10th International Rubber Glove Conference & Exhibition 2022
SOME UNIQUE PROPERTIES OF POLYISOPRENE LATEX
ENG Aik Hwee*
K&W Training & Consulting
Malaysia
*engaikhwee@gmail.com
Eng Aik Hwee obtained his engineering doctorate in Functional Materials from
Tokyo University of Agriculture & Technology in 1994. With more than 30 years
of experience in the latex and rubber glove research, he has conducted more
than 500 hours of technical training to many companies and associations since
2015, focusing on rubber glove manufacturing related subjects. In addition, he
has also given several educational talks on medical gloves in relation to
infection control to the healthcare workers in China, India, Myanmar, Vietnam,
Japan, and Malaysia. He is a fellow of Malaysian Institute of Chemistry.
ABSTRACT
Polyisoprene (PI) latex is produced by dispersing the rubber solution in water in the presence of a
dispersing agent. Like those of emulsion polymerised latexes, PI latex has a high surfactant content
and narrow latex particle size distribution. However, the particles size of PI latex about 1 m is much
larger than those of emulsion polymerised latexes of less than 0.2 micron. The compounded effects
of these factors are lower latex stability, shorter compounded latex pot-life, and thin film formation
more difficult than those of emulsion polymerized latexes. In addition, unlike natural rubber latex, PI
latex generally requires a high amount of curing agents to achieve good tensile properties. Because
of these, polyisoprene latex is normally processed under the conditions different from those of nitrile
and natural rubber latexes. It is important to understand how each of the latex properties affects the
processing conditions such that the production conditions could be optimised accordingly. This paper
describes the effects of some PI latex properties such as latex particles size and size distribution,
surfactant content, residual solvent and the bulk rubber properties on its processability in the rubber
glove production.
INTRODUCTION
Currently polyisoprene is produced mainly from the petroleum derivatives which is
expensive and environment unfriendly. Because of these, there is rising interest in
developing bio-based isoprene from the renewable sources such as biomass. The major
companies involved in the development of bio-based isoprene include DuPont, Amyris,
Good year Tire and Rubber Company, Genencor, Michelin, BioXcell, Ajinomoto Co. Inc,
Bridgestone Corporation, PolymerOhio Inc, GlycosBio and Danisco. 1 For the rubber glove
applications, polyisoprene (PI) rubber needs to be of high cis isoprene content. There are
two methods of producing the high cis polyisoprene rubber, both of which are solvent based
process. The anionic polymerisation method produces gel-free linear PI rubber while the
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coordination polymerisation method using the Ziegler-Natta catalyst produces branched and
crosslinked polymer with gel. PI latex can be produced by dispersing the solvent solution of
the polymer from the synthesis directly in an aqueous solution of surfactant followed by the
removal of the solvent. Alternatively, the rubber solution can be prepared by dissolving the
dry PI rubber in a solvent followed by the dispersing and solvent removal processing steps.
Since the second method requires the polymer to be fully soluble in the solvent, the gel-free
dry rubber produced by the anionic polymerisation is preferred. The latex thus produced is
called artificial latex, which has several unique properties that are different from those of
emulsion polymerised latexes such as nitrile and chloroprene latexes.
The PI rubber in this artificial latex has a chemical structure similar to that of natural rubber
(NR) and hence the mechanical properties such as elasticity, are quite similar too. Because
of this, the latex has been used as an alternative material to make surgical gloves. The
demand for such gloves is driven by the concern of protein allergy of the NR gloves. It is
expected to grow at a compounded annual growth rate of 8% for the period of 2020-2030 2.
Despite the strong growth rate of PI latex consumption, the understanding on the
processability of PI latex in the manufacturing of surgical gloves is still lacking.
This paper intends to provide an understanding on some of the unique PI latex properties of
anionic polymerisation origin that could potentially affect the latex processability into
surgical gloves.
RESULTS AND DISCUSSION
Table 1 shows the properties of PI latex in comparison with those of and NR and emulsion
polymerised latexes.
Table 1: Comparison of PI latex properties with those of other latexes
Properties PI Latex Emulsion NR Latex
Polymerised Latex*
Latex particle size Large ( 1m) Small ( 0.1 to 0.2m) Large ( 0.8m)
Latex particle size Narrow Narrow Wide
Distribution
Surfactant High High Low
Residual solvent Yes No No
Rubber MWD Narrow Broad Wide
Rubber gel No High High
Rubber polarity Low Moderate High for non-
rubbers
*Carboxylated nitrile latex and polychloroprene latex
The latex particle size of PI latex is in the similar range as that of NR latex. The narrow
particle size distribution of latex is very different from that of NR which is wide. The other
properties of PI latex shown in Table 1 are also very different from those of NR latex. In the
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case of emulsion polymerised latexes, only the particle size distribution and surfactant
content are like those of PI latex while the other properties are also very different. The
effects of these differences on the PI latex processability are described here.
a) Particle Size
PI latex has a comparatively large particle size because at the initial stage of dispersing
process, the particles are large oil droplets containing solvent and gradually reduced to
smaller droplets via dispersing action. The particle size of emulsion polymerised latex, on
the other hand, is normally much smaller because the latex particles are normally grown
from the surfactant micelles, the size of which is much smaller. Sodium dodecylbenzene
sulphonate (SDBS), a common surfactant for nitrile latex for example has a micelle size of
2nm.3
A large particle size latex will have a smaller number of “layers” stacking up to form a film
than those of smaller particle size latexes. As such, any surface imperfection, such as missing
of several layers of particles during film formation will significantly impact the film integrity
of large particle latex. It is therefore more difficult to make a thin PI glove than a thin nitrile
glove without having a high reject rate. A larger particle size will also mean that the surface
area per unit volume is smaller (r2/r3 = 1/r, where r is the radius), implying that the adsorbed
surfactant per unit volume is low while the momentum during collision among the particles
is high. This results in the latex having a property of low stability particularly at elevated
temperatures where the kinetic energy of the particles is high. A control of large size
particles is important in producing polyisoprene latex of good stability. 4 A low surface area
per unit volume also reduces the migration rate of the curing agents such as sulphur and
accelerator into the latex particles. Under normal circumstances, more curing agents are
required to accelerate the maturation or prevulcanisation process. This explains why a
higher loading of curing agents is normally needed for the latex. This reduces the pot life of
the compounded latex as the prevulcanisation is more difficult to control in the presence of
high level of curing agents.
Another reason for the need of using high curing agents in PI latex vulcanisation is to reduce
the impact of latex dilution after the maturation during compounding. This is because the
latex dilution will lower the concentration of curing agent outside the latex particles, causing
the adsorbed or migrated curing agents to migrate back to the latex serum. This may result
in the reduction tensile properties, when the curing agents are marginally sufficient for
vulcanisation.5
b) Particle Size Distribution
Like those of emulsion polymerised latexes, PI latex too has a narrow particle size
distribution. The drawback of having a narrow particle size distribution is the poor film
forming properties, i.e. the latex film tends to crack easily during drying and curing as the
latex particles integration is more difficult. This also includes poorer wet gel strength and
difficult to achieve full prevulcanisation in the latex. Natural rubber latex has a wide particle
size distribution, and it generally has good film forming properties as well as good wet gel
strength. In an experiment where the small particles size latex was removed from natural
rubber latex, the latex film was found to crack easily during drying indicating the important
roles played by these particles in the film formation. 6 In wide particle size distribution
latexes such as natural rubber, the small particles could occupy the smaller space among the
large particles, leading to a closer particle packing and hence better film forming properties.
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For the narrow distribution particles latexes, the absence of small particles will lead to the
high shrinkage of the latex, because the spaces among the particles are mainly occupied by
water and, to a lesser extent, water-soluble materials, which are substantially removed via
leaching and drying, contributing to poor film forming and poor wet gel strength properties.
c) Surfactant Content
PI latex has a high surfactant content because it is needed to emulsify a large quantity of
solvent (50-60%) that contains about 10-15% dissolved PI and to stabilise the subsequently
formed PI latex, or dispersion.7 During compounding, more surfactant is added to stabilise
the latex and the dispersed or emulsified compounding ingredients. The high surfactant
content of PI latex will tend to inhibit the inter-particles integration, which leads to the poor
film forming and wet gel strength properties of the latex. It is also contributing to the high
shrinkage properties of the latex as the space occupied by the surfactant will eventually
occupied by the latex particles via re-orientation, causing significant shrinkage to the film.
High surfactant also makes PI latex difficult to achieve full prevulcanisation in latex. Natural
rubber latex contains both natural occurring stabilisers such as proteins and phospholipids
and added surfactant. Most of the natural stabilisers are not removable by leaching while
the concentration of added surfactant is typically no more than 0.5 part per hundred rubber
by weight, which is much lower than that of PI latex. As such the shrinkage is normally lower
and the negative impact on the film forming properties upon leaching and drying is not as
high as that on PI latex.
d) Residual Solvent
Rubber solvents are non-polar liquids. When present in latex, the solvent is normally
absorbed by the rubber because both are non-polar. This increases the segmental mobility
of the rubber as it becomes softer, which in turns enlarges the size latex particles. All these
reduce the stability and wet gel strength of PI latex, which normally contains some residual
solvent. The extent of impact will depend on the amount of residual solvent in the latex.
Low stability latex will lead to the formation of latex scum while poor wet gel strength will
cause the film to tear and crack during glove beading and drying, respectively.
e) Gel Content
Gel is a component in the rubber that is not soluble in a rubber solvent. It is normally due to
the presence of crosslinks or polar association in the rubber. PI latex made from the anionic
polymerisation normally contains no gel. The rubber is therefore relatively soft. Soft rubber
normally has a poorer wet gel strength because of its high tendency to deform, making
beading process of the glove difficult. It has been shown that the wet gel strength of PI latex
could be improved by a certain level of prevulcanisation at elevated temperatures. 8
However, excessive prevulcanisation at elevated temperatures may cause the latex to
destabilise and reduce the tensile strength of the film due to the lower segmental mobility
which inhibits inter-particles integration. In more serious cases, the films may also crack
during drying.
The absence of gel also makes the latex film more difficult to cure and hence requiring a
higher level of curing agents than those with gel such as nitrile, chloroprene and natural
rubber latexes. Mixing Ziegler-Natta polyisoprene latex which contains gel with anionic
polyisoprene latex has been reported to produce a synthetic polyisoprene latex that is
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excellent in film forming properties and that can provide a dip formed article not only
excellent in tensile strength and elongation, but also having a flexible texture. 9
f) Molecular Weight and Molecular Weight Distribution
Polyisoprene is a polymer with a high double bond content which is susceptible to the
oxidative degradation reactions. When the rubber molecules in the PI latex is excessively
degraded, the rubber will turn softer and may develop holes and cracks during drying and
curing. It is also more difficult for the degraded rubber to achieve good tensile properties.
Therefore, just like any other latexes, PI latex should also be stored in a cool place avoid
direct exposure to sunlight and heat. The extent of PI rubber degradation can be estimated
by determining the aldehyde content such as the 2,4-dinitrophenylhydrazine method. 10
It is well known that natural rubber has a bimodal molecular weight distribution (MWD) 11
while PI latex has a unimodal MWD12 as shown in Figure 1. While it is not clear if the
bimodal MWD contributes to the high tensile properties of NR latex film, a recent
publication demonstrated that PI latex with a bimodal MWD had a higher tensile strength
than that of unimodal MWD.13 This is probably because the rubber chains with a unimodal
MWD tend to easily become highly restricted upon vulcanisation and therefore the chains
are unable to dissipate heat generated by the rubber deformation through molecular
motion, leading to the rapture of the rubber prematurely. With the presence of low
molecular component in the bimodal MWD rubber, which has a lower glass transition
temperature (i.e., the presence of a higher concentration of terminal groups), the segmental
mobility is much improved upon vulcanisation. This is expected to better dissipate the heat
generated by the rubber deformation leading to the better tensile properties.
g) Rubber Polarity
Although both PI and natural rubber contain the non-polar cis polyisoprene as the major
component, natural rubber molecule does contain substantial amounts of non-rubbers such
as lipids and proteins. Some of these non-rubbers are tenaciously held by the rubber
molecule while others bonded to the mainchain molecule. The major component of lipids in
natural rubber has been found to be triglyceride. 14 Early 13C-NMR analysis clearly showed
that presence of ester groups, methylene group and olefinic groups that due to fatty ester in
natural rubber which could not be removed by physical methods such as repeated
centrifugations and acetone extraction. The removal of such groups from natural rubber by
chemical methods, such as transesterification or saponification, caused a drastic reduction
in the green strength.15 PI latex film is known to have a poorer tear strength than natural
rubber film. Recently, the addition of triglyceride to PI has been found to significantly
improve the tear strength of the latex film.16 This indicates that polar association of non-
rubbers is important in contributing to the good tear strength of cis polyisoprene. This has
been further demonstrated by the introduction of an ionic bond to synthetic polyisoprene
which remarkedly improved the tensile strength of the rubber. When the rubber is
deformed, the ionic bond breaks preferentially, as it is less flexible, prior to the rupture of
covalent bond, leading to the efficient energy dissipation, in addition to promoting the
orientation process of rubber chains and enhancing the stretch induced crystallisation
capability of the rubber.17
CONCLUSION
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10th International Rubber Glove Conference & Exhibition 2022
The properties of PI latex are influenced by both the bulk properties of the latex such as
particle size and size distribution, surfactant content and residual solvent, as well as the
properties of the rubber in the latex such as molecular weight, molecular weight
distribution, gel content and rubber polarity. The PI film properties can be improved by
mimicking the bulk properties of natural rubber latex and the properties of the natural
rubber molecules. Among the latex properties, surfactant content, residual solvent,
molecular weight and its distribution as well as oxidative degradation by-products such as
aldehyde should be monitored to ensure the consistency of the raw material before
processing it into the rubber gloves. Since the PI latex stability is susceptible to the
processing conditions employed, it is therefore important to also monitor the critical
coagulation concentration.18
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13. Kodemura J, Aihara S, Satoh Y, Synthetic polyisoprene latex. US Pat. Appl. 20200062873
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polyisoprene with functional carbon nanodots. Adv. Ind. Eng. Polym. Res., 2, 25-31 (2019)
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Chapter 3, Page 139. (1991)
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a) Natural rubber
104 105 106 107
Molecular Weight
b) PI rubber
Figure 1: Molecular weight distributions of a) natural rubber, and b) anionic polymerised PI
