J. Rubb. Res.

, 10(2), 8996

REPRINT

Modied Natural Rubber Latex via in situ

Polymerization of Lignin Related Compound in the
Presence of Lignosulfonate Salt
ASRUL, M.*#, KAWAHARA, S.** AND AMIR-HASHIM M.Y.*

Modied natural rubber latex having relatively high resistance to thermo-oxidative ageing was
prepared from in situ polymerization of lignin related compounds in the presence of styrene and
lignosulfonate salt. High tensile strength retention of the modied rubber latex lms on ageing were
shown to be attainable by addition of appropriate lignin related compounds in the modication
reaction. Molecular weight and gel content determination indicated that the simultaneous effect
of rubber degradation as a side effect of modication was negligible in the batches comprising
ferulic acid and coumaric acid. The viability of the modied rubber in the use as technological
rubber latex products which requires higher resistance to oxidative ageing was assessed.
Key words: modied natural rubber; thermo-oxidative; polymerization; lignin; styrene;
lignosulfonate salt; tensile strength; molecular weight; gel content

phenylpropanoid units from three simple

monolignol compounds, namely, p-coumaryl,
coniferyl and sinapyl alcohol. In plants, these
monolignols together with hydroxycinnamate
are crosslinked to the polysaccharide wall
of the plant cell. The wall of the plant cell
consists of ferulic acid and coumaric acid with
approximately 1.5% of its total weight4. Its
abundance is one of the reasons which makes
lignin related compounds an important bioresource.

Preparation of polymeric material from

renewable resources has become an interesting
area of research13 due to the increase in
demand for newer, cheaper and more versatile
properties. The utilization of such resources
is also deemed to be important in nding
alternative polymers due to the shrinking oil
reserves and to address certain environmental
problems associated with petroleum-based
products.
One of the readily available and renewable
materials suitable for polymer application
is lignin. Lignin is a material derived from
plants, particularly in the noncellulosic
portion of wood. Lignin could be considered
as a polymeric material consisting of

Another well known and available

renewable material comes from the Hevea
brasiliensis tree, which is commonly known
as natural rubber (NR). Owing to certain
drawbacks, such as low resistance to solvent

*Rubber Research Institute of Malaysia, Malaysian Rubber Board, P.O. Box 10150, 50908 Kuala Lumpur, Malaysia
**Department of Material Science and Technology, Nagaoka University of Technology, Nagaoka, Niigata,
940-2188 Japan
# Corresponding author (e-mail: asrul@lgm.gov.my)

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Journal of Rubber Research, Volume 10(2), 2007

at 0.4 mol/kg dry rubber (TCI Chemicals,

Tokyo). The reaction was carried out at 60C
and continued for 6 h. Styrene was used in the
reaction to assist in the copolymerization of
the lignin related compound or cinnamic acid
derivatives which were found to be difcult to
polymerize as reported in the previous paper10.

and oil, the usage of NR products is limited to

certain areas. Hence, modication of NR is a
prerequisite in order to utilise this renewable
material beyond its conventional applications.
NR modications are usually associated
with changes in the unsaturation of the
ubiquitous carbon-carbon double bond present
in the rubber and also alteration of the rubber
matrix. Such modication may include graft
copolymerization and NR-polymer blending.
Both are well known techniques to incorporate
new properties in NR. The grafting of NR in
particular, has attracted considerable attention
in the preparation of grafted polymers58
and thermoplastic elastomers9. In some of
the work, consequent improvements in the
physical properties and introduction of new
properties were demonstrated.

The modication was carried out in a

series of batches using different lignin related
compounds as shown in Table 1. The resulting
modied rubber latex was then cast on glass
plates and left to stand at room temperature to
dry and lms of ca. 0.5 mm thickness were
obtained.
Fourier Transform Infrared (FT-IR)
Spectroscopy

In the present study, lignin related compounds, consisting of coumaric acid, ferulic
acid and cinnamaldehyde were utilised to attain
improvement in the inherent properties of NR
latex. Together with styrene, these compounds
were polymerised in situ in the presence
of lignosulfonate in NR latex. Physical
properties and molecular weight changes
as the effects of modication were evaluated.

FT-IR spectra were recorded with a

Perkin-Elmer Spectrum 2000 FT-IR spectrophotometer. Samples used for FT-IR measurements were dissolved in chloroform and
casted as lm onto the KBr plate. Thirty two
scans were accumulated with a resolution of
4 cm1.
Gel Content Measurement
Gel content was determined11 according to
ASTM D 3616-95, by treating the rubber with
dried toluene. The gel content was calculated
from the weight difference before and after
toluene treatment.

MATERIALS AND METHODS

Preparation of Modied Rubber

High ammonia (HA) latex was obtained
from Toptex Latex, Malaysia. Sodium
lignosulfonate (Lignotech Ufoxane 3A,
Norway) at 1% weight per gram rubber was
added as an emulsion stabilizer. The latex
was purged with nitrogen for 1 h after adding
the lignin related compound at 0.4 mol/kg
dry rubber. Potassium persulfate (Acros
Chemicals, Belgium) at 0.06 mmol/gram dry
rubber was then added to the reaction vessel,
followed by progressive addition of styrene

Gel Permeation Chromatography (GPC)

Measurement
The GPC analysis was carried out for the
soluble fraction of the rubber using a Waters
2690 Separation Module with a refractive
index detector. Two linear separation
columns (Polymer Lab, UK) were used with

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COPYRIGHT MALAYSIAN RUBBER BOARD

Asrul, M. et al.: Modied NR Latex via in situ Polymerization of Lignin Related Compound
TABLE 1. MODIFICATION BATCHES WITH DIFFERENT LIGNIN RELATED COMPOUNDS
Ingredients added (g)
HA latex
Lignosulfonate
Ferulic acid
Coumaric acid
Cinnamaldehyde
Styrene

Control batch

Batch 1

Batch 2

Batch 3

3.00

3.00
23.33

12.48

3.00

19.70

12.48

3.00

26.90
12.48

the lignin related compound in the modied

rubber.

tetrahydrofuran as eluent with a ow rate of

0.5 mL/min.

IR analysis did not provide tangible

evidence to substantiate the occurrence of
reaction or grafting of the lignin compound
with rubber. However, it is believed that in
the present investigation, indenite radical
reaction occurred between rubber, styrene,
lignosulfonate and the lignin related compound resulting in modied rubber. This
result is based on the work by Marvel et al.13
which describes the reaction of cinnamic acid
derivatives with butadiene in a free radical
initiated emulsion system.

Tensile Strength Measurement

Dumbell test pieces were prepared using the
type 2 die (ISO 37). Measurements of tensile
strength were carried out on an Instron 5565 at
25C and a crosshead speed of 500 mm/min.
Tensile test samples were aged at 70C for 22 h.
RESULTS AND DISCUSSIONS

FT-IR Analysis
Molecular Weight and Gel Content

The change in the chemical structure of

rubber after modication was analysed by IR
spectroscopy. The modied rubber exhibited
bands in the region of 1600 cm1 1700 cm1
corresponding to the non-conjugated ester
carbonyl group (Figure 1). These bands
which appeared at approximately 1600 cm1
could also be due to syringyl units of
lignosulfonate12. In comparison to the control,
more pronounced bands appeared at 1493
cm1 for the modied rubber, particularly for
Batch 1 which comprised ferulic acid. This
band may be attributed to the presence of
styrene units. A similar band appearance
was observed at approximately 1370 cm1
corresponding to phenolic hydroxyl groups.
The IR analysis indicated the presence of

Typical GPC curves for molecular weight

determination of the samples are illustrated
in Figure 2. Slight changes in the molecular
weight distribution and gel content were
observed for the batches containing ferulic
acid and coumaric acid (Batch 1 and 2). As
for the batch containing cinnamaldehyde
(Batch 3), the shift in distribution and peak
molecular weight was quite obvious. Relative
difference of gel content and molecular weight
in the modied rubber compared to the control
sample could reect rubber degradation as an
effect of free radical reaction, in particular if
molecular weight and gel content are reduced.
On the contrary, relatively higher gel content

91

Figure 1. FT-IR spectra of control and modied rubber.

Figure 2. GPC curves for molecular weight determination.

Asrul, M. et al.: Modied NR Latex via in situ Polymerization of Lignin Related Compound

and molecular weight most probably indicate

adsorption of high molecular weight material
to rubber.

fraction of the rubber, resulting in lower

molecular weight fraction. Thus, it could be
suggested that the usage of cinnamaldehyde
in the modication could inuence the
physical properties of latex lms.

In contrast to the control sample (Table 2),

slightly higher average molecular weight
(Mw), average molecular weight number (Mn)
and gel contents were observed for the batches
containing ferulic acid and coumaric acid
(Batch 1 and 2). However, the emergence of
these high molecular weight fractions in the
modied rubber could not be conclusively
deduced. The marked reduction in the Mw
and gel contents of Batch 3 containing
cinnamaldehyde indicated that degradation
occurred in the high molecular weight

Tensile Properties
The tensile properties are shown in
Table 3. In general, the modulus at 300%
and 500% elongation were fairly similar
for all the unaged samples. The modied
rubber containing coumaric acid exhibited
higher tensile strength in comparison to the
control. While the modied rubber comprising

TABLE 2. GEL CONTENT AND MOLECULAR WEIGHT

Sample

Gel contenta (%)

Mw/106

Mn/105

Mw/Mn

Control
Batch 1
Batch 2
Batch 3

52.32
48.69
51.08
23.91

2.28
2.54
2.45
1.97

6.03
7.29
7.54
4.58

3.78
3.48
3.24
4.30

Values are average of two readings.

TABLE 3. TENSILE STRENGTH PROPERTIES

Sample
Unaged
Control
Batch 1
Batch 2
Batch 3
Aged (70C/22 h)
Control
Batch 1
Batch 2
Batch 3

Tensile Stress
at Max Load
(MPa)

Modulus at
300%
(MPa)

Modulus at
500%
(MPa)

1.89 0.28
1.24 0.10
2.30 0.40
1.03 0.17

0.37 0.03
0.34 0.04
0.40 0.10
0.31 0.03

0.47 0.04
0.53 0.05
0.60 0.05
0.40 0.03

1.64 0.56
1.38 0.82
3.83 1.26
0.74 0.14

0.31 0.02
0.33 0.04
0.32 0.04
0.31 0.04

0.36 0.02
0.47 0.05
0.47 0.05
0.45 0.04

Values are average of ve readings.

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Journal of Rubber Research, Volume 10(2), 2007

It was expected that the batch containing

cinnamaldehyde had lower tensile strength
values due to the lower gel content and molecular weight which indicated the occurrence of
degradation. However, the lower tensile strength
value exhibited by the batch containing ferulic
acid was unclear. It could be hypothesised that
the presence of the lignin related compound in
the modied rubber comprising lignosulfonate
and ferulic acid might exist in three distinct
types. The rst type may possibly be in a free
form without reaction and attachment to the
rubber. The second type is probably the
reacted form with subsequent attachment to
the rubber backbone. The third represents
the reacted form but having an indistinct
attachment to the rubber. If the ferulic acid
happened to copolymerise with lignosulfonate
or styrene without attaching itself to the
rubber, it would most likely move freely and
in turn inuence the strength of the rubber
network.

ferulic acid and cinnamaldehyde (Batch 1

and 3) exhibited lower values of tensile
strength relative to the control.
In order to exclude any ambiguity, rubber
latex was blended with equivalent amount
of lignin compound as Batch 13, and tested
for tensile properties. The tensile properties
as tabulated in Table 4 indicated that the
increment in tensile strength before ageing
might be due to the reinforcing ability of
the lignin compound. Particularly, the blend
containing coumaric acid exhibited a marked
increase in tensile strength. Dissimilarity of the
blended rubber and the modied rubber was
found in the ability to resist ageing. The blended
rubber did not exhibit any increase in tensile
strength after ageing and the tensile retentions
were fairly similar to the control sample. Thus,
the stabilization effect could not be obtained
with the mere blending of the lignin related
compound with natural rubber latex.

TABLE 4. TENSILE STRENGTH PROPERTIES OF BLENDED RUBBERa

Tensile Stress at
Max Load
(MPa)

Modulus at
500%
(MPa)

(HA latex lm)

(HA mixed with ferulic acid)
(HA mixed with coumaric acid)
(HA mixed with cinnamaldehyde)

2.01 0.35
1.92 0.52
2.74 0.42
ND

0.45 0.07
0.49 0.04
0.52 0.03
ND

Aged (70C/22 h)
Control
(HAb latex lm)
Batch 1a
(HA mixed with ferulic acid)
Batch 2a
(HA mixed with coumaric acid)
Batch 3a
(HA mixed with cinnamaldehyde)

1.50 0.48
1.60 0.80
2.02 0.32
ND

0.36 0.02
0.48 0.05
0.46 0.07
ND

Sample
Unaged
Control
Batch 1a
Batch 2a
Batch 3a

Average of ve readings
HA: High ammonia
ND: not detectable (samples coagulated)

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Asrul, M. et al.: Modied NR Latex via in situ Polymerization of Lignin Related Compound

Figure 3. Tensile strength retention of control and modied rubber.

free lignin as a potential antioxidant in carbon

black lled natural rubber. Eventhough the
increase in tensile strength on ageing is
unclear, it is plausible that the presence of
lignin compound and lignosulfonate inuenced the rubber network on ageing in a similar
manner to stabilisation against oxidation.

The obvious effect of modication could

be observed in the aged samples as shown
in Figure 3, in which the modied rubber
exhibited considerable ageing resistance
relative to the control sample. The retention
in tensile strength was about 110% for the
batch containing ferulic acid and 160%
for the batch containing coumaric acid. As
expected, the modied rubber which contained
cinnamaldehyde which had undergone
degradation during modication exhibited
lower ageing resistance with about 70% of
the initial strength retained after ageing.

CONCLUSION

Modied rubber having relatively high

resistance to thermo-oxidative ageing was
prepared from in situ polymerization of
lignin related compounds in the presence
of lignosulfonate salt in natural rubber with
judicious addition of styrene. The rubber
exhibited adequate tensile properties with
enhancement in ageing resistance. Attainment
of modication could be correlated to the
relative differences in IR analysis, tensile
strength and a minor difference in the
molecular weight distribution in comparison
to the control sample. In the present study, it

It is known that a rubber subjected to

heat ageing undergoes degradation with
subsequent loss in its mechanical properties.
The ability to resist ageing as demonstrated
by the modied rubber may be due to the
synergistic effect of the lignin compound
and lignosulfonate having phenolic hydroxyl
groups which are known to act as stabilizers
against thermo-oxidation in rubber. Gregorov
et al.14 reported a similar ability of sulphur-

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Journal of Rubber Research, Volume 10(2), 2007

was also shown that only certain lignin related

compounds could be utilized to achieve the
desired stabilization against thermo-oxidative
ageing.

6. NAKASON C., KAESAMAN, A. AND

SUPASANTHIKUL, P. (2004) The
Grafting of Maleic Anhydride onto Natural
Rubber. Polymer Testing, 23, 3541.

ACKNOWLEDGEMENTS

7. FUKUSHIMA, Y., KAWAHARA, S. AND

TANAKA, Y. (1998) Synthesis of Graft
Copolymers from Highly Deproteinised
Natural Rubber. J. Rubb. Res., 1(3), 154
166.

Technical assistance rendered by Che Rasnah

and Noorshahila of the Latex Science and
Technology Unit is gratefully acknowledged.
We also thank Fauziah Abdul Rahman for the
literature search.

8. CAMPBELL, D.S. (1988) Graft Copolymers

from Natural Rubber. Natural Rubber
Science and Technology (Roberts, A.D.,
ed.), pp. 679727. Oxford: Oxford
University Press.

Date of receipt: April 2007

Date of acceptance: July 2007

9. CAMPBELL, D.S. (1988) Blends of Natural

Rubber with Thermoplastics. Natural
Rubber Science and Technology (Roberts,
A.D., ed.), pp. 327357. Oxford: Oxford
University Press.

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