Liquid Natural Rubber: Preparation and Application

Ibrahim Abdullah

Chemistry Department
Universiti Kebangsaan Malaysia
43600 UKM Bangi, Malaysia

ABSTRACT

Liquid natural rubber (LNR) is a modified form of natural rubber (NR) with a shorter
polymeric chain. The preparation of LNR can either be done via mechano-oxidation or redox
reaction or photosensitized oxidation. Mechanooxidation, being the earliest method to be
developed, is still widely used with some modifications. Pilot plant scale has already been
tested on two redox reaction methods using phenylhydrazine-air and sodium nitrite/chlorite -
hydrogen peroxide as oxydo-reducing couples. Photosensitized oxidation of NR is made
possible by using a ph<;>tosensitizer which is active in visible light and able to induce
degradative oxidation. Research in the field is quite active but so far no method has developed
into a commercial scale. TIle short nature of the LNR polymeric chain allows many chemical
modifications possible and thereby enlarging the field of applications of NR. The potential
applications of LNR are in the preparation of themloplastic NR, adhesives. binders, bitwllen,
low hardness vulcanizates, paints and varnishes.

INTRODUCTION

Chemical modifications of NR vary rrom very low mole percent in the incorporation of
antioxidants and cross-linkings without affecting the physical properties, to a more than 50
mole percent in the epoxidation, hydrogenation, cyclization etc., and may result in changing
the nature of the polymer from a rubber to a more plastic-like or resinous materials. Some of
the modified forms of NR are hydrogenated, hydrohalogenated, chlorinated, polymer grafted,
epoxidised, cyclised and depolymerised or liquid NR. Liquid NR (LNR) is a product of NR
depolymerization and as such it is not in a true sense a modified NR. The LNR has received a
lot of attention lately due to the high potential as a starting material for a wide range of
products.

The physical properties of processed rubber is greatly influenced by the molecular weight and
molecular weight distribution of the vulcanised NR. Uniformation of the molecular weight
through mastication which result ill the chain degradation is usualIy done prior to processing

K.P. Ghiggino (Ed.)

Progress in Pacific Polymer Science 3
© Springer-Verlag Berlin Heidelberg 1994
352
with the aim of facilitating easy processing. addition or incorporation of fillers. vulcanizing
additives and other chemicals. Molecular weight reduction mainly concerns NR only as in the
case of synthetic rubber the molecular weight is well controlled during production. and only a
specific molecular weight rubber is produced for certain application. A method of controlling
the molecular weight of NR would be advantageous as it allows a greater flexibility Oil the
production of various grades ofNR.

Liquid rubber is defmed in the UNID0 1 report s a class of elastomers or elastomer precussors
that can be poured or pumped at temperature below 100°C without the assistance of an
external medium. Frequently liquid natural rubber (LNR) can be defmed as a form ofNR with
a similar microstructure but shorter polymeric chain and with molecular weight, Mw, lower
than lOS. A much shorter polymeric chain LNR is more open to structural design such as
a dditlon cHona I groups or actIve
' 0 f new fun' . . groups onto th e cam:
h' 123
.•

PREPARATION OF LIQUID NATURAL RUBBER

According to RAPRA, most of the LNRs produced in recent years belong to the first
generation liquid rubber which implies the lack of active terminal groups on the polymer
chain. The nature of LNR is greatly influenced by the manner in which the NR is degraded
leading to depolymerizatlon. Mechanochemical oxidation, redox reaction and photosensitized
oxidation are the three general techniques of molecular weight reduction of NR exploited
thus far. Other methods like exposing NR to high energy radiation are found to be not very
suitable on a large scale and thus are not exploited.

Mechanochemical Oxidation

Mechanical degradation, nomlally known as mastication, of NR in air is the earliest known

method of molecular weight reduction process tried and still in use till the present. Although
it is far from efficient but is the most convenient, easy and free from any kind of chemical
complexities. The earliest reported patent on the depolymerization of NR to LNR is by
Hardman et. al in 19444. They described a process of making articles such as drums, cans,
tauks and pipes from depolymerised natural rubber (DPNR) via casting-vulcanization process.
The degradation apparently occurs during the extensive mastication in air at high temperature
around 300°C for 2-4 hours.

In 1952, the British Rubber Producers' Research Association (BRPRA) had reported a detail
method ofNR depolymerisation through masticationS. TIle stages of the process are;
- mastication in a mill or internal mixer until the viscosity drops to about 20 Monney;
- further milling with a Z-blade mixer at 120 - 140°C for 6-8 hours until the viscosity
drops to 50.000 -70,000 poises and finally;
 353
-the semifluid material is heated at 250 to 300°C for about 2 - 2.5 hours until the product
reaches a viscosity of the order 2500 poises.

Chloride Lorival of United Kingdom later adopted this method to produce depolymerised
natural ruber in 1953. This method of depolymerization is still in use today with some
improvements. Instead of milling at high temperature. the mastication is done in an intemal
mixer at about 120°C in the presence of a peptizer over a long period 6 . Some of the
commonly used peptizers are hydrazine derivatives and organic sulphur like thio-f3-naphthol,
pentachlorothiophenol and dibenzoyl disulphide. Being easy to process without any complex
chemistry is an advantage but it is overshadowed by its high cost as the method consumes too
much energy. However the method is largely employed to produce depolymerised NR for
in-house use only.

Redox Reaction

The chain degradation in this method involves catalytic oxidation of rubber in an oxidising
agent such as air and a catalyst or a reducing agent. The first patent on catalysts for the
oxidation of rubber was by Stevens who patented the use of lead, cobalt and manganese
!inoleates 7. However this process was not further developed and soon discarded in favour of
the simpler mechanochemical oxidation method.

In 1984 UNIDO has set up a pilot plant to produce LNR in Ivory· Coast. The aim of the
project is to select the best and most promising teclmique of LNR generation and also to
evaluate the industrial applications base on physical properties and economics. The
technology adapted is based on the process developed by the Rubber Research Institute of
Africa (IRCA) and patent registered by Institute Francais du Caoutchouc. FranceS. TIle
reaction involves the use of an oxydo-reducing couple of oxygen-phenylhydrazine to
depolymerise natural polyisoprene in latex phase. TIle depolymerization mechanism is as
shown in Figure I.

In the study. the nature of the latex, the phenylhydrazine concentrations. temperature and air
flow were the parameters investigated in detail. As shown in Table I, the degree of
polyisoprene degradation depends on the concentration of phenylhydrazine relative to rubber.
The other reaction conditions were found to be not very sensitive and thus the reaction
conditions adapted were:
Latex concentration - 30% rubber content
Phenylhydrazine - 8 x 10.4 mole Ig of rubber
Temperature - 65°C
Effective reaction - 24 hours
354

Although the project seems to be quite promising but it never proceed any further due to the
highly toxic nature of the phenylhydrazine and the search for an alternative reducing agent is
still very active.

~NHNH2
Q.zIalrl

~
>
o

[ R-ctr+L
o
II
C-R II
0
l
Figure 1 : Depolymerization mechanism of 1A-cis-polyisoprene

Table 1: The influence of phenylhydrazine concentration on the molecular

weight of LNR or degree of depolymerization

Phenyl hydrazine (mole/g rubber) Mol. wt. (Mv) of LNR

17,000

12,000

8,000

12x 10.4 8,000

The Malaysian Rubber Producers' Research Association (MRPRA) in 1985 9 has developed a
method of generating LNR base on a redox reaction on NR in latex phase. The reducing agent
 355
is either sodiwll chlorite or sodium nitrite and the oxidising agent is hydrogen peroxide. The
depolymerization seem to occur efficiently at around pH = 7 and the LNR produced has a
wide spread of molecular weights, 20,000 to 150,000 depending on the peroxide
concentration. The reaction is believed to involve singlet oxygen which attack the double
bonds to form allylic/ hydroperoxides attached to the polymer chain 10. Subsequent
decomposition of these hydroperoxides leads to chain degradation.

CH3 CH3 CH3

I 02 I I
--CH2 - C = CH - CH2 -- ------ > --CH2 - C - CH= CH -- + -- CH = C - CH - CH2--
j
I o
o
I I
1
OH OH

hydroperoxides decomposition and

subsequent chain degradation

Photosensitized Oxidation

The photochemical reaction occurring in natural rubber on exposure to visible light is most
likely to be sensitised by any reagent present in it as the polyisoprene molecule does not
absorb any light at that frequencies. It was reported that the depolymerization of NR was
found to be quite significant when rubber solution in the presence of nitrobenzene was
exposed to sunlight l2 . As discussed by Rabek II the most probable reaction pathway is the
abstraction of hydrogen by the excited nitrobenzene from the polyisoprene chain producing a
macroradical which proceeds to oxidation and degradation.

Ravindran et a1. 13 had reported the generation of hydroxyl- terminated LNR by exposing the
rubber solution to UV light or sunlight in the presence of hydrogen peroxide. The degree of
depolymerization of rubber was found to be about the same in UV- light and in sunlight and
the rate was proportional to the exposure time. The suggested mechanism is as shown in
Figure 2.

In our study on the photostability of NR towards visible light, we observe only a slight
degradation of rubber on exposing the solution to light. However in the presence of a
photosensitizer, chain degradation on a massive scale is recorded. One set of photosensitizer
used are benzophenone, flavone and xanthone which have a common carbonyl fllllctional
14
group .

These molecules have an absorption shoulder at around 360 nm due to the (mt)" transition l5 .
On absorption of light energy, excitation of the molecule into the singlet excited state, l(n7t)·
356
" *
occurs which then crossover into the triplet excited state. ~(nn) . Interaction of this state with
the polyisoprene chain. leads to hydrogen abstraction and an isoprenyl macroradical is
formed. Molecular rearrangement of the macroradicalleading to chain scission subsequently
occurs. However. in the presence of oxygen. the radical will be oxidised to form
hydroperoxides which on decomposition results in further chain degradation. Thus an
increase in the degree of depolyrnerization will be observed in the undegassed sample. The
reaction mechanism concluded is summarised in Figure 3.

Iw
,----
----~

CH 3 CH 3
I I
- CH 2 - C = CH - CH 2 - CH 2 - C = CH - CH 2 -

l·OH
CH 3 CH 3
I I
-.CH 2 - C = CH - CH 2 - OH + .CH 2 - C = CH - CH 2 -

CH 3
I
HO - CH 2 - C = CH - CH 2 -

Figure 2 : Photodepolymerization of polyisoprene in the presence of H202

Recombination of radicals forms crosslinks among the chains and will give rise to gel. As
expected the yield of gel increases with the increase in the concentration of rubber. The
relative effectiveness of the photosensitizing ability of these molecules are of the order
benzophenone > xanthone> flavone.

As discussed above, the main primary step is hydrogen abstraction and hence the different
a bilities of these molecules to sensitize degraclation of the polyisoprene chain lie in their
efficiency to promote hydrogen abstraction. Consequently the interaction between the \nn) *
an d 3(1t1t )*.IS the d etermmmg
.. ~
lactor 15 ' 16'17. Th e degree 0 fconJugatlon
" WI·thin th e mo I ec uI e

which influence the mixing of the two excited triplet states is most extensive in flavone and
 357
least in benzophenone. TIle 3( n1t) * state of benzophenone is thus least influence by the
neighbouring 3(1t1t)* and thereby becomes the most active in the hydrogen abstraction. TIle
activity of xanthone is between the two molecules as its conjugation state lies somewhere
between them.

The effect of ferrocene and benzoylferrocene on the photodegradation of natural rubber has
also been studied l8 . Ferrocene apparently causes a very small effect on rubber photolysis.
However benzoylferrocene with an active carbonyl group induces a greater degree of
depolymerization.

The photosensitised isomerization and dimerization of conjugated dienes by ferrocene had

been reported 19 ,20. The activity was rationalised as due to the ability offerrocene to form a
complex with the polymer. On excitation by light, the complex is excited and interact with
the diene resulting in energy transfer to the diene to form triplet excited diene:

1(complex) *
Ferrocene + diene complex

(dlene) * + ferrocene -
3. 3
1
(complex)
*

1
Isomerization of diene

This reaction pathway is not very favourable with the polyisoprene ofNR as the formation of
the complex is expected to be incomplete and thus restricts the transfer of energy. However if
a triplet excited isoprene is formed a slUall degree of molecular weight reduction will be
observed according to the following pathway:

CH3 CH3
3 I • I
( - CH2 - C = CH - CH2 ) ( - CH2 - C - CH - CH2 - )

1
Isomerization and chain scission

Benzoylferrocene, however, can also induce NR degradation through hydrogen abstraction

reaction facilitated by the carbonyl group. The photosensitizing effect of ferrocene,
benzoylferrocene and benzophenone is found to increase significantly on addition of carbon
tetrachloride to the solvent. The rate of degradation increases with the increase in carbon
358
Carbonyl excita~ion

RCO -------> l(RCO)* ------> 3(RCO)*

Hydrogen abst=ac~ion, radical rearrangement and

chain scission

3(RCO)*

c:..:r 3 CH 3
I I
- CH 2 · - C = CH - CH 2 - CH 2 - C = CH - CH-

CE 3 J CI-1 3
I I
- CH 2 - C C'".d - CH
2 - CH 2 - C - c:-r c:-r -

CH 3 I
v- CH
I I 3
-.CH 2 - C - CH CH 2 + H 2 C= C - CH CH-

oxidation of mac=oradical

CH 3 CH 3
I I
- CH 2 - C - CH CH - -> - CH 2 - C - CH CH-
I I
o OH

~H ~
CH 3 CH 3
I I
- CH - C - C1.! CH- + C - CH CH-

"o/ II
o

Figure 3: Carbonyl photosensitised degradation of natural rubber

 359
tetrachloride until the composltIon of the solvent becomes 10% in carbon tetrachloride.
Further addition of carbon tetrachloride does not seem to enhance the rate but instead a steady
drop is observed. A similar enhancing effect of carbon tetrachloride was also observed in
other photo degradation studies on polymers 21 and high energy irradiation curing of natural
rubber22.

The role of carbon tetrachloride in the polymer degradation can be seen from it ability to
enhance radical reactions. Figure 4 shows the generation and role oftrichloromethyl radical in
the photo degradation of polyisoprene chain. Ferrocene and carbon tetrachloride form a
charge-transfer complex in solution which on irradiation decomposes to form a
trichloromethyl radical. The triplet carbonyl regenerates the radical on reacting with the
CHC13 produced. This extended reaction is very likely in the benzoylferrocene case where
both functional groups are present in the same molecule. As shown in Table 2, however the
degradation ofNR in the presence of carbon tetrachloride is about the same in ferrocene and
benzoylferrocene. The increase in the stearicity of the molecule from ferrocene to
benzoylferrocene leads to a decrease in the stability offerrocene - CCl4 complex whi.ch does
not favour the generation of the active CC13.

<0I
Fe
<0I Cl
!
Fe ... Cl-C-CI ->
o I
Fe~ + Cl- .;- .CCl.
CCl.

o
, '
I A I i

CH.
(!!) Cl
.0 ~R;
I '
.CCl; + - c~ - C = CH - CH2 - - > CHCI; + - CH.--t=CR-CH-

--->

+ CRCl., --> >C-OH + .CCl;

--->

Figure 4: Generation oftrichloromethyl ra.dical

360

Table 2: The molecular weight of degraded NR after 20 hours of exposure to visible light in
the presence offerrocene. benzoylferrocene and carbon tetrachloride

lrradiated system

NRonly 970

NR + Ferrocene 460

NR + Ferrocene + CC14 60

NR + Benzoylferrocene 380

NR + Benzoylferrocene + CCl4 70

Infrared spectrum of the products i.e degraded rubber. shows all similar peaks to that of the
original NR except for a broad peak at around 3450 cm- l and two sharp peaks at 725 cm- l ,
and 1250 cm- I The assignment as reported in the literature 23 .24 are the 3450 cm- l to -OH
vibration, 1725 cm-! to C = 0 vibration and 1250 cm-! to CoO vibration of epoxide.

Figure 5 shows the pioton nmr spectra of degraded rubber taken immediately after
preparation of sample and retaken five days later. A summary of peaks with assignment is
depicted in Table 3 25 . The proton nmr analysis thus comfirms the observation in infrared
study.

i
I
.\
"
'I
, J;v\
,,
"
.',

\::
: I

-----~!------"
___________ - - J -----_ ..
'bl

Figure 5: Proton nmr spectra ofLNR for a fresh sample (a) and retaken five days later (b).
 361

Table 3: The NMR spectral assignment ofLNR in C6D6 solvent

Fresb Sample S days sample Assignment

1.40 broad 1.40 broad -CH3-C-C

o
1.61 -CH3

1.62 trans CH3-CH=

1.72 1.78 -CH3

2.20 2.20 -CH2-

2.70 broad 2.60 broad -C-CH-

o
4.30 broad 3.80 broad -O-OH, -CH-OOR

5.30 5.30 -CH=

These new groups formed are the products resulting from the oxidation of rubber. The
appearance of -OOH and -OOR groups in the freshly prepat;ed sample implies the
involvement of hydroperoxides in the intermediate stage which over a period decompose to
more stable products like hydroxide, expoxide and carbonyl as shown in Figure 3. Although
these groups are presence in very small amount as terminal active groups on the polyisoprene
chain, they are very important in determining the reactivity ofLNR.

APPLICATIONS OF LIQUID NR

The potential commercial applications of LNR have been exhaustively studied in a project
sponsored by the United Nations Industrial Development Organisation (UNIDO) at the
Rubber Research Institute of Africa (IRCA), Invory Coast, in 1985. The physical properties of
LNR and related products, and the relevant economics are the main factors considered in
evaluating the applicability ofLNR. Table 4 lists some of the important applications explored
and general comments about the products.

Low hardness vulcanisates can be prepared by vulcanisation of LNR at moderate

temperatures; a few hours at 100°C or several days at ambient temperature. Coating of toxic
chemicals used in the rubber processing has been shown to be feasible by mixing them with
LNR but the coating technology is inadequate. In the processing of high molecular weight
polymers, LNR is found to be effective in replacing aromatic oil where it also act as a reactive
plasticiser.These vulcanisates seem not only able to maintain the physical properties but also
362

to enhance 111 some aspects like green strength and improve oxidative ageing property.
[ncoporating LNR as a component in bitumen fomlUlation helps to improve the
waterproofiless property of the product.

Due to the complex nature of NR. chain grafting reaction is either difficult or impossible but
it is otherwise in LNR. Antioxidanti 6,27. such as 4-nitrosodiphenylamine. can be grafted
onto the poly isoprene chain of LNR quite easily and this provides a method of introducing
rubber bonded antioxidants into any rubber network. Chlorination of LNR is possible by
bubling chlorine gas into LNR solution in carbon tetrachloride. The chlorinated LNR has a
high potential application in the manufacture of anticorrosive paints and adhesives. Addition
of maleic anhydride to LNR chain is possible via moderate heating the mixture in the
presence of free radical catalyst or strong heating without any catalyst. The grafted polymer
finds application in adhesive industry.

Wider application of LNR is not possible due to the ill-defined nature of the molecular
dimension of LNR. Reactive sites or active terminals which is a very important feature in
facilitating chemical modifications is lacking in LNR 28 and thus restricts the field of
applications. However the LNR produced by photo degradation carries active groups on the
chain and the hydroxyl group is the most prominent. Appropriate active groups can also be
implanted onto the polyisoprene chain of LNR to suite certain application. 29

A new role ofLNR as an NR-plastic compatibiliser in the preparation of thermoplastic based

on natural rubber (TPNR) is being investigated in our laboratory. The ability of the
photogenerated LNR to compatibilised NR-plastics has been tested on NR-Polypropylene
(PP). NR-high density polyethylene (HOPE) and NR - Low linear density polyethylene
(LLDPE) systems. The TPNR is prepared by melt-blending in a mixer at a temperature close
to the melting point of the plastic component. For NR-PP, NR-HOPE and NR-LLDPE, the
processing temperatures are 170°C. 150°C and 135°C respectively and all the mixes are
processed between 12 to 15 min. Table 4 shows a typical set of mechanical and themlal
properties of the material prepared.

The strength of the material as expressed by the stress and strain at break increases
significantly with the addition of LNR for both systems, NR-PP and NR-HDPE. For the
NR-PP, the optinlUm value of LNR is about 15% whereas in the NR-HOPE, 27% LNR yields
the maximum physical properties. A single glass transition temperature, Tg, strongly indicates
a high homogeneity of the blend in both thermoplastics NR.

A complete Wlderstallding Oll how the LNR function in compatibilising the NR-plastic phase
is difficult. However for simplicity it can be rationalised in term of inducing interaction
between the phases. As reported by Gelling and Mente 30• the role of LNR in influencing the
physical properties of the vulcanizate depends on the chain length of polyisoprene. At
molecular weights arowld 6000 LNR acts as bulk viscosity modifiers and this role decreases
 363
with increasing molecular weights. Covulcanization of LNR into the rubber network is
optimum at molecular weight around 30,000 and yields vulcanizate with high hardness and
modulus.

Table 4 : The potential commercial applications of Liquid Natural Rubber

Application Remark

Low hardness vulcanizates Hardness IS to 30 degrees Shore

Ingredient coating for rubber Safer handling of chemicals

chemicals

Inadequate technology

Processing aid or reactive Substitute for oil

plasticizer

Improve tensile strength

Formulating high hardness mixes

Non-extractible plasticizer

Bitumen Good waterproof properties

Flexible Moulds Cheaper than silicon moulds

Paint and varnish LNR needs modification

Adhesive and binder High tackifying and filler

acceptance

Improve with chemical

modification

Restricted to coloured products

Our photogenerated LNR has moleculer weight around 50,000 and reactive terminals such as
OR and C=O groups. The LNR is soluble in NR and as such all kind of interactions, chemical
and physical are possible in the rubber network, but on the other hand, migration of LNR into
the plastic matrix is very unlikely or impossible. Through these active terminals, interaction
between the polyisoprene chain of LNR and the polymer chain of thermoplastic is believed to
occur. Thus the overall role of LNR in the preparation of TPNR are as cross-linking agent
within the NR phase and bonding agent between the NR and thermoplastic interphase.
Excessive addition of LNR above the optimal concentration results in the overall increase in
364
the low molecular weight rubber component in the mixture which causes the TPNR to
become soft and have lower tensile properties.

Table 5 : The mechanical and thermal properties ofNR-PP and NR-HDPE thermoplastics

Composition Maximum Hardness Tg

Blend
---%.NR------O/~LNR·----_St~;~~-----S~ain--r-Sh~re Shore D' oC
MPa % I A
··~~~·~~~~~~~~~~.:.;;::.,;,:..~~~~r~~~-~-' -~- .. --~.~.

NR-PP I: 50 5 7.9 450 93 42 II

I' 10 8.3 670 94 43 -45

17 8.8 500 95 44
NR-HDPEI
60 7 4.3 580 90 33
13 5.3 650 93 35 -55
Ii
I: 20 6.2 700 94 37
27 7.1 760 94 38

CONCLUSION

It is clear that LNR has unfolded a new era in natural rubber industry. With new forms of
natural rubber, new applications are expected to develop. The technological requirements of
the present industry are too demanding to be satisfied by the conventional natural rubber and
in most cases it loses out to synthetic materials. The most versatile rubber would be the form
that can easily be modified to meet the specification set by the product to be manufactured.
Although LNR, to an extent is able to cope with this demand, it is far from satisfactory as the
most important aspect of modification, that is, polymerisation of LNR to give NR of specific
molecular weight with attached functional groups and thereby the physical properties
required, is not possible at the moment. However'LNR has created new avenues in rubber
research long lost to the synthetic polymers. With our ever-increasing knowledge in polymer
and related chemistry, the chemical modifications ofLNR and thus new NR applications look
very promising.

REFERENCES

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3 Capitoni Clito (1975) Annual Meet Proc Intern Inst Synth Rubb Prod. 15: 16
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5 BRPRA (1954) Tech Bull No I "Heveaplus M". London
 365

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7 Stevens HP (1934) British Patent 407.038
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