reducing the amount of OH groups on the
ment of renewable polymers. In this sense, Brazil is a cellulose chain leads to the formation of derivatives read-
country with predominantly tropical climate and vast ily soluble in conventional solvents. The modification of
area for the cultivation of agriculture and forestry; has a cellulose normally forms a less crystalline material due
great production and supply of cellulose, favoring the re- to reduced intra and intermolecular hydrogen bonding.
search in this area. Cellulose is one of the most abun- The nature of the substituent group and the extent, to
dant raw materials in our country, proof of this is that which the hydroxyl groups are replaced, can provoke
Brazil is the fourth biggest producer of cellulose, and different thermal, mechanical and physical properties in
which in 2010 had 2.2 million hectares of planted forests the cellulose derivatives [5].
in national territory [4]. The formation of polymeric network occurs with the
crosslinking of the linear chains bearing free OH groups
*
Corresponding author. and crosslinking agents as dianhydrides [6]. The proper-

Copyright © 2012 SciRes. OJPChem

 P. A. DANTAS, V. R. BOTARO 145

ties of a polymer network are determined by the structure tion in homogeneous medium and at room temperature.
and by the length of the segments between the junction In addition, the gel can be easily purified and presents a
points in the 3D structure of gel [7]. In the polymerize- great potential for swelling in various solvents. There are
tion, the number of reactive groups of a macromolecule great possibilities for use of gels in drug controlled re-
is growing with the increase in the number of branches, lease systems that are being investigated.
leading to the formation of complex networks. The
branch of the structure can be precisely controlled and 2. Experimental
network growth is limited only by the volume of the re-
2.1. Materials
action mixture [8]. The swelling balance depends on the
entropy of heat of dilution, the dilation and the entropy of A cellulose acetate Propionate (CAP) with average Mn
polymer networks. The swelling balance for a system of ~25,000 with ~2.5 wt% Acetyl, ~2.6 wt% Hydroxyl and
polymer-solvent is the density function of interweaving ~45 wt% Propionyl, was provided by SIGMA-ALDRI-
[9]. The swelling has a theory that was developed by CH®. Pyromellitic Dianhydride (PMDA) and 3.3, 4.4
Flory and Rehner in 1943, which considered that the Benzophenone Tetracarboxylic Dianhydride (BTDA) with
phenomenon of swelling is basically side by three control 96% and 97% of purity respectively, both provided by
forces: 1) The variation of entropy by mixed solvent- SIGMA-ALDRICH® were employed as crosslinkers. The
polymer; 2) conformational entropy variation caused by solvent was acetone (propanone) with 99% of purity. The
the reduction in the number of conformations of chains, catalyst was the triethylamine with a minimum purity of
in consequence of their stretch and 3) Enthalpy of mixing 99%. CAP was placed in the vacuum Oven under 625
solvent and polymer. Thus, the swelling of a given poly- mm Hg vacuum, by 5 h at 110˚C in order to eliminate
mer is dependent on the degree of interaction between any trace of water. The total absence of water is extre-
the polymer and solvent molecules, which can be refer- mely important because crosslinking agents react quick-
enced with the solvent/polymer interaction parameter, χ ly with water and turn into their respective acids, inhibit-
pointed out by Flory, 1943 [6]. ing the reaction with OH groups present in the substrate.
The research on superabsorbent material began in
1960, and continues until the present day. Many poly- 2.2. Degree of Substitution (DS) Determination
mers have been employed in the production of gels and (ASTM D 871-96)
generally three classes are important: 1) natural [6]; 2)
0.5 g of CAP samples were accurately weighted and then
polyacrylamide [9] and 3) polyacrylate polymers [9-11].
transferred to a 250 mL flask. 20 mL of 75% aqueous
The applicability of these materials depends mainly on
ethanol were added to each sample and then each one
its ability to absorb water or fluids. The ability of swell-
was heated for 30 min at 60˚C. Then, 20 mL of 0.49 N
ing is normally associated with the presence of hydro-
NaOH solution was added to each sample and again,
philic groups like -OH, -CONH-, -COOH, -SO3H and
heated at 60˚C for 15 min. The same procedure was also
-CONH2 in its polymer network [12].
done for a control system (not containing CAP). The
The synthesis of gels can be carried out by the same
flasks were stoppered and allowed to stand at room tem-
methods used for the synthesis of polymeric materials in
perature for 72 h. The excess of alkali in the sample and
general. Crosslinking reactions are made by introducing
in the control was titrated with HCl (0.5 M) using phe-
one or more multifunctional monomers during the
nolphthalein as indicator. An excess of the acid was
growth of the polymeric chains or between two or more
added (1 mL) and the alkali was allowed to diffuse from
polymeric chains. The polymerization reaction can be
the regenerated cellulose overnight. The disappearance of
initiated using radicals generated by heating, radiation
the pink color indicated complete neutralization of the
ionization, by reducing agents or oxidizing [7]. The syn-
alkali. The small excess of acid was then back titrated
theses of new products with 3D polymeric structures in
with sodium hydroxide to a phenolphthalein end-point
this work are quite new. Typically, the products are
[7].
formed at room temperature its development based on
the reaction of the linear chains of CAP bearing free OH
2.3. Gel Synthesis
groups with crosslinking agents as dianhydride. These
reactions form of a very absorbent material, typically a A solution of CAP in acetone was prepared by adding c.a.
gel. The syntheses were performed in homogeneous me- 1.00 gram of the cellulose derivative in 10 mL of solvent
dium with acetate propionate in a very dry atmosphere by under vigorous agitation. The purified anhydride was
employing PMDA (Pyromellitic Dianhydride) and added also under agitation. The amount of modifying
BTDA (3,3’, 4,4’ Benzophenone Tetracarboxylated Di- agent was the same as the molar quantity of free OH
anhydride) as crosslinking agents. One of the advantages groups, considering the DS of CAP determined experi-
of the process is the possibility of carrying out the reac- mentally. Finally 1% of the catalyst in relation to CAP

Copyright © 2012 SciRes. OJPChem

146 P. A. DANTAS, V. R. BOTARO

mass was added. The reaction was processed in a closed 2.4. Polymer Characterization
reflux system under N2 (g) atmosphere, at 76˚C until
there was visible formation of a solid in the medium. The Fourier Transformed Infrared spectroscopy (FTIR) was
gel was placed in a dish and dryed in an oven at 60˚C for performed by using KBr pellets methodology on a Nico-
96 hours. The gels obtained with BTDA and PMDA let IR 200®. A total of 25 cumulative scans were taken
were named CAPB and CAPP respectively. All gels were with a resolution of 2 cm−1 in transmission mode. The
cleansed exhaustively to remove all excess of unreacted thermo gravimetrical analyses (TGA) were carried out
reagent and catalyst by employing a Soxhlet with acetone with in a TGA Q50-TA Instruments at heating speed of
for 45 hours. Finally, the products were washed for 18 20˚C·min–1 at room temperature up to 800˚C, under N2
days in ethanol at room temperature. The gels were dried atmosphere (100 mL·min–1). SEM analysis: samples of
for 48 hours at 50˚C. the gels were completely dried in an oven and after
Scheme 1 Shows partials structures of CAPP and treated by employing a Sputter Coater equipment of Bal-
CAPB. Tec. Another details included the use of gold and Sput-
tering with Argon, SCD 050. The analysis was per-
formed in the scanning electron microscope Philips
XL30 model.

2.5. Degree of Swelling in Equilibrium and

Solubility Parameter of Gels
The degree of swelling is expressed by Q parameter,
which is also called coefficient of swelling in balance
and is determined experimentally by Equation (1)
Q   mi  mo  mo x  (1)
Were: mo = dry polymer mass; mi = polymer mass af-
ter immersion; ρ = solvent density.
(a)
2.6. Determination of Density of Crosslinks
The crosslink density was calculated according to Equa-
tion (2):
   ln 1  Vr   Vr  Vr 2  V 1Vr 1 3  Vr 2  (2)
 is the density of crosslink that corresponds to the
number of actual chains per unit of volume. Mc and  are
the average molar mass between the crosslinkings and
the density of the polymer respectively. Specimens with
a mass of about 0.400 g, cylindrical shape were cut and
immersed in solvents with different solubility parameters:
[ethyl ether 7.4 (cal/cm3)1/2], [ethyl acetate 9.05 (cal/
cm3)1/2], [benzene 9.2 (cal/cm3)1/2], [chloroform 9.3
(cal/cm3)1/2], [acetone 9.9 (cal/cm3)1/2], [ethanol 26.2
(cal/cm3)1/2] and [water 23.4 (cal/cm3)1/2]. The speci-
mens remained submerged in 50 ml Falcon tubes in the
total absence of light to achieve equilibrium, according to
ASTM471 and ASTM 1239-55 [12,13].

3. Results and Discussion

The determination of the DS and wt% Acetyl of CAP has
confirmed the values informed by suppliers. The stan-
(b)
dard deviation for the number of three analyses was
Scheme 1. Partials structures of CAPP (a) and CAPB (b). 0.11.

Copyright © 2012 SciRes. OJPChem

 P. A. DANTAS, V. R. BOTARO 147

3.1. FTIR Analysis 70

New bands in gel structure gave evidence of a new mate- 60

rial formation [2,14]. The typical spectrum of the CAPP
1746
shows that the product is composed of a polymer net- 50

work formed with new covalent bonds and aromatic CAP

CAPB
group inclusion in 3D structure. The total absence of 40

T%
802
axial deformation of NH salt of tertiary amine at 2680
30
cm–1 is an evidence of the washing process efficiency. 3485
1083

Figure 1 shows typical FTIR spectra of CAP and CAPB 20

BTDA

gel.
Some bands are typically important in a comparative 10
point of view; the 807 cm–1 band are assigned to angular
vibration out of the plane of C-H bonds of the aromatic 0
4000 3500 3000 2500 2000 1500 1000 500
ring present only at the CAPP structure. The formation of
new esther linkages after crosslinkings provokes modify- (cm ) -1)
(cm
-1

cation at the bands in the region of 1083 and 1740 cm–1 Figure 2. FT-IR spectra of BTDA, CAP and CAPB.
related to typical axial symmetric deformation of C-O-C
and axial deformation of C=O from esther respectively. axial OH deformation is related to intermolecular hydro-
Other important differences include the angular vibra- gen bonding which is less intense in the gel due to modi-
tions out of the plane of CH bonds of the ring to 753 fication reactions. The formation of new esther linkages
cm–1 and the axial deformation of C-O in the aromatic after crosslinkings provokes modification at the bands in
acid ester 1246 cm–1 visible in CAPP structure. Finally, the region of 1083 and 1740 cm–1 related to typical axial
another important observation is the change at the bands symmetric deformation of C-O-C and axial deformation
of OH groups. In CPA spectrum the absorption band of C=O of esther respectively.
occurs at 3480 cm–1, typical of aliphatic hydroxyl groups.
In the gel, the OH groups are, to a large extent, groups of 3.2. TGA analysis
carboxylic acids formed following the crosslink of the Figures 3(a) and (b) clearly shows that the gels have
polymer chains of CAP. In this case, absorption occurs in lower thermal stability when compared to the CAP. The
these hydroxyl 3440 cm–1 with typical enlargement ex- ester bonds formed in the gel formation process are less
pected for carboxylic acids. stable and are more easily broken by thermal degradation.
Figure 2 shows comparative FTIR Spectra of CAPB, This behavior has been observed for other gels obtained
crosslinker and CAP. in our research group and published in the literature [6,
In a general way, the same discussions presented to 7,14].
Figure 2 for CAPP may be considered in the discussions TGA and mainly DTG curves of gels of CAPB and
for the CAPB. An important band at 3485 cm–1 due to the CAPP show two mass loss events. The first event was
attributed to the degradation of the cellulose chain re-
60
placements and the second one was attributed mostly to
55 the degradation of the polymer chain of cellulose acetate
50 PMDA propionate. When the maximum degradation tempera-
45 tures is observed, it was possible to conclude that CAPB
40 has a degradation temperature slightly higher when com-
35
pared to gel CAPP. The presence of a greater quantity of
CAPP
ester links in CAPP decreases the thermal stability of
T%

30
gels, because these links are less stable as pointed out
25 807
PAC earlier. These results are in accordance to results obtain-
20
3456 ed to Mc values in Table 1.
1740 1083
15

10 3.3. Solubility and Density of Crosslinkings

5
4000 3500 3000 2500 2000 1500 1000 500
The solubility parameter is an important result which
-1 -1
characterizes the miscibility of a system under the quali-
(cm
(cm ) ) tative aspect. Figures 4(a) and (b) show the solubility
Figure 1. FT-IR spectra of PMDA, CAP and CAPP. parameter of CAPB and CAPP respectively.

Copyright © 2012 SciRes. OJPChem

148 P. A. DANTAS, V. R. BOTARO

110 3,0
3.0

100 CAP
2.5
2,5 CAP
90

der. (% / C)
80
2,0
2.0

o
CAPP

der.(%/˚C)
70
CAPB
60 1,5
mass%

1.5
CAPB
50

first
40 1,0
1.0

Flrst
CAPP

mass.
30
0,5
0.5

mass.
20

10 0,0
0.0
0
0 100 200 300 400 500 600 700 800 900 0 100 200 300 400 500 600 700 800 900
o
T C o
T˚C T˚C
T C
(a) (b)

Figure 3. TGA and DTG analysis from CAP, CAPP and CAPB gels.

7 10
9,56
6,53 9
6
8

5 7
QMax (cm3/g )

6
g
︶

4
3/
m 5
c
3
4
︵

x
a
M
Q
2 3

2
1
1

0 0
5 10 15 20 25 30 5 10 15 20 25 30
,
c
a
l
/
c
m
3

1
/
2

 (cal / cm )
3 1/2 ︵ ︶

(a) (b)

Figure 4. Solubility parameters of CAPB(a) and CAPP(b).

Table 1. Experimental data according to Flory-Rehner theory.

Gel CAPB CAPP

Percentage of absorption in the equilibrium (%) 588 1062

Coefficient of maximum swelling, Qmax (cm3/g) 6.5 9.6

Reduced Volume, RV 0.2 0.14

Density of the gel, ρ2 (g/cm3) 1.5 1.1

Solubility parameter, δ2 (cal/cm3)1/2 6.5 9.6

Interaction parameter polymer-solvent, χ 0.34 0.34

Density of crosslinkings, ν (g/cm3) 5.82 × 10–4 2.38 × 10–3

Average molar mass between crosslinkings points, Mc (g·mol–1) 2596 589

Average numbers of repeating units between crosslinkings points 4.8 1.1

Copyright © 2012 SciRes. OJPChem

 P. A. DANTAS, V. R. BOTARO 149

According to Santos [12], the polymer-solvent inter- linkers employed in the modification reactions (scheme 1)
acttion parameter, can be decomposed into its entropic shows that the reagent PMDA is less bulky and may have
component (s) and enthalpy (h) components according less steric hindrance and can be more reactive to free
to the Equation (3) hydroxyl groups present in the structure of the CAP. Fi-
  h  s (3) nally, CAPP has both a higher density of crosslinks and a
higher Qmax. The increase of crosslinkings agents in-
In the maximum swelling conditions, the contribution creases significantly the character nonpolar of the gel.
of h is minimal and the interaction parameter value is The presence of aromatic rings, typical of the structure of
practically equal to the entropic contribution. The litera- anhydrides, significantly affects the power of swelling of
ture has used the value of 0.34 to s [14]. Table 1 show gels for the solvents employed.
the data of Flory-Rehner obtained for CAPP and CAPB
gels. 3.4. SEM Analysis
The swelling theory, developed by Flory and Rehner
in 1943, considerer that the phenomenon of swelling is The results of SEM show surface changes that occurred
controlled primarily by three forces: 1) the entropy varia- after the crosslinking reaction as indicated in Figures 5
tion by solvent-polymer mixture; 2) the conformational and 6.
entropy variation caused by the reduction in the number Observing the SEM images of CAPP and CAPB it can
of conformations of chains, in consequence of their be observed the gels has no well-defined contours. In the
stretch; and 3) the enthalpy of mixing solvent and poly- same way, has no preferred geometric shape, does not
mer [5]. The swelling of a given polymer is dependent on have a homogeneous surface, and has several fractures in
the degree of interaction between the polymer and sol- your outline and also on its surface.
vent molecules, which can be referenced with the pa- Gels have also been obtained in form of films. The
rameter of polymer-solvent interaction. The Mc, which is Figures 7 and 8 show the SEM analysis of films of CAPP
the value of the molar mass between crosslinkings points and CAPB respectively.
in 3D structure of the gel, reveals how much the gel is Figures 7 and 8 show that both films have no homo-
crosslinked. Some important points can be considered in geneous surfaces with internal fibrous appearance. Addi-
relation to the data presented in Table 1. The CAPB and tionally, internal structures show extremely porous mate-
CAPB gels have showed great power absorption and rial which explains the great absorption power in sol-
swelling in water with typical values above 500% and vents presented as percentage of absorption in the equi-
greater is the absorption of gel prepared with the librium (Table 1).
crosslinker PMDA. The interesting power of swelling of A comparative analysis of Figures 7 and 8 shows the
gels is also expressed by the variable Coefficient of gels CAPP and CAPB present some distinct characteris-
maximum swelling, Qmax. The Density of crosslinking tics. CAPP presents less gel surface homogeneity. This fact
and average molar mass between crosslink points show can be related with the highest degree of crosslinking and
that the gel prepared with PMDA has a greater number of greater reactivity of PMDA as shown in Table 1. Greater
crosslinkings suggesting greater reactivity with this agent. crosslinking leads to a more rigid material and greater dif-
A comparison between the structures of the two cross- ficulty in formation of homogeneous surface after reaction.

(a) (b)

Figure 5. (a) SEM analysis showing a particle of CAPB. (b) A detail of Figure 5(a).

Copyright © 2012 SciRes. OJPChem

150 P. A. DANTAS, V. R. BOTARO

(a) (b)

Figure 6. (a) SEM analysis showing a particle of CAPP; (b) A detail of Figure 6(a).

(a) (b)

Figure 7. (a) SEM analysis showing details of CAPB film.

(a) (b)

Figure 8. (a) SEM analysis showing details of CAPP film.

4. Conclusion and TGA methods. Reduction of hydroxyl groups in

PMDA and BTDA were used as a crosslinker to cross- FTIR spectra and the presence of typical aromatic bands
link a commercial esther derivative of cellulose, CAP, in were observed after modifications. The ester bonds for-
this study. By changing the crosslinker agent in a homo- med in the gel formation process are less stable and are
geneous reaction, CAP gels with different degree of cro- more easily broken by thermal degradation as showed by
sslinking density have been prepared successfully. The TGA analysis. The swelling theory, developed by Flory
crosslinked products have been characterized by FTIR and Rehner in 1943, has successfully employed in order

Copyright © 2012 SciRes. OJPChem

 P. A. DANTAS, V. R. BOTARO 151

to calculate de Mc data. The Density of crosslinking and 458. doi:10.1007/s10570-005-2203-2

average molar mass between crosslink points show that [6] V. R. Botaro, V. Alvarenga and V. A. Leão, “Swelling
the gel prepared with PMDA has a greater number of Kinetics of Hydrogels of Cellulose,” Polymeric Materials:
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456.
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[7] V. Oliveira, “Synthesis and Characterization of Cellulose
5. Acknowledgements Acetate Gels Crosslinkeed with Pyromelitic and 3 3’ 4 4’-
Benzophenone Tetracarboxylic Acid Dissertação de Mes-
The authors are extremely grateful to FAPESP-project JP trado REDEMAT,” Ouro Preto, Brasi, 2008.
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