Chemical Modification of Natural Rubber under Supercritical Carbon

Dioxide Based Hydroxyl Telechelic Liquid Natural Rubber and to

Prepare the Polyurethane
Alif Duereh, Chokchai Boonchuay and
School of Chemical Engineering, Faculty of Engineering, King Mongkuts Institute of Technology Ladkrabang,
Surat Areerat*
Bangkok, 10520, Thailand
E-mail: a.duereh@gmail.com, chokchai.bc@gmail.com
Corresponding Author: kasurat@kmitl.ac.th; Phone: (+66)2-329-8360-3; Fax: (+66)2-3298360-3 press 4
ABSTRACT
This research presents the method of preparing hydroxyltelechelic liquid natural rubber (HTNR) as a renewable
source for preparing soft segment in polyurethane precursor. For this study, two key parameters: amount
of hydrogen peroxide (H
2
O
2
, 10-30 phr) and temperature (60-80
o
C) were studied at a constant pressure of 120 bar,
to prepare liquid natural rubber (LNR) by oxidative degradation of 0.02 wt% natural rubber/toluene solution in
the presence of supercritical carbon dioxide (scCO
2
) atmosphere. The reaction was carried out in two phases
system of scCO
2
/toluene/NR - H
2
O
2
/H
2
O. The average molecular weight, microstructure and functional group
were determined by GPC,
1
H-NMR and FT-IR. As the results, decreasing in molecular weight ( )
n
M down to
4,956 gmol
-1
was indicated that 100 times of virgin natural rubber. Moreover, the degradation of LNR in
organic solvent medium leading to HTNR, were studied which the OH-number of 60.23 mgKOH/g,
the activation energy of degradation reaction of 37.55 kJ mol
-1
, and ( )
n
M of 1,069 g mol
-1
were obtained.
Afterwards, the preparation of HTNR based polyurethane elastomer (PU) by a one-shot technique was purposed.
The formations of urethane linkage were analyzed by FT-IR technique. Thermal degradation of PU investigated
by using thermo gravimetric analysis (TGA) was occurred in two steps, urethane linkage degradation and
oligoisoprene as soft segment of polyurethane.
INTRODUCTION
In the view point of natural resource with aspects related to sustainable hydrocarbon feedstock,
Natural Rubber (NR) is an important elastomeric raw material. However, NR always contains ultra high
molecular weight up to 10
6
which causes some difficulty and energy consuming in the processing line.
Therefore, a developing of molecular weight reduction process for NR allows us to utilize its as an alternative
hydrocarbon feedstock for production of functionalized elastomers or bio-elastomeric materials from NR base.
Moreover, low molecular weight NR has potential to be used as a plasticizer or processing aid for rubber
compound because of its advantage of being both chemically and physically compatible with
poly-diene elastomers [1, 2].
Nowadays, the development of a method to modify the molecular structure of NR was used as produced
functionalized elastomer materials from natural based because NR has structure of which cis-1, 4-polyisoprene,
unsaturated polymer and many double bonds on the structure. For this reason, the oxidation of NR into reactive
functional groups was possible. Previous studied showed that the oxidation of NR was hydroxyl and carbonyl
terminates functional group [3-5]. Importantly, natural rubber based hydroxyl functional group, which can use
as polyurethane precursors.
Typically, to breakdown the molecular structure of NR as so-call the mastication is carried out both from
mechanical shear force and from chemical peptization [6-7]. After breakdown process, much attention has been
paid to effective controlling of its molecular weight. Thus, this present utilizes the advantage of supercritical
carbon dioxide (sc-CO
2
) as a plasticizer for reducing of NR molecular weight [8] and intermediary for the
chemical reaction to modify the structure of the polymer [9].
The objective of this research was to produce hydroxytelechelic liquid natural rubber (HTNR) by using a
chemical peptizing agent in the presence of sc-CO
2
with a considerable molecular weight controlling and prepare
polyurethane elastomers based HTNR.


MATERIALS AND METHODS
Materials
Natural Rubber grade STR 5L (Standard Thai Test Rubber, dirt less than 5%) was used as received.
Hydrogen peroxide (H
2
O
2
) of a purity of 30% was supplied from Fluka Chemical, Ltd., Thailand and
used as peptizing agent. Toluene, Methanol, Tetrahydrofuran AR grade and Chloroform HPLC grade from
RCI Labscan, Ltd. Thailand were used as solvent. Pure liquid CO
2
with a purity of 99.95% was purchased from
United Industrial Gases Co.,Ltd, Thailand. Periodic acid (H
5
IO
6
) and sodium borohydride (NaBH
4
) were
obtained from ACS Reagent Chemical, Ltd., Thailand and used as precursor for preparing carbonyltelechelic
liquid natural rubber (CTNR) and hydroxytelechelic liquid natural rubber (HTNR) respectively.
Dibutyltin Dilaurate (DBTDL) from Air Products & Chemicals, Ltd., Thailand was used as catalyst for
Preparation of polyurethane elastomer by a one-shot method. Toluene Diisocyanate (TDI) was supported by
IRPC, Ltd., Thailand.

Experimental Methods
Preparation of Liquid Natural Rubber (LNR) by oxidation reaction under sc-CO
2

In this study, NR was dissolved into toluene to prepare the NR solution at constant concentration
0.02%w/v. The NR solution was mixed with peptizing agent, Hydrogen peroxide, of 10, 20 and 30
part per hundred rubber (phr) by using a magnetic stirrer at temperature 40
o
C for 5 hr to ensure a well mixing.
The NR solution sample was filled inside the high pressure vessel (Taiatsu Techno/J apan SUS316 15 ml)
vial about 5 ml, stirred the solution all times with Magnetic stirrer. After locking and sealing the vessel finished,
low pressure CO
2
was charged to flush out trapped air inside the vessel several times. After that
CO
2
was discharged into the high pressure vessel through an ISCO Syringe Pump (Model 260D/USA.) at 60
o
C
until a desired pressure was reached to 120 bar. After a given soaking time at 6 hr, CO
2
was discharged from the
vessel and then unlock a vessel cap and the NR solution was taken out. Prior to prepare the sample for GPC
measurement, CO
2
was removed naturally from the sample at atmospheric.
For the determination of molecular weight distribution, the NR solution was diluted by using chloroform
HPLC grade with a volumetric flask 10 ml to obtain sample solution about 0.5 %wt/vol. The measurement was
determined by a Gel Permeation Chromatography, GPC model LC 20AD from Shimadzu corp., J apan.

Preparation of polyurethane elastomer
Firstly, the functional groups of LNR were modified into carbonyltelechelic liquid natural rubber (CTNR)
reacting with periodic acid (H
5
IO
6
) 1.1 mol equivalent and reaction time 6 hr at 30
o
C as shown in figure 1.

Figure 1 Ring opening epoxidationof LNR for preparing CTNR
Secondly, hydroxytelechelic liquid natural rubber (HTNR) prepared from CTNR was reacted to sodium
borohydride (NaBH
4
) 5 mol equivalent and reaction time 6 hr at 30
o
C as shown in figure 2. After
reduction reaction, HTNR was analyzed molecular weight by GPC and functional groups by FTIR and
1
H-NMR


Figure 2 Reduction reactionof CTNR for preparing HTNR


O O
m
H
5
IO
6
/THF
30
o
C , 6 h




O
y x

O O OH O H
m m
1) NaBH
4
/ THF 60
o
C /6 h
2) H
2
O /THF RT
In this research, polyurethane elastomer was prepared by a one-shot method [10] as shown in figure 3.
HTNR oligomer was dissolved into THF to prepare the HTNR oligomer solution at constant concentration
0.5%w/ v. The HTNR solution was mixed with catalyst DBTDL in a ratio of [DBTL]/ [OH] =0.045 and
then TDI was added to HTNR solution with a ratio of [NCO]/ [OH] =1.2 together with using a magnetic stirrer
at temperature 60
o
C for 20 min to ensure a well mixing. After that the sample was molded in floyd aluminum
moulds and formed after solvent evaporation were cured for 48 hr at 40
O
C then polyurethane elastomer
was analyzed functional groups by FTIR and Thermal properties by TGA.


Figure 3 Preparing polyurethane elastomer by a one-shot methodfrom HTNR oligomer

RESULTS AND DISCUSSION
In this section was divided into 2 parts as chemical degradation of NR in the presence of sc-CO
2
for
producing LNR and preparing polyurethane elastomer from HTNR

1. Chemical degradation of NR in the presence of sc-CO
2

1.1 GPC Molecular Weight Analysis
Effect of peptizer concentration and temperature
As typically observation the effect of peptizer concentration on molecular weight reduction, NR with
different Mw was obtained by dissolving NR into toluene and the molecular chain breakdown by using chemical
peptizer, hydrogen peroxide. The log(Mw) for NR mixed 10, 20 and 30 phr of peptizer at constant reaction time
5 hr, constant pressure 120 bar and given temperature 60-80
O
C determined by GPC are illustrated in figure 4.
As the results, hydrogen peroxide was found to be the effective peptizing agent to breakdown the molecular
chain of NR. Effect of peptizer concentration on the molecular weight reduction was decreased dramatically with
increasing peptizer concentration between 10-20 phr. However, at peptizer concentration 30 phr,
effect of peptizer concentration on the molecular weight reduction was less significant than effect of peptizer on
concentration between 10-20 phr because this concentration has much more hydrogen peroxide which affects
repolymerization of NR oligomer that molecular weight of NR was increased.



Figure 4 Effect of peptizer concentration and temperature on molecular weight reduction


OH O H
m
CH
3
NCO
NCO
+
1) THF, RT,DBTL ,20 min
2) 60
o
C ,12h
Polyurethane
Effect of temperature (60-80
O
C) on molecular weight reduction was decreased with increasing
temperature as can be seen in figure 4. For increasing temperature, decomposition of H
2
O
2
was taken place to
obtain O
2
which highly oxidizing agent. The suitable conditions for study effect of sc-CO
2
and reaction time are
20 phr of H
2
O
2
and temperature of 80
O
C because these conditions can be most reduced molecular weight of
3.5810
4
g/mol.

Effect of Supercritical Carbon Dioxide
Experimental GPC curves plotting between log(Mw) and % weight distribution for pure NR solution and
mixed 20 phr chemical peptizer are shown in Fig 5. This figure presents the effect of sc-CO
2
on the
degree of Mw breakdown as it can be seen that under pressurized sc-CO
2
at 120 bar, reaction time 5 hr and
temperature 80
o
C, the circular symbol peak shifted to the left indicating a reduction of Mw down to 1.05 x 10
4
together with a narrow peak which reveals a low polydispersity of 2.12. It obviously demonstrates that sc-CO
2
can enhance the chain scission by chemical peptizer. By this process, the reduction of NR Mw about 100 times
from 1.41 x 10
6
of original NR and broad distribution with polydispersity factor of 5.44 could be achieved.


Figure 5 GPC chromatographs of NR Mw reduction


Effect of reaction time
As the above discussion, combining sc-CO
2
with a chemical peptizer was found to be the promising
effective chain scission breakdown process. However, the processing condition for controlling over molecular
weight is also an important key. Therefore, the effect of reaction time was conducted. The effect of temperature
on degree of chain breakdown at a constant pressure 120 bar is shown in Fig 6. For the Mw analysis, the data
show an initial rapid chain breakdown from both with and without CO
2
at reaction time in rang 1-3 hr and 80
o
C
of temperature to a level 3.2 x 10
4
for with CO
2
and 7.1 x 10
4
for without CO
2
, followed by a leveling off at
1.05 x 10
4
for the reaction time above 5 hr until 10 hr with CO
2
.







Figure 6 Effect of reaction time on molecular weight reduction (a) with CO
2
(b) without CO
2



(a)


(b)


Kinetics of NR degradation
In order to investigate more detailed information of reaction time affect to the degree of Mw reduction.
Kinetics of NR degradation was performed as described in the literature [11] and can be defined as follow;


1

()

(
0
)
= (1)

(2)
where DPn is number-average degree of polymerization which estimated by GPC at the initial time (t =0) and
time t, respectively. For this research, M
monomer
is isoprene of 68 g/mol. The kinetic rate constant (k) of NR
degradation can be calculated with DPn(0) and DPn(t) are the DPn valuesat the initial time (t =0) and time t,
respectively.






Figure 7 plot of 1/DPn(t) -1/DPn(0) at various reaction times of NR (a) with CO
2
(b) without CO
2

Degree of polymerization of NR solution both without and with CO
2
at 60-80
o
C and
peptizer concentration 20 phr starts to be estimated when reaction time increases as illustrated in Fig. 7.
The kinetic rate constant of the degradation reaction can be calculated by using slope of the plot of
1/DPn(t) -1/DPn(0) at various reaction times as can be seen in table 1. These results of K value showed
that chemical degradation of NR with CO
2
presented a higher rate constant than the without CO
2
. Moreover,
using equation 1 can be explained the behavior of molecular weight reduction. Therefore, the degradation
reaction was second order.

Table 1 Results of kinetic rate constant at various temperature
T (
o
C)
K (min
-1
)
with scCO
2
Without scCO
2

60 1.0710
-5
8.0010
-7

70 1.5710
-5
4.9010
-6

80 2.3010
-5
9.3010
-6


For determination the activation energy of the degradation reaction, the kinetics of degradation of NR
both without and with CO
2
at 60, 70, and 80
o
C were evaluated. The activation energy of rubber molecule
was estimated by the Arrhenius. The activation energy values of the degradation reaction of both without
and with CO
2
were calculated by using slope of the plot ln k versus the reciprocal of a various temperature
as shown in figure 8.As the results, the activation energy of the degradation reaction of NR without and
with CO
2
were 37.55 and 120.50kJ mol
-1
respectively. This result showed that the chemical degradation of
NR with CO
2
is much faster than the degradation of NR without CO
2
. Therefore, it obviously demonstrates
that sc-CO
2
can enhance the chain scission by chemical peptizer.



(a)


(b)




500 1000 1500 2000 2500 3000 3500 4000
%

T
r
a
n
s
m
i
t
t
a
n
c
e
wavenumber (cm
-1
)
OH
3440 cm
-1

CH2, CH3
C-O-C
870 cm
-1

C=O
1720 cm
-1

NR Original
30 phrH2O2
20 phrH2O2

10 phrH2O2

O H
C
OOH
O
H
2
O
2
CO
2 +
O H
C
OOH
O
+


n




O
x y
m

O H OH +
Carbon
Dioxide
Hydrogen
Peroxide
Peroxycarbonic Acid
Peroxycarbonic Acid Natural Rubber Glycol Epoxidized
Aqueous H
2
O
2
Phase
Organic/Fluid Phase


n
Natural Rubber CO
2

(1)
(2)





Figure 8 Kinetic rate constant with CO
2
and without CO
2

1.2 FTIR and
1
H-NMR Functional Groups
The functional groups of LNR at 80
o
C and reaction time 5 hr were analyzed by FTIR technique.
The infrared spectrum of degraded NR in Figure 9 (a) indicates the appearance of characteristic signals
of hydroxyl at 3440 cm
-1
, epoxide at 1720 cm
-1
and carbonyl at 870 cm
-1
.












Figure 9 FTIR spectra (a) LNR (b) HTNR

These results are in accordance with the results reported previously in the literature [5, 11]
that the products of epoxidation reaction are epoxidize NR and Glycol as shown in figure 10. Therefore,
the infrared spectrum was responded to the products from epoxidation reaction.







Figure 10 NR Epoxidation in biphasic system of H
2
O
2
/H
2
O scCO
2
/Toluene/NR

For
1
H-NMR analysis, the spectrum of LNR in Figure 11(b) at 80
o
C and reaction time 5 hr
was indicated the signal at 5.10 and 2.70 ppm assigned to the olefinic proton of cis-1, 4-polyisoprenic structure
and the methane proton adjacent to the epoxide ring, respectively. Moreover, integrating area under signal
at 5.10 and 2.70 ppm can be calculating the number of epoxide functional group of 5.66 %




(a)


(b)












Figure 11
1
H-NMR spectrum (a) NR (b) LNR with CO
2

2. Preparing polyurethane elastomer
The LNR as low molecular weight of 1.05 x 10
4
and number of epoxide functional group of 5.66 %
was successfully prepared by using chemical peptizer of which degraded NR under sc-CO
2
. Because LNR has
epoxide functional group, it can be modified functional into carbonyltelechelic liquid natural rubber (CTNR) by
reacting with periodic acid. After that HTNR was prepared by CTNR reacting to sodium borohydride (NaBH
4
).
The infrared spectrum of HTNR in Figure 9 (b) indicates the appearance of characteristic signals
of hydroxyl at 3440 cm
-1
and disappearance signals of carbonyl at 870 cm
-1
. Moreover, OH-number of HTNR
calculating with calibration curve of standard solution via FTIR was 60.2 mgKOH/g.
For
1
H-NMR analysis, the spectrum of LNR in Figure 12 demonstrated that the ethylenic proton
(5.10 ppm) is unchanged and the complete disappearance of both peaks of aldehyde proton at 9.80 ppm and
methylic proton in ketone end group at 2.13 ppm as well as the peak of CH
2
in and of terminal carbonyl
functions between 2.20 and 2.60 ppm. The new peak of methylic protons adjacent to secondary alcohol at
1.20 ppm and two peaks corresponding to CH (3.80 ppm) and CH
2
(3.68 ppm) adjacent to alcohol groups at
the chain-ends was founded.











Figure 12
1
H-NMR spectrum of HTNR

Polyurethane elastomer was prepared by a one-shot method [10] as HTNR oligomer was reacted TDI
concurrently with catalyst DBTDL. The chemical structures of all the polyurethanes were confirmed by
the existence of absorption bands at around 3440 and 1720 cm
-1
of FTIR analysis in figure 13 which correspond
to N-H and C=O stretching vibrations of urethane functional group, respectively. The small appearance
of absorption peak at 2270 cm
-1
showed that there was residual of NCO in the HTNR based PU.













Figure 13 FT-IR spectrum of PU
(a)


(a)


(b)


From thermal analysis, two step degradation of PU was observed; 1
st
step is urethane function
as accordance with the results reported previously in the literature [4] and 2
nd
step is polyisoprene backbone of
oligomers.


Figure 14 TGA thermogram of PU

CONCLUSION
Molecular weight reduction of natural rubber (STR 5L) was carried out by using chemical peptizer
10-30 phr in the presence of sc-CO
2
via decomposition of H
2
O
2
at temperature within the range 60 to 80
o
C. The
molecular weight reduction and its polydispersity were determined by GPC. By this process, the significant
reduction of molecular weight about 100 times with narrow molecular weight distribution could be observed to
be 1.05 x 10
4
and polydispersity factor about 2.12, respectively at 80
o
C and H
2
O
2
peptizer concentration 20 phr.
Moreover, the hydroxyl techelic liquid natural rubber, HTNR was successfully prepared via oxidation in
the presence of scCO
2
and modifying in organic solvent medium which the OH-number of 60.23 mgKOH/g and
( )
n
M of 1,069 gmol
-1
was obtained. Besides, polyurethane elastomer based HTNR was successfully prepared
by a one-shot technique.

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