10.1002/spepro.

003383
Interpenetrating polymer
network of blocked
polyurethane and phenolic resin
Chin-Hsing Chen
Simultaneous polymerization enables synthesis of interpenetrating
polymer networks.
Interpenetrating polymer networks (IPNs) represent a special class of
blends in which the polymers are crosslinked. These materials are char-
acterized by the presence of two networks that are strongly entangled,
ideally only by topological constraints. We synthesized an IPN based
on blocked polyurethane (BPU) and phenolic (PF) using simultane-
ous polymerization. The resulting properties are tightly related to both
the chemical structure of the networks and their synthesis path. We
used two main routes, including sequential
13
and simultaneous IPN
46
synthesis (referred to as SIPN and SIN, respectively). SIPN works by
swelling a polymer network with a monomer mixture, which is poly-
merized in situ. In SIN, both monomers/prepolymers and their curing
agents are simultaneously polymerized and crosslinked based on non-
interfering reactions. In this case, if one of the two polymers reaches
the gelation point before the other, it will tend to be more continuous
in space and dominate the materials properties. SIN generally reaches
the highest degree of intermixing compared with SIPN because of the
compatibility of the monomeric mixture, which is much higher than
that of a polymeric mixture.
7
We simultaneously mixed the BPU pre-
polymer with m-xylylenediamine (MXDA) as a chain extender and PF
prepolymer using p-toluene sulfonic acid (PTSA) as catalyst at room
temperature, and triggered an interpenetrating reaction at an elevated
temperature of 140

C. Our synthesis followed the chemical reactions

shown in Equations (1) and (2),
Figure 1. Fourier-transform IR spectra of the reaction system of
blocked polyurethane (BPU) and phenolic (PF) at (a) time t D 0,
(b) 3min, and (c) 16h, all at a temperature of 140

C. NCO: Isocyanate.
OH: Hydroxyl.
Continued on next page
10.1002/spepro.003383 Page 2/3
Equation (3) represents the chemical structure of PF,
Figure 1 shows Fourier-transform IR (FTIR) spectra of the BPU/PF
reaction system without either MXDA or PTSA at various reaction
times and a constant temperature of 140

C. At the start of the re-

action, we measured an absorption-peak intensity of hydroxyl (OH)
at 1000cm
1
(associated with PF) but not of isocyanate (NCO) at
2270cm
1
. After heating for 3min, an NCO absorption peak (related
to BPU) appeared. After 16h, both absorption peaks disappeared at
the same time. We found that in the BPU/MXDA system, the NCO
absorption peak disappeared within 4h. However, in BPU/PF without
an MXDA/PTSA system, it required 16h for the NCO peak to disap-
pear. Our results indicate that the NCO group of BPU reacts slowly
with the OH group of PF compared with the reaction rate between
NCO and the NH
2
amino group of MXDA. Based on our FTIR spec-
tral analysis, we also conrmed that in the BPU/PF IPN (composed
of BPU/MXDA/PF/PTSA), the major reactions are the polymerization
of BPU/MXDA and the self-polymerization of PF. The BPU/MXDA
reaction process is described by Equations (4) and (5), while the PF
polymerization reaction is expressed by Equation (6).
Figure 2. Scanning-electron micrographs of fracture surfaces of the
BPU/PF interpenetrating network of (a) 0/100, (b) 15/85, (c) 25/75,
(d) 50/50, (e) 75/25, and (f) 100/0 (BPU/PF fractions).
Figure 2 shows scanning-electron micrographs of the fracture sur-
faces of pure components of both PF and BPU and of BPU/PF IPNs
for a range of BPU content. Pure PF expressed a smooth and glossy
microstructure because the material is brittle, while BPU exhibited
a rough microstructure because it is a ductile material. As the BPU
content of the BPU/PF IPN was increased, the IPNs microstructure
became rougher and the compatibility of the BPU/PF IPNs improved.
Our morphology study showed that the IPN system is heterogeneous
and that more than one phase exists in the networks.
Figures 3 and 4 show tensile strengths and moduli versus BPU con-
tent for unlled and 10 per hundred resin (phr) lled (kaolin) BPU/PF
IPNs. All of the properties investigated decreased with increasing
BPU content. The explanation of this is that the hard segments of PF
appeared to have greater strengths and moduli compared to the soft
BPU segments. The BPU soft segments may be partially dissolved in
the PF matrix (as can be seen from the scanning-electron micrographs).
Therefore, all tensile strengths and moduli decreased with increasing
BPU content.
We next plan to focus on kinetic formation, swelling ratio, thermal
properties, and ame resistance of BPU/PF IPN systems. We have al-
ready begun studying the kinetic aspects of the formation of a second
Continued on next page
10.1002/spepro.003383 Page 3/3
Figure 3. Tensile strength versus BPU content for unlled and 10 per
hundred resin (phr) lled (kaolin) BPU/PF IPN.
Figure 4. Tensile modulus versus BPU content for unlled and 10phr
lled (kaolin) BPU/PF IPN.
network in the presence of the rst. We will examine the effects on
kinetics of parameters such as BPU content and reaction temperature.
Our studies of the swelling ratio, thermal properties, and ame resis-
tance of IPNs will focus on quantication of the effects of BPU and
ller content.
Author Information
Chin-Hsing Chen
Department of Chemical and Materials Engineering
Chinese Culture University
Taipei, Taiwan
Chin-Hsing Chen obtained his PhD from the National Tsing Hua Uni-
versity (Taiwan). He is currently professor and department chair.
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c 2011 Society of Plastics Engineers (SPE)