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Study on the Properties of Natural Rubber during Maturation

Article  in  Journal of Polymer Materials · July 2009

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 Study on the Properties of Natural Rubber during
Maturation

JIE-PING ZHONG1, CHENG-PENG LI1,2, SI-DONG Ll1*, LING-XUE KONG2, LEI YANG1,
SHUANG-QUAN LIAO3 AND XIAO-DONG SHE3
1
College of Science, Guangdong Ocean University, Zhanjiang 524088,
People’s Republic of China
2
Centre for Material and Fibre Innovation, Deakin University
Geelong Campus at Maurn Ponds, Australia
3
College of Chemistry and Material, Hainan University, Haikou 570228,
People’s Republic of China

ABSTRACT

Spontaneous coagulation NR, acid coagulation NR and constant viscidity NR were prepared
and their properties were studied. The results show that acid coagulation NR can possess best
anti-aging performance, while spontaneous coagulation NR may have good mechanical properties
and high cure rate. As to the constant viscidity NR, its mechanical properties and cure rate
decreases compare to the NR without the addition of hydroxylamine hydrochloride. For all
samples, the cure process can be divided into two stages: the stage I following first-order
kinetics and the stage II following n ≠ 1 order. Besides, with the prolonging of maturation
process, the mechanical properties, the cure rate and the maximum torque of spontaneous
coagulation NR increase gradually, while the nitrogen content and the PRI decline.
KEYWORDS: Spontaneous coagulation, acid coagulation, hydroxylamine hydrochloride, maturation.

INTRODUCTION coagulation, the carbohydrates in NRL are

Natural rubber latex (NRL) is a polycolloidal
system of rubber particles as well as
nonrubber particles in an aqueous serum. In
Hevea brasiliensis, the rubber particles are
principally cis-1,4-polyisoprene enrobed in a
monolayer of protective phospholipid-protein
membrane [1-2] . During spontaneous
J. Polym. Mater. Vol. 26, No. 3, 2009, 351-360
© MD Publications Pvt. Ltd.
*Correspondence author e-mail: Iisidong2210491@yahoo.com.cn
oxidated to formic acid, acetic acid and
propionic acid etc by the bacterials and the
protein-phospholipid complex is hydrolyzed by
the enzymes[2-3], which destory the stability of
NRL. When the NRL is coagulated, some
nonrubber components may remain in the
coagulum. This makes NR differ from its
synthetic counterparts through its more
352 Jie-Ping Zhong et al.
complex microstructure[4]. For example, the
interaction of nonrubber compounds with the
polyisoprene chains is formed which will
improve the mechanical properties of NR.
Meanwhile there are some antioxidants such
as the amino acids, phenols and phospholipids
in the remained nonrubber components which
have a great effect on the stability of NR[5]. Due
to the complexity, the microstructure and
property of NR has been studied intensively in
recent years[6-10]. But the reports on the variation
of NR structure and property during maturation
are very few. In our previous work, we reported
that the molecular weight and total gel content
of unvulcanized (raw) NR increased with the
prolonging of the accelerated storage[6]. In 2002,
E. Ehabe etc also reported that the freshly
coagulated NR was variable in its molecular
weight and microstructure during maturation
and the variation was depended on the
metabolic activity of the Hevea tree[9], but they
did not study the effect of the variation on
vulcanized NR, meanwhile the effect of the
maturation on curing characteristics was not
discussed. As the past studies on NR
properties during maturation have been carried
out only with unvulcanized NR. A systematical
understanding of the effect of maturation on
unvulcanized and vulcanized NR properties is
needed. To systematically study the effect of
maturation and effectively control the variation
during maturation, we present results on the
change of the NR bulk properties, NR
vulcanizing properties and vulcanized NR
mechanical properties during the maturation.
Also hydroxylamine hydrochloride (HAHC) was
used as viscosity stabilizer to adjust the
variation during maturation and its effect was
discussed in this article.
Journal of Polymer Materials September 2009
Preparation of NR Samples
Acid coagulation NR: fresh NRL (clone PR 107)
was coagulated by acetic acid (pH=5.2) at room
temperature (Sample 1) , and then made in
crepe, granulated and dried.
Spontaneous coagulation NR: fresh NRL (clone
PR 107) was coagulated naturally and matured
for 3d (sample 2), 15d (sample 3) and 30d
(sample 4), respectively, and then made in
crepe, granulated and dried.
Constant viscidity NR: 1%o HAHC solution (w/
w=0.1%) was added into fresh NRL (clone PR
107), then the latex was coagulated naturally
and matured for 30 days (Sample 5) at room
temperature. Finally the coagulum was made
into crepe, granulated and dried.
Vulcanization recipe
Samples were prepared with this formula: NR
100.00, ZnO 6.00, S 3.5, stearic acid 0.5,
captax 0.50.
Testing of properties
The initial Wallace plasticity number (P0), the
plasticity retention index (PRI) and the Mooney
viscosity were determined according to ISO
2000 norm.
The vulcanization characteristics test was
carried out with a RHEOMETER MDR 2000
rotorless curometer made by ALPHA company
in U.S.A. The oscillating degree of the lower
cavity of the curometer is ±0.5°C, the oscillating
frequency is 1.7Hz, the experimental
temperature is 160°C.
The tensile test was conducted on an Instron
Series IX Automated Materials Testing System
(lnstron, Acton, MA) with a cross head speed of
500 mm/min and the sample length between
the jaws was 115 mm, the sample width 25 mm
 Study on the Properties of Natural Rubber during Maturation 353

and the thickness 2 mm. The measurement where M2 is the deswollen weight of the test
was done at room temperature. specimen, M1 is the weight of the swollen test
piece reaching diffusion equilibrium. (M1 −M2)
Swelling measurements
is the weight of the solvent absorbed, ρ ρ and
A test piece weighing about 0.2 g was cut from ρ s are the density of the polymer and solvent
the NR sample vulcanized for 15, 20, 30 and respectively. The crosslink density was
40 minutes respectively. The sample was determined by the Flory-Rehner equation[14].
immersed in pure toluene at 25°C to allow the
swelling to reach diffusion equilibrium [11]. At (2)
the end of this period the test piece was
removed, the loose liquid rapidly removed by where Vs is the molar volume of the solvent
blotting with filter paper and the swollen weight
and χ the interaction parameter. For NR-toluene
immediately measured. The samples were dried
system the value of χ could be taken as a
in vacuum to constant weight and the desorbed
constant (0.39)[15].
weight was taken. The concentration of the
crosslinks were determined the equilibrium
RESULTS AND DISCUSSION
swelling data [12]. The volume fraction of rubber
(Vr) in the swollen network was then calculated The effects of maturation time on the
by the method reported by Ellis and Welding[13] nitrogen contents and bulk properties
using the following equation. Fig. 1 shows the nitrogen contents of the
Vr = (M2ρ )/(M2ρ + (M1 −M2)/ρ s )
ρ
−1 −1
ρ
−1
(1) samples from NR-1 to NR-5. It can be seen

Fig. 1. Nitrogen content of natural rubber

Journal of Polymer Materials September 2009

354 Jie-Ping Zhong et al.
that the nitrogen content (corresponding to
protein content) of NR decrease from NR-1 to
NR-5. Usually, NR latex contains 1-3%
proteins. When the latex was coagulated by
acid, most of the protein was precipitated and
remained in NR. While in spontaneous
coagulation, the protein may be damaged by
the bacterial and enzymes[2-3]. So the nitrogen
Fig. 2. Bulk properties of natural rubber
highest. During the maturation, the
hydroperoxidation of polyisoprene chains and
the competing reactions of peroxy-radicals
during the maturation process could either lead
to degradation or crosslinking[16]. The increase
of P0 and mooney viscosity of spontaneous
coagulation may indicate that the maturation
process would favor the crosslinking of the long
polyisoprene chains. The results are different
from Pamela[17] etc, the reason may be the
Journal of Polymer Materials September 2009
content decreases with the prolonging of
maturation time.
Fig. 2 shows the bulk properties of NR-1 to
NR-5. It is shown that, the P0 and mooney
viscosity of raw NR decrease significantly after
the adding of HAHC. And the P0 and mooney
viscosity of spontaneous coagulation are
different temperature and environment. Besides
the PRI of NR-1 was the highest among all
samples, and the PRI of NR-3, NR-4 and NR-5
are all lower. It’s similar to the low of nitrogen
contents to some extent. PRI is used to rapidly
assess the susceptibility of a raw natural rubber
sample to heat and oxidative aging. The higher
the PRI, the better the resistance of the natural
rubber analysed to heat and oxidative aging[4,9].
As the protein in the latex is the Natural
 Study on the Properties of Natural Rubber during Maturation 355

antioxidant[5], so the higher the nitrogen content,
the better anti-aging property.
The effects of maturation time on the
mechanical properties of vulcanized
rubbers
The mechanical properties of vulcanized rubbers
are given in Table 1. From the results shown in
Table 1, the shore A hardness, 300% tensile
TABLE 1. Mechanical properties of vulcanized rubber
stress, 500% tensile stress and tensile
strength of NR-2, NR-3, NR-4 and NR-5, are all
higher than NR-1, while the elongation at break
of NR-2, NR-3 , NR-4 and NR-5, are all lower
than NR-1. Besides, the shore A hardness,
300% tensile stress, 500% tensile stress and
tensile strength of NR-2, NR-3 , NR-4 are all
higher than NR-5, and with the prolonging of
the maturation time, the shore A hardness,

Item Samples

NR-1 NR-2 NR-3 NR-4 NR-5

Shore A hardness 32 34 35 36 34

300% tensile stress,Mpa 1.53 1.76 1.75 1.76 1.56

500% tensile stress,MPa 3.17 4.03 4.06 4.64 3.42
Tensile strength, MPa 19.46 22.26 26.41 28.40 26.37

Elongation at break,% 932 848 884 868 916

The effects of maturation time on curing

300% tensile stress, 500% tensile stress and
tensile strength of spontaneous coagulation NR
increase. Generally speaking, the mechanical
properties of NR can be markedly improved
through spontaneous coagulation and the
maturation.
characteristics
The important cure characteristics are given in
Table 2. For the spontaneous coagulation, it
can be seen that the optimum cure time and
scorch time decrease with the prolonging of

TABLE 2. Curing characteristics of vulcanized rubber

Item Samples

NR-1 NR-2 NR-3 NR-4 NR-5

Optimum cure time (min) 13.25 9.08 8.32 7.78 9.18

Scorch time (min) 2.70 1.93 1.87 1.80 2.17

Maximum torque (N m) 1.57 1.76 1.85 1.94 1.77

Minimum torque (N m) 0.45 0.41 0.46 0.46 0.35

Journal of Polymer Materials September 2009

356 Jie-Ping Zhong et al.
maturation, and the maximum torque and
minimum torque increase with the prolonging
of maturation. Compared to the acid
coagulation, the optimum cure time and scorch
time of spontaneous coagulation is shorter, and
the maximum torque is higher. Besides, the
optimum cure time, the maximum torque and
scorch time of spontaneous coagulation with
HAHC is between NR-4 and NR-1, which
indicates that HAHC will prolong the scorch
and optimum cure time and decrease the
maximum torque.
As we all known, a typical accelerated sulfur
vulcanization reaction of natural rubber is
usually be divided into three stages: the scorch
Fig. 3. Vulcanization curve of natural rubber
Journal of Polymer Materials September 2009
period or induction period, curing period and
overcure period. And the vulcanizate properties
strongly depend on the vulcanization reaction,
especially the curing period, during which the
torque increases quickly.The curing period can
be divided into two stages. stage I and stage
II. The goal here was to evaluate the effect of
maturation and HAHC on the curing rate.
The rate equation of rubber vulcanization by
vulcameter can be expressed in the velocity
(V) of the torque change[18]
V = −d ( MH −Mt) / d t = k( MH −Mt )n (3)
Where MH is the maximum torque, Mt is the
torque at vulcanization time t, k is the rate
 Study on the Properties of Natural Rubber during Maturation
constant and n is the reaction order. For a first-
order reaction, eq. (3) can be written as:
In(MH −Mt ) = B − kt (4)
where B is a constant. For a reaction order
n ≠ 1, eq.(3) can be written as:
(5)
Where C is a constant.
The stage I of rubber vulcanization is generally
fitted with first-order kinetics well, and the stage
II follows the eq.(5). In this article, the curing
period was treated as two stages with different
reaction orders according to eqs. (4) and (5),
Fig. 4. Relation between ln (MH − Mt) and t for stage I of cure
357
for some understanding of the curing rate of
different NR samples.
A plot of torque against vulcanization time
for the curing period at 160°C is shown in
Fig. 4 and Fig. 5, where the values of B and k
in Table 3 were calculated according to eq. (4)
by linear regression, and the values of (1-n)
and k were calculated according to eq. (5) by
non-linear regression.
For all samples, the cure process fit the eq.
(4) and eq. (5) well, and the rate constant of
the stage I following first-order kinetics is much
faster than that of the stage II following
n ≠ 1 order. During the stage I, the rate constant
of spontaneous coagulation is higher than acid
Journal of Polymer Materials September 2009
358 Jie-Ping Zhong et al.

TABLE 3. Kinetic parameters of cure process

n=1 n ≠1
Samples
n k R n k R2

NR-l 1.00 0.2252 -0.9949 0.5415 0.0716 0.9798

NR-2 1.00 0.2995 -0.9964 -0.0288 0.0191 0.9944

NR-3 1.00 0.3703 -0.9857 -0.1429 0.0133 0.9945

NR-4 1.00 0.3930 -0.9984 0.5908 0.1112 0.9960

NR-5 1.00 0.3185 -0.9971 0.6628 0.1389 0.9862

Fig. 5. Relation between (M H − Mt) and t for stage II of cure

coagulation, which increases with the
prolonging of maturation time. And the HAHC
can decrease the rate constant obviously. The
reasons may be that during the spontaneous
coagulation, some protein is changed to the
cure accelerator, whose content increase with
the prolonging of maturation time, while the
HAHC may produce a negative effect on the
conversion. During the stage II, all the cure rates
are very low and all the n are less than 1. The
low rate constant may be due to the effect of
the aging of cross-linking network.

Journal of Polymer Materials September 2009

 Study on the Properties of Natural Rubber during Maturation
Fig. 6. Variation of crosslink density with vulcanization time
The Variation of crosslink density with
vulcanization time
Fig. 6 shows the trend of crosslink densities of
different samples, which can be divided into
two stages. At the initial stage, all the crosslink
densities go down with the prolonging of
vulcanization which belongs to the curing
period. At the second stage, all the crosslink
densities increase with the prolonging of
vulcanization which correspond to the apparent
overcure period. During the curing period, with
the prolonging of maturation, crosslink densities
of spontaneous coagulation decrease notably.
While the crosslink densities of NR-5 are close
to NR-2 and much higher than NR-4. During
the overcure period, it is interesting to find that
the enhancement trend of crosslink density
359
(represent ageing process) of NR-1 is much
slower than any other samples, which is the
proof of good anti-aging performance.
CONCLUSION
(1) During the spontaneous coagulation, with
the prolonging of maturation, the nitrogen
content and the PRI decrease, while P0 and
mooney viscosity increase. Besides, the
nitrogen content and the PRI of spontaneous
coagulation NR are lower than acid coagulation
NR, while their P0 and mooney viscosity are
higher than acid coagulation NR. With the
addition of HAHC, P0 may decreases.
(2) The spontaneous coagulation and the
maturation process may lead to the increase
of mechanical properties, while the HAHC may
Journal of Polymer Materials September 2009
 360 Jie-Ping Zhong et al.

lead to the decrease of mechanical properties. 3.
(3) For all samples, their cure process can be 4.
divided into two stages. The cure rate of the
stage I following first-order kinetics is much
5.
faster than that of the stage II following n ≠ 1
order. During the spontaneous coagulation, the
maturation process can promote the cure rate 6.
and increase the maximum torque. While the
HAHC lead to the decrease of the cure rate 7.
and the maximum torque.
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Seiichi Kawaahara, Takashi Kakubo, Naoyuki
Nishiyama, etc. J Polym Sci, 78 (2000) 1510

(4) As to the spontaneous coagulation, with
the prolonging of maturation, crosslink densities
of NR decrease notably during the curing
period. While the NR produced by acid
coagulation possess good anti-aging
performance during the overcure period.
ACKNOWLEDGEMENTS
The authors greatly acknowledge the financial
support of the National Natural Science
Foundation of China (Grant No. 50573064 and
No. 50773013), the Natural Science Foundation
of Guangdong Province (Grant No. 04011 483)
and the science and technology plan
of Guangdong Province (Grant No.
2007 A020200006-16).
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ACCEPTED : 23 September 2009

Journal of Polymer Materials September 2009

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