Preparation of NBR Polyol by Oxidative Degradation

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Original Article
Journal of Cellular Plastics
0(0) 1–10
Preparation of natural ß The Author(s) 2015
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DOI: 10.1177/0021955X15583882
oxidative degradation cel.sagepub.com
under supercritical
carbon dioxide for
flexible bio-based
polyurethane foams
Thidarat Amnuaysin, Piyapong Buahom
and Surat Areerat
Abstract
Nowadays, polyurethane foams play a key role in widespread applications, and their
market demand is still growing globally. This work aims to prepare hydroxyl telechelic
liquid natural rubber, a bio-based polyol, as a sustainable raw material and to enhance
elastic properties of soft segment bio-based polyurethane foams. A hydroxyl telechelic
liquid natural rubber with a viscosity-average molecular weight of 4.2 103 g/mol was
successfully produced by oxidative degradation of natural rubber with hydrogen per-
oxide in the presence of supercritical carbon dioxide, then modifying the chain-end
functionality to obtain hydroxyl number of 59 mg KOH/g. The functionality of hydroxyl
telechelic liquid natural rubber was confirmed by FT-IR and 1H-NMR. Bio-based poly-
urethane foams were then prepared by mixing the synthesized hydroxyl telechelic liquid
natural rubber with commercial diisocyanate. Morphological properties and thermal
stability of polyurethane foams were investigated.
Keywords
Flexible polyurethane foams, oxidative degradation, epoxidized natural rubber,
hydroxyl-terminated liquid natural rubber, sorbitol
School of Chemical Engineering, Faculty of Engineering, King Mongkut’s Institute of Technology Ladkrabang,
Bangkok, Thailand
Corresponding author:
Surat Areerat, School of Chemical Engineering, Faculty of Engineering, King Mongkut’s Institute of Technology
Ladkrabang, Bangkok 10520, Thailand.
Email: kasurat@kmitl.ac.th
Downloaded from cel.sagepub.com at DALHOUSIE UNIV on May 18, 2015

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2 Journal of Cellular Plastics 0(0)
Introduction
Polyurethane (PU) foams are promising for applications leveraging their proper-
ties. These kinds of cellular materials are prepared by reacting isocyanates with a
polyol—an organic compound containing hydroxyl groups on the structure.
Besides other renewable feedstock, such as soybean oil, cotton seed oil, palm oil,
and rape seed oil,1–3 natural rubber (NR) attracts many researchers to be an alter-
native, sustainable bio-based raw material for preparation of the polyol.4–7
As the repeating unit of NR—cis–1, 4–isoprene—consists of double bonds
which can be modified towards specific functional groups, this advantage leads
to high-functionality derivatives of NR such as epoxidized natural rubber
(ENR), carbonyl telechelic natural rubber (CTNR), and hydroxyl telechelic
liquid natural rubber (HTNR).8 However, there are some drawbacks of NR that
lead to difficulties in preparing bio-based PU foams: high molecular weight of
about 106 g/mol and a wide range of molecular weight distribution. It is therefore
needed to provide a low-molecular weight NR-based polyol with specific functional
groups in order to prepare a PU foam with high uniformity.
Since the issue with a particular low molecular weight NR-based polyol has been
taken, methods for molecular weight reduction of NR have been increasingly
developed. Phetphaisit et al.9 succeeded in breaking down the molecular structure
of NR by oxidizing with potassium sulfate (K2SO4) for 30 h, preparing a liquid
natural rubber (LNR) with low viscosity-average molecular weight (MV) of
3.2 103 g/mol. Periodic acid was also used as an oxidizing agent in oxidative
degradation of NR to prepare an LNR with MV ¼ 2 103 to 5 103 g/mol.5
Duereh et al.10 applied advantages of supercritical carbon dioxide (scCO2) to oxi-
dative degradation of NR with hydrogen peroxide so that peroxycarbonic acid was
generated. This intermediate substance opened the epoxide rings on the NR’s
structure, breaking the long chain into lower molecular weight CTNR and
HTNR with carbonyl and hydroxyl end-groups, respectively.
The aim of this research was to prepare an HTNR polyol from ENR and then
produce bio-based PU foams. In this work, hydrogen peroxide was used as an
oxidizing agent of the emulsifier-assisted oxidative degradation of NR under
scCO2, and sorbitol was added into the system as the emulsifier in order to facilitate
the interfacial area of reaction between the two immiscible phases: organic phase
(ENR50/toluene/scCO2) and aqueous phase (H2O2/H2O). The bio-based PU foams
were prepared by reacting the HTNR with a commercial diisocyanate.
Experimental section
ENR purification
ENR 50% mol (ENR50, SAN-THAP) 5 g was refluxed with toluene (HPLC grade
from RCI Labscan) 100 ml, in a 500-ml tree-necked round bottom flash, at 70 C
for 24 h, before precipitating in methanol and drying in a vacuum oven at 40 C for
24 h. The schematic of experimental setup is shown in Figure 1.

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Amnuaysin et al. 3
Figure 1. A schematic of equipment used in the experimental setup.
CO 2
x y
Organic/Fluid Phase
Aqueous H2 O 2 Phase
O
CO 2 + H2O 2 HO OOH
Carbon Hydrogen Peroxycarbonic Acid
Dioxide Peroxide
O O
O
X X'
HO OOH
+
m n x y
TLNR Peroxycarbonic Acid ENR
Figure 2. Oxidative degradation of ENR and peroxycarbonic acid in a two-immiscible-phase

system of scCO2 organic (upper) phase and aqueous (lower) phase.
TLNR: telechelic liquid natural rubber; ENR: epoxidized natural rubber.
Synthesis of ENR-based LNR

After preparation by dissolving purified ENR50 into toluene, an ENR solution
(2.00%w/v) was oxidized with hydrogen peroxide (H2O2/H2O 30%wt, AR grade
from UNIVAR) of 10 and 20 part per hundred rubber (phr) as an oxidizing agent
mixed with emulsifier 0, 0.01, 0.03, and 0.05 g sorbitol/ml. Sorbitol was added into
the system as the emulsifier in order to facilitate the interfacial area of reaction
between the two immiscible phases as shown in Figure 2: organic phase (ENR50/
toluene/scCO2) and aqueous phase (H2O2/H2O). The solution was added to a high-
pressure vessel (Taiatsu Techno/Japan SUS316 15 ml) vial about 5 ml and stirred
with a magnetic stirrer. Then carbon dioxide was supplied into the high-pressure

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o
1) NaBH4 / THF 60 C /6 h
O O HO OH
2) H2O /THF RT
m m
Figure 3. HTNR from oxidative reaction of CTNR.
vessel through ISCO Syringe Pump (Model 260D/USA.) at 40 C and 60 C until
pressure reached to 120 bar. After 6 h, the solution was taken out and a limiting
agent was added, propanal aldehyde (97% from ALDRICH). The resulting solu-
tion was washed with water and dried in a vacuum oven at 40 C for 24 h.
Functional groups of the LNR were analyzed by FT-IR and 1H-NMR. MV of
LNR was determined by Ubbelohde viscometric method together with Mark-
Sakurada-Honwink equation
½ ¼ 5:0 104 M0:67

V ð1Þ
Preparation of LNR-based HTNR and PU foams

LNR was dissolved into tetrahydrofuran (THF, AR grade from RCI Labscan) to
prepare 0.01 mol/L LNR solution. HTNR polyol prepared from LNR was reacted
to sodium borohydride (NaBH4 98% from ALDRICH) 5 mol equivalent for 6 h at
30 C. The reaction is shown in Figure 3. Then, HTNR was analyzed the functional
groups by FT-IR and 1H-NMR and determined the hydroxyl number of HTNR by
ASTM D 4274-99. Then, bio-based PU foams were prepared by mixing the synthe-
sized HTNR with diisocyanate.
Results and discussion

Molecular weight of LNR
Figure 4 shows the effects of hydrogen peroxide and temperature on molecular
weight of LNR after oxidative degradation with H2O2 under scCO2 at 120 bar,
compared with that of the virgin ENR50 (3.0 105 g/mol). MV of NR is reduced to
1.3 105 g/mol (about a half of the virgin ENR50) at both 40 C and 60 C at 10 phr
H2O2. Increasing temperature from 40 C to 60 C at 10 phr H2O2 had less signifi-
cance to MV reduction of NR, in other words. However, increasing amount of
H2O2 to 20 phr resulted in a dramatic molecular weight reduction to
MV ¼ 9.30 104 g/mol at 40 C and 1.90 104 g/mol at 60 C (about 7-fold reduc-
tion compared with that at 10 phr, 16-fold reduction compared with the virgin
ENR50). As the oxidative degradation is an endothermic reaction, increasing tem-
perature and the amount of H2O2, which directly determines the amount of the
used ENR50, resulted in MV reduction of NR.

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Amnuaysin et al. 5
1,000,000
10 phr H2O2
300,000
20 phr H2O2
130,000 130,000
93,000
100,000
19,000
MV (g mol )
14,000
10,000
4,200 5,400
1,000
100
40 °C 60 °C 60 °C 60 °C 60 °C
ENR50 0 gsb/mlH2O2 0 gsb/mlH2O2 0.01 gsb/mlH2O2 0.03 gsb/mlH2O2 0.05 gsb/mlH2O2
Figure 4. Viscosity-average molecular weight of original ENR50 rubber and LNRs from oxi-
dative degradation using H2O2 under scCO2 at 120 bar, 40 C, and 60 C, with and without
sorbitol. ENR: epoxidized natural rubber.
Considering the effect of sorbitol on molecular weight reduction of NR, it can be

seen that higher amount of emulsifier, in terms of the sorbitol/H2O2 ratio,
employed the better molecular weight of the LNR, as emulsifier of the ENR50
oxidative degradation with 20 phr H2O2 under scCO2 at 60 C and 120 bar. This is
because the emulsifier facilitates reaction interface between organic (ENR50/tolu-
ene/scCO2) and aqueous phase (H2O2/H2O). At 0.03 g sorbitol/ml H2O2, LNR had
an average molecular weight of 4200 g/mol.
Functional groups and chemical structure of LNR

Figure 5(a) and (b) shows infrared spectra of ENR50 and LNR prepared by H2O2
of 10 and 20 phr at 40 C and 60 C without emulsifier assist under scCO2. The
infrared spectrum of ENR50 indicates the absorption peaks of epoxide ring
(C-O-C) at 1250 cm1 (symmetric stretching of epoxide ring). Comparing FT-IR
spectra of ENR50 with those of LNRs, it was found that the peak of epoxide ring
at 1250 cm1 disappeared, whereas the absorption peaks of carbonyl (C ¼ O) at
1720 cm1 were still observed and the peaks of hydroxyl (OH) at 3440 cm1
appeared. This means that increasing amount of H2O2 and temperature resulted
in higher FT-IR spectra levels of carbonyl and hydroxyl groups, as molecular
weight of ENR reduced.
Figure 5(c) illustrates the significant effect of adding emulsifier, sorbitol/H2O2
ratio of 0.05 g/ml, on the strong signal of carbonyl function (at 1720 cm1). As
emulsifier, sorbitol increased the reaction interface between the organic and aqueous
phases, resulted in higher degree of depolymerizing the cleavage epoxide ring unit.
Figure 6(a) and (c) provides 1H-NMR spectra of ENR50 and LNR prepared by
20 phr H2O2 and emulsifier (0 and 0.05 g sorbitol/ml) under scCO2 at 60 C and 120
bar. It is obviously the proton signal of the epoxide ring (at 2.7 ppm) for ENR50

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Figure 5. FT-IR spectra of (a) ENR50 and LNRs prepared by oxidation with H2O2 at 60 C
and 120 bar without emulsifier assist, (b) ENR50 and LNRs prepared by oxidation with H2O2
20 phr at 120 bar without emulsifier assist, (c) LNRs prepared by oxidative degradation with
H2O2 20 phr at 60 C and 120 bar, and (d) those of the CTNR and HTNR.
ENR: epoxidized natural rubber; CTNR: carbonyl telechelic natural rubber; HTNR: hydroxyl
telechelic liquid natural rubber.
figure that disappears after the LNRs were synthesized as well as the signals of
methylene protons (at 2.09 ppm) and the methylic protons in ketone end-group (at
2.17 ppm) at the chain-ends that were observed for 1H-NMRs’ spectra. This con-
firms that the ENR50-based LNRs both with and without using emulsifier were
CTNRs. In addition, the figure for emulsifier-assisted CTNR shows greater signal
intensity of carbonyl chain-end characteristic than that of CTNR without emulsi-
fier assist; this means that the emulsifier enhanced the CTNR reaction, increasing
the specific chain-end functionality.
LNR-based HTNR
Figure 5(d) compares FT-IR spectra of CTNR and HTNR (MV ¼ 4200 g/mol). It
was found that the characteristic signal of hydroxyl (–OH) groups (at 3440 cm1)

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Amnuaysin et al. 7
Figure 6. 1H-NMR spectra of (a) ENR50, (b) LNR without emulsifier assist, (c) emulsifier-
assisted LNR, and (d) HTNR polyol.
was still exhibit in both CTNR and HTNR, while the signal of carbonyl (C ¼ O)
groups (at 1720 cm1) disappeared. In addition, as shown in Figure 6(d), the
1
H-NMR spectrum of HTNR demonstrates that the new signal of CH adjacent
to alcohol group at the chain-end (at 3.80 ppm) was observed. Regarding to the

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Figure 7. Morphology of NR-based PU foams: (a)–(c) PU1 foam and (d)–(f) PU2 foam.
results, this means that the LNR-based HTNR was modified the terminated car-
bonyl groups into hydroxyl chain-ends.
Moreover, OH-number of the prepared HTNR was 59 mg KOH/g (ASTM D
99-4274), which is the range of polyol for preparing flexible PU foams.11
NR-based PU foams
Properties and morphology of the NR-based PU foams were prepared by the
HTNR and diisocyanate. The foam has an average bubble size of 250 mm, with
bubble density of 7.9 103 cell/cm3, and bulk density of 0.63 g/cm3. Water was
added into the preparing process, producing a foam with bubble size of 8 mm,

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Amnuaysin et al. 9
100 Without water

Adding water
80
Weight (%)
60
40
20 Zone Zone Zone

1 2 3
0
0 100 200 300 400 500 600
Temperature (°C)
Figure 8. DSC thermograms of the NR-based PU foams prepared with and without water.
2.2 107 cell/cm3, and bulk density of 0.51 g/cm3. Their foam morphologies are
shown in Figure 7.
As shown in Figure 8, thermal gravimetric analysis claims the three-step thermal
degradation of the PU foams: degradations of (1) water and solvent, (2) the ureth-
ane linkage, and (3) the polyisoprene backbone, at approximately 100 C, 280 C,
and 370 C, respectively.
Conclusions
In this work, CTNR LNRs with MV of 1.90 104 g/mol (about 16-fold reduction
compared with the original ENR50) were prepared by oxidative degradation of
ENR50 with 20 phr hydrogen peroxide under scCO2 atmosphere at 60 C and 120
bar for 6 h. Adding emulsifier by 0.03 g sorbitol/ml H2O2 enhanced the reaction so
that the molecular weight of NR reduced to 4.2 103 g/mol. By reduction with
sodium borohydride and hydrolysis with ice, the prepared CTNR was then mod-
ified their functional end-groups into hydroxyl chain-end to produce HTNRs with
hydroxyl number of 59 mg KOH/g. This HTNR polyol was then used as a reactant
for preparing bio-based flexible closed-cell PU foams.
Funding
This research received no specific grant from any funding agency in the public, commercial,
or not-for-profit sectors.
Conflict of interest
None declared.
References
1. John J, Bhattacharya M and Turner RB. Characterization of polyurethane foams from
soybean oil. J Appl Polym Sci 2002; 86: 3097–3107.

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Preparation of NBR Polyol by Oxidative Degradation

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oxidative degradation cel.sagepub.com

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2 Journal of Cellular Plastics 0(0)

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Figure 1. A schematic of equipment used in the experimental setup.

Figure 2. Oxidative degradation of ENR and peroxycarbonic acid in a two-immiscible-phase

Synthesis of ENR-based LNR

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4 Journal of Cellular Plastics 0(0)

Figure 3. HTNR from oxidative reaction of CTNR.

½ ¼ 5:0 104 M0:67

Preparation of LNR-based HTNR and PU foams

Results and discussion

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Considering the eﬀect of sorbitol on molecular weight reduction of NR, it can be

Functional groups and chemical structure of LNR

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6 Journal of Cellular Plastics 0(0)

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8 Journal of Cellular Plastics 0(0)

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100 Without water

20 Zone Zone Zone

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10 Journal of Cellular Plastics 0(0)

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½ ¼ 5:0 104 M0:67