REACTIVE

&
FUNCTIONAL
Reactive & Functional Polymers 67 (2007) 675–692
POLYMERS
www.elsevier.com/locate/react

Review

Methods for polyurethane and polyurethane

composites, recycling and recovery: A review
Khalid Mahmood Zia, Haq Nawaz Bhatti *, Ijaz Ahmad Bhatti
Department of Chemistry, University of Agriculture, Faisalabad-38040, Pakistan

Received 16 May 2006; received in revised form 13 February 2007; accepted 5 May 2007
Available online 18 May 2007

Abstract

Recent progress in the recycling and recovery of polyurethane and polyurethane composites is reviewed. The various
types of polyurethane waste products, consisting of either old recycled parts or production waste, are generally reduced
to a more usable form, such as flakes, powder or pellets, depending on the particular type of polyurethane that is being
recycled. The various recycling technologies for material and chemical recycling of PU materials have greatly contributed
to improve the overall image regarding the recyclability of polyurethanes in recent years, by far the most important being
regrinding and glycolysis. These technologies open an emerging, effective and economic route for recycling polyurethane
rigid foams and composite. Polyurethane foam in automotive seating has been successfully recycled using regrind technol-
ogy. Glycolysis of polyurethanes can be economically acceptable, but still requires more development in order to tolerate
more contamination in the post-consumer material. Current technologies can recover the inherent energy value of poly-
urethanes and reduce fossil fuel consumption. Energy recovery is considered the only suitable disposal method for recov-
ered material for which no markets exist or can be created. Increasing waste-to-energy and other thermal processing
activities involving gasification, pyrolysis and two-stage combustion has contributed for the disposal of significant amounts
of scrap PU without many difficulties. It is concluded that many of the plastic feedstock recycling processes appear to be
technically feasible and robust enough to warrant further development in the future.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Polyurethane; Recycling; Recovery; Regrinding; Glycolysis; Energy recovery

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
2. Mechanical recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
2.1. Regrinding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
2.1.1. Two-roll mill process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
2.1.2. Precision knife cutting. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 679

*
Corresponding author. Tel.: +92 41 9200161-70/3309; fax: +92 41 9200764.
E-mail address: hnbhatti2005@yahoo.com (H.N. Bhatti).

1381-5148/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.reactfunctpolym.2007.05.004
676 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692

2.1.3. Pellet mill . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 679

2.1.4. The grind flex process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 679
2.2. Re-bonding. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
2.3. Adhesive pressing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 681
2.4. Compression moulding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 681
2.5. Injection moulding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 682
3. Chemical processing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 683
3.1. Hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 683
3.2. Glycolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 683
3.3. Alcoholysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
3.4. Fractionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
3.5. Hydroglycolysis (Ford hydroglycolysis) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 686
3.6. Aminolysis (Dow’s aminolysis) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 686
4. Thermo chemical processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 686
4.1. Pyrolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 686
4.2. Gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 687
4.3. Hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 688
5. Energy recovery. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 688
5.1. Municipal waste combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 689
5.2. Fluidised bed combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 689
5.3. Two stage incineration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 689
5.4. Rotary kiln combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 689
5.5. Thermal degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 689
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 690
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 690

1. Introduction of urethane groups (–HN–COO–), regardless of

Polyurethanes are one of the most versatile mate-
rials in the world today. Their many uses range
from flexible foam in upholstered furniture, to rigid
foam as insulation in walls, roofs and appliances to
thermoplastic polyurethane used in medical devices
and footwear, to coatings, adhesives, sealants and
elastomers used on floors and automotive interiors
[1,2]. Polyurethanes have increasingly been used
during the past thirty years in a variety of applica-
tions due to their comfort, cost benefits, energy sav-
ings and potential environmental soundness. What
are some of the factors that make polyurethanes
so desirable? Polyurethane durability contributes
significantly to the long lifetimes of many products.
The extensions of product life cycle and resource
conservation are important environmental consider-
ations that often favor the selection of polyure-
thanes [3–5]. Polyurethanes (PUs) represent an
important class of thermoplastic and thermoset
polymers as their mechanical, thermal, and chemical
properties can be tailored by the reaction of various
polyols and polyisocyanates. The PUs includes
those polymers, which contain a significant number
what the rest of the molecule may be [6,7].
Worldwide, more and more attention is being
focused on polyurethane recycling due to on-going
changes in both regulatory and environmental
issues. Increasing landfill costs and decreasing land-
fill space are forcing consideration of alternative
options for the disposal of polyurethane materials
[8]. Polyurethane is successfully recycled from a
variety of consumer products, including: appliances,
automobiles, bedding, carpet cushion, upholstered
furniture [9].
The polyurethane industry has identified work-
able technologies for recovering and recycling poly-
urethane waste materials from discarded products
as well as from manufacturing processes. For exam-
ple, in 2002, 850 million pounds of polyurethane
were used to make carpet cushion [10], of which
830 million pounds were made from scrap polyure-
thane foam. Of the total scrap used, 50 million
pounds came from post-consumer waste. EC Draft
directive [11] for end-of-life vehicles (ELV) disposal
reported that in the year 2005, 15.0% of vehicle
weight is disposed (maximum) to landfill, and pre-
dicted that in the year 2015, only 5.0% of vehicle
 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692 677

weight will be disposed (maximum) to landfill. The

polyurethane industry is committed to meeting the
current needs of today without compromising the
needs of tomorrow. The continued development of
recycling and recovery technologies [12–14], invest-
ment in infrastructure necessary to support them,
the establishment of viable markets and participa-
tion by industry, government and consumers are
all priorities.
Years of research, study and testing have resulted
in a number of recycling and recovery methods for
polyurethanes that can be economically and envi-
ronmentally viable [15]. The four major categories
[16] are mechanical recycling, advanced chemical
& thermo chemical recycling, energy recovery and
product recycling (Fig. 1). Each method provides
a unique set of advantages that make it particularly
Fig. 2. Closed loop polyurethane recycling as proposed by
beneficial for specific locations, applications or ISOPA [18].
requirements [12,13]. Mechanical recycling (i.e.,
material recycling) involves physical treatment,
chemical & thermo chemical recycling (i.e., feed- ing them to be reused in the production of new foam
stock recycling) involves chemical treatment that as filler. The methods of reuse are flexible foam
produces feedstock chemicals for chemical process bonding, adhesive pressing, and compression mold-
industry, and energy recovery (including waste-to- ing [18]. Flexible foam bonding utilizes foam pieces
energy) involves complete or partial oxidation of and adheres them together to make padding type
the material [17], producing heat and power and/ products. Adhesive pressing is where the polyure-
or gaseous fuels, oils and chars besides by-products thane granules are coated with a binder (glue) then
that must be disposed of, such as ashes [9]. Due to cured under heat and pressure to make parts like
the typically long lifetime of PU-containing prod- floor mats for cars or tire covers. Compression
ucts the fourth option of product recycling or molding is where the polyurethane granules are
‘‘closed loop” recycling (Fig. 2), is limited [8,18], molded under high heat and pressure to create rigid
because markets change rapidly and the concept or hard parts such as pump and motor housing.
of ‘‘down cycling” or ‘‘open loop” recycling strongly Energy recovery is a method in which polyurethane
applies to products based on bulk chemicals such as can be burned efficiently resulting in a total con-
PU. sumption of the material. Chemical & thermo chem-
Mechanical, chemical & thermo chemical recy- ical recycling has several different methods such as:
cling and energy recovery, are all ways to recycle glycolysis, hydrolysis, pyrolysis, hydrogenation, etc.
polyurethane [19]. Mechanical recycling is done by Glycolysis [20,21] is where polyurethane is chemi-
regrinding polyurethane foams into powders allow- cally mixed and heated to 200 °C and produce

Fig. 1. Overview of options for polyurethane recycling [16].

678 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692
polyol, which can be used to make more polyure-
thane or it, can be used as a fuel. Hydrolysis [22]
is like glycolysis however it produces polyol and
amine intermediates can be used for fuel and pro-
ducing more polyurethane. Pyrolysis creates gas
and oil under heated, oxygen-free conditions.
Hydrogenation, like pyrolysis, creates gas and oils
but under heat and pressure and the hydrogen pro-
duced is purer [6]. The technology is claimed to be
well-suited for semi-rigid and rigid polyurethane
applications such as fascias, body parts and trim,
bumper covers and cores, steering wheels, wheel
covers, quarter panels and spoilers. It is claimed to
be both practical and economical.
Like all plastics recycling processes, technical and
economic feasibility and overall commercial viabil-
ity of advanced recycling methods must be consid-
ered in each step of the recycling chain [13,14].
Collection, processing, and marketing are each
critical to the success of chemical and feedstock
recycling. Today, with few exceptions, these tech-
nologies remain developmental and have not yet
proven them sustainable in a competitive market.
Nevertheless, they remain of considerable interest
for their longer term potential. The aim of this
review is to focus on the various recycling methods
i.e., mechanical, chemical & thermo chemical recy-
cling and recovery of polyurethane and polyure-
thane composites and to develop cost effective
process for the competitive recycling of automotive
plastic from end of life vehicle (ELV).
2. Mechanical recycling
This technology opens an emerging, effective and
economic route for recycling polyurethane rigid
foams and composite. The first step necessary for
the potential recycling of polyurethane involves
one of a number of processes required to reduce
the particle size of the original foam product to a
level that will allow the material to be reprocessed
in a secondary manufacturing process. The various
types of polyurethane waste products, consisting
of either old recycled parts or production waste
(e.g., trimmings, scrap parts, etc.), are generally
reduced to a more usable form, such as flakes, pow-
der or pellets, depending on the particular type of
polyurethane that is being recycled. In most cases,
this can be accomplished by either shredding or
grinding the polyurethane in order to provide the
necessary media for recycling. This waste is usually
a direct result of the trimming of the slab stock buns
and the subsequent fabrication into the finished
product. For molded foam operations, the waste is
typically generated during the manufacturing pro-
cess as a result of the flashing at the mold closing
edges and the venting holes, which in extreme cases
may amount to a total of 6% of material waste,
depending on the size of the overall part. In the case
of slab stock or flexible foam, up to 12% of cut-off
waste is to be expected, depending on the particular
manufacturing process [23]. Five major processing
routes determine mechanical recycling field [9,12–
14,16,18,24,25].
2.1. Regrinding
Industrial and post-consumer flexible polyure-
thane foam (Fig. 3) is regrinded into powders for
producing new foam [18]. Regrind technology,
sometimes described as powdering, is a process that
reuses ground production trim or post-consumer
parts as filler in polyurethane foams or elastomers.
This entails grinding material into a fine powder,
and mixing the powder with a polyol component
used to make new polyurethane [26]. For optimum
processing, the final particle size for regrind is usu-
ally less than 200 lm (0.2 mm), and preferably less
than 100 lm, depending on the application. Poly-
urethane foam in automotive seating has been suc-
cessfully recycled using regrind technology.
Regrind technology involves the processes [27]:
(i) Two-roll mill process
(ii) Precision knife cutting
(iii) Pellet mill
(iv) The grind flex process
(v) Impact disk mill
(vi) Cryogenic grinding
(vii) Extruder
2.1.1. Two-roll mill process
This process consists of at least one pair of rollers
(Fig. 4), rotating in opposite directions at different
velocities [12]. During the early 1990s two-roll mill-
ing (Fig. 3) was found to give the best result for flex-
ible PU foam grinding, whilst for rigid PU foams
ball mills may yield particle sizes as small as
85 lm. One factor that limits the amount of
scrapped PU foam that can be recycled by regrind-
ing is the viscosity of the polyol/fine particle mixture
that can be handled by the processing equipment. In
practice this typically allows for up to 15%-wt
 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692
Fig. 3. Schematic of a regrinding [18].
Fig. 4. Schematic of a two-roll milling process [12,27].
regrind when MDI polyol is used, up to 25% with
TDI [12]. The major problem of grinding processes
for waste processing is that of economy: grinding
scrap PU foam to size below 100–125 lm is no
exception to that. Development work during the
679
late 1990s reported by Stone et al. [28] has shown
that two-roll milling can be economically viable
alternative to cryogenic processes.
2.1.2. Precision knife cutting
For powdering foams to particle sizes less than
0.25 mm, special types of knife cutters can be used.
Precision knife cutters are characterized by a large
number of static and rotating knives.
2.1.3. Pellet mill
This consists of two or more metal rollers, which
press the polyurethane foam through a metal plate
with small holes (die). This process has been used
successfully at pilot scale.
2.1.4. The grind flex process
A joint development between Metzeler Schaum
GmbH and Hennecke GmbH [29] has already been
successfully proven in a full-scale production appli-
cation. This process was made possible through a
reliable processing technology that is applicable to
most polyurethane types and can readily be imple-
mented at the production level. Implementation of
the regrind powder processing technology requires
the following main production steps:
 Generation of powder
 Metering of powder
680 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692

 In-line mixing of powder and polyol
 Foaming new foam
 Adjusting the chemical formulation [27,29]
Other regrind technologies include impact disk mill,
cryogenic grinding and extruder [27–29].
2.2. Re-bonding
Re-bonding is most widely used recycling process
for more than 30 years [18]. In the rebond process
(Fig. 5), recycled foam flakes originating from flex-
ible slab stock foam production waste are usually
blown from storage silos into a mixer that consists
of a fixed drum with rotating blades or agitators,
where the foam flakes are sprayed with an adhesive
mixture. In rebonding we are able to achieve new
properties of PU i.e., higher density and lighter
hardness [18].
In re-bonding of PU waste, to the 90.0% PU
scrap, 10.0% binder (NDI) is added. Waste is shred-
ded and mixed with binder, dyes can also be added,
and the mixture is then compressed. Steam is pro-
vided (Fig. 5) to complete the binding [18]. PU
recyclate granules used as filler in polyester mould-
ing compounds and gives added toughness to mate-
rial. Re-bonding yields a variety of padding
products, such as carpet underlay and athletic mats,
from recovered pieces of flexible polyurethane foam.
Flexible foam bonding utilizes foam pieces and
adheres them together to make padding type prod-
ucts (Fig. 6). The rebond process incorporates both
a surprising amount of flexibility and a wide vari-
ability in the mechanical properties of the final

Fig. 5. Schematic of flexible foam re-bonding [18].

Fig. 6. Rebonded foam: homogeneous distribution of the flake binder mixture [18].
 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692
product. The enormous potential associated with
the rebond process is based on the establishment
of a first class, independent group of materials,
which can take advantage of the traditional proper-
ties of slab stock foam and take these to another
level with the higher densities that can be offered
with rebonded material. Modern rebond plant con-
cepts have provided the necessary means to fulfill
these requirements and are capable of consistently
producing top quality molded parts from rebonded
material. As a result of the tremendous advance-
ment in this technology segment, the rebonded
material molded from leftover foam flakes has
established a separate class of materials, which is
able to provide material properties and processing
advantages that are quite unique.
2.3. Adhesive pressing
Adhesive pressing coats polyurethane granules
with a binder (Fig. 7) and then cures them under
heat and pressure [18]. Contoured parts, like auto-
motive floor mats and tire covers, are made with this
method. Adhesive pressing is applicable to many
types of plastics wastes and mixtures of these, this
is a short route to a semi-finished product [13,14].
Probably being the oldest method for flexible PU
foam recycling this allows for the production of
mats, carpet underlay, sports hall floor parts and
automotive sound insulation. PUR foam scrap can
be rebonded by mixing scrap particles (size 1 cm)
Fig. 7. Schematic of an adhesive pressing [18].
681
with di-isocyanate MDI followed by form-shaping
at 100–200 °C, 30–200 bar. PU construction boards
with excellent water and moisture resistance are
obtained, or insulation panels for use in new refrig-
erators or freezers. PUF foam can likewise be reb-
onded to blocks that find use in carpets, sports
hall mats or furniture. The enormous amount of
PUF foam recovered from scrapped vehicles may
satisfy a large part (in the US almost 50%) of the
market of carpet underlay [12]. For PUR foam from
scrapped buildings this recycling option is very
important as well but is more complicated and often
impossible due to the use of flame-retardants in
these materials [16].
2.4. Compression moulding
Compression molded parts contain 100% recy-
cled material. Compression molding, used primarily
with reaction injection molded (RIM) polyure-
thanes, is capable of producing high performance
recycled products. RIM and reinforced RIM parts
are ground into fine particles and subjected to high
pressure and heat to generate a solid material that is
ideal for many automotive applications. Recycling
initiatives in this area have focused on production
trim from polyurethane processing and polyure-
thanes retrieved from scrapped vehicles. Glycol
extended RIM parts, compression molded at
195 °C, have certain mechanical properties that
actually can be superior to those of virgin polyure-
thane material. Compression moulding [30] involves
moulding PU particles at temperatures and pres-
sures high (180 °C, 350 bar) enough to generate
the shear forces needed to flow the particles
together, without the need for additional binders.
Compression Molding produces rigid and 3-D
parts, such as pump and motor housings, when
polyurethane granules are molded under heat and
pressure. This method is successfully applied to
reaction injection moulding (RIM) PU recycling
into automotive parts (so-called fascias) although
the recycling of painted parts is problematic. For
example mud-flaps and athletic fields can be pro-
duced, often co-processed with rubber chips. Door
panels and dashboard panels for cars can be pro-
duced using around 6% regrinded RIM plus 15%
glass fibres. Especially important is SRIM (struc-
tural reaction injection moulding) recycling for
coarsely grinded PU scrap (Fig. 8), where the recy-
cled PU material (which may be up to 30%-wt) is
‘‘sandwiched” between fiberglass reinforcements
682 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692

Fig. 8. Structure reaction injection moulding (SRIM) recycling of PU scrap [12].

covered by a two-component PU resin. This proce-
dure gives products with increased stiffness for use
in automotive parts [12]. A recent study from the
UK [30] showed that polyester resins compounded
with RIM PU granulates gives increased flexibility
and toughness to mouldings when compared to
compounds with mineral (e.g., talc) fillers.
2.5. Injection moulding
Injection moulding also allows for (moderately)
cross-linked PU recycling. This method also allows
for processing of mixes of PU and other plastics,
addition of some thermoplast is actually preferable.
In one application, (Bayer’s hot compression
moulding, or HCM process) granulated PU (250–
1000 lm) is processed at 180 °C and high shear
compression (>350 bar) to produce thermo shaped
products such as automotive parts [12].
Regrind technology has proven difficult with
RIM parts. Recent studies have developed a three-
stream process for recycling reground RIM. The
three streams include:
(i) Amine and polyol with glass filler.
(ii) Amine free polyol and RIM regrind filler.
(iii) Diisocyanate [9,12,18].
Recycled powder from rigid PU is an excellent
material for absorbing oil spills, and as officially
approved oil binder is commercially available for
that purpose, and recycled RIM PU powder has
used, up to 10%-wt, in new and approved RIM
PU vehicle parts in Europe and USA [16]. Hulme
[31] developed techniques for recycling and reuse
of thermoplastic and thermoset waste by introduc-
ing dual injection moulding process (Fig. 9) stating
its advantages:
 improved mechanical properties
 improved surface finish
 moulding can be any color

Fig. 9. Recycling and reuse of thermoplastic and thermoset waste by dual injection moulding process [31].
 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692
3. Chemical processing
3.1. Hydrolysis
Hydrolysis is the reaction of polyurethane with
water, and can produce both polyols and amine
intermediates [9,12,18,22] from polyurethane pro-
cess and post-consumer scrap (Fig. 10). When
recovered, the polyols can be used as effective fuels,
and the intermediates can be re-used to produce
other polyurethane components. This method uses
a heated, oxygen-free environment to break down
polyurethane and plastics into gases, oils and solids
[32–34]. Material recovery by hydrolysis was
applied to PU foam waste from junk cars already
during the 1970s in the USA. Superheated steam
of 200 °C was found to convert PU foam from
scrapped car seats into a two-phase liquid within
around 15 min, at a volume reduction by a factor
of 30. The chemistry can be summarised as:
R0 –NH–CO–O–R00 þH2 O!R–NH2 þHO–RþCO2
R0 –NH–CO–NH–R00 þH2 O!2R–NH2 þCO2
It was at that time suggested that the liquids can be
land filled or distilled, separating the polyols and
diamino toluenes (DATs) for reuse [22]. Focusing
later on the recovery and recycling of the polyol
showed that superheated steam temperature should
be around 288 °C, producing a polyol that gave
excellent new PU foam for seat cushions when
mixed at 5% to virgin material. Too high tempera-
ture gives a decrease in useful polyol recovery,
while polyol recovered at too low steam tempera-
ture produces unstable new PU foam [35]. PU
hydrolysis suffers from unfavorable economics and
Fig. 10. Chemistry of hydrolysis of PU results in the formation of diamines like diphenyl methane diamine (MDA) [12].
683
lack of markets for the recyclate products [12,16].
Recent studies nonetheless address the recovery of
other products besides polyols, and the alkaline
compounds that may accelerate the hydrolysis [36].
3.2. Glycolysis
When polyurethane is reacted with diols at tem-
peratures above 200 °C, this is called glycolysis. Gly-
colysis is by far the most widely used chemical
recycling method for PU, mainly PU rigid (PUR)
and PU flexible (PUF) foam. The aim is the recovery
of polyols for the production of new PU material
[37,38]. The chemistry is summarised in Fig. 11 [12].
Glycolysis implies the heat-up of pre-grinded (6-
mm granules) PU scrap for several hours [9,18],
preferably rigid PU foam to 180–220 °C in high-
boiling point glycols with a catalyst (Fig. 12). The
glycol is usually diethylene glycol (DEG) with co-
reagent diethanol amine (DEA). A temperature
below 180 °C gives too low catalyst activity; a tem-
perature above 220 °C gives undesired side reactions
towards amines. After the chemical reaction is com-
plete, the material is cooled, filtered and/or blended
with virgin polyol and formulated into polyol/isocy-
anate systems that is marketed to manufacturers of
polyurethane products. The whole process takes
about 8 h. For the catalyst it is important that the
formation of aromatic amines is avoided. Since the
glycol is a reactant and a solvent, glycol/PU scrap
ratios 60/40 are necessary [20,21]. The glycolysis
process is based on a thermo chemical interaction
between polyurethanes and hydroxyl-containing
compounds. Because of the presence of end hydro-
xyl groups, the glycolysis products obtained from
rigid PU foam, known as secondary polyols, may
684 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692
Fig. 11. Chemistry of glycolysis of PU results in the formation of ether polyol [12].
Fig. 12. Schematic of glycolysis process for PU foam recycling
[9,18].
be useable as hydroxyl-containing components in
secondary PU synthesis, including foams, sealants
and adhesives [39]. PUF dissolution depends on
the molecular weight of glycol. Dipropylene glycol
and tetra ethylene glycol dissolved PUF in the
shortest time among polypropylene glycols and
polyethylene glycols, respectively. PUF dissolution
time was reduced to one-half for each 10 °C rise in
the range of 170–200 °C. Also PUF dissolution time
was inversely proportional to KOH (catalyst) con-
centration. Dibutyltindilaurate concentration had
less influence on PUF dissolution time than KOH
concentration. Smaller PUF particles dissolved in
a shorter time. Especially, the initial glycolysis con-
version of PUF was proportional to the total sur-
face area of PUF particles [40].
Members of the European Diisocyanate and Pol-
yol Producers Association (ISOPA) and indepen-
dent researchers have optimized single-phase
glycolysis [18]. Split-phase glycolysis [12], (Fig. 13),
where the product separates in two phases, has been
developed up to pilot scale for MDI flexible foams.
The viability of glycolysis appears to be in the area
of recycling production waste as opposed to post-
consumer waste.
Scheirs [12] distinguishes two approaches, wherein
(1) a single polyol is recovered or (2) flexible and
rigid polyols components are recovered. An exam-
ple of a process where a single polyol is recovered
is the alcoholysis process developed by Getzner
Werkstoffe Austria. A process for double recovery
of polyols was developed by ICI, referred to as the
split-phase glycolysis (SPG) process, as shown in
Fig. 13. In the SPG process scrap PU foam, prefer-
ably based on MDI, is reacted with DEG producing
a two product phases in the reactor. The lighter
layer contains the flexible polyol, the heavier layer
contains the MDI-derived compounds that are con-
verted into a rigid polyol using propene oxide. The
recovered polyols can be used to produce new PUR
and PUF foams. Reaction times, at 200 °C, are sev-
eral hours. PU foam waste densified to around
1100 kg/m3 is used. The SPG process is sensitive
to contamination by styrene-acrylonitrile (SAN)
[12,41]. In the presence of hexamethylenetetramine
(HMTA) the glycolysis of water-blown PUF foams
in ethylene glycol (EG) yields the polyol and a
solution of urea carbamates and amines in the EG.
 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692 685

Fig. 13. Schematic of the split- phase glycolysis (SPG) process for PU foam recycling [12].

The HMTA suppresses the formation of solid phases
in the products, and diaminotoluene (DAT) content
below 100 ppm [42].
3.3. Alcoholysis
(Fig. 14). The various components are then sepa-
rated in order to permit their reprocessing and
reuse. This method uses a heated, oxygen-free envi-
ronment to break down polyurethane and plastics
into gases, oils and solids.

Alcoholysis is a process in which, polyurethane 3.4. Fractionation

foam is reacted with alcohol under pressure and at
an elevated temperature [12–14]. This produces the The present invention [9] comprises a method of
original polyols together with urethane products recycling polyurethane-containing material as

Fig. 14. Chemistry of alcoholysis of PU results in the formation of urethane products [12].
686 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692
depicted in Fig. 15. The method comprises combin-
ing a polyurethane-containing material with a sol-
vent and forming a solution of the polyurethane-
containing material and the solvent [43]. Next, a
non-solvent is added to the polyurethane solution
to form a suspension of polyurethane in a solvent/
non-solvent mixture. Finally, the solvent is removed
to form a suspension of polyurethane in a nonsol-
vent. The solvent is preferably a polar, aprotic
solvent. The solvent may be chosen from the group
consisting of dimethylsulfoxide (DMSO), 1-methyl-
2-pyrrolidone (NMP), N,N-dimethylformamide
(DMF), acetonitrile, tetrahydrofuran (THF), hex-
amethylphosphoric acid triamide (HMPT) and mix-
tures thereof. The polyurethane-containing material
may be chosen from the group consisting of foam
trimmings, foam buns and foam skin, changeover
blocks, off-specification material, polyurethane
powder, molding mushrooms, fabrication scrap
and post-consumer waste. In addition, the polyure-
thane-containing material may be prime polyure-
thane material. Finally a filtration step may be
added to filter the solution before the non-solvent
is added to form the suspension.
3.5. Hydroglycolysis (Ford hydroglycolysis)
Hydroglycolysis basically implies adding water to
a glycolysis process with the use of the catalyst
Fig. 15. Schematic of fractionation process for PU foam recy-
cling [9].
LiOH, at around 200 °C. Ford Motor Company
develops this process, it is claimed that this pro-
duces a simpler and more valuable product mixture.
Although it is more expensive than conventional
glycolysis as the purification of the polyol-rich prod-
uct is more complicated. It has the advantage that
complex mixtures of dirty and contaminated PU
wastes can be processed as well, which otherwise
would have to be land filled [44]. The recovered pol-
yol may replace up to 50% of virgin polyol material
for PUF foams. The extraction of pure polyether
triols from the products is accomplished using hex-
adecanes or similar boiling point hydrocarbons [45].
The Ford hydroglycolysis process is shown sche-
matically in Fig. 16.
3.6. Aminolysis (Dow’s aminolysis)
A process similar to the split-phase (Fig. 13) gly-
colysis (SPG) process yet somewhat different, where
PU foams are converted into the original flexible
polyol plus a rigid polyol [12–14]. In aminolysis,
polyurethane foam is reacted with amines under
pressure at elevated temperatures. Amines used in
the process include dibutylamine, ethanolamine,
lactames or lactam adducts. Aminolysis is still in
the research stage. The PU waste is dissolved (at
up to 1 m3 foam in 1 L solution) in a KOH/alkanol-
amine solution at 120 °C. The three main products
from the first step are polyols, aromatic amines
and carbamates. In a second step ethene oxide or
propene oxide is used to convert the amines, after
which the polyols are separated [12–14]. This can
be used without further purification to produce
new PU foams that can completely replace PU
foams produced from virgin polyol.
4. Thermo chemical processing
An overview of thermo chemical processes for
recovery of chemicals, fuels and recovery from PU
(containing) waste streams [12,46] is detailed below.
4.1. Pyrolysis
Pyrolysis uses a heated, oxygen-free environment
to break down polyurethane and plastics into gas
and oil [47,48]. Pyrolysis of a PU adhesive as widely
used in the furniture industry (for example in Spain)
was analysed using TGA up to 450 °C (in nitrogen,
5–20 K/min heat-up) and a ‘‘pyroprobe” pyrolysis
reactor composed of a platinum coil around a
 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692 687

Fig. 16. The Ford hydroglycolysis process [44,45].

2 mm quartz tube at 500–800 °C (in nitrogen, heat-

up 300 K/s) plus a secondary reactor [49]. A study
by Rogaume et al. [50] addressed the pyrolysis of
PUF foam from automobile seats. First, thermo
gravimetric, calorimetric (TGA/DTA + DSC) tests
were made under airflow. Mass loss starts at
250 °C and levels off at a mass loss of 80% at
300 °C, while the remaining 20% is decomposed until
temperature reaches 500 °C. The DSC shows several
exothermic peaks, the most important being at 250–
300 °C and others at the start (340 °C) and end
(490 °C) of the second decomposition stage [51,52]. Fig. 17. Pyrolysis reactor using PU char as promoter of
secondary pyrolysis reactions [53].
RIM PU pyrolysis typically gives (at >450 °C)
5–25%-wt char, 10–45%-wt liquids and >40%-wt
gases. The liquid is red-colored viscous single-phase suggested [53], with PU char as promoter for the
oil with a viscosity that increases with time. In order secondary reactions.
to increase the amount, quality and marketability of
especially the liquid product, the use of activated 4.2. Gasification
carbon and PU chars in a secondary pyrolysis reac-
tion step was tested [53]. First goals were to achieve Gasification of (waste derived) fuels is an exo-
a maximum char yield and minimum liquid product thermic process that produces heat, ashes plus a
viscosity. Using activated carbon gave less viscous product gas (or synthesis gas, ‘‘syngas”) that con-
oil that eventually separated into an organic frac- tains large fractions of combustible gases H2 and
tion plus water; char amounts remained the same. CO [12,17,54–56]. Examples for plastics waste pro-
Using PU char gave a much higher char yield (up cessing by this route are given in Fig. 18a and 18b
to 40%-wt), slightly less liquid, which again sepa- [12,18]. For mixed waste streams, gasification is an
rates in oil + water, and much less gases. A two- option. In this process, plastic is heated and then
zone pyrolysis reactor as shown in Fig. 17 was combined with air/O2.This forms a CO + H syngas,
688 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692

Fig. 18a. Plastics waste liquefaction/gasification [18].

Fig. 18b. Plastics waste liquefaction/gasification [12].

which can go into refinery processes and help to
make methanol, ammonia and oxo-alcohols. The
process given above needs a pump able liquid feed-
stock that is obtained by liquefaction; the gasifica-
tion takes place in oxygen at 1200–1500 °C, 20–
80 bar, where a residence time of a few seconds gives
a 98–99% conversion into gases plus a slag. The CO
produced can be used to produce isocyanates for
new PU material; the hydrogen can be used to pro-
duce other PU feedstock such as formaldehyde and
polyether.
4.3. Hydrogenation
Hydrogenation can be seen as a compromise
between pyrolysis and gasification; the effect of heat
and high-pressure hydrogen (H2) results in gaseous
and liquid products [57]. Hydrogenation takes pyro-
lysis one-step further to produce even more pure
gases and oils through a combination of heat, pres-
sure and hydrogen. Viability of this method requires
resolution of two important issues – the purity of
gases and oils derived from pyrolysis and hydroge-
nation, and the associated costs to produce func-
tional finished products. These can be used as fuel
(partly used as energy source for the process) and
chemical feedstock [9].
5. Energy recovery
Energy recovery is often considered the only suit-
able disposal method for recovered material for
which no markets exist or can be created. This
strongly applies to scrap with PU laminates to wood,
 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692
leather or fabrics, or commingled materials. Also,
flame retarded materials make recovery and recy-
cling very difficult. Incineration of a PU foam results
in a volume reduction of around 99% which has
large implication to reduce the land filling of this
material, at the same time destroying CFCs and
other harmful foam blowing agents [12]. Yet again
the presence of flame-retardants complicates things,
and the effect of these compounds on combustion
processes receives much attention nowadays [58].
5.1. Municipal waste combustion
Current technologies can recover the inherent
energy value of polyurethanes and reduce fossil fuel
consumption [59]. In US experiments conducted by
APIs [9] Polyurethanes Recycle and Recovery Coun-
cil (PURRC), adding flexible polyurethane foam to
common municipal solid waste (MSW) – up to
20% by weight – produced significant BTU value,
while ash generation remained constant and emis-
sions were below operating limits. In Europe,
ISOPA [18] continues to support the use of carefully
controlled incineration to convert post-consumer
waste into valuable energy. MSW combustors with
state-of-the-art energy recovery and flue gas cleaning
technology are located in several European nations.
Switzerland, Sweden, Germany and Denmark are
using the process to provide local communities with
electricity and heat energy. Up to 10% of domestic
electricity requirements can be generated by these
units. The European PU industry, specifically for
rigid PU foam, consider the recovery of energy from
scrap material PUR foam from construction and
demolition waste to be the best disposal option as
laid down in various position papers [60,61]. Refer-
ence is usually made to a detailed study by Rittmeyer
et al. [62,63] on the co-firing of CFC-containing
PU foams in municipal solid waste incineration
plants (MSWIPs). Two facilities were used, being
the TAMARA test incinerator at the Karlsruhe
Research Centre and a full-scale MSWIP plant, in
Germany. In the TAMARA facility, a counter-cur-
rent grate furnace with gas cleans up.
5.2. Fluidised bed combustion
Another German study addressed the co-firing of
PU wastes in a 39 MW Thermal coal-fired bubbling
fluidised bed combustion (FBC) plant (steam
parameters 475 °C, 64 bar) [64]. The coal/brown
coal mix had a heating value of 17.6 MJ/kg; to this
689
a pulverised (70–700 lm) PUF foam waste from
mattresses, car seats and furniture compressed to a
bulk density of 300 kg/m3, with heating value 24–
30 MJ/kg was fed at 13–20% energy input. No oper-
ational problems were found during 35 h of testing,
in fact a burner for burnout of flue gas CO could be
turned off. Emissions of pollutants or carbon-in-ash
did not increase, except for the concentration of the
ten trace elements grouped as Sn + As + Pb + Cr +
Co + Cu + Mn + Ni + V + Sn which increased by
a factor of three to four (0.06–0.09 ? 0.22–
0.32 mg/m3) which is mainly due to the presence
of Sn (tin) in the PU foam (used as catalyst in PU
production) [64]. Rigid and flexible PU foams from
furniture without flame retardants were considered
suitable for co-firing with coal in an FBC. It was
expected that the combustion of RIM PU waste in
an FBC will lead to problems due to the large
amount of glass fibres in that material. Also rigid
PU foams from construction waste were claimed
to be problematic for FBC due to the high chlo-
rine/fluorine content [64].
5.3. Two stage incineration
In another study, the combustion of PUF foams
from automobile seats under grate incineration
exhaust gas recirculation conditions was studied
by Rogaume et al. [50], aiming at optimising com-
bustion conditions that result in minimal NO and
CO emissions.
5.4. Rotary kiln combustion
The behaviour of nitrogen from polymers and
plastics in waste-derived fuels during Rotary kiln
including PUF foam was considered in a Finnish
study [13,65–67]. It was found that the emissions of
NO + NO2during rotary kiln combustion in an
entrained gas quartz tube reactor (at 750–950 °C,
in 7% O2/93% N2) depended strongly on the amount
of char produced from high-nitrogen fuels (PU
foam, nylon, RDF, MSW, urea/formaldehyde glue,
sewage sludge) and the nitrogen content of the fuels.
At nitrogen content of 6.6%-wt, less than 10% of the
PUF nitrogen was emitted as NO + NO2.
5.5. Thermal degradation
The thermal degradation of PU foams and elas-
tomers has been studied extensively since the
690 K.M. Zia et al. / Reactive & Functional Polymers 67 (2007) 675–692
Table 1
Thermal dissociation temperature ranges for linkages in PU [6]
Linkage Onset of
dissociation (°C)
Allophanate Aliphatic/aromatic 85–105/100–120
Biuret Aliphatic/aromatic 100–110/115–125
Urea Aliphatic/aromatic 140–180/160–200
Urethane Aliphatic/aromatic 160–180/180–200
Disubstituted urea 235–250
1950s, with inevitable scatter and inconsistencies in
the reported results due to a wide range of PU types
and products. Factors of importance are the isocya-
nate, polyol and chain extender used to produce the
PU, since the different linkages in the polymer chain
have different thermal dissociation temperatures
[6,68,69], as illustrated in Table 1. Depending on
the PU considered and the analysis method used
(typically at atmospheric pressure), thermal degra-
dation of PU has been reported to start in the tem-
perature range 110–270 °C. Cullis and Hirschler [70]
give the mechanism thermal degradation which
involves three routes for the cleavage of PU linkages
at 200–300 °C which are summarized as:
 Dissociation into isocyanate and alcohol
 Dissociation into carbamic acid and olefin
 Dissociation of carbamic acid into CO2 and
secondary amine
Ravey and Pearce [71] for example, pyrolysed PU
foam based on toluene di-isocyanate (TDI) which
can be recovered, unless it is rapidly removed from
the reaction zone. When confined in the reaction
zone for a longer time the formation of diamino
toluene (DAT) sets in.
6. Conclusion
Polyurethanes are derived from oil and therefore
can have a recoverable energy value that in some
cases can be comparable to coal and slightly less
than that of fuel oil. Waste-to-energy combustion
can reduce the volume of solid waste as well as
dependence on fossil fuels, which can lead to conser-
vation of natural resources. The various recycling
technologies for material and chemical recycling of
PU materials have been developed and presented
as part of this technical paper have greatly contrib-
uted to improve the overall image regarding the recy-
clability of polyurethanes in recent years, by far the
most important being glycolysis and regrinding.
Commercial polyurethane depolymerization has
been done by glycolysis. Glycolysis of polyurethanes
can be economically acceptable, but still requires
more development in order to tolerate more contam-
ination in the post-consumer material increasing
waste-to-energy and other thermal processing activ-
ities involving gasification, pyrolysis and two-stage
combustion (removing problematic components in
a first stage) will also allow for the disposal of signif-
icant amounts of scrap PU without many difficulties.
Reaction injection molded (RIM) is not being
replaced by thermoplastic because of recycling, but
replacement is driven by lower cost of polyolefins.
In order for the practical application of any of
these recycling methods to be successful, it should
be stressed that the secondary products resulting
from these process technologies should by all means
still exhibit the unique properties of polyurethane. It
is critical that the future recycling of polyurethane is
taken into consideration during the product design
phase of a new product, making it more probable
to be recycled at the end of its product life cycle.
All of these efforts to improve recycling technologies
together with the implementation of new design
concepts will undoubtedly lead to the increased
recycling of polyurethane in the new millennium.
It is concluded that many of the plastic feedstock
recycling processes appear to be technically feasible
and robust enough to warrant further development
in the future.
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