Accepted Manuscript

NMR study of ring opening reaction of epoxidized natural rubber in presence of

potassium hydroxide/isopropanol solution

Omar S. Dahham, Rosniza Hamzah, Mohamad Abu Bakar, Nik Noriman Zulkepli,
Saad S. Dahham, Sam Sung Ting

PII: S0142-9418(16)31346-0
DOI: 10.1016/j.polymertesting.2017.01.006
Reference: POTE 4892

To appear in: Polymer Testing

Received Date: 2 December 2016

Accepted Date: 6 January 2017

Please cite this article as: O.S. Dahham, R. Hamzah, M.A. Bakar, N.N. Zulkepli, S.S. Dahham, S.S.
Ting, NMR study of ring opening reaction of epoxidized natural rubber in presence of potassium
hydroxide/isopropanol solution, Polymer Testing (2017), doi: 10.1016/j.polymertesting.2017.01.006.

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 ACCEPTED MANUSCRIPT
Analysis Method
NMR study of ring opening reaction of epoxidized natural
rubber in presence of potassium hydroxide/isopropanol
solution
Omar S. Dahham1a, Rosniza Hamzah1b, Mohamad Abu Bakar2c, Nik Noriman
Zulkepli1d, Saad S. Dahham3e, Sam Sung Ting4f

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1
Center of Excellence Geopolymer and Green Technology, Faculty of Engineering
Technology, Universiti Malaysia Perlis, 02100 Padang Besar, Perlis, Malaysia
2
Nanoscience Research Laboratory, School of Chemical Sciences, Universiti Sains

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Malaysia, 11800 Minden, Penang, Malaysia
3
EMAN Research and Testing Laboratory, School of Pharmaceutical Sciences,

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Universiti Sains Malaysia, 11800 Minden, Pulau Pinang, Malaysia
4
School of Bioprocess Engineering, Universiti Malaysia Perlis (UniMAP), Kompleks
Pengajian Jejawi 3, 02600 Arau, Perlis, Malaysia

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a
eng.omar@mail.com, brosnizahamzah@unimap.edu.my, cbmohamad@usm.my,
d
niknoriman@unimap.edu.my, ehawk_dijla@yahoo.com, fstsam@unimap.edu.my
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Correspondence to:
Name: Rosniza Hamzah
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E-mail: rosnizahamzah@unimap.edu.my

Abstract: The ring opening reaction of epoxidized natural rubber (ENR-50) in the
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presence of potassium hydroxide/isopropanol solution was studied using NMR, and

it’s thermal characteristic was investigated using TG/DTG and DSC. 1H-NMR
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showed that 16.9% of epoxide units was ring-opened in treated ENR-50, which was
also supported by quantitative FTIR spectroscopy. 13C-NMR proved the location of
alkyl group (isopropyl) in the polymer chain of treated ENR-50. The attachment
location of isopropyl occurred at both most (↑) and least (↓) hindered carbons of the
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epoxide. 2D-NMR was used to identify and scrutinize the triad assignment of treated
ENR-50. The TG/DTG results presented three decomposition steps at 190-331, 331-
521 and 521-706 °C due to the existence of mixtures of polymer chains i.e. ring-
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opened and intact epoxide of ENR-50, which also led to increase in Tg of treated
ENR-50 at 13.2°C compared with purified ENR-50 at -17.7°C.
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Keywords: epoxidized natural rubber, ring opening reaction, epoxide, nuclear

magnetic resonance, thermal characteristic.

1.Introduction
Nuclear magnetic resonance spectroscopy (NMR) techniques are extensively used for
polymeric materials characterization either in solid or liquid phase. 1D NMR provides
structural explanation on monomer units and reactive groups in the polymer chain. 2D
NMR gives detail structural arrangements on the f monomer units in the polymer
chain. The 1D NMR technique or both 1D NMR and 2D NMR techniques were
 ACCEPTED MANUSCRIPT
applied previously to epoxidized natural rubber (ENR), such as ENR25 [1], ENR50
[2-6], ENR75 [3] and other ENR type [7,8]. Nevertheless, most of these researches
didn’t give complete structural studies because of the overlapping of signals arising
from the random distribution of isoprene (C) and epoxidized isoprene (E) monomers
[9,10]. A triad of ENR is made up of three possible sequences of C and E units. All
the possible ENR-50 triad sequences are shown in Figure 1. For nomenclature
purposes, the common structure and the carbon atoms numbering of the E and C units
in ENR-50 is shown in Scheme 1. In a triad, the neighbouring units may dictate the

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1
H and 13C environments of the middle unit. It is the middle unit that will reveal the
triad structure. For example, an ENR chain fragment may be comprised of C unit
attached to an E unit which in turn is attached to another E unit. Thus, this triad

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sequence is denoted as CEE. Triad comprising of similar unit is only denoted by a
single unit. Triad CCC is denoted as C and triad EEE is denoted as E. The methyl of
the middle unit in the CEE and CCC triads are denoted as CE10E and C5, respectively,

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where the superscript refers to the (methyl) carbon (C) number in the ENR-50
structure, as shown in Scheme 1. This nomenclature also applies to the proton in the

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ENR-50 structure.
Prior to the advent of the triad sequence, previous researches have only ascertained
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the 1H chemical shifts assignments of methine proton of E and C units but
sporadically to either the methyl and/or methylene protons of E and C units of the
ENR [5-8,11,13]. Furst and Pretsch have reported the use of computer simulation to
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predict chemical shifts of these protons and their triad assignments [10]. On the other
hand, Gelling has assigned the triad sequence based on 13C-NMR chemical shifts for
ENR-20 [12]. However, the assignment deals with certain triad sequences only and
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the position of carbon represented by the triad sequences was found to be

inconsistent. Consequently, Saito et al. have successfully interpreted the 13C-NMR
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spectra for the ENR related compounds and assigned their triad sequence [13]. The
manipulating of ENR pH below or above 7 can play an important role to catalyse the
epoxide ring opening reaction and provides crosslinking among polymer chains. The
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existence of acid accelerates the addition of most nucleophiles to the epoxide carbon
atoms, which in turn led to ring opening reaction [14]. The reaction of ring opening in
the presence of acid produces an alcohol group along with formyl ester. Furthermore,
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acid could catalyse the epoxide ring opening and produce ether crosslinking [9]. In
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the common base, a nucleophile attacks the less substituted carbon of the epoxide
causing the β-opening at the epoxide ring [15]. In rubber processing via vulcanization,
the excess of base will cause premature curing and accelerate the reaction. This
premature curing is due to the epoxide ring opening reaction under basic condition
[16,17].
Our previous work has studied the influence of acetic acid as a mild acidic condition
on the ring opening reaction of epoxidized natural rubber using 1D and 2D NMR
supported with thermal analyses (TG/DTG and DSC). The 1H-NMR result showed
that 19.56% of epoxide ring opening took place in the acid treated ENR-50 and 13C-
NMR suggested the acetate group location in the polymer chains. Furthermore, the
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alkyl groups attached to the ring-opened epoxide unites have improved the thermal
characteristics of the acid treated ENR-50 [18].
The main objective of our current work is to introduce a comprehensive study of ring
opening ENR-50 in the presence of potassium hydroxide/isopropanol solution. This
study included FTIR, 1D and 2D NMR in addition to TG/DTG and DSC for thermal
characteristics study. The rubber type used in this work is a low molecular weight
ENR-50 which was obtained by a sol-gel technique. This work differs from other
stated works in regard of the epoxidation degree and physical form of epoxidized

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natural rubber [13,19].

2. Experimental

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2.1. Materials
Toluene, chloroform, n-hexane, 2-propanol, IPA (Systerm, Malaysia), Potassium

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hydroxide, 85.0%, KOH (Q Rec Asia, Malaysia), Deuterated chloroform and CDCl3
(Fluka Chemicals, Switzerland) were all purchased commercially and used without
additional treatment unless otherwise stated. ENR-50 was obtained from the Rubber

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Research Institute, Kuala Lumpur - Malaysia.
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2.2. Preparative Procedure
2.2.1. ENR-50 Purification
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20.00 g of ENR-50 was swelled in 400 mL of chloroform and stirred for 24 h at 25°C.
A cotton gauze pack was used to filter the solution and separate the low molecular
weight ENR-50 from the high molecular weight ENR-50. The low molecular weight
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ENR-50 was precipitated in n hexane and then stirred manually using a glass rod. The
white precipitate stuck on the glass rod was moved to a Teflon petri dish. The samples
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were dried using vacuum oven at 50 °C for 48 h. The dried samples represented the
purified ENR-50.
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2.2.2 Treated ENR-50

A 0.21 M (14.09 mg mL-1) KOH/IPA solution was prepared by dissolving
1.41 g (21.35 x 10-3 mol) of KOH pellets in 100 mL IPA. In a typical preparation,
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about 200 mg (1.32 x 10-3 mol) of purified ENR-50 was dissolved in 40 mL toluene
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with stirring. The pH of the solution was adjusted to pH 12 by addition of a 10 mL of

KOH stock solution. The mixture was then refluxed at 85 °C for 3 hours. It was then
left to cool to room temperature. The reaction mixture was washed with 150 mL of
water until the washing attained a neutral pH. On separation, the organic layer was
cast into Teflon dishes followed by drying in a vacuum oven at 80 °C for 24 hours.

2.3. Measurements and Characterization Techniques

The NMR spectra were obtained using a Bruker Avance 500 MHz instrument in
CDCl3 at 25 °C. A sample was swelled for 4 days in a NMR tube before conducting
tests. About 10mg of prepared solution was used for 1H Spectroscopy and 50 mg was
 ACCEPTED MANUSCRIPT
used for the 13C-NMR, heteronuclear multiple bond coherence (HMBC),
heteronuclear multiple quantum coherence (HMQC) and correlation spectroscopy
(COSY) analyses. The spectra respective range and scan number for 1H and for 13C-
NMR measurements were 15–0 ppm with 16 scans and 200–0 ppm with 8,000 scans,
respectively.
A Perkin-Elmer 2000-FTIR spectrometer was utilized with single beam transmittance
onto a film of sample on zinc selenide (ZnSe) window in the wavelength range of
4,000–600 cm−1. The FTIR samples were prepared using 5 mL of chloroform to swell

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100.00 mg of the samples. After sample swelling, the solution was cast into a 3.0 cm
x 1.0 cm x 0.5 cm Teflon mould and air dried. The vacuum oven was used at 50 °C
and 1 hour for further drying and the sample then transferred onto the ZnSe window.

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A thermal gravimetric (TG) analyser, model Perkin-Elmer TGA7 was used to assess
the samples’ thermal stability. A 10mg sample was heated from 30°C to 900°C at 20
°C min-1 under nitrogen atmosphere. Differential scanning calorimetry (DSC) was

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done using a Perkin-Elmer Pyris6 instrument. About 10. mg sample was sealed in an
aluminium pan. The thermograms were recorded over a temperature range of -50 to
140 °C at a heating rate of 20 °C min-1 under nitrogen atmosphere. First, the sample

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was heated from -50 to 140 °C and held at 140 °C for 1 minute. Then, it was
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quenched to -50 °C and held for another 5 minutes. The final step was the reheating
from -50 to 140 °C at the same heating rate.
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2.4. Theoretical Treatment

In 1H-NMR, the amount of epoxide before and after reaction, and the percentage of
ring opening in a sample was determined using Equation (1) [1,2,12]. I2.7 is the
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integrated area of the methine proton of epoxidized isoprene and I5.2 is the integrated
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area of the methine proton of isoprene. In Equation (1), I2.7 is chosen because it is the
initial reactive site for the reaction and, for purified ENR-50, the integrated area of
this peak is one proton. Typically, the integrated area at I2.7 after reaction is less than
the I2.7 before reaction, while I5.2 remains similar before and after the reaction. This is
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because methine proton of isoprene is not involved in this reaction. In Equation (2),
the percentage of ring opening in the sample is a deduction of the percentage of
epoxide in purified ENR-50 with the percentage of epoxide left in the ring opened
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sample after reaction.

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The semi quantitative analysis of FTIR was based on the peak area of epoxide and
methyl functional groups. The percentage of epoxide in the sample was calculated
using Equation (3). In equation (1), Nmethyl is the methyl normalized peak area, A
epoxide sample is the epoxide functional group peak area and A epoxide ENR-50 is the peak
area of respective functional group stretching peak in purified ENR-50. The
percentage of epoxide in the sample was calculated using Equation (1) [5].

% Epoxide in sample = I2.7 * 100% / I2.7 * I5.2 (1)

 ACCEPTED MANUSCRIPT
% Ring opening in sample = (% epoxide in purified ENR-50 - % epoxide in sample) (2)
* 100% / % epoxide in purified ENR-50
% poxide = Nmethyl * Aepoxide sample * 100% / Aepoxide ENR-50 (3)

3. Results and Discussion

3.1. NMR

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1 13
3.1.1. H- and C-NMR Spectroscopy
The 1H- and 13C-NMR spectra of treated ENR-50 are shown in Figure 2, and the

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respective chemical shifts are tabulated in columns 1 and 2 of Table 1. From Figure
1(a), chemical shifts of C2 at δ 5.13-5.17 and E7 at δ 2.73 ppm are similar to the
purified ENR-50 [20]. However, the integral of E7 (m, 0.797H) is slightly decreased

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(viz. 0.203H) as compared to C2 (m, 1.000H). This small decrement is due to 16.9 %
of ring opening reaction (Equation 2). The region of hydroxyl proton of E7 and E6 is
shown at δ 3.00-4.20 ppm (br s, 0.122H) and δ 4.70-5.00 ppm (br s, 0.122H),

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respectively [1,2]. This shows that the reaction has taken place at most hindered
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carbon and less hindered carbon positions abbreviated as (↑) and (↓), respectively.
The reason for broadness for these peaks is fast proton exchange between hydroxyl
group and the solvent in the system [21-23].
The peak at δ 1.31 ppm (Figure 1, a) is a mixture of methyl protons of E10 of the
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ENR-50 and methyl protons of isopropyl (IP) E21 (Scheme 2). The peak at δ 1.57 ppm
indicates the methylene protons at (↑) and (↓) positions for E8, EE8C, CE8E, CE8C and
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at (↓) position for CE9C, EE9C. It also belongs to the methylene protons of E8, EE8C,
CE8E, CE8C, CE9C and EE9C of the ENR-50. The peak at δ 1.69 ppm represents
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methylene protons at (↑) and (↓) positions for E9, CE9E as well as methylene protons
of E9, CE9E and methyl protons of C5 of the purified ENR-50. The methylene protons
of C3, CC3E, C4, EC4C and CC4E, EC4E, EC3C, EC3E are located at δ 2.06 and 2.18
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ppm respectively.
Typically, the peak at δ 2.73 ppm belongs to the methine proton of E7 which remains
intact in the polymer chains. However, it also represents the methine proton at (↑) and
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(↓) positions for E7, CE7E, EE7C, CE7C as well as methine proton of IP E20 (Scheme
2).
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The 13C-NMR spectrum of treated ENR-50 is shown in Figure 1 (b) and tabulated in
column 2 of Table 1. The presence of IP group within the ENR-50 structure is
evidenced via methine carbon of IP (E20) and methyl carbon of IP (E21). The chemical
shift of methyl carbon E21(↑) and methine carbon E20(↓) is at δ 22.2 and δ 73.7 ppm
respectively.
As shown earlier, the (↑) position produces ether carbon E6 and the (↓) produces ether
carbon E7. The ether carbon E6 shows a single peak at δ 84.5 ppm while the ether
carbon E7 shows 2 peaks at δ 77.7 and 86.5 ppm. Both of the hydroxyl carbons E6, E7
are at a similar chemical shift i.e δ 77.7 ppm, regardless of the (↑) or (↓) positions.
This is due to the similar electron environment for the respective hydroxyl. The
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methine carbon E7, which is not involved in ring opening reaction, remains similar to
the purified ENR-50 at δ 64.5 ppm.
The methyl carbon E10 is represented by 3 peaks at δ 22.2, 23.3 and 23.9 ppm. The
peak at δ 23.3 ppm is when attachment of methyl is at (↑), while at δ 23.9 ppm it is at
(↓). The methyl carbon E10 which is not involved in the ring opening reaction remains
at δ 22.2 ppm.
The methylene carbon E8 shows 6 peaks at δ 29.7, 32.0, 33.1, 35.0, 36.5 and 41.0
ppm. The peak at δ 32.0, 35.0, 36.5 ppm belongs to E8 and EE8C. The methylene at

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(↓) gives a peak at δ 35.0 ppm. The attachment at (↑) produces two peaks at δ 32.0,
36.5 ppm. This is due to the additional ring opened epoxide of L and R units of these
triads. The peak at δ 41.0 ppm corresponds to triads CE8E and CE8C due to the

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attachment at (↑) and (↓) positions. The peak at δ 29.7 and 33.1 ppm represents the
methylene of EE8C, E8 and CE8C, CE8E of the ENR-50, respectively.
The methylene carbon E9 shows 6 peaks at δ 23.3, 23.9, 24.6, 26.2, 27.0 and 29.7

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ppm. Both peaks at δ 23.9 and 29.7 ppm represent the methylene at (↓) for CE9C and
EE9C. Similarly, peaks at δ 23.3 and 26.2 ppm belong to methylene at (↓) of E9 and
CE9E. The methylene at (↑) produces a peak at δ 27.0 ppm for these triads. The peak

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at δ 27.0 ppm belongs to EE9C and CE9C while for E9 and CE9E it is located at δ 24.6
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ppm respectively.
The methylene carbon of C3 shows 2 peaks at δ 26.2 and 28.7 ppm. The peak at δ
26.2 ppm corresponds to the C3 and CC3E while the peak at δ 28.7 ppm is for EC3C
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and EC3E triads. Similarly, the peak due the methylene carbon of CC4E and EC4E is
at δ 23.9 ppm and δ 26.2 ppm for C4 and EC4C triads, respectively. Finally, the
quaternary carbon C1 and methine carbon C2 remains at δ 134.7 and 125.1 ppm
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respectively.
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3.1.2 HMQC
Figure 3 shows HMQC spectra of treated ENR-50, and the assignments are tabulated
in Table 1 (3rd column). The HMQC spectra are used to verify the ring opening
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product and the attachment of IP from its contour correlation. The correlation of
methyl of IP (E21) is shown at the most upfield region in the spectra and similar to the
methyl of E10 for purified ENR-50. This is followed sequentially by methyl at (↑) and
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(↓) positions of E10.

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The correlation of methylene E8 and E9 which remains intact and ring opened in the
polymer chains shows that E9 occurs at a slightly more upfield region than E8.
Particularly, the correlation of methylene E9 is arranged accordingly due to the (↓),
the middle unit which is not ring opened, and the (↑), while the correlation of
methylene E8 is arranged accordingly due to the (↑), the middle unit which is not ring
opened, and the (↓).
The methine E7 of the middle unit remains similar to ENR-50 as it is not ring opened.
The correlation of methine of IP (E20) is overlapped with methine E7 and ether E7 in
1
H-NMR spectrum. However, E20 is located at a more upfield region than ether E7 in
13
C-NMR spectrum. The ether E7 has more electron density than methine E7. The
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hydroxyl E7 is a 3° substituted carbon as compared to hydroxyl E6 which is a 2°
substituted carbon. Thus, the correlation between hydroxyl E7 is located at a more
upfield region than hydroxyl E6.
Typically, the correlation of methylene of C4 is positioned at a slightly more upfield
region than the methylene of C3, even although the ring opening reaction does not
apply in C units. The correlation of the quaternary carbon of C1 and methine carbon
of C2 are shown at δ 134.7 and 125.1 ppm, respectively.

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3.1.3 HMBC
Figure 4 shows HMBC spectra of treated ENR-50, and the assignments of the middle
unit of the triad sequence are tabulated in Table 1 (4th column). The attachment of IP

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at the ring opened epoxide is further scrutinized in HMBC spectra via 1H- and 13C-
NMR correlation. The HMBC spectra show correlation of methyl of IP (E21), methine

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of IP (E20) and ether E7. The correlations of the hydroxyl E6 and E7 are not obtained in
the spectra due to the intramolecular hydrogen bond of the similar polymer chains,
intermolecular hydrogen bond amongst the polymers chains, as well as the rapid

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exchange of the hydroxyl with the solvent [22]. The correlation of the methylene of
E8, E9 at (↑) or (↓) showed slightly different correlation. Typically, the methylene of
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E8 (↓) and E9 (↓) showed correlation at a downfield region as compared to the
methylene of E8 (↑) and E9 (↑). The correlation of methyl of E10, methylene of C3, C4,
quaternary carbon of C1 and methine carbon of C2 is similar to the ENR-50 [20].
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3.1.4 COSY
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The COSY of treated ENR-50 is shown in Figure 5, and the respective data
are tabulated in Table 1 (5th and 6th column). The COSY spectra show correlation at δ
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1.30, 1.57, 1.69, 2.06, 2.18, 2.73 and 5.13-5.17 ppm. The signal at δ 1.30 ppm
correlates with the methine proton of IP (E20) at δ 2.73 ppm of the middle unit within
the triad sequence.
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The signal at δ 1.57 ppm correlates with the signal at δ 1.69, 2.18 and 2.73
ppm. The signal of methylene protons of E9 at δ 1.69 is correlated with the methylene
protons of ring opened E8, EE8C, and CE8E within same unit of triad sequences. The
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signal of methylene protons of C3 and C4 at δ 2.18 ppm correlates with the methylene
protons of ring opened CE9C, EE9C and CE8E, CE8C, respectively, within same unit
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of triad sequences. The signal of methine proton of E7 at δ 2.73 ppm correlates with
the methylene protons of ring opened CE9C, EE9C of the middle unit. The signal that
represents the methylene protons of epoxide ring opened E9 and CE9E at δ 1.69 ppm
is correlated with the signal at δ 1.57 and 2.73 ppm. The methylene protons of E8 at δ
1.57 ppm correlates with the methine proton of E7 at δ 2.73 ppm of the middle unit of
the triad sequence. The methylene proton of C3, CC3E, C4 and EC4C at δ 2.06 ppm
correlates with the signal at δ 2.06 ppm and methine proton of C2 at δ 5.13-5.17 ppm.
The correlation at δ 2.06 ppm is within the same unit, and at δ 5.13-5.17 ppm is in the
middle unit of the triad sequence. The signal at δ 2.18 ppm correlates with signals at δ
1.57 and 5.13-5.17 ppm. The methylene protons of E8 at δ 1.57 ppm correlates with
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the methylene protons of epoxide ring opened EC4E, CC4E, EC3E, EC3C at δ 1.57
ppm. The methine proton of C2 at δ 5.13-5.17 ppm also correlates with methylene
protons of EC4E and CC4E of the middle unit of triad sequence. The signal at δ 2.73
ppm correlates with the signal at δ 1.30, 1.57, 1.69 and 2.18 ppm. The signal of
methyl protons of IP (E21) at δ 1.30 ppm correlates with methine proton of IP (E20).
The proton signal of methylene of E9 at δ 1.57 ppm correlates with methine proton of
epoxide ring opened EE7C and CE7C of the middle unit of triad sequence. The signal
of methylene protons of E9 at δ 1.69 ppm correlates with methine proton of epoxide

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ring opened E7 and CE7E triads. The signal of methylene protons of E8 at δ 2.18 ppm
correlates with methine proton of EE7C and CE7C triads. The signal at δ 5.13-5.17
ppm correlates with the signal at δ 2.06 and 2.18 ppm. The signal of methylene

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protons of C4 at δ 2.06 ppm is correlated with methine proton of the middle unit of
triad C2, EC2C and CC2E, while signal of methylene protons of C4 at δ 2.18 ppm
correlates with methine proton of the middle unit of triad EC2E and CC2E.

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3.2 FTIR Spectroscopy

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Figure 6 shows FTIR spectra of pure and treated ENR-50. The FTIR spectra
of ring opened ENR-50 via KOH/IP solution show the characteristic of ENR-50 and
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OH peaks. The additional ether peak is shown for treated ENR-50. In Figure 6 (b), the
characteristic of ENR-50, OH and ether peaks are observed. The OH peak is at 3490
cm-1 includes the intermolecular and intramolecular hydrogen bonds due to hydroxyl
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attached at (↑) and (↓) positions. The ether peaks at 1150, 1113 cm-1 corresponds to
asymmetric and symmetric C-O-C stretching vibrations, respectively. The epoxide
peak remains at 877 cm-1. Comparison of the treated ENR-50 spectra (Figure 6, b) to
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the purified ENR-50 spectrum (Figure 6, a), indicates a decrease in the intensity of
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epoxide peak after the reaction [24]. The reaction extent is calculated using equation
3. The peak of methyl at 1378 cm-1 was used as the internal standard for the current
study [5]. According to the approach of semi-quantitative FTIR, out of the original
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epoxide ring, 17.1% of the ring opening reaction has occurred in treated ENR-50.
This proves the previous results of 1H-NMR at 16.9% for treated ENR-50.
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3.3 Thermal Analysis

3.3.1 TG/DTG
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The TG and DTG results of purified and treated ENR-50 are shown in Figure
7. TG and DTG thermograms of purified ENR-50 shows a single step degradation
range and maximum temperature degradation (Tmax) at 331-493 °C and 408 °C
respectively [25,26], while treated ENR-50 shows 3 steps of degradations over the
temperature range studied. The temperature ranges for treated ENR-50 are at 190-331,
331-521, 521-706 °C with Tmax at 256, 441 and 628 °C, respectively. The treated
ENR-50 first step represents water molecules removal that originates from the ring
open structure of ENR-50 i.e. hydroxyl groups. In theory, the hydroxyl amount in
treated ENR-50 is 10.49 %wt while the experimental amount is 11.8 %wt, indicating
that part of the hydroxyl groups degrade through the second stage of degradation. The
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second stage represents the polymer chains pyrolysis including the breakdown of the
side and main chains of polymer such as IP groups [27,28]. This type of degradation
occurs at a wider range of temperature compared with purified ENR-50. This could be
due to the existence of polymer chain mixture i.e ring-opened and intact epoxide of
ENR-50. The third stage is the carbonaceous materials rearrangement from the
polymer chains degradation as an aromatic carbon which is later present as char
residue [27,29]. Based on these temperature ranges, it shows that the thermal profile
of treated ENR-50 is more stable than pure ENR-50. This is due to the alkyl group

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that is attached to the carbons of the ring opened epoxide, which in turn led to
improvement in the thermal stability of treated ENR-50 more than pure ENR-50. The
char residue of ENR-50 and treated ENR-50 are 0.07 and 1.55 %wt, respectively.

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This may be related to the percentage of the ring opening that is available in alkali as
compared to pure ENR-50, as mention earlier in 1H-NMR.

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3.3.2 DSC
DSC results of purified and treated ENR-50 are shown in Figure 8. The

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purified and treated ENR-50 show a single glass transition (Tg) at -17.7 and 13.2 °C
respectively. The Tg of treated ENR-50 was higher than purified ENR-50 due to the
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presence of ring opened epoxide. Typically, a single Tg in the polymer indicates good
miscibility among the intact and ring opened epoxide in the ENR-50 [30,31]. This is
attributed to the similar polymer backbone of the ring-opened product. The IP group
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attached to the ring-opened epoxide produces a rigid polymer at higher temperature

than pure ENR-50. The presence of IP group in treated ENR-50 has restricted the
polymer chains motion via filling more holes and voids among the polymer chains.
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Further, the presence of hydrogen bonds in the polymer contributes to this

phenomenon [32].
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4. Conclusions
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The epoxide ring opening reaction of ENR-50 with KOH/IPA solution

suggested the attachment of isopropyl group via ether link and hydroxyl groups
formation in the polymer chains. The reactions of treated ENR-50 produced a mixture
C

of ring-opened products at most (↑) and least (↓) positions of the epoxide carbon, and
were effectively assigned using 2D-NMR techniques. Moreover, the thermal stability
AC

of treated ENR-50 was improved. This is agreement with the DSC profiles where
isopropyl group is able to restrict motion of the polymer chains in ENR-50.

5. Acknowledgements: The authors would like to acknowledge the Fundamental

Research Grant Scheme (FRGS) Phase 1/2015 (9003-00523) under Ministry of
Higher Education, Malaysia.

References
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Figure Captions
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Figure 1 The possible triad sequences of epoxidized natural rubber (ENR-50)
Scheme 1 The general structure and the numbering of carbon atom of C and E units
in epoxidized natural rubber (ENR-50) employed in this work
Scheme 2 Reaction of isopropyl alcohol/ potassium hydroxide with epoxidized
isoprene and its carbon numbering
Figure 2 (a) 1H- and (b) 13C-NMR spectra of treated epoxidized natural rubber
(ENR-50) in deuterated chloroform (CDCl3)
Figure 3 (a) heteronuclear multiple quantum coherence (HMQC) spectra of
treated epoxidized natural rubber (ENR-50) and (b) enlargement of the

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box region in (a)
Figure 4 (a) heteronuclear multiple bond coherence (HMBC spectra of treated
epoxidized natural rubber (ENR-50) and (b,c) enlargement of the box

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region in (a)
Figure 5 Correlation spectroscopy (COSY) spectra of treated epoxidized natural
rubber (ENR-50)

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Figure 6 Fourier transform infrared spectroscopy (FTIR) spectra of (a) purified
epoxidized natural rubber (ENR-50) and (b) treated epoxidized natural
rubber (ENR-50)
Figure 7 (a) Thermogravimetric (TG) and (b) derivative thermogravimetric

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(DTG) thermograms of (i) purified epoxidized natural rubber (ENR-50)
and (ii) treated epoxidized natural rubber (ENR-50)
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Figure 8 Differential scanning calorimetry (DSC) thermograms of (a) purified
epoxidized natural rubber (ENR-50) and (b) treated epoxidized natural
rubber (ENR-50)
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Tables:
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Table 1: 1H-, 13C-NMR chemical shifts and HMQC, HMBC and COSY spin coupling
correlations of treated ENR-50.
1 13
H C HMQC HMBC coupling COSY coupling
chemical chemical correlation correlation
shift, shift, Triad assignments Middle unit, δ (ppm) Middle Within
δ (ppm) δ (ppm) unit, same
δ (ppm) unit,
δ
(ppm)

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10 8 6
1.30 22.2 E 29.7 (E ), 60.8 (E ), 64.5 None None
(E7)
22.2 {E21, EE21C, 73.7 (E20)

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CE21E, CE21C}
(↑& ↓)
23.3 {E10, EE10C, 32.0, 35.0, 41.0 (E8), 77.7

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CE E, CE C} (↑) (E7), 84.5 (E6)
10 10

23.9 {E10, EE10C, 36.5, 41.0 (E8), 77.7 (E6),

CE E, CE C} (↓) 86.5 (E7)
10 10

{CE9C, EE9C} (↓) 77.7 (E6), 86.5 (E7) 2.73 (E7) 2.18

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1.57 23.9
(C3)
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27.0 CE9C, EE9C 60.8 (E6), 64.5 (E7)
8 8
29.7 EE C, E 22.2 (E10), 60.8 (E6), 64.5 None 1.69
(E7) (E9)
29.7 { CE9C, EE9C} (↓) 77.7 (E7). 84.5 (E6) 2.73 (E7) 2.18
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(C3)
8 8 10 7
32.0 {E , EE C} (↓) 23.3 (E ), 77.7 (E ), 84.5 None 1.69
(E6) (E9)
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33.1 CE8C, CE8E 22.2 (E10), 60.8 (E6), 64.5 2.18

(E7) (C4)
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35.0 {E8, EE8C} (↑) 23.3 (E10), 77.7 (E7), 84.5 1.69
(E6) (E9)
36.5 {E8, EE8C} (↓) 23.9 (E10), 77.7 (E6), 86.5
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(E7)
41.0 {CE8E, CE8C} (↑ 23.3, 23.9 (E10), 77.7 (E7), 2.18
& ↓) 84.5 (E6) (C4)
1.69 23.3 C5 32.0 (C3), 125.1 (C2), 134.7 None
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(C1)
{E9, CE9E} (↓) 77.7 (E6), 86.5 (E7) 2.73 (E7) 1.57
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23.3
(E8)
24.6 CE9E, E9 60.8 (E6), 64.5 (E7)
9 9
26.2 {E , CE E} (↓) 77.7 (E6), 86.5 (E7)
27.0 {E9, CE9E} (↑) 77.7 (E7), 84.5 (E6)
3 3
2.06 26.2 C , CC E 23.3 (C5), 125.1 (C2), 134.7 None 2.06
(C1) (C4)
26.2 C4, EC4C 125.1 (C2), 134.7 (C1) 5.13-5.17
(C2)
4 4 2 1
2.18 23.9 CC E, EC E 125.1 (C ), 134.7 (C ) 1.57
(E8)
28.7 EC3C, EC3E 23.3 (C5), 125.1 (C2), 134.7 None
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(C1)
- 60.8 E6 - - -
84.5 {E6, EE6C, CE6E,
CE6C} (↑)
2.73 64.5 E7 22.2 (E10), 24.6 (E9), 29.7 1.69 (E9) None
(E8), 60.8 (E6)
73.7 {E20, EE20C, 22.2 (E21) 1.30
CE20E, CE20C} (↑ (E21)
& ↓)

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77.7 {E7, CE7E} (↑) 23.3 (E10), 27.0 (E9), 32.0, 1.69 (E9) 1.57
35.0, 41.0 (E8), 84.5 (E6) (E8)
77.7 {EE7C, CE7C} (↑) 23.3 (E10), 29.7 (E9), 32.0, 1.57 (E9) 2.18

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35.0, 41.0 (E8), 84.5 (E6) (C4)
86.5 EE7C (↓) 23.3 (E9, E10), 36.5 (E8),
77.7 (E6)

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86.5 E7 (↓) 23.3 (E9), 23.9 (E10), 36.5 1.69 (E9) 1.57
(E8), 77.7 (E6) (E8)
86.5 CE7E (↓) 23.3 (E9), 23.9 (E10), 41.0
(E8), 77.7 (E6)

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86.5 CE7C (↓) 23.9 (E9, E10), 41.0 (E8), 1.57 (E9) 2.18
77.7 (E6) (C3)
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86.5 {E7, CE7E} (↓) 23.9 (E10), 26.2 (E9), 36.5, 1.69 (E9) 1.57
41.0 (E8), 77.7 (E6) (E8)
3.00- 77.7 {E7, CE7E, EE7C, None None None
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4.20 CE7C} (↑)

4.70- 77.7 {E6, EE6C, CE6E,
5.00 CE6C} (↓)
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5.13- 125.1 C2 23.3 (C5), 26.2 (C4), 32.0 2.06 (C4) None
5.17 (C3), 134.7 (C1)
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- 134.7 C1 - - -
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