Composites: Part A 38 (2007) 666–681

www.elsevier.com/locate/compositesa

Review

Reactive processing of textile fiber-reinforced thermoplastic

composites – An overview
K. van Rijswijk *, H.E.N. Bersee
Delft University of Technology, Faculty of Aerospace Engineering, Design and Production of Composite Structures,
Kluyverweg 3, 2629 HS, Delft, The Netherlands

Received 20 December 2005; received in revised form 14 May 2006; accepted 14 May 2006

Abstract

Thermoplastic composites offer some interesting advantages over their thermoset counterparts like a higher toughness, faster manu-
facturing and their recyclable nature. Traditional melt processing, however, limits thermoplastic composite parts in size and thickness. As
an alternative, reactive processing of textile fiber-reinforced thermoplastics is discussed in this paper: a low viscosity mono- or oligomeric
precursor is used to impregnate the fibers, followed by in situ polymerization. Processes that are currently associated to manufacturing of
thermoset composites like resin transfer molding, vacuum infusion and resin film infusion, might be used for manufacturing of
thermoplastic composite parts in near future. This paper gives an overview of engineering and high-performance plastic materials that
are suitable for reactive processing and discusses fundamental differences between reactive processing of thermoplastic and thermoset
resins.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Thermoplastic resin; A. Fabrics/textiles; E. Resin transfer moulding (RTM); Vacuum infusion

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
2. Reactive thermoplastic material systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 668
2.1. Vinyl polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 668
2.2. Ring-opening polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 668
2.3. Reactive processing of engineering plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
2.3.1. Thermoplastic polyurethanes (TPU) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
2.3.2. Polymethylmethacrylate (PMMA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
2.3.3. Polyamides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
2.3.4. Polyesters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
2.3.5. Polycarbonate (PC). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
2.4. Reactive processing of high-performance plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 672
2.4.1. Polyetheretherketone (PEEK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 673
2.4.2. Polyetherketone (PEK) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 673
2.4.3. Polyethersulfone (PES) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674
2.4.4. Polyphenylenesulfide (PPS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674

*
Corresponding author. Tel.: +31 15 2788981; fax: +31 15 2781151.
E-mail address: K.vanRijswijk@LR.TUDelft.NL (K. van Rijswijk).

1359-835X/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2006.05.007
 K. van Rijswijk, H.E.N. Bersee / Composites: Part A 38 (2007) 666–681 667

2.4.5. Polyethylenenaphthalate (PEN) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674

2.4.6. Polybutylenenaphthalate (PBN) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
3. Reactive processing of textile reinforced thermoplastic composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
3.1. Reactive processes for thermoplastic composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
3.1.1. Structural reaction injection molding (SRIM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
3.1.2. Vacuum infusion (VI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
3.1.3. Resin film infusion (RFI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 677
3.2. Differences between reactive processing of thermoplastic and thermoset composites . . . . . . . . . . . . . . . . . . . . . . . 677
4. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678

1. Introduction A solution to improve the fiber impregnation is to bring

Thermoplastic composites (TPCs) offer some substantial
advantages over thermoset ones [1]. Due to the higher
toughness of the matrix, they offer a higher impact resis-
tance. Manufacturing cycle times consisting of melting
the matrix, shaping and consolidation by cooling are signif-
icantly shorter than for their thermoset counterparts,
which require a time consuming curing step. In addition,
TPCs can be welded [2] and recycled [3].
In structural composite applications, textiles are com-
monly applied as reinforcement because of the high fiber
volume fractions that can be obtained and because of the
possibility to tailor the load bearing capacity through the
fiber lay-up. Traditionally, textile fiber-reinforced TPCs
are melt processed by stacking alternating layers of fiber
textiles and polymer sheets in a hot-press [4]. After heating
the package above the polymer melting point, the press is
closed to obtain the required product shape. In a subse-
quent cooling step the product solidification takes place
followed by demolding.
The main disadvantage of TPCs is the need for high pro-
cessing temperatures and pressures, caused by the high
melt viscosity of the matrix. In addition, proper impregna-
tion of the fiber at a microlevel might prove difficult and
often results in products with a locally high void content.
the matrix and the fibers in more intimate contact before the
final molding step, or in other words, to reduce the required
flow length of the polymer matrix. Various concepts of
these intermediates have been developed [1] such as co-min-
gled textiles that consist of both reinforcing and polymer
fibers, textiles made of powder coated fibers and partially
or fully consolidated panels (semi-pregs and pre-pregs [4]),
see Fig. 1. Besides the additional costs of these intermediate
products, additional disadvantages are encountered such as
the de-bulking of commingled textiles and the occurring
fiber waviness, the adherence of the powder coatings and
the occurrence of electrostatic discharges during processing
of powder coated textiles. Semi- and pre-pregs have poor
drapability and often contain some solvent residue when
they are made by solution impregnation: when PEI (polye-
therimide) pre-pregs are heated for instance evaporation of
the NMP (N-methylpyrrolidinone) solvent can be easily
seen. The additional remark has to be made that although
most plastics can be remolded numerous times without los-
ing properties, some high-performance plastics slightly
degrade during processing due to their high melting points:
cross-linking occurs for instance in molten PPS (polyphen-
ylenesulfide) [5]. Any intermediate processing step that
requires melting therefore increases the number of cross-
links, hence resulting in a more brittle matrix.

Fig. 1. Processing steps for manufacturing thermoplastic composite parts through melt- and reactive processing.
668 K. van Rijswijk, H.E.N. Bersee / Composites: Part A 38 (2007) 666–681
An alternative solution to melt processing presented in
this article is reactive processing of TPCs: after impregnat-
ing the fibers with a low viscosity mono- or oligomeric pre-
cursor, polymerization of the thermoplastic matrix is
conducted in situ. Polymerization can be initiated by heat
or UV radiation and might require the addition of a cata-
lyst system, which can be added to the precursor prior to
impregnation. Due to their low molecular weight, precur-
sors have extremely low melt viscosities and proper fiber
impregnation is therefore achieved without the need for
high processing pressures.
Moreover, through reactive processing, textile fiber-
reinforced TPCs can be even manufactured through low-
pressure infusion processes such as resin transfer molding
(RTM) [6], structural reaction injection molding (SRIM)
[6] and vacuum infusion [7]. These are all classic manufac-
turing processes for manufacturing of thermoset compos-
ites. In these processes, a dry fiber pre-form is placed into
a closed mold after which the precursor is infused by
applying vacuum or pressure, typically less than 10 bar.
Following polymerization, the composite product is
demolded. Additional advantages of this type of processing
are:
 Larger, thicker and more integrated products can be
obtained than what is currently achievable with melt
processing.
 A thermoplastic composite with a chemical fiber-to-
matrix bond can be obtained, due to the fact that poly-
merization takes place around the fibers. This can for
instance be accomplished by using silane coupling
agents [8].
 In addition to the textile reinforcement, nano-particles
can be added to the unreacted monomer in order to
obtain a fiber-reinforced polymer nano-composite
through for instance exfoliation [9–13].
In this article, an overview is given on thermoplastic
material systems that can be reactively processed; a distinc-
tion is made between engineering and high-performance
plastics. Various reactive processes are discussed for the
manufacturing of fiber-reinforced thermoplastic products
and the differences between reactive processing of thermo-
plastic and thermoset resins are highlighted.
O C N R1 N C O + HO
a) Polyurethane
O C N R1 N C O + H2N
b) Polyurea
Fig. 2. Free radical vinyl polymerization of polyurethanes and polyureas.
2. Reactive thermoplastic material systems
For reactive processing of thermoplastic composites, the
in situ polymerization of the matrix basically has to meet
the following requirements: a high molecular weight linear
polymer has to be formed at sufficiently high conversions
without the generation of unwanted by-products. Suitable
polymerization types are consequently narrowed down to
addition polymerizations of mono- and difunctional spe-
cies, of which vinyl polymerization and ring-opening poly-
merization are most common.
2.1. Vinyl polymerization
Vinyl polymers are polymers made from vinyl mono-
mers; small molecules containing carbon–carbon double
bonds. During polymerization the double bonds are bro-
ken into single bonds, resulting in two free electrons. The
free electrons are used to join monomer units to form a
long chain of many thousands of carbon atoms containing
only single bonds between atoms, see Fig. 2.
2.2. Ring-opening polymerization
As the name already suggests, ring-opening polymeriza-
tion (ROP) is based on a polymerization mechanism in
which ring-shaped molecules (cyclics) are opened into lin-
ear monomers or oligomers and subsequently connected
into high molecular weight polymers without generating
by-products, see Fig. 4. ROP initially received attention
as clean alternative for polymerization routes that result
in the generation of nasty by-products or require the use
of large amounts of hazardous solvents. Production of
PEEK and PPS for instance makes use of high-boiling sol-
vents such as diphenyl sulfone and dichlorobenzene [14,15],
whereas toxic phosgene gas is used for interfacial phosgen-
ation polymerization of polycarbonates [16]. In addition,
molecular weights obtained through ROP are generally
higher than for the same polymer obtained through poly-
condensation reactions. The first reason for this is that
polymer chains are broken in a subsequent purification
step, during which unreacted monomer and catalyst resi-
dues are removed by applying heat, solvents and high shear
forces. A second reason is that molecular weights are kept
O O
R1
R2 OH C N
H
N
H
C O R2 O
n
O O
R1
R2 NH2 C N
H
N
H
C N
H
R2 N
H n
 K. van Rijswijk, H.E.N. Bersee / Composites: Part A 38 (2007) 666–681
low deliberately in order to keep the melt viscosity reason-
able low for further processing through the melt. The fact
that a so-called ring-chain equilibrium exists, which can
be shifted by temperature or the addition of cleverly
selected catalysts not only offers the possibility for in situ
polymerization of polymer stock shapes and composites
but also for recycling through cyclo-depolymerization
(CDP) [17].
In the following sections, suitable thermoplastic mate-
rial systems for reactive processing are introduced. A dis-
tinction is made in reactive processing of engineering and
high-performance plastics.
2.3. Reactive processing of engineering plastics
2.3.1. Thermoplastic polyurethanes (TPU)
Polyurethanes are among the most widely applied resin
materials specifically developed for reactive processing [18].
Di-isocyanates react with di-alcohols through free radical
vinyl polymerization in a matter of seconds when processed
at around 60–80 °C, as is shown in Fig. 2a. Sometimes, di-
amines are used instead of di-alcohols to polymerize so-
called polyureas, see Fig. 2b. Most polyurethanes have a
thermoset nature, although thermoplastic polyurethanes
exist. These are however commonly sold as fully reacted
granules or powder for melt processing. Dubé et al. [19],
however, demonstrated the feasibility of reactive injection
pultrusion (RIP) of TPU composites based on the above-
mentioned chemistry. They pointed out that the high reac-
tivity of the resin requires a fast responding process control
system, since any deviation from ideal conditions can easily
lead to a significant reduction in the final polymer
properties.
Reactive processing of TPU based on a different type of
chemistry was recently developed by Dow Chemicals
(USA) and is currently applied by the Fulcrum Compos-
ites Company for the manufacturing of continuous fiber-
reinforced TPU pultrusion profiles [20–22]. Whereas most
polyurethanes are reactively processed from their mono-
mers, Fulcrum TPU uses high molecular weight linear
polymer as starting point and makes use of a depolymer-
O R
R O 2 R O
R
CH3
O CH3
H2C
CH2
R O + O
O
CH3
Fig. 3. Free radical vinyl polymerization of PMMA.
669
ization–repolymerization (DPRP) mechanism. Upon heat-
ing, depolymerization into lower weight fractions takes
place, which results in a significant viscosity reduction.
Subsequent cooling induces repolymerization and molecu-
lar weight rises again up to its starting value. A minimum
viscosity of a few Pa s is obtained at a processing temper-
ature of 270 °C. Although further heating reduces the
viscosity into the mPa s-range, the material loses its ability
to repolymerize [23]. Recyclability of the Fulcrum resin
through re-grinding and injection molding without
the loss of mechanical properties has been demonstrated
[24].
2.3.2. Polymethylmethacrylate (PMMA)
Free radical vinyl polymerization of the methylmethac-
rylate monomer (MMA) into its polymer PMMA is usually
conducted at temperatures in excess of 40 °C using perox-
ide initiators [25], see Fig. 3. At lower temperatures the
reaction time will soon exceed 16 h, whereas at higher tem-
peratures the danger exists that due to the exotherm of
462.2 J/g the monomer will soon start to boil, resulting in
voids in the final product. During polymerization the
density increases from 0.9 g/cm3 (monomer) to 1.2 g/cm3
(polymer), and in order to reduce shrinkage, usually a
pre-polymer (solution of PMMA in its monomer) is used.
The melt viscosity of the pre-polymer is higher than that
of the monomer (0.10 Pa s at 50 °C), but is still low enough
to cast (PlexiglasÒ or LuciteÒ) windows, which is the main
application of PMMA due to its transparent nature. As far
as composite processing is concerned, a monomer impreg-
nation method of natural fibers [26] and a reactive injection
pultrusion process are mentioned in literature [27,28]. In
order to increase the reaction rate, which is necessary in
a continuous process, the reaction temperature of the
pre-polymer had to be increased to 160 °C, which is well
above the glass transition temperature of the amorphous
polymer.
2.3.3. Polyamides
Anionic polymerization of lactams is the oldest and up
to now the most developed way for reactive processing of
CH3
H2C
C
n
O
O
O
O
CH3 CH3
670 K. van Rijswijk, H.E.N. Bersee / Composites: Part A 38 (2007) 666–681

thermoplastics through ROP. In the early 1940s, ROP of
caprolactam into PA-6 was discovered and has been com-
mercially exploited by for instance BASF, Bayern, DSM
and Monsanto. Anionic polymerization of laurolactam
into PA-12 has recently gained interest due to the work
conducted at EMS Chemie A.G. and the Ecole Polytech-
nique Fédérale de Lausanne, both in Switzerland.
2.3.3.1. Polyamide-6 (PA-6). The anionic ROP of e-capro-
lactam (Tm = 69 °C) into high molecular weight polyam-
ide-6 (PA-6), see Fig. 4, is a catalyzed reaction performed
at 130–170 °C [29]. Final conversions of up to 99.3% can
be obtained in 3–60 min, depending on the type and
amount of activator and catalyst added. Typical activators
used are N-acyllactams, whereas metal caprolactamates are
commonly used as initiator [30–36]. Commonly two mate-
rial batches are prepared, which after mixing start to
polymerize: a monomer–activator batch and a monomer–
initiator batch. Due to the anionic nature, the reaction is
easily terminated by proton donating species, such as for
instance moisture. Therefore, storage and processing have
to be conducted in an absolutely moisture free environ-
ment. Since processing takes place below the polymer
melting and crystallization point, polymerization and crys-
tallization take place simultaneously, resulting in solid
highly crystalline PA-6 [37–39]. The reaction is exothermic
(DHpolymerization = 166 J/g, DHcrystallization = 144 J/g),
which leads to a significant temperature increase during
polymerization [40]. The complex kinetics of the anionic
polymerization of caprolactam have been studied exten-
sively, mainly focusing on the autocatalytic effect of the
exothermic temperature rise [40–48]. Numerous reactive
processes have already been developed for unreinforced
and reinforced PA-6 such as (rotational) casting [49–53],
reaction injection molding (RIM) [54–56], reinforced reac-
tion injection molding (RRIM) [57,58], structural reaction
injection molding (SRIM) [59–61] and reactive injection
pultrusion (RIP) [62,63]. Technology developed by DSM
allows PA-6 to be fully depolymerized in a cost-effective
way into caprolactam of virgin quality [64]. In order to
reduce mold shrinkage and to increase the toughness,
a rubber-modified block-copolymer called NyrimÒ was
developed by DSM and is currently traded under the name
AP NylonÒ by Brüggemann Chemical, Germany [65–69].
Due to the pre-polymer activator of AP NylonÒ, the vis-
cosity is slightly higher (g = 60–90 mPa s [66]) than of the
unmodified resin (g = 10 mPa s [70]). In addition to these
rubber block copolymers also varieties with branches and
cross-links have been investigated [71,72]. A vacuum infu-
sion process for manufacturing of polyamide-6 composite
wind turbine blades is currently being developed at The
Delft University of Technology [70,73–77].
2.3.3.2. Polyamide-12 (PA-12). Polyamide-12 is anioni-
cally polymerized from x-laurolactam (Tm = 154 °C) using
similar activators and initiators as discussed in the previous

R
O +
O M O
H -
N N N O

m. + +
(CH2) (CH2) (CH2)
n n n
Lactam monomer: Initiator: Activator:

Caprolactam (n=5) Metal caprolactamate N-Acyllactam

Laurolactam (n=11)

Anionic ring opening polymerization

O
(CH2)
O n NH R
-
N
(CH2) Polyamide:
n
+ O PA-6 (n=5)
M
PA-12 (n=11)
m
Fig. 4. Anionic ring-opening polymerization of polyamides.
 K. van Rijswijk, H.E.N. Bersee / Composites: Part A 38 (2007) 666–681
paragraph on PA-6, see Fig. 4 [78]. In contrast to anionic
PA-6, polymerization has to be conducted above the final
polymer melting point (175 °C) to increase the polymeriza-
tion rate and to avoid premature crystallization [79]. As a
consequence, when processing at 180–240 °C, an additional
cooling step is required prior to demolding [80]. The molten
monomer has an initial viscosity of 23 mPa s [81] and has
to be kept in nitrogen protective environment to prevent
initiator deactivation. The reaction exotherm is about
53 J/g [79] and total mold shrinkage is 8.3–9.6% [82]. Reac-
tive PA-12 is currently marketed by EMS Chemie A.G.,
Switzerland, who also developed a one part activator–initi-
ator solution called GrilonitÒ that can be stored indefi-
nitely in inert atmosphere. This solution, which can also
be used for anionic polymerization of PA-6, no longer
requires pre-mixing of two separate material batches that
slowly polymerize over time. Pultrusion [83] and SRIM-
like processes [84–87] for PA-12 composites are currently
being developed at the Ecole Polytechnique Fédérale de
Lausanne (EPFL), Switzerland, the National University
of Ireland, Ireland and the Institut für Verbundwerkstoffe,
Germany.
Caprolactam and laurolactam can be anionically
copolymerized to tailor polymer properties. Material prop-
erties such as the strength and stiffness, glass transition and
the melting point are in direct relation with the monomer
ratios [88–90].
2.3.4. Polyesters
Synthesis of macrocyclic polyesters and the ring-opening
metathesis polymerization (ROMP) thereof was initially
developed by D.J. Brunelle and his research group at the
General Electrics Corporation, USA, in the late 1980s and
early 1990s. Initially aiming at polycarbonates, see next par-
agraph, reactive processing of both polyetherteraphthalate
(PET) and polybutyleneteraphthalate (PBT) was devel-
oped. The latter is currently being marketed specifically
for the production of composites under the name CyclicsÒ
by the Cyclics Corporation, USA [91–93].
2.3.4.1. Polyethyleneteraphthalate (PET). Macrocyclic
oligomers can be obtained through cyclodepolymerization
(CDP) of linear PET and subsequently repolymerized
through ROMP into high MW PET [94,95]. Fig. 5 shows
H H
O O
O
O
H Ring opening
H H H
H
H H metathesis polymerization
H
H
H H H O
O O
O
H O
H
Fig. 5. Ring-opening metathesis polymerization of PET.
671
polymerization of PET using a cyclic dimer (Tm =
225 °C). Up to 100% conversion at 250–325 °C are obta-
ined in several hours without a catalyst, whereas addition
of a catalyst reduces the reaction time to 3–15 min at
225 °C. The initial melt viscosity of the cyclic precursors
is 30 mPa s [96,97].
2.3.4.2. Polybutyleneteraphthalate (PBT). Depolymeriza-
tion of linear PBT yields a macrocyclic oligomer mixture,
which can be repolymerized directly into solid high molec-
ular weight (Mw = 445,000) semi-crystalline PBT at 180–
200 °C by addition of a titanium initiator [98,99], see
Fig. 6. The oligomer mixture has a melt viscosity of
150 mPa s at 150 °C, which drops to 30 mPa s at 190 °C.
When processed at 190 °C in protective atmosphere, the
viscosity reaches 1 Pa s after approximately 5 min and final
conversions of 95–99% are obtained within 30 min [100].
Although polymerization itself is not exothermic, approxi-
mately 67 J/g of heat is generated in the subsequent crystal-
lization phase. Final polymer properties strongly depend
on the polymerization temperature. When isothermally
polymerized below its melting point (Tm = 220–267 °C),
the PBT obtained is highly crystalline and tends to become
brittle (i.e. elongation at break = 1.8%), due to a phenom-
ena called cold-crystallization [101] A subsequent melting
and cooling cycle brings back the more ductile behavior.
Properties of initially reactively processed PBT are largely
unaffected after mechanical–thermal recycling (re-grinding
followed by injection molding) [3]. In addition, PBT
can be recycled chemically by depolymerization into the
cyclic oligomers or all the way into its monomers
dimethylterephthalate and butanediol [17]. RTM-like
processes for manufacturing fiber reinforced PBT are
developed at Delaware University (USA) and KU Leuven
(Belgium) [102–105], whereas the National University of
Ireland is developing Resin Film Infusion technology,
making use of a one-component monomer–catalyst system
[106,107].
Through ring-opening polymerization, PBT copolymers
with PET can be easily obtained [91].
2.3.5. Polycarbonate (PC)
Macrocyclic Bisphenol-A (Tm = 200–210 °C) can be
polymerized into polycarbonate through ROMP conducted
O O (C2H4)
O
n
672 K. van Rijswijk, H.E.N. Bersee / Composites: Part A 38 (2007) 666–681

O Cl

O O

Cyclic oligimer
+ HO(CH2)4OH
formation
O O (CH2)4
m

m = 2-7
Cl O

Ring opening metathesis polymerization

Initiation by Ti(OR)4

O O O O
Propagation

Ti(OR) 3 Ti(OR) 3
R O O (CH2)4 O R O O (CH2)4 O

n m

Fig. 6. Ring-opening metathesis polymerization of PBT.

H3C CH3 H3C CH3

Cyclic oligomer formation
from Bisphenol-A

O OH O

O O O O
Cl Cl m

H3C CH3

O Ring opening metathesis polymerization

using anionic initiators
O O
n
Fig. 7. Ring-opening metathesis polymerization of polycarbonates.

at 240–280 °C using anionic activators [108], see Fig. 7.
When polymerized at 250 °C in protective atmosphere,
the initial viscosity of the macrocyclic melt is 1 Pa s and
in 2–5 min high molecular weight PC is obtained
(Mw = 300,000) with conversions of over 99% [109]. The
reaction is entropy driven, which means that no exothermic
heat is generated during polymerization. ROMP of macro-
cyclics consisting of Bisphenol-A and hydroquinone at
300 °C results in a solvent resistant PC, which can be
obtained in either amorphous or semi-crystalline form
[16,110]. Other versions reported in literature are cross-
linked [111] and copolymerized PCs [112]. Salem et al. suc-
cessfully produced glass fiber reinforced PC composites
through reactive processing, although an additional consol-
idation step in a hot-press was necessary to reduce the void
content [113].
2.4. Reactive processing of high-performance plastics
After the successes of reactive processing of engineering
plastics such as PU, PMMA and PA-6, several attempts
were made to develop similar technology for processing
of high-performance plastics, mainly focusing on ROP of
polyarylethers. Initial results, however, brought complica-
tions to light, which were directly related to the inherent
properties of high-performance plastics, which make them
so interesting in the first place: an extreme stiff polymer
backbone combined with outstanding chemical resistance
 K. van Rijswijk, H.E.N. Bersee / Composites: Part A 38 (2007) 666–681
and thermal properties. Whereas the relatively flexible engi-
neering plastics are easily converted into cyclic precursors
of only a single or a few monomer units, a much larger
number of monomer units is required to form so-called
macrocyclic precursors of the more rigid high-performance
plastics. The higher molecular weight of the cyclic precur-
sors brings up the following problems:
 Synthesis of the cyclic precursors has to be conducted in
high-dilution or pseudo-high-dilution conditions, which
is explained by the fact that just before ring closure the
ends of the relatively long polymer chains are rather far
apart from each other. In case the solid concentration
during synthesis is too high, it is more likely that a chain
will react with a neighboring chain rather than having its
two ends react together to form a cycle. Synthesis there-
fore requires a lot of solvent and leads to relatively low
yields [17].
 The macrocyclic precursors obtained are often an oligo-
mer mixture, rather than a substance consisting of single
sized rings, which is related to matters discussed in the
previous point. Various oligomers might differ in prop-
erties such as melting points, solubility in the other olig-
omers within the same mixture or even in being
amorphous of crystalline [114,115]. These differences
complicate synthesis and further processing.
 In order to obtain high conversions, polymerization has
to be conducted at high temperatures for two reasons: (i)
the processing temperature has to exceed the melting
point of all oligomers, and (ii) the viscosity of the grow-
ing polymer chains has to be kept low enough to induce
sufficient chain mobility. Unfortunately, at temperatures
ranging from 300 to 400 °C side reactions like cross-link-
ing are unavoidable, which strongly reduce the polymer
performance [115].
Recent advances in cyclics technology are (i) the use of
monomer units containing meta and ortho rather than para
HO OH
DMAc Macrocyclic oligomer
Toluene + formation
O O
K 2CO3 O
F F
O
O O C
Fig. 8. Reactive processing route of PEEK.
673
linkages in order to produce macrocyclics with a lower
molecular weight (at a slight reduction of thermal stability
of their equivalent polymer) and (ii) isolation of specific
oligomers with a low melting point or an amorphous char-
acter in order to reduce the required polymerization tem-
perature [114]. In the next paragraphs an overview of
reactive processing equivalents of common high-perfor-
mance plastics is given.
2.4.1. Polyetheretherketone (PEEK)
Literature mentions synthesis of 45–60–90 membered
macrocyclics from 4,4-difluorobenzophenone and hydro-
quinone in pseudo-high-dilution conditions at a yield of
60%, which polymerized at 350 °C in 5 min using caesium
fluoride as initiator [116], see Fig. 8. Another source
reports synthesis of cyclic 2-mers, 3-mers and 4-mers, but
fails to discuss ring-opening polymerization [15].
2.4.2. Polyetherketone (PEK)
According to Jiang et al. [117–119], macrocyclic oligo-
mers for polyetherketones (PEK) were produced at a yield
of 54%. These cyclics (Tg of 127 °C) formed a clear melt at
280 °C and could subsequently be polymerized for 1 h at
the same temperature up till a conversion of 93.5%. The
resulting linear polymer is slightly branched and has a Tg
of 216 °C, which is slightly lower than commercially pro-
duced PEK (Tg = 228 °C) due to the presence of oligomers
that failed to polymerize. Ring-opening polymerization at
390 °C for 30 min of a cyclic PEK di-mer into an amor-
phous polymer (Tg = 162 °C) was reported by the same
authors [120].
The potential of reactive processing of high performance
thermoplastics is clearly demonstrated by the work con-
ducted at McGill University, Canada [121,122]. It was
shown that macrocyclic PEK containing a 1,2-dibenzoyl-
benzene moiety, see Fig. 9, has a stable melt viscosity
(80 mPa s at 330 °C) and could be polymerized at 340 °C
in 30 min after addition of a nucleophilic initiator.
O
C
m = 45, 60 or 90
Ring opening polymerization
Initiation by CsF, 350 oC
674 K. van Rijswijk, H.E.N. Bersee / Composites: Part A 38 (2007) 666–681

CH3 generated during production of commercial PEK-390 and

O polymerize these in 25 min at 385 °C [123].
CH3
2.4.3. Polyethersulfone (PES)
O ROP of PES cyclic precursors, conducted at 300 °C for
2 h, is shown in Fig. 10 [124]. Different types of poly aryl-
ene sulfone cyclics are discussed in [125,126].

2.4.4. Polyphenylenesulfide (PPS)

O
n in [127], see Fig. 11. The resulting high molecular weight
Fig. 9. Macrocyclic precursor for PEK.
Baxter et al. managed to polymerize cyclic PEK in
30 min at 300 °C using a Caesium fluoride initiator into a
semi-crystalline polymer (Tg = 168 °C, Tm = 302 °C) [114].
In addition, they showed that instead of using macrocyclics
specifically synthesized for ring-opening polymerization,
one could also use the cyclic oligomer byproduct that is
Melt polymerization of cyclic PPS pentamer and hexa-
mer at 300 °C under Nitrogen environment is discussed
polymer is highly crystalline and has a melting point of
277 °C, which is comparable to that of commercial grades
PPS (Tm = 285 °C). An alternative method for preparing
the same cyclic PPS precursor is discussed in [128].
2.4.5. Polyethylenenaphthalate (PEN)
According to [129], a PEN (polyethylenenaphthalate)
macrocyclic oligomer mixture with a melting point of
250–285 °C was prepared in a 57% yield. In 25 min ROP

F S F O

O Macrocyclic oligomer S O
DMSO + formation
O O
m

HO S OH

Ring opening polymerization

S O
Initiation by CsF, 300 oC
O
n

Fig. 10. Reactive processing route of PES.

S
Macrocyclic oligomer formation S
S
from diphenyl disulfide
m

Free-radical ring opening polymerization

S
Initiation by DTB, 300 oC

Fig. 11. Reactive processing route of PPS.

 K. van Rijswijk, H.E.N. Bersee / Composites: Part A 38 (2007) 666–681 675

Cl
O
Macrocyclic oligomer
Cl
formation O O (CH2)
x

O
DABCO
O
CH2Cl2 +
m
x = 2: PEN
HO (CH 2) OH x = 4: PBN
x

Ring opening polymerization

O O (CH2)x
Initiation by Bu2 SnO, 275 oC

Fig. 12. Reactive processing route for PEN and PBN.

was conducted in the presence of a peroxide initiator at weight impurities in the cyclic oligomer mixture strongly
295–300 °C, see Fig. 12. The final polymer (Tm = 261 °C) affected the final polymer properties [129].
suffered from impurities present in the cyclic oligomer To summarize this chapter, Fig. 13 shows the melt vis-
mixture and initiator residue. cosities and processing temperatures of various mono-
and oligomeric thermoplastic precursors. For comparison,
2.4.6. Polybutylenenaphthalate (PBN) the same data is also given for common thermoset resins
PBN (polybutylenenaphthalete) macrcocylic precursors and thermoplastic polymers suitable for melt processing.
containing various size oligomers (Tm = 150–220 °C) were Table 1 compares the processing temperatures for some
prepared at a 75% yield. ROP was subsequently conducted common thermoplastic matrices for both melt- and reactive
in the presence of a tinoxide catalyst at 275 °C and was processing. It can be seen that whereas the reduction
completed in 15 min, see Fig. 12. The linear low molecular in processing temperatures for engineering plastics is

100000

10000
PES PEEK
PMMA
PA-12 PEKK
1000 Melt processing of
engineering plastics PA-6 PEI
PBT
Melt viscosity [Pa·s]

100 PPS
Melt processing of high-
performance plastics
10
Reactive processing of
thermoset resins
PC Reactive processing of
1 vinylester thermoplastic oligomers
epoxy
ETPU
polyester
0.1
PMMA PBT PEK

0.01 PA-6 PA-12

Reactive processing of
thermoplastic monomers
0.001
0 50 100 150 200 250 300 350 400 450
Processing temperature [°C]

Fig. 13. Melt viscosities and processing temperatures of various matrix materials for both reactive and melt processing.
676 K. van Rijswijk, H.E.N. Bersee / Composites: Part A 38 (2007) 666–681

Table 1 3.1. Reactive processes for thermoplastic composites

Comparison of processing temperatures for melt- and reactive processing
for some common thermoplastic matrix materials
3.1.1. Structural reaction injection molding (SRIM)
Thermoplastic matrix Processing temperature (°C) SRIM uses high pressure (8–10 bar) to impregnate a dry
Melt Reactive Reduction fiber pre-form, which is placed between two solid mold
processing processing halves, see Fig. 14a [80–82,84–87,101–104,138–140]. The
PA-6 230–290 140–160 70–150 process is closely related to Resin Transfer Molding
PA-12 230–270 180–245 0–90 (RTM) of thermoset composites [6]. In order to obtain a
PBT 250–270 180–200 50–90
PMMA 220–260 120–160 60–140
proper fiber impregnation, 1 Pa s is generally regarded as
PC 265–360 250 15–110 the maximum viscosity limit of the reactive mixture [141].
PET 265–325 250–325 0–15 Upon completion of polymerization, the composite part
PES 330–390 300 30–90 can be demolded. As the size of the product increases so
PPS 330 300 30 does the clamping force required to keep the mold closed
PEEK 380–390 350 30–40
during injection of the resin. As a consequence, the size
of parts manufactured through SRIM is limited. The reac-
tive material systems are separated into two material feeds,
significant, the difference for high-performance plastics is in order to prevent premature polymerization. Just before
relatively small. The reason for this is the high melting entering the mold, the material feeds from two tanks are
point of the oligomeric precursors for high-performance mixed and polymerization commences. The big advantage
plastics, which are almost as high as their high molecular of SRIM is the fast cycle time, whereas the high tooling
weight linear equivalents. costs are the main disadvantage.
The next section discusses three potential manufacturing
processes to produce textile fiber-reinforced thermoplastic 3.1.2. Vacuum infusion (VI)
composites from the resin materials introduced previously. As the name suggests, vacuum is used to compact
and impregnate a dry fiber pre-form, which is placed
3. Reactive processing of textile reinforced thermoplastic between a solid and a flexible mold half, see Fig. 14b
composites [60,61,70,73–77]. Although the impregnation speed is lower
compared to SRIM, the fact that atmospheric pressure is
In this section, three reactive processes for manufactur- sufficient for mold clamping causes that the maximum
ing of textile fiber-reinforced TPCs are introduced: struc- achievable part size is only limited by the pot-life of the
tural reaction injection molding, vacuum infusion and reactive system. After mixing the contents of the two mate-
resin film infusion, see Fig. 14. Reactive processes for neat rial tanks, the reactive mixture (maximum viscosity: 1 Pa s)
polymer parts like casting [49,51,53,130,131], reaction is dispensed into a buffer vessel, which is required to sepa-
injection molding (RIM) [54–56,66,132,133] and rotational rate the pressure required for dispensing and the vacuum
molding [50,67–69,134], and for manufacturing of short necessary to promote infusion. The big advantages of VI
fiber reinforced composite parts like reinforced reaction are the virtually unlimited size of the parts that can be pro-
injection molding (RRIM) [57,58,135,136] are discussed duced and the low cost tooling due to the low pressures
in literature, as well as reactive injection pultrusion involved. The disadvantages are related to the flexible mold
(RIP) of continuous fiber-reinforced profiles [19,28,63, half, which often can be used only once and leads to a poor
80,83,137]. surface quality on one side of the product.

Fig. 14. Schematic representation of three reactive processes for manufacturing of thermoplastic composites: (a) structural reaction injection moulding
(SRIM), (b) vacuum infusion (VI) and (c) resin film infusion (RFI).
 K. van Rijswijk, H.E.N. Bersee / Composites: Part A 38 (2007) 666–681
3.1.3. Resin film infusion (RFI)
RFI is similar to pre-pregging of thermoset composites:
hand lay-up is used to stack alternating layers of fiber tex-
tiles and sheets of unreacted reactive mixture in a mold, see
Fig. 14c [106,107]. Upon applying heat and pressure, the
sheets melt and impregnate fibers, after which polymeriza-
tion initiates. In case the sheets do not have sufficient
mechanical properties for handling, they can be directly
cast on top of a supporting fiber textile. Also powder-
impregnated textiles can be used. To maintain reactivity,
no premature solid-state polymerization or deactivation
during storage or handling of the unreacted sheets or
pre-pregs should take place. During melting and impregna-
tion a significant volume reduction of the lay-up takes
place and often multiple de-bulking steps are necessary to
compress the lay-up. The atmospheric pressure is usually
sufficient for de-bulking of thin-walled parts and allows
the use of a flexible mold half. In this case, the viscosity
of the reactive mixture is again limited to 1 Pa s. De-bul-
king of thicker parts is more difficult and often required
a second solid mold half and significant pressure, which
simultaneously allows the use of oligomeric precursors with
a higher melt viscosity. The ease of preparing the lay-up
and the fast impregnation are regarded as the main advan-
tages of RFI, whereas de-bulking is the main disadvantage.
3.2. Differences between reactive processing of
thermoplastic and thermoset composites
Reactive processing of thermoplastic composites seems
to have a lot in common with manufacturing of thermoset
ones. There are however a few significant differences, which
are briefly summarized below:
 The polymerization rate increases with increasing
temperature, which is true for both thermoplastic and
thermoset resins. When processing reactive thermoplas-
tic materials with a semi-crystalline nature, however,
one has to keep in mind that crystallization is adversely
affected by temperature. The processing temperature has
to be chosen such that polymerization and crystalliza-
tion are well balanced. When the temperature is too
low, crystallization will be too fast and reactive chain-
ends and monomer can get trapped inside crystals before
they can polymerize. On the other hand, when the tem-
perature is too high, the final degree of crystallinity is
reduced, which reduces the strength, stiffness and chem-
ical resistance of the polymer [73].
 Some reactive thermoplastic materials, like PA-6, PA-12
and PBT, have a melt viscosity, which is an order of
magnitude lower than of common thermoset resins. As
a consequence, the occurring capillary forces during
impregnation of the fiber pre-form are significant and
form a potential source for voids and runner formation
[81,138].
 Whereas most thermoset resins are liquid at room tem-
perature, most thermoplastic precursors are still solid.
677
Heated equipment is therefore necessary to keep the
unreacted mixture in the melt state.
 Demolding techniques that make use of the brittle nat-
ure of thermoset resins, such as peel plies in vacuum
infusion and break lines through resin rich areas, are
not applicable due to the tough nature of the thermo-
plastic material.
 In contrast to thermoset resin waste during processing,
reacted and unreacted resin in tubes (vacuum infusion)
can be fully recycled, as well as waste from mechanical
trimming such as flashes.
 The performance of composites in not solely determined
by the fibers and the matrix, but also by the fiber-to-
matrix interphase. In order to improve this bond, glass
fibers for instance are usually coated with silane cou-
pling agents: di-functional compounds with the ability
to bond with both the fibers and a polymer matrix of
choice. A non-compatible coupling agent results in a
weak interphase or even prevent the polymerization of
reactive resins. Coupling agents have been developed
for numerous thermoset composites resins and for ther-
moplastic composites manufactured through melt pro-
cessing. Coupling agents specifically for reactive
processing of thermoplastic composites have not been
developed yet, but have recently become a topic of inter-
est [142,143].
 In addition to fibers with suitable coating, processing
aids for, for instance, vacuum infusion of thermoplastic
resins such as transport tubes, vacuum bagging films
and sealant tape are not commercially available as such.
Suitable high-temperature consumables, which are
chemically resistant against the unreacted thermoplastic
materials, therefore still need to be selected.
Perhaps the most striking difference is the fact that
whereas reactive processing of thermoset composites forms
the mainstay of the composite industry worldwide, the
potentially great thermoplastic resins presented in this
study have not found any significant composite application
so far. This cannot be related to the expected properties of
reactively processed thermoplastic composites, given the
fact that their melt-processed equivalents have already
found extensive application. Careful examination of the
references of this study demonstrates the lack of coopera-
tion between polymer chemists and composite processing
engineers. The presented material systems are mainly devel-
oped for processing of neat polymer products and are yet
to be adapted to meet the specific requirements for com-
posite processing. Being unable to address critical process-
ing issues with the currently available resin systems and not
being persistent enough in having the resin materials
adjusted to its specific needs, the composites industry has
not been able yet to bring reactive processing of thermo-
plastic composites to the next level. More recent publica-
tions give evidence of cooperation initiatives between
chemists and engineers, which is paramount for putting
an end to the current standstill and for bringing reactive
678 K. van Rijswijk, H.E.N. Bersee / Composites: Part A 38 (2007) 666–681
thermoplastic processing into commercial practice. Only
then a comparison between the presented material systems
can be made to determine which is best suitable for manu-
facturing of composites, in terms of storage, handling, pro-
cessing and of course composite properties. It will be
interesting to know which of these materials will ultimately
become the ‘epoxies and polyesters of reactive thermoplas-
tic composite processing’.
4. Conclusions
Reactive processing of textile fiber-reinforced thermo-
plastic composites has been discussed as an alternative to
melt processing for manufacturing of larger, thicker and
more integrated parts. An overview of suitable thermoplas-
tic material systems for reactive processing was given rang-
ing from commercially available engineering plastics to
high-performance plastics that are still in the pioneering
stage. Three manufacturing processes, commonly used for
reactive processing of thermosets, were introduced and dif-
ferences between reactive processing of thermoset and ther-
moplastic composites were pointed out. The recent focus of
both polymer chemists and composite engineers on reactive
processing of thermoplastic composites not only demon-
strates the interest in expanding the application field of
thermoplastic composites but also provides the necessary
means to accomplish this.
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