Interpenetrating Polymer Networks

272 INTERCALATION POLYMERIZATION Vol.
10
INTERPENETRATING
POLYMER NETWORKS
Introduction
An interpenetrating polymer network, IPN, is defined as a combination of two

polymers in network form, at least one of which is synthesized and/or cross-linked
in the immediate presence of the other (1). An IPN is distinguished from other
multipolymer combinations such as Polymer Blends (qv), blocks, and grafts in two
ways: (1) An IPN swells, but does not dissolve in solvents; and (2) creep and flow
are suppressed (see BLOCK COPOLYMERS; GRAFT COPOLYMERS).
The above represents the classical definition of an IPN. The term interpen-
etrating polymer network was coined before the extent or consequences of phase
separation were fully realized. This article covers sequential and simultaneous
types of IPNs made in bulk and also includes such materials as IPNs based on
latexes and suspension-sized particles; thermoplastic IPNs, which contain physi-
cal cross-links in one or both polymers, and hence may be (partly) soluble; and a
number of other closely related materials.
Some applications of IPNs of note include sound and vibration damping,
biomedical applications, natural products and renewable resources, tough and
impact-resistant materials, etc. IPN review articles include those by Sperling and
Hu (2), Lipatov (3), and Athawale and co-workers (4). There are also papers of
note by Srivastava and co-workers (5), and edited books by Klempner and co-
workers (6), and Kim and Sperling (7). Two older books review early references,
and develop the concepts of IPNs (1,8).
Nomenclature. The IPNs have a well-developed nomenclature (9), as do
most multicomponent polymeric materials (10). Thus, a cross-linked polymer net-
work is indicated by the prefix net-, and an IPN is indicated by the connective
-ipn-. Thus, an IPN of polybutadiene and polystyrene is written as
Encyclopedia of Polymer Science and Technology. Copyright John Wiley & Sons, Inc. All rights reserved.
Vol. 10 INTERPENETRATING POLYMER NETWORKS 273
(net-polybutadiene)-ipn-(net-polystyrene)
and if copolymers and/or two-worded mer structures are needed, brackets are
employed:
{net-poly(styrene-stat-butadiene)}-ipn-{net-poly(ethyl acrylate)}
Synthesis and Structure of IPN and SIN Materials
Figure 1 models the structure of interpenetrating polymer networks and related

materials. Solid and dotted lines indicate polymer 1 and polymer 2, respectively.
The dots indicate cross-links. Structure a indicates a polymer blend, where the
two polymers are mixed, but not bonded together anywhere. Structure b indi-
cates a graft copolymer (qv), where polymer 2 is bonded along the side of poly-
mer 1. Structure c indicates a block copolymer (qv), where polymers 1 and 2 are
bonded end-on-end. These three structures are all thermoplastic, in that, not be-
ing cross-linked, they flow if heated above their glass transition and/or melting
temperatures.
Structure d illustrates an AB–cross-linked copolymer. In this case, polymers
1 and 2 are bonded to each other. Structure e indicates an IPN, sometimes called a
Fig. 1. Six basic combinations of two polymers, represented by solid and dashed lines,
respectively, and the dots representing covalent bonds. (a) A polymer blend, with no bonding
between the chains; (b) a graft copolymer, with the dashed polymer bonded to the side of the
solid line polymer; (c) a block copolymer, where the chains are bonded end-on-end; (d) an
AB-cross-linked copolymer, where one polymer is bonded to the other, but not to itself; (e) an
interpenetrating polymer network of two cross-linked polymers; (f) a semi-interpenetrating
polymer network, where only one of the polymers is cross-linked.
274 INTERPENETRATING POLYMER NETWORKS Vol. 10
full IPN, where both polymers are cross-linked. Structure f illustrates a semi-IPN,
where one polymer, but not both, are cross-linked. These last three structures are
all thermoset, because at least one polymer network pervades the entire material.
Thus, they will not flow on heating.
Of course, one may imagine many related structures and/or more complex
topologies. By simple analogy, three or more polymers may coexist in any one of
the topologies of Figure 1. Some quite different materials include the polyrotax-
anes, where rings encircle a polymer chain (11); catenanes (12), where a series of
rings form a chain (13); and dendrimers. These latter are hyperbranched, fractal-
like structures emanating from a central core and containing a large number of
terminal groups (14) (see DENDRONIZED POLYMERS). Noting that the polyrotaxanes,
catenanes, and dendrimers are usually one-phase polymers, their behavior is quite
different from that of any of the structures shown in Figure 1.
Figure 2 (15) outlines the two basic methods of IPN synthesis. In
Figure 2, the boxes indicate monomers, the X’s indicate cross-links, and the sub-
scripts indicate whether it goes to make up polymer 1 or polymer 2. As in Figure
1, the lines indicate the polymers and the dots indicate cross-links. The P1 and P2
above the arrows indicate polymerization of polymer 1 and polymer 2, respectively.
The general procedure to synthesize a sequential IPN calls for mixing
monomer 1 and cross-linker 1 and polymerizing to form network 1. Then, monomer
2 and cross-linker 2 are swollen in, and polymerized in situ.
A simultaneous interpenetrating network, SIN, as the name suggests, starts
with a mix of both monomers and both polymers. These are polymerized simul-
taneously, but by different routes, such as chain and step polymerization. Thus,
while reacting, the two polymers do not interfere with each other, but merely dilute
Fig. 2. Two basic synthetic methods of preparing IPNs, sequentially and simultaneously.
(a) Sequential IPNs; (b) simultaneous interpenetrating network (SIN).
each other. Of course, the rates of the two reactions need not be equal. As explored
below, if one polymer or the other reacts faster, different morphologies may result,
with concomitant different physical and mechanical behavior patterns.
Besides sequential and simultaneous IPN synthetic methods, there are sev-
eral other methods of preparation:
Latex IPNs. The polymers are made via emulsion polymerization, each par-
ticle constituting a micro-IPN. Frequently, one monomer and cross-linker
are polymerized, followed by addition of a second monomer and cross-linker,
which is also polymerized. Depending on the rates of monomer addition rela-
tive to the rates of polymerization, various degrees of interpenetrating and/or
core-shell morphologies may result.
Gradient IPNs. The overall composition and/or cross-link density of the ma-
terial varies from location to location on the macroscopic scale. One way of
preparing these materials involves partial swelling of the first polymer net-
work by the second monomer mix, followed by rapid polymerization before
diffusional equilibrium takes place.
Thermoplastic IPNs. These materials utilize physical cross-links rather than
chemical cross-links. Thus, the materials may be made to flow at elevated
temperatures. As such, they are hybrids between polymer blends and IPNs.
Such cross-links may involve block copolymers, ionomers, and/or semicrys-
tallinity.
Semi-IPN. As illustrated in Figure 1f, a semi-IPN is composed of a cross-linked
polymer and a linear polymer. If one is making a sequential synthesis, the
terminology semi-I and semi-II IPNs refers to having the first or second
polymer cross-linked, respectively.
Homo-IPNs. These materials consist of two networks prepared from substan-
tially the same cross-linked polymer.
Special Considerations in IPN and SIN Synthesis. Most of the IPNs

and SINs made to date rely on chain and/or step polymerization, although other
methods, such as anionic polymerization, have been occasionally employed. Of
course, appropriate cross-linkers, initiators, and so forth must be added.
For very many IPN and SIN syntheses, except for phase separation aspects,
the interaction between the two materials during polymerization has often been
ignored. However, to greater or lesser extents in real systems, of course, there is
some interaction. A few examples are helpful:
(1) In sequential IPNs, if polymer I is based on a diene, and monomer II (such

as styrene) is polymerized via free-radical polymerization, some grafting
will occur. Of course, this grafting is important for interfacial bonding in
such related materials as high impact polystyrene (HIPS) and acrylonitrile–
butadiene–styrene (ABS) materials.
(2) If polymer I is an acrylic, the labile hydrogen may be abstracted, providing
another type of grafting site.
(3) In a SIN polymerization, the high viscosity of one of the polymers, or its lack
of high viscosity as a slow-polymerizing component, may alter the phase
morphology or other features.
(4) Vitrification of one of the polymers may slow or stop the polymerization of
the other component.
Some specific investigations of the chemical interactions include the

following:
Tabka and Widmaier (16,17) undertook the study of the interactions of azo-
bis(isobutyronitrile) (AIBN), free-radical initiators with stannous and stannic
organotin polyurethane catalysts. These workers found a synergistic effect of stan-
nous octoate on the AIBN on the radical polymerization (qv) of methyl methacry-
late, increasing the reaction rate and shortening the gelation time. While there
was a severe deactivation of the tin(II) atom by the AIBN, there was no measurable
effect using organotin(IV) stannic catalysts.
Michal’chuk and co-workers (18) investigated the changes in mobility dur-
ing formation on the basis of epoxy and allylic oligomers. Using pulse NMR
spectroscopy, these workers concluded that SIN formation results in mutual hin-
drances to the full conversion of the reactive groups, and a concomitant increase
in the number of defects in the IPNs. This results in greater molecular mobility
in the final materials than might otherwise be expected.
Polymer Blend and IPN Classification Scheme. Of course, all of the
various compositions of matter composed of two polymers are related to each
other. Figure 3 (19) illustrates how the major kinds of polymeric materials based
on two kinds of mers are related to each other. The IPNs are shown here under
the occasional grafts heading, because many of the preparations have a few grafts
between the two polymers as a consequence of free-radical chemistry, etc. Since
one network of these materials is always polymerized in the presence of the other
Fig. 3. A polymer blend classification scheme.

network, some grafting is hard to avoid, and in many cases is desired. However,
an IPN (or SIN) can be distinguished from a graft copolymer (qv) because the
morphology (qv) and mechanical behavior are primarily controlled by the cross-
links rather than the grafts.
IPN Morphology and Physical Behavior
Most compositions of matter made up of two polymers (see Fig. 1) exhibit some
degree of phase separation. This is caused by the very small entropy of mixing two
high molecular weight materials, and the very frequent positive heat of mixing
of two different chemical structures. In simple polymer blends (qv), the mixing
tends to be relatively coarse, although many routes to complex and relatively
finely divided morphologies have been developed. Block copolymers (qv) domain
sizes are largely controlled by the molecular weight of the individual blocks, and
the domain shape by the relative proportions of the two blocks (20,21).
Electron Microscopy Studies. In sequential IPNs and semi-IPNs, the
size and shape of the polymer II domains are controlled by the cross-link density
of polymer I and the relative proportions of the two polymers. Figure 4 illustrates
Fig. 4. Transmission electron microscopy of OsO4 -stained polybutadiene and polystyrene

(white) combinations.
the two-phased morphology of IPNs, semi-IPNs, and polymer blends prepared

from styrene-butadiene copolymers (qv) (SBR) and polystyrene (22) (see STYRENE
POLYMERS). The double bonds in the butadiene polymers (qv) are stained dark
with osmium tetroxide. In this series of transmission electron micrographs, the
samples are sliced to about 60 nm thickness, sometimes called salami slices.
The upper left photo in Figure 4 is of HIPS, a material known for its toughness
(23). This material is a type of polymer blend made by dissolving polybutadiene or
SBR in styrene monomer, and polymerizing with stirring. The SBR is first soluble
in the styrene monomer, but phase separates after a few percent conversion. Part
of HIPS toughness comes from having grafts between the polybutadiene and the
polystyrene, and part of the toughness comes from a phase-within-a-phase-within-
a-phase morphology (24). Shortly after polymerization is initiated, the growing
quantity of polystyrene makes the SBR insoluble in the mix. At first, the SBR
phase is the continuous phase. On continued polymerization, the growing volume
and increasing viscosity of the polystyrene-rich phase causes a phase inversion,
helped by the stirring.
Of course, the styrene within the polybutadiene droplets is also polymerizing,
but cannot get out. It forms a very fine structure, also visible in the upper left photo
of Figure 4.
HIPS gets its toughness in part from this fine structure, and in part from the
grafting that takes place between the SBR and the polystyrene, increasing the
interfacial bond strength. (Commercially, block copolymers of polybutadiene and
polystyrene are often added to further increase the interfacial bond strength.)
The upper right photo has substantially the same composition as that in
the upper left, but was made without stirring. This material was first made in
1927 (25). It did not undergo phase inversion, and hence the SBR remains the
continuous phase. This material is adhesive in nature, but not commercial.
The corresponding sequential IPN morphology of the same overall compo-
sition is shown in the lower left photo. In this case, a sheet of SBR was cross-
linked, followed by swelling in styrene plus divinyl benzene and polymerizing in
situ. The phase domains are of the order of 100 nm, with both phases exhibiting
co-continuity. An increased cross-link level for the SBR results in a finer phase
domain structure, as shown in the lower right of Figure 4.
The two semi-IPNs are shown in the middle left and right photos of Figure 4.
The semi-I IPN resembles the full IPN, but the morphology is coarser. The semi-II
IPN resembles the upper right morphology. Of significant interest here was that
the HIPS exhibited a toughness value of about 80 J/m (1.5 ft·lb/in.) of notch, while
the middle left had about 160 J/m (3.0 ft·lb/in.), and the lower left had about 267
J/m (5.0 ft·lb/in.) of notch.
The development of the morphology in both the HIPS-type material and
the IPNs requires several steps (see Fig. 5) (26). The original polymer I swollen
with monomer II solution first has one phase. After a few percent of polymeriza-
tion, it phase separates via nucleation and growth kinetics. This tends to produce
spheroidal-shaped particles, the white material in Figure 5a. (Super-saturated
salt solutions often follow nucleation and growth phase separation kinetics.) On
further polymerization, the phase separation kinetics follows spinodal decom-
position, leading to interconnected cylinders (Fig. 5b) (27–29). Close examina-
tion of both the HIPS and IPN morphologies strongly suggests that spinodal
Fig. 5. Transmission electron microscopy of the polymerization of substantially the same

composition as shown in the lower left portion of Figure 4.
decomposition plays a strong role in the final morphology of these materials.

(Note that a thin section of a cylinder cut at an angle looks like an ellipsoid.)
Figures 5c, 5d, and 5e have something of an appearance of a snowstorm, because
the continued cross-linking limits phase separation.
Thus, as illustrated in Figure 6, the initial mix first has one phase, then
undergoes a region of nucleation and growth. Then, the composition enters the
spinodal decomposition region, arriving at the final morphology. Note that if phase
separation is more or less complete, the final composition will be a mix of nearly
pure polymer I and polymer II, with the final composition being an average.
Phase diagrams of IPNs have also been researched. Sophia and co-workers
(30) found that the phase diagram of a semi-IPN indicates a lower critical solution
temperature for these materials (Fig. 7), similar to that of polymer blends. Seem-
ingly strange, these materials are more mutually soluble at lower temperatures
than at higher temperatures, a consequence of their low entropy of mixing.
Fig. 6. A generalized phase diagram for the polymerization shown in Figure 5. OP = One
phase, NG = nucleation and growth, and SD = spinodal decomposition.
Fig. 7. A phase diagram of a polyurethane–poly(vinyl chloride) semi-IPN, showing a lower

critical solution temperature.
Fig. 8. A comparison of two possible morphologies of IPNs, based on (a) {poly(ethyl

acrylate)}-ipn-{poly(methyl methacrylate)} and (b) {poly(ethyl acrylate)}-ipn-polystyrene.
The relative miscibility (qv) of the two polymers in IPNs is controlled not only
by the thermodynamics of mixing, but to some extend also by the cross-link den-
sity and exact method of preparation. Huelck and co-workers (31) learned that
while IPNs of poly(ethyl acrylate) and polystyrene exhibited two distinct glass
transitions (qv) and two observable phases via transmission electron microscopy,
the corresponding {net-poly(ethyl acrylate)}-ipn-{net-poly(methyl methacry-
late)} compositions, being isomeric, had a microheterogeneous morphology
(see Fig. 8).
Ma and Tang (32) showed that increasing cross-link density of SINs of poly(n-
butyl acrylate) and epoxy 10:90 compositions tends to increase molecular inter-
penetration, and thus entanglement between the two networks.
Glass-Transition Behavior. Sánchez and co-workers (33) studied the sys-
tem {net-poly(methyl acrylate)}-ipn-{net-poly(methyl methacrylate)}, which is
not chemically isomeric, but close to being so. They varied the cross-linking level of
both polymers of these sequential IPNs. When the poly(methyl acrylate) was cross-
linked with 10% of ethylene glycol dimethacrylate (EGDMA), dynamic mechanical
studies on midrange compositions showed that the system had a single glass tran-
sition, showing it to be substantially miscible (see Fig. 9) (33). The poly(methyl
acrylate) network was polymerized first with 0.1% (open circles), 0.5% (squares),
and 10% (triangles). In each case, the PMMA network contained 10% EGDMA.
It must be noted that this apparent miscibility is only mechanical in nature,
a product of the high cross-link level of a sequential IPN. Sánchez and co-workers
(33) note that the key factor controlling the apparent miscibility in sequential
IPNs is the cross-linking density of the network polymerized first.
In related work, Dueñas and co-workers (34) found a similar effect with the
system poly(butyl acrylate) and poly(butyl methacrylate). At 10% cross-linking
level, the forced miscibility was sufficient to allow the glass transitions of the
IPNs to follow the Fox equation (35).
Fig. 9. Sequential IPNs of poly(methyl acrylate) and poly(methyl methacrylate) as a func-

tion of cross-linking level with EGDMA.
In block copolymers composed of random-coiled polymers, the molecular

weight of the blocks and their relative proportions controls the domain size and
shape (36,37). A somewhat similar relationship exists in IPN.
Domain Size Theory. Assuming spherical domains, Yeo and co-workers
(38) derived equations for the domain size in sequential IPNs. The domain di-
ameter of polymer II, DII , was related to the interfacial tension γ , the absolute
temperature T times the gas constant R, and the concentration of effective net-
work chains, cI and cII , occupying volume fractions vI and vII , respectively:
4γ
DII = (1)
RT(AcI + BcII )
where
1 1/3 4/3
A= 3vI − 3vI − vI ln vI (1a)
2vII
and
1 2/3
B= ln vII − 3vII + 3 (1b)
2
The quantity γ is experimentally determined from the work to create a

unit interface. For many polymer/polymer interfaces, the value is in the range of
20–60 J/µm2 (39). Although equation 1 was derived for spheres, it yields a reason-
able estimation of the cylindrical diameter of spinodally phase-separated IPNs.
Phase Continuity in Sequential IPNs. The question has been repeatedly

raised: Do IPN morphologies really exhibit dual phase continuity? Evidence for
dual phase continuity in sequential IPNs was examined by Widmaier and Sperling
(40,41). A series of sequential IPNs were prepared from poly(n-butyl acrylate) and
polystyrene. Two cross-linkers were used, divinyl benzene (DVB), which forms
ordinary covalent cross-links, and acrylic anhydride (AA), which forms labile cross-
links. The AA cross-links were cut by soaking the samples in a 10% aqueous
ammonium hydroxide solution for about 12 hours.
Some of the samples had the AA cross-links in the acrylic component and
some of them had it in the styrenic component. After de–cross-linking one com-
ponent or the other, the materials were subjected to a Soxhlet extractor. The re-
maining materials were examined by scanning electron microscopy. The density
of the remaining material was also determined.
For both types, nearly the whole amount of de–cross-linked polymer could
be extraced, indicating a low level of chemical grafting between the two polymers,
and/or little entrapped material. When polymer II (polystyrene) was de–cross-
linked and extracted, one still recovered polymer I (the acrylic) without substan-
tial damage as shown by its density, equilibrium swelling degree, and scanning
electron micrographs.
When polymer network I was de–cross-linked and extracted, the remaining
network II presented a porous structure as indicated by reduced density and scan-
ning electron microscopy. The void regions, corresponding to the location of the
poly(n-butyl acrylate) before extraction, appeared interconnected. However, the
extent of continuity of polymer II depended on its concentration. For midrange
compositions, there was good evidence for dual phase continuity. However, when
the amount of polymer II was decreased below 30%, the sample crumbled by itself,
indicating a macroscopically discontinuous second phase. At a microscopic level,
though, some degree of connectivity could still be detected. In summary, greater
than 20–30% of polymer network II, its phase domain structure was continuous.
Throughout the composition range studied, polymer network I was continuous.
The foregoing finding was important especially in the light of transmission
electron micrograph studies, resulting in thin salami slices of osmium tetroxide
stained samples. The observation of polymer network II could be interpreted as
spherical domains in many such cases, but suggestive of ellipsoidal structures in
others. The above discussion leads to the conclusion that the spherical and/or ellip-
soidal structures, being two-dimensional, are better interpreted as interconnect-
ing structures containing spheroidal and other morphologies (26,42). The modulus
evidence for dual phase continuity will be presented below.
Modulus vs Composition. The modulus of IPNs as a function of com-
position yields information about their relative phase continuity. The first such
study on polyacrylate/polyurethane latex interpenetrating elastomeric networks
(IENs) was carried out by Matsuo and co-workers (Fig. 7) (43). Note that in the
midrange of composition, the modulus begins to follow the parallel Takayanagi
model (44). This suggests that the stiffer acrylic phase is becoming a continu-
ous phase, as predicted from percolation models of three-dimensional mosaics of
compressed spheroidal structures.
Yeo and co-workers (Fig. 10) (45) compared several models of phase conti-
nuity with the behavior of {net-poly(butyl acrylate)}-ipn-(net-polystyrene). The
Fig. 10. Sequential IPNs of poly(butyl acrylate) and polystyrene as a function of compo-
sition. A: Upper–Lower Bound Model; B: Hashin–Shtrikman Model; C: Davies Model; D:
Budiansky Model; and E: Coran–Patel Model. dyne/cm2 = 0.1 Pa.
S-shaped curve has the greatest slope near the 50/50 composition. The Budiansky
model (46,47) was the only model to follow the S-shaped curve.
Ramis and co-workers (48) made a similar study of SINs prepared from un-
saturated polyester–styrene mixes with MDI-poly(propylene glycol). When the
storage modulus, E , was plotted through a range of compositions, the Budiansky
equation (47) was again found to fit better than several other relationships.
Phase Separation and Gelation Studies. A phase diagram of linear
poly(ethylene oxide) (LPEO) and divinyl benzene (DVB) cross-linked poly(methyl
methacrylate) as a function of polymerization of the latter was also researched by
duPrez and co-workers (49) (Fig. 11). The temperature of measurement was also
a variable, but the curve separating the one-phased system from the two-phased
system did not change much in the narrow temperature range covered.
A time–temperature-transformation (TTT) diagram (50,51) study on a
poly(ether sulfone)-ipn-net-epoxy semi-II IPN was carried out by Kim and co-
workers (Fig. 12) (52). Note the several regions delineated by the progressive
polymerization and cross-linking of the epoxy. Several steps in the transforma-
tion during polymerization were identified:
(1) Onset of phase separation

(2) Gelation of the epoxy
(3) Fixation of the phase-separated morphology
(4) End of phase separation
(5) Vitrification (glass forming) of the epoxy phase.
Fig. 11. A ternary phase diagram of the semi-IPN based on methyl methacrylate,
poly(methyl methacrylate), and linear poly(ethylene oxide).
These workers also found that the lower critical solution temperature for the
material was at 265◦ C.
The development of SINs requires three steps: gelation of polymer I, gelation
of polymer 2, and phase separation of 1 from 2. Since these three events may occur
Fig. 12. A time–temperature-transformation (TTT) cure diagram for the system

poly(ether sulfone)-ipn-epoxy.
in any order depending on concentration, cross-linker level, initiator, temperature,

etc, there are 3! = 6 different morphologies and physical behavior patterns that
may be observed.
This led to the development of a series of metastable phase diagrams for
(net-polyurethane)-ipn-{poly(methyl methacrylate)} SINs (see Figs. 13 and 14)
(53). The term metastable derived from the realization that none of the IPNs
or SINs are truly at thermodynamic equilibrium relative to phase separation.
Two figures were utilized to illustrate the phenomena more clearly. Since both
monomers and both polymers needed to be represented, a tetrahedron structure
was utilized, where the four pure components occupy the four vertices. The four
triangular faces of both figures represent the ternary systems delineated by the
compositions indicated in the vertices. Since the methyl methacrylate mix con-
tained 0.5% tetraethylene glycol dimethacrylate as a cross-linker, it gelled after
about 8% conversion, indicated by the G1 -U-PU plane in Figure 13. The phase
separation curve for the ternary system MMA-PMMA-“U” on polymerization of
only the methyl methacrylate is indicated by the points C-D-A-E. In a similar
fashion, the phase separation curve for the MMA-PMMA-PU system, rear trian-
gle in Figure 13, is shown by the points J-B-K-L. The entire tetrahedron volume
is divided into two regions: one phase-separated and the other single-phased, sep-
arated by C-D-A-E-L-K-B-J. Tracing the sail-like characteristics of this surface
aids in following the separation of the two regions of space. The curvilinear line
A-B indicates the intersection of the PMMA gelation plane with that of the phase
Fig. 13. A tetrahedron metastable phase diagram for the SIN polymerization of
poly(methyl methacrylate) and polyurethane.
Fig. 14. Continuation of Figure 13, illustrating the gelation planes of both the poly(methyl
methacrylate), G1 and polyurethane, G2 .
separation sail-like surface. It represents the critical line along which there is
simultaneous gelation of the PMMA and phase separation of the PU from that of
the PMMA. Thus, reactions moving to the left of this curve will have the PMMA
gel before phase separation, while reactions to the right of A-B phase separation
before gelation.
Figure 14 illustrates the gelation plane of the polyurethane, G2 -MMA-
PMMA, as well as the G1 gelation plane of the PMMA (also shown in Figure 13).
The intersection of the two planes, G1 -G2 , indicates the line of simultaneous gela-
tion of both polymers. The line G1 -G2 also intersects the line A-B of Figure 13,
not shown. This intersection represent a triple critical point. Here, both polymers
simultaneously gel and phase-separate. This defines an ideal SIN synthesis.
All SIN and IPN polymerizations must begin somewhere along the edge of
the line MMA-“U”, and end along the edge line PMMA-PU. However, the lines
need not be straight or even single lines. When phase separation ensues, the line
divides into two portions, ending at points J and L of Figure 13.
Since the polymerization rates can be controlled, and in general will not be
equal, and the cross-linker levels independently control the gelation planes, all
six possibilities of SIN morphologies can be envisioned. Also, as an extreme, a
sequential IPN synthesis can also be traced on these figures. The semi-IPNs will
clearly lack one of the gelation planes. A polymer blend polymerization will have
only the phase separation curvilinear plane, without either gelation plane. Thus,
Figures 13 and 14 provide a kind of map to determine how and why different mor-
phologies and concomitant physical and mechanical behavior patterns emerge.
Of course, these maps serve as a guide to bring about specific morphologies and
concomitant behavior profiles of the IPNs.
Following the work of Mishra and co-workers (53), Dean and co-workers
(54,55) investigated the SIN syntheses of dimethacrylate- and epoxy-based ma-
terials by near-infrared and other methods. The rates and order of the polymer-
izations were systematically altered. The final conversion of the dimethacrylate
was limited by the vitrification or topological restraint of the SIN. Whether one or
two glass transitions are observed depends on the relative rates and order of the
polymerizations.
Of course, the relative reaction rates of the two polymers in SINs may be
controlled by the quantity of cross-linker, temperature, initiator level, concentra-
tion of the two monomers, level of light intensity, time and completeness of phase
separation, etc. The above assumes that there is no interference between the two
reactions, except for the mutual dilution effect.
Thermoplastic IPNs
Thermoplastic IPNs are hybrids between the polymer blends and the IPNs. Often,
physical cross-links are used to bond the chains in one or both polymers. In other
cases, one of the phases actually has chemical cross-links, but it constitutes a
discontinuous phase so as to allow flow. In this latter case, the discontinuous case
is often cylindrical in shape, highly elongated.
The most important commercial thermoplastic elastomers are based on
polypropylene (PP) and ethylene–propylene–diene monomer (EPDM) elastomer
(see ETHYLENE-PROPYLENE ELASTOMERS). The diene portion of the elastomer is
cross-linked, frequently by dynamic vulcanization, ie, chemical cross-linking dur-
ing melt shearing.
The PP/EPDM thermoplastic elastomer was modeled by Kresge (56) to show
the morphology of the material after crystallization (see Fig. 15). To allow for ex-
traction of the elastomer, he used EPM, lacking in chemical cross-linking. The PP
clearly exhibits phase continuity, resembling an open-celled sponge with micron-
sized porosity. Careful examination of the micrograph indicated that the voids
were also continuous. (Otherwise, the EPM could not have been extracted.) There-
fore, the material formed an interpenetrating two-phased structure. However, it
is probable that the increase in viscosity of the EPDM phase, brought about by
cross-linking, would reduce the continuity of the elastomer phase.
Coran and Patel (57) point out several examples of the improvements
achieved:
(1) Reduced permanent set

(2) Greater ultimate mechanical strength
(3) Greater fatigue resistance
(4) Improved fluid resistance to hot oils
(5) Greater high-temperature stability
(6) Greater stability of the phase morphology in the melt; the phase domain
size does not increase.
Fig. 15. A scanning electron micrograph of a model thermoplastic IPN based on a binary
(70/30) blend of EPM and polypropylene. The EPM phase was removed, then the sample
fractured under liquid nitrogen to illustrate the dual phase continuity of the material.
(7) Greater green strength, ie, greater melt strength

(8) More reliable fabricability
The PP/EPDM materials are most famous for being tough, energy-absorbing
materials, which led them to be used as the plastic component of automotive
bumpers.
Davison and Gergen prepared thermoplastic IPNs based on block copolymers
and semicrystalline polymers (see Table 1) (58). Here, a hydrogenated version of
the styrene–butadiene–styrene triblock copolymer was utilized, ie, SEBS, where
the EB stands for ethylene-butylene (saturated 1,2-polymerized butadiene mers).
Table 1. Composition of Co-Continuous Interlocking

Network Phases
Composition by parts
Component A B
25,000-100,000-25,000 SEBS 100 100
Poly(butylene terephthalate) 100 70
Shellflex 790 extending oil 100 –
Tuffto 6050 oil – 50
Polypropylene 10 10
Irganox 1010 antioxidant 0.2 0.2
Dilaurothiodipropionate antioxidant 0.5 0.5
TiO2 5 5
Fig. 16. Various morphologies illustrating the development of dual-phase continuity. (a)
Dispersed sphere, clearly discontinuous in space; (b) dispersed fibers or cylinders. Figures
(c) and (d) together illustrate dual-phase continuity, where both phases are interlocked in
a kind of three-dimensional puzzle.
By blending these polymers, taking care to match melt viscosities and

volume fractions (see eq. 2 below), dual-phase continuity can be achieved (see
Fig. 16) (59). In Figure 16a, droplets of material are dispersed in a continuous ma-
trix, a morphology observed in rubber-toughened plastics. Figure 16b illustrates
dispersed fibers, observed in liquid crystal polymers and some thermoplastic elas-
tomers. If the fibers or cylinders are infinitely long, they exhibit one-dimensional
phase continuity.
Figures 16c and 16d constitute the important figures that model the materi-
als in Table 1. These two figures together depict a co-continuous morphology, where
the two phases are interlocked or interpenetrating. Note that three polymers are
presented in Table 1. The major components are the SEBS and the poly(butylene
terephthalate). The third polymer is the polypropylene, used as a compatibilizer. It
appears at the interfaces between Figures 16c and 16d. Thus, three co-continuous
phases are formed in this material! These materials are useful as under-the-hood
electrical insulators because they have substantially constant modulus between
the glass transition of the EB center block and the melting temperature of the
poly(butylene terephthalate).
The requirements for both dual phase continuity and phase inversion for
polymer blends and thermoplastic IPNs alike require the specification of the melt
viscosity and the volume fraction of each component. Some melt shearing is as-
sumed. These concepts were formulated quantitatively by Paul and Barlow (60)
and Jordhamo and co-workers (61):
V1 η2
× =X (2)
V2 η1
where if
X > 1, phase 1 is continuous

X ≈ 1, dual phase continuity or phase inversion
X < 1, phase 2 is continuous
In equation 2, V represents the volume fraction and η represents the melt

viscosity of phase 1 or 2, as per subscript. Equation 2 is true in the limiting case
for zero shear. Utracki (62) proposed somewhat more complex relationships for
finite shear rates.
However, in many experimental and industrial situations, equation 2 pro-
vides a reasonable approximation, as reviewed by Jordhamo and co-workers (see
Fig. 17) (61). Note especially the dual phase continuity region in Figure 17. If the
shearing action is stopped while the composition is within this region, it may re-
main dual phase continuous. Here, the phase continuity of a number of materials
was examined and plotted. It must be noted that dual-phase continuity and/or
phase inversion took place over about a factor of 4 in the data. Thus, some as-
pect of dual phase continuity exists via equation 2 as X varies from about 0.5 to
about 2.
Thermoplastic IPN technology was also explored by Han and co-workers
(63). In this case, thermoplastic IPNs based on polypropylene (PP) and EPDM
were prepared using supercritical solution technology. Propane was used as the
supercritical fluid. The synthesis steps were as follows:
Fig. 17. Phase continuity and inversion diagram for polymer blends and IPNs during
polymerization and under shear.
(1) PP and EPDM were dissolved in propane; a homogeneous solution was

formed.
(2) t-Butyl peroxide was injected.
(3) EPDM was cross-linked for one hour at 175◦ C and 65 MPa.
(4) The polymers could be precipitated by two independent methods:
a. Reducing the pressure below the cloud point, followed by lowering the
temperature; or
b. Isobaric cooling to ambient temperature, then reducing the pressure.
(5) Residual solvent was vented.
(6) Dried thermoplastic IPN was recovered.
The morphologies using the 4a route were fibrous in nature (64); those uti-
lizing route 4b resulted in a porous spheroidal structure for the PP phase (65). In
all cases, the morphology was significantly finer than that available with the then
commercial routes of preparing PP/EPDM thermoplastic IPNs.
Siegfried and co-workers (66,67) investigated thermoplastic IPNs based on
SEBS triblock copolymers with a polystyrene ionomer. Two subclasses of ther-
moplastic IPNs were identified: those prepared by a sequential polymerization
method, and those prepared by mechanically blending separately synthesized
polymers. In each case, a polystyrene acid sulfate was neutralized dynamically
in the melt with a concentrated solution of sodium hydroxide. The water steamed
off rapidly under the reaction conditions. The first subclass resulted in lower melt
viscosities, but more nearly equal dual-phase continuity was achieved with the sec-
ond subclass. The subject of thermoplastic IPNs was recently reviewed by Sperling
(68).
Latex IPNs
Latex IPNs, by definition, have their origin in emulsion polymerization. Several

types of latex IPNs exist. If one blends two kinds of latex particles, followed by
film formation and cross-linking of both polymers, the material is called an in-
terpenetrating elastomeric network, IEN. Usually, IENs form a three-dimensional
mosaic structure (69,70).
Latex IPNs are often made by sequential polymerization of two (or more)
cross-linked polymers utilizing emulsion polymerization (71). For core-shell latex
IPN synthesis, first a cross-linked seed latex of polymer 1 is synthesized (2). Then,
a second monomer and cross-linker are added to the system, usually with no
added surfactant. Often, a starved polymerization route is employed, ie, the rate
of polymerization equals or exceeds the rate of monomer addition. This reduces
the swelling of the seed latex by the monomer 2 mix, producing a two-layer latex
having a spherical core, and an overlaying shell. Obviously, multiple shells can be
added for different purposes.
Some possible morphologies of latex IPNs having three polymers are illus-
trated in Figure 18 (72). Note that in Figure 18a, the monomer B mix first dissolves
Fig. 18. Some possible latex IPN particle morphologies. (a) IPN core/shell particles; (b)
separated core/shell particles; and (c) multilayered particles.
in polymer A, then polymerizes and phase separates to form internal domains.

Then, polymer network C forms a shell around the A-B core.
If the glass transitions of the three polymers are sufficiently different, and
the three polymers are phase-separated, then one obtains three glass transi-
tions, as illustrated in Figure 19 (73). In this case, the three polymers were ob-
tained by blending two latexes having different cores but the same shell, as in
Figure 18b. G and G represent the dynamic shear modulus. Both latexes have a
core of poly(butadiene-stat-styrene), with some of the latexes having a SAN shell
and some having a shell of poly(ethylhexyl methacrylate-stat-styrene). In both
cases, the polymerizations were carried out under starved conditions.
Silverstein and co-workers (74), Silverstein and Narkis (75), and Nemirovski
and Narkis (76) studied the morphology and rheological behavior of latex IPNs
and related materials (see Fig. 20) (75). After water evaporation, some degree
of phase continuity of individual phase domains is achieved in this case. All of
these compositions were based on polyacrylates and polystyrene. After polymer-
izing and drying, the latex particles do not interdiffuse to form a monolithic solid
because of the cross-links in each latex particle. However, being moderately soft,
they flow together as modeled in Figure 20 (75). The solid black spheres repre-
sent polystyrene domains, and the cross-hatched material represents an acrylic
Fig. 19. The dynamic mechanical behavior of a mix of two latexes or the morphologies
represented by Figure 18b.
Fig. 20. Model of a latex IPN.
network. The rheological behavior of these materials resembles the flow behavior
that might be expected for a room full of underinflated beach balls.
Sound and Vibration Damping Behavior
Sound and vibration damping are important throughout the world today for the
automotive industry, appliances, aircraft, tall buildings, submarine technology,
etc. However, the frequencies of the sound or vibration differ greatly, from a frac-
tion of a Hertz for tall buildings to 103 –104 Hz for cars and appliances. This is
important, because the WLF equation shows that the glass transition increases
some 6–7◦ C with each decade of frequency increase (77). One of the most im-
portant methods of damping involves polymeric materials in or near their glass
transitions temperatures where the loss tangent tan δ and/or the loss modulus E
are high.
Many IPNs exhibit a microheterogeneous morphology. When the domains are
of the order of 10–20 nm, the whole system becomes substantially all interphase
material, ie, it is extensively but incompletely mixed, with different microregions
having different compositions (see Fig. 8) (31). In the transmission electron mi-
crograph of Figure 8a, the microheterogeneous morphology is made from the iso-
meric pair, poly(ethyl acrylate) and poly(methyl methacrylate). When polystyrene
is used as the second polymer, the cellular structure in Figure 8b emerges.
Whereas an immiscible IPN pair will have two distinct glass transitions, the
microheterogeneous morphology often results in one broad glass transition, cov-
ering the temperature range between both homopolymer glass transitions. Thus,
more or less constant E or tan δ can be obtained.
Fig. 21. Damping effectiveness as a function of temperature for several commercial ma-
terials compared to an IPN, composition A.
There are two basic engineering mechanisms for the use of damping poly-
mers:
(1) Extensional damping, where a polymer is placed as a free layer on the

resonating vibrating system; and
(2) Constrained layer damping, where a stiff material is placed on the top of
the damping polymer to increase the shearing action. Sometimes a simple
sandwich arrangement is used, where two thin layers of sheet metal (the
bread) have a thin layer of polymer between them (the jelly).
The damping of an IPN constrained layer system based on an

acrylic/methacrylic IPN and an epoxy constraining layer is compared with sev-
eral other commercial homopolymers and statistical copolymers in Figure 21 (78).
Hitachi Chemical has a high temperature sound and vibration damping material
based on vinyl–phenolic compositions (79).
Natural Products/Renewable Resource-Based IPNs
Of increasing importance in modern society are polymeric materials that either

originate from plants or animals, are naturally degradable, or both. One of the
major approaches utilizes triglyceride oils with functionality other than double
bonds. For example, most of the edible oils such as corn oil are triglycerides con-
taining one or more double bonds in the side chains. Usually, the double bonds are
structurally cis. An exception is tallow, which is a saturated oil.
Castor Oil-Based IPNs. Those triglyceride oils with functionality other
than double bonds such as hydroxyl or carbonyl groups are generally considered
inedible, although they are sometimes used for medicinal purposes. Prime among
these materials is castor oil, containing one hydroxyl group per side chain (see
eq. 3):
(3)
In medicinal applications, the hydroxyl group irritates the stomach lining.

Chemically, the hydroxyl group can react to form urethanes or esters, and hence
form a polymer network. Polyurethane foam rubber frequently contains large
amounts of reacted castor oil, for example. The glass transition of castor oil
polyesters are of the order of −50◦ C (80).
If styrene (or other vinyl monomer) plus cross-linker is swollen in and poly-
merized, an IPN is formed. The products tend to be tough, leathery materials.
Research on castor oil-based IPNs began in 1974 as a cooperative research pro-
gram between the Universidad Industrial de Santander, Bucaramanga, Colombia,
and Lehigh University in the United States (81,82).
Castor oil hydroxyl groups can be easily reacted with either isocyanate
groups to form polyurethanes, or with carboxyl groups to form polyesters. The
synthesis scheme for forming polyester-based SINs from castor oil is illustrated
in Figure 22 (80). Here, sebacic acid (itself a derivative of castor oil) is reacted with
Fig. 22. A synthesis scheme for castor oil-polyester based SINs with polystyrene being
the second component. = polyester is the continuous phase; = polystyrene
is the continuous phase; and = Stirring.
Fig. 23. Stress–strain curves for several castor oil (CO), polyester (PE), polyurethane
(PU), and polystyrene network (PSN) materials. A: COPEN; B: COPEUN; C: COPUN;
D: 40/60 COPEN/PSN; E: 40/60 COPEUN/PSN; F: 40/60 COPUN/PSN; and G: 40/60
COPUN/PSN.
castor oil. Note that stirring is required after phase separation to obtain phase
inversion.
A number of polyester, polyurethane, and mixed structures were made into
IPN. Stress–strain curves on these compositions are illustrated in Figure 23 (83).
In some cases, the castor oil was first reacted with a diacid, then finished with
an isocyanate to form a urethane. Here, COPEN stands for castor oil polyester
network, U stands for urethane, and EU stands for the mixed ester–urethane
derivative. PSN stands for polystyrene network. Compositions 1, 2, and 3 are
relatively soft and weak. Compositions 4 and 5 are somewhat higher modulus,
more energy-absorbing materials. Composition 6 is much tougher. The sequential
IPN, composition 7, is identical to composition 6, except that the sequential mode
of IPN formation replaced the SIN mode. The yield point in the stress–strain curve
of composition 7 suggests greater phase separation with the polystyrene being a
more continuous phase. It must be pointed out that composition 6 is tough enough
to make long-lasting shoe heels.
Castor oil has also been made into semi-IPNs with poly(ethylene terephtha-
late) (PET). Typical time–temperature reaction conditions are shown in Figure 24
(84). Since the castor oil is an ester as well as the PET, significant bond interchange
takes place at elevated temperatures, as indicated. If the material is heated too
long, a statistical copolymer will result. Under the given reaction conditions, the
mix goes from a two-phase mix to a one-phase mix. On cooling, it phase separates
again.
Tan (85) investigated SIN compositions based on castor oil polyurethanes
and styrene–acrylic mixes. Under these conditions, there is considerable grafting.
Abrasion resistance to jetting sand was very high, leading to a coating application
of the Ge Zhou Ba hydroelectric power station dam in the desert region of western
China (86).
Other triglyceride oils that are being investigated as IPN monomers in-
clude vernonia oil and lesquerella oil. Vernonia oil, a naturally epoxidized oil,
Fig. 24. A typical time–temperature cure cycle illustrating bond interchange and phase
behavior of castor oil/urethanes and poly(ethylene terephthalate) semi-IPNs. Axes not
drawn to scale.
was combined with poly(ethylene terephthalate) to make semi-IPNs (87). Les-

querella oil comes from a wild flower growing in the desert of southwest United
States and Mexico. It, too, makes tough IPNs (88). It is thought that lesquerella
could be grown where no crop exists today. Other functionalized oils of interest
include crambe, epoxidized linseed oil, and epoxidized soybean oil (89).
Natural Rubber Latex-Based IPNs. Another kind of natural product
IPN is based on natural rubber latexes. After processing, this rubber is in wide
use today for truck and aircraft tires (see RUBBER, NATURAL). While still in the
latex form, these latexes can be treated just like their synthetic counterparts and
used as the core material for IPN production. An interesting material, prepared
by polymerizing methyl methacrylate in the rubber latex, is called Hevea Plus
MG (90–92). This makes an impact-resistant composition somewhat resembling
ABS. Polystyrene as well as PMMA was used variously as the second polymer.
Notched Izod impact strengths were increased over those of the pure plastics by
a range of 10–15, reaching over 30 kJ/m2 .
Polysaccharide-Based IPNs. Cellulose (qv) and cellulose derivatives
have been the largest tonnage single polymer sold in the world since the beginning
of civilization until the present. Kamath and co-workers (93) prepared IPNs and
related AB–cross-linked copolymers using compositions such as allyl cellulose cin-
namonate and cross-linked acrylics, polystyrenes, or vinyl acetates. An improved
thermal stability was noted. Hydrogel materials prepared from cellulose esters
and polyacrylamide have also been investigated (94) (see HYDROGELS).
Combinations of both polysaccharides and castor-oil–based polyurethanes
have also been investigated. Semi-IPNs of castor-oil–based polyurethanes and
nitrokonjac glucomannan (NKGM) were investigated by Gao and Zhang (95).
The konjac glucomannan is a natural polysaccharide, and was nitrated for these
studies. Possible substitution of the semi-IPN for some petrochemical products
was mentioned, along with biodegradability. Films made from the semi-IPN were
found to be highly transparent, with a breaking strength of some 30 MPa.
Table 2. History of IPNs and Related Materials

Event Investigators Year Ref.
Vulcanization of rubber Goodyear 1844 96
First IPN Aylsworth 1914 97
Macromolecular Hypothesis Staudinger 1920 98
Graft Copolymers Ostromislensky 1927 25
Homo-IPNs Staudinger and Hutchinson 1951 99
Block copolymers Dunn and Melville 1952 100
HIPS and ABS Amos, McCurdy, and McIntire 1954 23
Block copolymer surfactants Lunsted 1954 101
Interpenetrating polymer network Millar 1960 102
term used
Thermoplastic elastomers Holden and Milkovich 1966 103
AB–Cross-linked copolymers Bamford, Dyson, and Eastmond 1967 104
Interphase characteristics of IPNs Lipatov and Sergeeva 1967 105
Sequential IPNs Sperling and Friedman 1969 106
Latex IENs Frisch, Klempner, and Frisch 1969 107
SINs Sperling and Arnts 1971 108
Thermoplastic IPNs Davison and Gergen 1977 109
Modern IPN nomenclature Kahovec and co-workers 1997 9
History of Interpenetrating Polymer Networks and Related Materials
The patent literature shows that IPNs were invented over and over again, begin-
ning in 1914 (see Table 2). Each time, the idea was lost and reinvented.
Aylsworth (97) was the first person known to invent an IPN. In 1914 he com-
bined the then new phenol–formaldehyde compositions with natural rubber and
sulfur. Of some historical interest is that Jonas Aylsworth was Thomas Edison’s
chief chemist (110). Edison had just switched from the cylinder-type record to the
platter, using the new phenol–formaldehyde materials. However, these phenol–
formaldehyde materials were brittle, and the first phonograph records had to be
made very thick to prevent breakage.
In effect, by adding natural rubber and sulfur, Aylsworth made not only the
first IPN, but also the world’s first rubber-toughened plastic. This was decades
before rubber-toughened styrenics were commercial. The West Orange, NJ, Edi-
son Museum has evidence that Aylsworth’s composition was used for toughening
phonograph records from 1914 to 1929, stopping only when Edison left the phono-
graph record business. Then, the idea was apparently lost.
Aylsworth’s patent (97), however, does not mention IPNs and polymer net-
works, or even use the term polymer. Note that that date was six years prior to H.
Staudinger’s enunciation of the macromolecular hypothesis, which was, of course,
the first statement that certain colloids had the structure of long chains.
Several other independent discoveries of IPNs followed. J. J. Staudinger (son
of H. Staudinger) and Hutchinson have a 1951 patent (with a 1941 application
date!) to smooth the surfaces of transparent plastic sheeting for esthetic purposes
(99). These men took sheets of cross-linked polystyrene or PMMA and swelled the
sheets with the same monomer mix as the first network. This stretched the sheets,
and after polymerization of the second monomer mix the waviness or surface
imperfections of the original material were reduced. These were the first homo-
IPNs.
The next independent invention of IPNs was by Solt in 1955 (111). Solt in-
vented anionic–cationic ion exchange resins with the idea of having both charges
on the same suspension-sized particle. The idea was that the exchange efficiency
would be improved if both charges were in juxtaposition, but still separated in
space. Indeed, the charges must be separated, even by a fraction of a nanometer,
to prevent coacervation.
The term interpenetrating polymer network was first coined by Millar in
1960 (102). These were polystyrene–polystyrene homo-IPN suspension-sized par-
ticles. The idea was that some particles, the fines, were too small. On adding more
monomer and cross-linker, larger and more satisfactory particles could be made.
Early works by Shibayama and Suzuki (112), Lipatov and Sergeeva (105), Frisch
and co-workers (107), and Sperling and Friedman (106) set the pace for the modern
development, founding the field of IPNs (1).
In Table 2, there is an apparent gap of two decades (1977–1997) between
thermoplastic IPNs and the modern IPN nomenclature; in fact many people were
busy characterizing a number of new materials and developing their applications,
as described above. Application-oriented papers and patents are delineated below.
Actual or Proposed IPN Applications
A number of commercial IPN materials and their applications are summarized in

Table 3. The value of IPNs to society, of course, lies in their usefulness. IPNs can
and are being made into rubber-toughened plastics and a special value seems to lie
in their capability of forming tough but flexible materials. IPNs often have another
unusual property: that of forming co-continuous, very finely divided phases. These
tough but flexible materials have suggested biomedical applications.
Biomedical Applications. Dillon (114) synthesized IPN membranes
from polytetrafluoroethylene (PTFE) and poly(dimethyl siloxane) (PDMS) (see
PERFLUORINATED POLYMERS, POLYTETRAFLUOROETHYLENE; SILICONES). These flexi-
ble membranes are used for a variety of medical purposes, especially second-
degree burn care. These materials are commercially available under the trade
name Silon. The PDMS component rapidly transports body fluids away from the
burn site, while the PTFE provides mechanical strength. The PTFE is also wa-
terproof, so that when the wound area is washed, water beads up on the film. An
additional valuable feature is that the films are highly transparent, so that the
doctor can observe the wound area easily, making early treatment of any infection
or other problem possible.
Salmerón Sánchez and co-workers (115) prepared sequential IPNs based on
{net-poly(ethyl acrylate)-ipn-{net-poly(hydroxyethyl acrylate)}. These two poly-
mers differ primarily in the presence or absence of a hydroxyl group. Investiga-
tion via differential scanning calorimetry indicated three qualitatively different
kinds of thermograms depending on the initial quantity of water present. The wa-
ter present is primarily associated with the poly(hydroxyethyl acrylate), but the
Table 3. Selected Commercial IPN Materialsa

Trade
Manufacturer Name Composition Application
Shell Chemical Co. Kraton IPN SEBS–polyester Automotive parts
LNP Plastics Rimplast Silicone Gears or medical
rubber–nylon or
PU
DSM N.V. Kelburon PP–EP or Automotive parts
rubber–PE
Uniroyal (Reichhold TPR EPDM–PP Auto bumper parts
Chemical Co.)
Rohm & Haas – Anionic–cationic Ion-exchange resins
Monsanto Santoprene EPDM–PP Tires, hoses, belts, and gaskets
BF Goodrich Telcar EPDM–PP or PE Tubing, liners, and wire and
cable insulation
Exxon Vistalon EPDM–PP Paintable automotive parts
Cook Composites Acpol Acrylic–urethane– Sheet molding compounds
polystyrene
Dentsply Trubyte, Acrylic–based Artificial teeth
International Bioform
Hitachi Chemical – Vinyl-phenolics Damping compounds
Bio Med Sciences Silon PDMS–PTFE Burn dressing, scar abatement
a Updated from Table 10.5 in Ref. 113.
poly(ethyl acrylate) component clearly interferes with water transport and freez-
ing. Whereas this was a basic study of hydrogel behavior, other systems examined
below have several potential applications, particularly to the biomedical field (see
HYDROGELS).
Polymer gels based on poly(N-isopropylacrylamide) [P(N-iPAAm)] in aque-
ous media undergo a temperature-induced collapse of the chains from a perturbed
random coil to a globular structure known as a coil-to-globular transition. This
is macroscopically observable as a sudden decrease of the degree of swelling at a
sharp first-order phase transition known as a lower critical solution temperature
(LCST) at 32◦ C. The P(N-iPAAm) gels exhibit the sharpest transition of the class
of thermosensitive alkylacrylamide polymers examined (116) (see ACRYLAMIDE
POLYMERS).
Since this LCST occurs between room temperature and body temperature,
there has been great interest in this and related materials from a biomedical point
of view. In order to adjust the LCST to meet various proposed objectives, a number
of copolymers and IPNs of P(N-iPAAm) and have been prepared.
Zhang and Peppas (117) examined sequential IPNs of poly(methacrylic acid)
(PMAA) and P(N-iPAAm) hydrogels as a function of pH and temperature. pH
is critically important to studies involving PMAA, since the carboxyl group is
ionized at higher pH but in the acid form below about 5.5. The IPNs had a
swelling/deswelling transition in a range that included that of pure P(N-iPAAm),
32◦ C, but was broader.
An important possible use of such IPNs involves drug delivery. A number
of model drugs was examined by Zhang and Peppas (117). As expected, higher
permeability was observed for the smaller model drug compounds (see CON-
TROLLED RELEASE TECHNOLOGY).
At low water contents, the LCST depends on the water concentration for P(N-
iPAAm) (118), being constant for high swelling ratios (as most often needed), but
shifting to higher temperatures when the initial water concentration is below 50%.
Hydrophilic poly(acrylic acid) (PAA), when added in IPN form, tends to increase
the LCST. In the case of P(N-iPAAm) and PAA sequential IPNs, the association
between the complementary binding sites produces complexes that decrease the
ability of the hydrogel to swell in water. For the various copolymers and IPNs, a
major effect was the broadening of the transition.
The first-order LCST of P(N-iPAAm) leads to many possible applications
in the biomedical field. Wu and Jiang patented an IPN hydrogel based on {net-
poly(N-isopropylacrylamide)}-ipn-{net-gelatin} (119). These materials also swell
greatly at room temperature, but can be made to undergo a rapid reduction in
volume at blood temperature, 37◦ C. When formed into a tube, these hydrogels
can be placed over the cut ends of a blood vessel. The material shrinks rapidly as
the material increases in temperature from room temperature to body tempera-
ture, grasping both ends of the blood vessel and allowing blood to be temporarily
transported in a normal manner.
There are two ways of bending light. The most common is to present the light
with a material surface at an angle to the direction of the light’s travel. However,
light waves can also be bent by changing the refractive index internally in the
material. This latter fact has been used to prepare gradient IPN compositions in
soft contact lenses. By using computer-controlled laser polymerization of polymer
II in gradient IPNs (polymers of two different refractive indices), it is possible to
have improved astigmatism control (120,121).
Another class of IPNs are the homo-IPNs, made of two more or less identical
polymers. An example are the homo-IPNs prepared from cross-linked poly(methyl
methacrylate) (PMMA) (122,123). In this case, densely cross-linked material of
suspension-sized PMMA particles are prepared. These are mixed with a very sim-
ilar monomer mix, and polymerized. Some, but not all, of the second monomer mix
swells into the suspension particles.
Homo-IPNs of PMMA are used commercially for artificial teeth, the kind
that come out at night (122,123). One trade name is Bioform IPN (Table 3). In
one example, suspension-sized particles of cross-linked PMMA were mixed with
linear PMMA, MMA monomer, cross-linker, and initiator. After polymerization,
the teeth have two superior properties. First, because a suspension polymerization
route is used, the dentist can grind the teeth to a fine powder. This is important
when fitting the new teeth to the opposing set of teeth. They can be ground better
because the interface between the suspension-sized particles and the surrounding
phase is slightly weaker than the bulk material. A single network of a similar
composition may char under the dentist’s drill.
Second, a densely cross-linked polymer is required. Salad oil, butter, and
similar materials are excellent plasticizers (qv) for linear PMMA, which cause the
teeth to swell.
Smart Materials. Eck and co-workers (124) developed a smart material
for solar energy management. It seems that the use of solar energy to heat water
in some tropical areas results in water that is too hot. Usually, the water pipes to
be heated are in a panel covered by glass, and exposed to the sun. The material
of Eck and co-workers makes use of a lower critical solution temperature (see
Fig. 7 for example) with an IPN based on {net-poly(propylene oxide)}-ipn-{net-
poly(styrene-stat-2-hydroxymethyl acrylate)}. A film of this material is placed on
the underside of the glass. At low temperatures, the film is clear, transmitting the
light. When the temperature exceeds a certain value, the film clouds up, increasing
reflection back into the atmosphere.
A polymer blend of the same or similar composition cannot be used because
the phase domains that will form will become large enough to take many hours
to diffuse back to a single phase. The IPN forms domains of only some tens of
nanometers, allowing diffusion back and forth between one phase and two phases
in minutes. Interestingly, this appears to be the only application suggested for the
LCST of polymer blends or IPNs.
Pervaporation Membranes. Pervaporation membranes for separation of
ethanol and water and other types of solutions are being investigated by Kim
and his students (125,126). Some of these membranes are anionic/cationic IPNs.
Starting with a 10% ethanol feed, after three stages the retentate is 94% ethanol.
Water vapor passes through the membrane as the pervaporate.
Other Applications. Another new material, developed by Lipatov and
Karbanova (127) and Bukhbinder and Kosjakov (128) flies under the designation
gradans. Cylindrical glass or polymer fibers are widely used to transmit light or
other electromagnetic energy for communication purposes, optoelectronics, inte-
grated optics, and medical engineering. A major problem is that the electromag-
netic energy tends to leak out of the surface of the fiber, shortening the useful
path. If the fiber is made so that its refractive index has an increasing gradient
from the center to the surface, the energy will be bent back towards the center
as it moves through the fiber. One way to accomplish this is through making a
gradient IPN, with the second monomer making a polymer of higher refractive
index than the first.
Some of the materials mentioned in Table 3 have already been discussed. The
reader will recognize the Silon and Bioform materials described above. Kraton
IPN is also discussed above (see Figs. 16c and 16d and Table 1). Several of the
materials manufactured are based on EPDM–PP thermoplastic IPNs.
Current Literature Suggestions and Applications. In 2004, the pro-
duction of IPN-based papers is averaging about 100 papers a year. This contrasts
to the fact that up to 1979, there was a total of about 125 scientific papers and
about 75 patents issued on the subject. The number of IPN-related patents has
also increased accordingly.
Many of the most recent papers mention possible applications (see Table 4).
Again, possible medical applications stand out the most.
Kim and Kim describe a most interesting material in Reference 134 of
Table 4. The need for synthetic blood vessel sections is great. A blood vessel must
be both flexible and strong. However, a major problem with materials has been
that the inner surface may abrade red blood cells and cause adsorption of materials
such as the fibrinogens and platelets, important in coagulating blood. (The life-
time of red blood cells passing various surfaces is inversely related to the modulus
of the material of contact.) Fibrinogen is one of the most important globular pro-
teins circulating in the blood, playing a central role in the regulation of hemostasis
Table 4. Actual and Proposed IPN Applications from Select Recent Literature
Composition Application Ref.
Biomedical/Pharmaceutical
Poly(ε-caprolactone) semi-homo-IPNs Bone implant composites with 129
hydroxyapatite
Poly(N-isopropylacrylamide-stat-acrylic Engineered cartilage, polymer 130
acid) + grafted polyacrylamide scaffolds
copolymers
Acrylic resin IPNs Acrylic false teeth 131
Poly(acrylic acid) + cross-linked gelatin Hydrogel drug release systems. 132
Segmented polyurethane + Blood compatibility, no platelet 133
poly(2-methacryloyloxyethyl phosphoryl adhesion
chloride)
Polyurethane + polystyrene with pendant Blood compatibility; adsorption of 134
poly(ethylene oxide) chains fibrinogens and platelets
suppressed.
Chitosan + poly(ethylene oxide) semi-IPN Drug release 135
Sodium alginate + cross-linked gelatin or Controlled release of medication 136
egg albumin
Poly(vinyl alcohol) + poly(dimethyl Drug release 137
siloxane) hydrogels
Chondroitin + poly(acrylic acid) semi-II Controlled drug release 138
IPN
Polyurethane + polystyrene IPNs Adhesion of endothelial cells 139
Poly(hydroxyethyl methacrylate) + Antithrombogenic material 140
poly(ethylene glycol) semi-IPN
Polypropylene + polyacrylamide mix Controlled release of drugs 141
Poly(vinyl alcohol) + poly(2-hydroxyethyl Prosthetic disc nucleus 142
methacrylate)
Poly(2-hydroxyethyl methacrylate) + Lysozyme adsorption 143
chitosan
Polysiloxane + poly(vinyl alcohol) with Immobilize antigens 144
ferromagnetic derivate
Electrical
Polystyrene or poly(methyl methacrylate) Underfill adhesive for electronic 145
+ modified epoxy applications
Castor oil-based polyurethane + Electrical conducting properties 146
poly(methyl methacrylate) + polyaniline
Polyaniline + poly(vinyl alcohol) semi-IPN Electrical conducting materials 147
Poly(vinyl alcohol) + chitosan hydrogel Bends in electric field; smart 148
material
Polyaniline + poly(vinyl acetate) semi-II Electrical conductivity 149
IPN
Polyaniline + melamine-urea Electrical conductivity 150
Poly[methoxyoligo(oxyethylene) Electrochemical conductivity 151
methacrylate] + poly(methyl
methacrylate)
Poly(sodium acrylate) + poly(N-isopropyl Intelligent hydrogels, 152
acrylamide) semi-II IPN thermovolume sensitive, heavy
metal ion recovery
Table 4. (Continued)
Composition Application Ref.
Poly(vinyl alcohol) + poly(diallyl dimethyl Samples bend in electric field 153
ammonium chloride)
Damping
Vegetable oils Damping materials 154
Polyester + epoxy with carbon black Heat-resistant damping 155
Poly(dimethyl siloxane) + polyacrylates + High temperature damping 156
polymethacrylates
Polysiloxanes + poly(methyl methacrylate) Sound and vibration damping 157
Ion exchange
Sulfonated polystyrene + poly(vinyl Cation exchange membranes 158
chloride) semi-I IPNs
Poly(hydroxyethyl methacrylate) + Removal of heavy metal ions from 159
chitosan aquatic systems
Poly(vinyl chloride) + polystyrene with Cation exchange membrane 160
cation exchange groups
General
Polyimides + alkoxysilane dye Second-order nonlinear optics 161
Epoxy + unsaturated polyester Rubber-toughened plastics 162
Poly(vinyl alcohol) grafted with Pesticide release 163
acrylamide + sodium alginate
Poly(acrylic acid) + poly(butyl Pervaporation membrane 164
methacrylate-stat-methyl methacrylate)
Natural rubber + polystyrene High transport membranes 165
Carboxymethyl cellulose + poly(ethylene Controlled release of KNO3 166
glycol) + cross-linked polyacrylamide agricultural fertilizer
Unsaturated polyester + Improved flame resistance 167
poly(2-hydroxyethyl methacrylate)
and thrombosis. It participates in blood coagulation and facilitates adhesion and

aggregation of platelets. The result might be thrombosis in the patient.
Mother Nature makes the inner lining of blood vessels very soft, so that the
probability of coagulation is far reduced. The hydrophilic pendant poly(ethylene
oxide) (PEO) chains, described in Reference 134, stick out from the inner side of
the blood vessel, creating a soft gel environment. The presence of the pendant
PEO chains significantly suppresses the adhesion of fibrinogens and platelets on
the surface of the polymeric blood vessel by steric repulsion. In these IPNs, the
blood compatibility increases with both the length of the pendent chains and the
density of grafting.
Thus, the polyurethane and polystyrene, main components of the IPN, pro-
vide both the strength and the flexibility, and the grafted PEO provides a soft,
gelatinous inner surface, mimicking Mother Nature. Besides possible use as arti-
ficial blood vessels, there is a wide range of blood-handling equipment now in use
for surgery, etc, as possible applications.
A similar effect arises in the materials described in Reference 133 of
Table 4. Segmented polyurethanes, of course, are a type of block copolymer. These
materials are very strong elastomers, which are in wide use as the elastic fiber in
undergarments, bathing suits, etc. The poly(2-methacryloyloxyethyl phosphoryl
chloride) forms a highly swollen, soft gel partly exposed on the IPN blood vessel
surface.
However, there are possible applications to optoelectronics, agriculture, and
other topics as well. References 148, 152, and 153 in Table 4 mention smart ma-
terials, particularly those that bend in an electric field. These are widely being
investigated as sensors of various kinds.
Concluding Comments
In a certain sense, the term interpenetrating polymer networks is a misnomer,

since most of these materials phase separate, rather than being mutually soluble
on the molecular level. One could argue that the phases interpenetrate, and/or
that true molecular interpenetration takes place at the interphase. However, the
term describes the general synthesis and structure of the materials.
The field of interpenetrating polymer networks now takes its place parallel
to the fields of polymer blends, grafts, and blocks. Indeed, most of these materials
are useful because they undergo some kind of phase separation. Many IPNs seem
to work best when the degree of phase separation is only partial or the size of the
domains is in the tens of nanometer range. Those IPNs composed of an elastomer
and a plastic to make flexible materials seem to be the most unique among these
materials.
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L. H. SPERLING
Lehigh University
IONOMERS. See Volume 6.
ISOBUTYLENE POLYMERS. See BUTYL RUBBER.
ISOCYANATE-DERIVED POLYMERS. See Volume 6.

Interpenetrating Polymer Networks

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Interpenetrating Polymer Networks

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272 INTERCALATION POLYMERIZATION Vol.

An interpenetrating polymer network, IPN, is deﬁned as a combination of two

Synthesis and Structure of IPN and SIN Materials

Figure 1 models the structure of interpenetrating polymer networks and related

Special Considerations in IPN and SIN Synthesis. Most of the IPNs

(1) In sequential IPNs, if polymer I is based on a diene, and monomer II (such

Some speciﬁc investigations of the chemical interactions include the

Fig. 3. A polymer blend classiﬁcation scheme.

IPN Morphology and Physical Behavior

Fig. 4. Transmission electron microscopy of OsO4 -stained polybutadiene and polystyrene

the two-phased morphology of IPNs, semi-IPNs, and polymer blends prepared

Fig. 5. Transmission electron microscopy of the polymerization of substantially the same

decomposition plays a strong role in the ﬁnal morphology of these materials.

Fig. 7. A phase diagram of a polyurethane–poly(vinyl chloride) semi-IPN, showing a lower

Fig. 8. A comparison of two possible morphologies of IPNs, based on (a) {poly(ethyl

Fig. 9. Sequential IPNs of poly(methyl acrylate) and poly(methyl methacrylate) as a func-

In block copolymers composed of random-coiled polymers, the molecular

The quantity γ is experimentally determined from the work to create a

Phase Continuity in Sequential IPNs. The question has been repeatedly

(1) Onset of phase separation

Fig. 12. A time–temperature-transformation (TTT) cure diagram for the system

in any order depending on concentration, cross-linker level, initiator, temperature,

(1) Reduced permanent set

(7) Greater green strength, ie, greater melt strength

Table 1. Composition of Co-Continuous Interlocking

By blending these polymers, taking care to match melt viscosities and

and Jordhamo and co-workers (61):

X > 1, phase 1 is continuous

In equation 2, V represents the volume fraction and η represents the melt

(1) PP and EPDM were dissolved in propane; a homogeneous solution was

Latex IPNs, by deﬁnition, have their origin in emulsion polymerization. Several

in polymer A, then polymerizes and phase separates to form internal domains.

Fig. 20. Model of a latex IPN.

Sound and Vibration Damping Behavior

(1) Extensional damping, where a polymer is placed as a free layer on the

The damping of an IPN constrained layer system based on an

Natural Products/Renewable Resource-Based IPNs

Of increasing importance in modern society are polymeric materials that either

In medicinal applications, the hydroxyl group irritates the stomach lining.

was combined with poly(ethylene terephthalate) to make semi-IPNs (87). Les-

Table 2. History of IPNs and Related Materials

History of Interpenetrating Polymer Networks and Related Materials

Actual or Proposed IPN Applications

A number of commercial IPN materials and their applications are summarized in

Table 3. Selected Commercial IPN Materialsa

and thrombosis. It participates in blood coagulation and facilitates adhesion and

In a certain sense, the term interpenetrating polymer networks is a misnomer,

11. P. E. Mason, W. S. Bryant, and H. W. Gibson, Macromolecules 32, 1559 (1999).

50. J. K. Gillham, Polym. Eng. Sci. 19, 676 (1979).

84. L. W. Barrett, L. H. Sperling, J. W. Gilmer, and S. G. Mylonakis, in D. Klempner,

124. W. Eck, H. R. Wilson, and H. J. Cantow, Adv. Mater. 7, 800 (1995).

162. Z. G. Shaker, R. M. Browne, H. A. Stretz, P. E. Cassidy, and M. T. Blanda, J. Appl.

IONOMERS. See Volume 6.

ISOBUTYLENE POLYMERS. See BUTYL RUBBER.

ISOCYANATE-DERIVED POLYMERS. See Volume 6.

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