Waste Biomass Valor (2013) 4:9–21

DOI 10.1007/s12649-012-9159-x

ORIGINAL PAPER

Recent Advances in Polycarbonate Recycling: A Review

of Degradation Methods and Their Mechanisms
E. V. Antonakou • D. S. Achilias

Received: 1 November 2011 / Accepted: 18 August 2012 / Published online: 5 September 2012
Ó Springer Science+Business Media B.V. 2012

Abstract Polycarbonate, poly(bisphenol A carbonate), phosgene in pyridine but the crystalline polymers produced
PC, is an important engineering polymer with a variety of were of low quality, that is brittle and difficult to process. The
optical and technical applications, whose demand is second attempt for the polymer’s preparation was in 1941,
increasing year by year. Its consumption in 2008 was when a crosslinked resin was prepared by a peroxide initiated
estimated to have reached 3.3 Mt and to increase by a 7 % radical polymerization of the bisallyl carbonate of diethylene
per year. The three different routes for PC recycling are: glycol. This time the product was a colorless, transparent
direct recycle (mechanical recycling or blending with other plastic which was the first available PC [2].
materials), treatment via chemical methods and thermo- Poly (bisphenol A carbonate) or PC, is an important
chemical methods (pyrolysis). The aim of the current polymer which exhibits a variety of optical and technical
review paper is to visit all the available methods for PC applications and its demand is increasing year by year. It is
recycling and their mechanisms and record their potential widely used in optical data storage devices, such as CD,
and weaknesses. Apart from methods such as pyrolysis and CD–R and DVD discs, bulletproof windows, food pack-
degradation via chemical routes, novel methods, such as aging and mineral water bottles [3, 4]. Because of a series
decomposition in the presence of enzymes, are been of properties such as optical clarity, excellent thermal and
reported. Finally, the main degradation methods of PC flame resistance, high impact strength and high stability to
blends and WEEEs applications are also been presented. different environmental conditions, PC is used in a wide
range of industrial applications, such as automotive,
Keywords Polycarbonate
Recycling
WEEE
transportation, building and construction, packaging,
Pyrolysis
Bisphenol-A medical, optical media and also electrical, audio, video and
laser-optical data-storage systems [1, 5, 6]. Some disad-
vantages of PC are softness, high melt viscosity and notch
Introduction sensitivity and its mechanical properties could be improved
by the addition of reinforcement material or blending with
Polycarbonate (PC) resins can generally be divided in two other thermoplastic polymers [7, 8].
chemical categories: straight chain (aliphatics), which are not The PC capacities of the global markets- including
used as thermoplastics, and aromatics, which are useful North America, South America, Europe, and Asia- were
engineering thermoplastics. The most common aromatic PC, increased from 1.5 Mt in 1999, to 1.7 Mt in 2001 [5]. Since
poly(bisphenol A carbonate) is also the most widely used [1]. then PC seems to be a polymer with extremely high growth
The first aromatic PCs were prepared in the late 1890s rates with a world wide and a 7 % increase in consumption.
introducing a reaction of hydroquinone or resorcinol with 2.3 Mt were produced in 2004 [9], 3 Mt in 2006 [10] and
in 2008 the approximate consumption reached 3.3 Mt [11].
The price of PC is between the commodity plastics and the
E. V. Antonakou
D. S. Achilias (&)
special engineering thermoplastics which makes this
Department of Chemistry, Aristotle University of Thessaloniki,
54124 Thessalonı́ki, Greece material the second largest volume engineering thermo-
e-mail: [email protected] plastic, after the polyamides [12].

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10 Waste Biomass Valor (2013) 4:9–21

It is clear nowadays that it is not a suitable waste regarding the literature for decomposing PC, several
treatment method to landfill or incinerate the wasted PC (or studies of possible depolymerization processes have been
any other waste polymer for that matter), for this reason a reported, most of which lead to its original monomer,
resourceful and economically viable recycling process is bisphenol-A (BPA). BPA, on the other hand is a stable
important because of both environmental and economic molecule with limited commercial value and a series of
benefits [5, 13]. The methods proposed for polymer recy- undesirable properties, so the step of its further decomposi-
cling include [14]: Primary recycling (referring to the tion into more desirable phenolic compounds is the aim of
‘in-plant’ recycling of the scrap material of controlled his- many papers in the field. Several research groups suggest the
tory); Mechanical recycling (or secondary recycling), where introduction of different types of solvent systems and cata-
the polymer is separated from its associated contaminants lysts [16–20] such as methylene chloride with ammonia,
and it can be readily reprocessed by conventional melt phenol in combination with an alkali catalyst, tetralin, dec-
extrusion or dissolution/reprecipitation techniques; Chemi- alin and cyclohexanol or a method which resembles the
cal or Feedstock recycling (tertiary recycling) defined as the trans-esterification of fats in super- or sub- critical condi-
process leading in total depolymerization to the monomers, tions. There are two main problems regarding the use of an
or partial depolymerization to oligomers and other chemical effective solvent system in the degradation process: one has
substances; Energy recovery (Quaternary recycling) refer- to do with the high cost of the separation of the product (and
ring to the recovery of plastic’s energy content. the high contents of additives included in some of the poly-
PC recycling can be performed in three main different mer blends), and the second the environmental and safety
ways: direct recycling (mechanical recycling or blending problems related to the use of more or less toxic organic
with other materials), recycling via chemical methods and solvents.
thermochemical recycling (pyrolysis). The PC produced
after mechanical recycling exhibits a series of deteriorated Solvolysis (Liquid-phase Degradation)
properties, such as decreased impact resistance, when
compared to the parent PC polymer. A solution to this Sato et al. [20] studied the liquid-phase cracking of
problem can be addressed by blending with other materials bisphenol-A types of epoxy resin and PC resins (known
to modify impact resistance in recycled PC [8]. Degradation thermosetting polymers, used mainly in electrical and
after chemical treatment can yield to a high percentage of electronic appliances and automobile industry) and found
the monomer; nevertheless it requires a complicate product that at 440 °C in the presence of solvents such as tetralin,
separation scheme and it is related to a series of environ- decalin or cyclohexanol, more than 40 wt% of phenol and
mental and safety problems, due to the use of toxic organic isopropylphenol as monomers was recovered. On the other
solvents. Thermochemical degradation has been suggested hand, bisphenol-A, which was common monomer from
as a promising alternative for the polymers treatment since epoxy resin and PC resin, could also be recovered with
it can deal with high molar mass organic molecules, while high yield, when reaction was carried out at lower tem-
its disadvantages are related with the low selectivity in perature of 300–350 °C. After studying a series of solvent
terms of the monomer and the large amount of byproducts. systems and potential catalysts, the authors have suggested
The aim of this paper is to review all the available that the thermal cracking in polar solvents, such as cyclo-
methods for the PC recycling, with an emphasis on pyro- hexanol, at lower reaction temperature is recommended for
lysis and catalytic pyrolysis. Well-studied methods, such as the recovery of bisphenol-A from PC resin and also the use
the degradation via chemical routes as well as more novel of CaCO3 catalyst with non-polar solvent at 300 °C
methods such as decomposition in the presence of enzymes assisted the degradation of polymer resin to unit structure
are been reported. A short review of the mechanisms of the size molecules [20].
above mentioned methods and the main degradation Oku et al. investigated solvolytic monomer recycling of
methods of the PC blends and applications in WEEEs are PC resin into bisphenol-A and useful carbonate products
also been attempted. using liquid solvents, such as DMI (1,3-dimethyl-imida-
zolidin-2-one). This method was unique and proceeded
with very high conversion of almost 100 wt% of the ori-
Chemical Recycling Methods ginal polymer at the reaction temperature lower than
100 °C [21, 22].
Recycling of polycondensation polymers and especially
polyesters via pure chemical routes could be summarized Hydrolysis (Degradation in Sub-Super Critical Water)
by the following technologies: hydrolysis (in acid, neutral
or alkaline environment), glycolysis, hydroglycolysis, Supercritical and subcritical fluids are attractive solvents.
methanolysis and aminolysis [14, 15]. More specifically, They have unique properties since many of their physical

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and transport properties are intermediate between liquid In an early study of the 1990, Gaines [26] reported that
and gas. Problems of diffusion and accessibility between the hydrolysis of bisphenol A PC could be accelerated and
the polymer and the solvent are limited because of the also take place at lower temperatures when a small amount
enhanced solubilities and diffusivities. Polymers can of a hindered amine light stabilizers is incorporated in the
therefore be degraded to low molecular weight products by resin and it is exposed to elevated temperature and
thermolysis in supercritical fluids with high degradation humidity. The author also connected the degree of hydro-
rates. In most of the cases the role of the sub- or super- lysis with the structure (primary, secondary or tertiary) of
critical fluids is to act both as a solvent reaction medium the stabilizer and reported that secondary amines are better
and as a reactant. stabilizers than their tertiary counterparts. Huang et al. [27]
As expected, the most well-studied of the chemical examined the effects of plastic additives on depolymer-
recycling schemes is hydrolysis (refers to the reaction with ization of PC in sub-critical water. Depolymerization of PC
water) which can produce both polyols and amine inter- with two additives was carried out in an autoclave at
mediates [23]. Among the many possible solvents, high temperatures from 533 to 613 K for reaction times ranging
pressure high temperature water (HHW), that is also from 15 to 60 min. The additives used were a flame
referred to as hydrothermal or supercritical water, is the retardant (decabromodiphenyl ether, DBDPO) and a plas-
green-advanced solvent due to its environmental friendli- ticizer (di-n-octyl phthalate, DnOP). The main products of
ness. One of the major features of high pressure high PC depolymerization in the presence or absence of the
temperature water (HHW) is rapid hydrolysis without additives were bisphenol A and phenol. The addition of
catalyst. In the past, many studies on plastics degradation DBDPO accelerated the hydrolysis of PC while the addi-
in view of chemical recycling have been conducted in high tion of DnOP had the opposite effect, and both additives
density HHW and reported high yields of monomers [24]. reduced the yield of BPA. The activation energy for PC
The excess amount of water in the process requires excess depolymerization in sub-critical water was found to be
energy input, since hydrolysis is an endothermic reaction lower with DBDPO additive than with DnOP [27].
with high energy requirements. The excess amount of In one of the first studies of PC hydrolysis, the kinetics
water is disadvantageous considering the total energy input and mechanism of PC was studied in aqueous potassium
since separation of ethylene glycol from the aqueous hydroxide solutions. Exposure of PC to potassium
stream is required [24]. BPA’s decomposition in water hydroxide did not result in any significant change in the
becomes faster, and thus more economical, with increasing properties of the polymer [28]. Hydrolytic degradability of
temperatures and pressures. The decomposition rate of the PC polymer was examined in solutions containing
BPA was reported to be enhanced by adding acid or base in 10 wt% acidic or basic aqueous solutions of varying pH
high density HHW at 473–523 K (namely liquid water using viscometry and GPC analysis [29]. The difference in
phase, LWP) and thus, proton and hydroxyl ion were degradabilities of these polymers in acidic conditions is
promoters of BPA reaction in LWP. The maximum yield of associated with the different nucleophilicities of their car-
bisphenol A was around 80 %. In liquid water phase at bonyl oxygen atoms, while in basic conditions the differ-
573 K, PC still remained even for 3000 s (50 min). The ences are associated with the different electrophilicities of
high yield of bisphenol A in high pressure steam was due to the corresponding carbonyl carbon atoms.
the high stability of bisphenol A. The amount of water
required for PC degradation was drastically reduced and Use of Other Solvents (Methanolysis—Alcoholysis—
thus the high pressure high temperature steam process was Glycolysis)
energetically and economically preferable [24].
Tagaya et al. [25] decomposed PC by using subcritical Methanolysis and alcoholysis (the use of methanol and
water and in the temperature range 230–430 °C. An ethanol respectively for the decomposition of the poly-
increase in the reaction temperature seemed to favor the meric material) has been suggested as an appropriate
production of phenol, BPA and other substituted phenols method used to recover the pure monomer BPA. However,
but their yields would not be significantly increased even due to the low solubility of PC in the two solvents, most of
when prolonged reaction times were applied. NaCl and the researchers recommend either the introduction of sub-
CH3COOH which were used as catalysts, were found to be super critical conditions (higher temperatures and pres-
ineffective for the decomposition reaction and the only sures) or the presence of large quantities of concentrated
catalyst with a positive effect was suggested to be Na2CO3. acids or bases as catalysts.
At 300 °C and in the presence of Na2CO3 no BPA was Two research groups studied the effect of the solvent/
detected in the product due to its transformation in phenol. polymer ratio in the product yields. Apart from the obvious
The authors suggest that subcritical water is also an economic considerations there are also environmental and
advantageous medium for decomposing PC compounds. safety issues to be taken into account in these studies. Hu et al.

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[30] studied alkali catalysed methanolysis using a mixed Table 1 Mononer’s recovery from different chemical recycling
solvent of methanol and toluene. They found that, by using an methods of PC
excess of methanol, monomers were produced in higher Percentage recovery of monomer Reference
yields. Dongpil et al. [31] studied PC methanolysis mecha- (max) (% BPA)
nism in the temperature range 160–220 °C by increasing the
95.0 Liu et al. [4]
molar ratio between methanol and PC. They suggest that,
90.0 Pinero et al. [17]
despite the increase of the energy and cost requirements, a
15.5 Sato et al. [20]
higher molar ratio would increase the BPA yields.
100 Oku et al. [21]
Additionally, Pinero et al. [17] investigated alkali-cata-
80.0 Watanabe et al. [24]
lyzed depolymerization of PC wastes by alcoholysis in
97.0 Tagaya et al. [25]
supercritical or near critical conditions, for recovery of the
40.1 Huang et al. [27]
monomer BPA and dimethyl carbonate (DMC) as a valu-
96.0 Hu et al. [30]
able byproduct. The aim was to develop a continuous
90.7 Chiu et al. [33]
process that could be scaled up for depolymerization of
both commercial grade PC and waste PC, using methanol 90.0 Jie et al. [36]
as solvent/reagent and NaOH as alkali catalyst.
Chen et al. [32] reported that high yields of BPA and DMC
were obtained using methanol. The depolymerization of PC The characteristics of depolymerization of PC in
in supercritical methanol (MeOH) was also studied by Chiu supercritical ethanol were also investigated by Jie et al.
et al. [33], who obtained yields of BPA and DMC of 90.7 and [36], who proposed that the depolymerization process
95.2 %, respectively, in optimum conditions (513 K, molar consisted of a sub-critical region, transitional region and
ratio MeOH:PC 37.5, for 5 min). Kim et al. [31] studied the supercritical region. PC was degraded completely into
kinetics of depolymerization of PC in the MeOH/ethylene diethyl carbonate and BPA with yields of 89 and 90 %,
glycol (EG) co-solvent system. It was found that in com- respectively, in the supercritical region.
parison with MeOH, the EG/MeOH co-solvent system did Oku et al. [21] also reported the treatment of PC pellets
not improve the depolymerization yield. in EG with a catalytic amount of NaOH (0.1 equiv) to
Liu et al. [34] studied the methanolysis of PC to recover produce monohydroxyethyl ether of BPA (MHE-BPA,
bisphenol A(BPA) in a method by which PC could be met- 42 %), bishydroxyethyl ether of BPA (BHE-BPA, 11 %)
hanolyzed in an ionic liquid without any acid or base catalyst and BPA (42 %). When ethylene carbonate (EC) was
under moderate conditions. The effects of ionic liquid kinds, added to the same reaction system, BHE-BPA was pro-
temperature, time, and the amount of methanol on methan- duced almost quantitatively.
olysis results of PC were examined. The methanolysis of PC The percentage recovery of BPA from the aforemen-
was also studied by the same group by using ionic liquid tioned chemical recycling methods presented by different
1-n-butyl-3-methylimidazolium chloride ([Bmim][Ac]) as a authors is summarized in Table 1.
catalyst and the effects of temperature, time, amount of
methanol and [Bmim][Ac] on the methanolysis reaction were Polycarbonate Degradation Mechanism in Aqueous
examined. It was shown that the conversion of PC was nearly Solution
100 %, and the yield of bisphenol A was over 95 % under the
following conditions: m([Bmim][Ac]):m(PC) = 0.75:1; In an aqueous medium, the reaction scheme of PC and BPA
m(methanol):m(PC) = 0.75:1; a reaction temperature of conversions are known as shown in Scheme 1 [24]. In high
90 °C and a total time of 2.5 h. One of the most attractive pressure high temperature water, BPA is known to
properties of ionic liquid is its reusability when used as either decompose into phenol and isopropenyl phenol (IPEP) at
a catalyst or a reaction medium. The ionic liquid could be the first stage of the reaction, and subsequently, IPEP
reused up to 6 times with no apparent decrease in the con- decomposes into acetone and phenol. A determining step in
version of PC and yield of BPA. The kinetics of the reaction the recycling PC in water is the decomposition or the sta-
was also investigated [4]. bility of BPA and this has been the aim of study for several
Ethanol has a critical point practically at same temper- research groups. It has been suggested that the reaction is
ature and a lower pressure than that of methanol, allowing favored by high temperatures and pressures and also by the
lower operating temperatures and pressures. Chen et al. presence of acidic or basic compounds [37, 38].
[35] compared the use of methanol and ethanol as solvents, Concerning the effect of ethanol as a solvent, Jie et al.
it is reported that PC completely decomposes at lower [36] suggest that the mechanism consists of a random
temperatures in the presence of ethanol producing BPA and reaction along the polymer chain of the ester linkage with
diethylcarbonate (DEC). the solvent, producing two smaller polymer chains, which

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material being processed. The char produced can either be

further processed onsite to release the energy content of the
carbon, or utilized offsite in other thermal processes [15].
Experimental and theoretical studies on the thermal
degradation of PC are of particular interest, because they
give information about its thermal stability and can be
applied in the tailoring of PC plastics for different purposes
[3]. An additional interest on these degradation studies was
received by the fact that it is an important engineering
thermoplastic material which is subjected to injection
moulding operations at temperature above 300 °C. At this
temperature, degradation reactions are likely to occur and
therefore, the understanding of its thermal behaviour is of
crucial importance in the end use application [42]. In
addition, PC exhibits flame retardancy and produces a large
fraction of char upon combustion and since the degradation
behavior of a polymer is closely related to its flame retar-
dancy it is crucial that the degradation pathway of the
polymer be well understood [43].
Scheme 1 Mechanism of PC hydrolysis for the synthesis of BPA or Pyrolysis has been suggested by several research groups
phenol [24] as one of the possible routes for PC recycling even from the
early nineties [42, 44–49] aiming at both an understanding
can still react by ester exchange reaction until the polymer of the degradation mechanism but also at the transforma-
is completely converted to BPA. This could be decom- tion of plastic wastes to fuels or valuable products. In most
posed into small molecular products by side reactions. of the above mentioned studies decomposition is reported
to occur at a temperature range of 300–500 °C, while the
remaining residue is in the range of 20–30 wt%.
Thermochemical Recycling Methods Concerning the pyrolysis products, the ratio and com-
position of solid, liquid and gaseous fractions depend, as it
Non-Catalytic Pyrolysis has already been mentioned, on the pyrolysis conditions in
terms of temperatures and residence times and also in the
Pyrolysis process is an advanced thermochemical conver- presence or absence of catalysts. The gas fraction is com-
sion technology that has the ability to produce clean, high posed (wt%) by: CO2, CO, CH4 and several low molecular
calorific value, valuable products from a wide variety of mass hydrocarbons. The pyrolysis liquid product has been
waste and biomass streams [15]. Pyrolysis takes place found to contain BPA and the polymers monomer, the
typically in the temperature range of 300–1000 °C in an composition again depending on the type of the reactor and
inert atmosphere (absence of oxygen). Large organic the operating conditions (such as time and temperature).
macromolecules decompose in liquid, gaseous and solid Several phenolic products, from simple substituted phenols
carbonaceous products of various compositions [39–41]. to different xanthone structures, have also been reported
After cooling, part of the vapors becomes a condensed [42, 45, 50].
mixture (tar). Gaseous products are typically CO2, CO, H2, Recent studies have introduced either a more oxidative
CH4 and other hydrocarbons with low molecular weight. atmosphere (air) in the pyrolysis reactor [43, 51] or an
The ratio among solid, liquid and gaseous products active catalyst aiming to reduce the presence of high
depends on the pyrolysis conditions in terms of tempera- molecular mass and BPA. Oxygen assimilates better the
tures and residence times. The liquid fraction can be used conditions in an incinerator and also enhances the forma-
either directly for energy recovery (fuel) or for the pro- tion of free radicals. It is suggested that oxygen encourages
duction of chemicals of economic importance. In the case the branching and cross-linking as well as radical forma-
of PC either the monomer (BPA) or a fraction of phenolic tion and thus the formation of smaller molecules such as
compounds can be recovered. The gaseous product is aldehydes, ketones and branched structures, through the
suitable for utilization in either gas engines, with associ- formation of peroxides. Analytical pyrolysis experiments
ated electricity generation, or in boiler applications without carried out under gradual and fast heating conditions
the need for flue gas treatment. This gas will typically have revealed that the thermal decomposition of PC is affected
a calorific value of 22–30 MJm-3 depending on the waste by the presence of certain flame retardant additives [52].

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Catalytic Pyrolysis their effect to the degradation process of the PC polymer.

All of the above mentioned catalysts seem promising, since
As it has already been discussed in the general character- they decrease both the degradation temperature of the PC
istics of thermal degradation, one of its main drawbacks is and, some of them, even the amount of the solid residue
the low selectivity of products, mainly due to the random compared to the non-catalytic experiments. The two cata-
free radical mechanism of the thermal decomposition. A lysts with the more desirable catalytic behavior are
solution to this disadvantage appears to be catalytic pyro- Ca(OH)2 and SnCl2.
lysis, since the introduction of a suitable catalytic material Grause et al. [9] have studied a series of basic catalytic
will favor the pyrolysis process both by tailoring the materials in the pyrolytic hydrolysis of PC, and they
composition of the products and by reducing the energy reported that Mg(OH)2 was found to be better than its Ca
needs by lowering of the reaction’s activation energy. In counterpart, while the differences between oxides and
the degradation process, adding an active catalyst to the hydroxides were negligible indicating the same mechanism
polymer has some advantages over a non-catalytic degra- for both, oxides and hydroxides. BPA was obtained as the
dation process. An active catalyst in the degradation pro- main product at 300 °C with a yield of 78 % with MgO [9].
cess is expected to lower the degradation temperature, An additional advantage of this process is that some these
shorten the degradation time, increase the extent of deg- oxides/hydroxides (e.g. Mg(OH)2) are widely used as fire
radation, reduce the proportion of solid residue in final retardants in many PC applications, and therefore, they are
products, and/or narrow the product distribution [5, 53]. expected to be present in waste electronic and electric
With the addition of active catalysts into PC, the proportion equipment (WEEE) [9].
of carbonaceous solid residues is significantly reduced, the Chiu et al. [5] reported pyrolysis experiments in the
percentage of liquid product, which is the most valuable presence of ten different metal chlorides. The catalytic
fraction, is expected to increase in the pyrolysis process. activity of the metal chlorides is concerned to be attributed
The literature on catalytic pyrolysis of PC is very lim- to the redox properties of the transitions metals involved.
ited [5, 9, 54] but the experience from well-studied poly- More specifically they have reported that four active metal
mers (e.g. [39–41, 55–60]) as well from the biomass chlorides SnCl2, ZnCl2, FeCl3, and MgCl2, can enhance the
pyrolysis field (e.g. [61–65]) is expected to be valuable for degradation of PC and increase the conversion from 8.5 %
the ongoing research on the field. to more than 70 %. Another study on a series of polymers,
Catalytic materials of zeolitic origin, typical cracking not involving the PC, suggested that another set of basic
catalysts of moderate or strong acidity, which have been catalysts (Na-zeolites) was effective for the elimination of
reported in the literature to enhance the degradation pro- brominated phenols from the pyrolysate of brominated
cess of well-studied polymers, such as polypropylene [55] epoxy resin [56]. Li et al. [54] observed on the thermal
could be promising catalysts for the degradation of PC, decomposition of the poly(propylene carbonate) PPC that a
nevertheless only preliminary applications on the PC have metal complex catalyst (zinc glutarate) has little effect by
been published. On-going TGA degradation experiments reducing the activation energy leading to an accelerated
currently performed by our research group [66] attempted depolymerization reaction. Day et al. [67] in a study of
an understanding of the catalytic effect of four zeolitic pyrolysis of polymers used by the electronics industry
materials in the presence of both PC and polypropylene reported the pyrolysis of PC in the presence of Cu. The
(PP). The experiments validate the catalytic activity of all results of the study suggest that the presence of copper can
four zeolitic catalysts in the presence of PP, since the influence the extent of degradation and the pyrolysis prod-
degradation process initiates at lower temperatures uct distribution. There appeared to be a significant increase
(between 320 and 400 °C) but not in the presence of the PC in many pyrolysis products when copper was present, the
material, since degradation at all catalytic experiments only two exceptions being 4,4 %-methylene bisphenol, and
starts at temperatures higher than the non-catalytic. Also, 3-methyldibenzofuran. The authors suggest that this could
the degradation conversion of PC is not at 100 % with the not drastically influence the value of the pyrolysis products.
zeolitic catalysts, which is the case when the PP has been The phenolic products identified in the liquid pyrolysis
used as model polymer, which means that part of the fraction from several literature sources are summarized in
undepolymerized PC, catalyst and other intermediates still Table 2.
exist in the solid residue. It is suggested that this action is It is worth mentioning at this point that, advances in the
due to its strong acidity then we can easily deduce that this area of designing and scaling up pyrolysis reactors suitable
sort of catalytic activity does not favor the PC degradation for polymers degradations, but also in the design and
and in that case trends are comparable for PP and PC. implementation of appropriate separation system for
Additionally a series of basic catalysts (CaO, Ca(OH)2, pyrolysis products recovery, are two factors that will
Ba(OH)2) and a metal chloride (SnCl2) have been tested for determine the progress of the research in the area.

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Table 2 Phenolic products in PC pyrolysis liquid fraction One of the first studies on PC decomposition dates back
on 1964 when Lee [68], and later Bartosiewicz et al. [69]
Phenolic products Reference
and Abbas [70] attempted, through preliminary but well-
Chiu et al. [3] designed thermogravimetric studies to explain the PC
OH Nam Jang et al. [43] degradation mechanism. They suggested that the PC deg-
Puglishi et al. [48] radation pathway follows chain scission. The initial step is
Davis et al. [50] oxidative hydrogen cleavage from isopropylidene linkage,
Bozi et al. [51] the second is hydrolysis and the third is alcoholysis of the
Lee [68] carbonate. McNeill et al. [72] also suggested that the ther-
Achilias et al. [71] mal degradation mechanism of PC followed a chain scission
Chiu et al. [3] mechanism and in order to verify his work, he managed to
H 3C OH Nam Jang et al. [43] detect cyclic oligomers of bisphenol A carbonate and var-
Puglishi et al. [48] ious phenol structures by using GC/MS. Davis et al. [50]
Davis et al. [50] suggested hydrolysis and alcoholysis as the main reactions
Bozi et al. [52] in the PC degradation and they also reported the formation
Lee [68]
of the xanthone unit in the final products.
Achilias et al. [71]
Puglishi et al. [48] have suggested the following reac-
tion scheme to describe the thermal degradation pathways
H3C Chiu et al. [3]
of PC (also depicted in Scheme 2). In the initial stage of
OH
Nam Jang et al. [43]
the thermal degradation of PC (400–500 °C) cyclic oligo-
Davis et al. [50]
mers are formed by an intramolecular exchange reaction
Bozi et al. [52]
(Scheme 2a). Hydrolysis reactions producing phenolic end
Lee [68]
groups and CO2 take place in this temperature range
Achilias et al. [71]
(Scheme 2b). The formation of ether bridges by decar-
H3 C Chiu et al. [3]
boxylation of the carbonate groups is also responsible for
Nam Jang et al. [43]
OH the evolution of CO2 (Scheme 2c). At higher temperature
Davis et al. [49]
H3 C (500–700 °C) other decomposition reactions involving
Bozi et al. [52]
molecular rearrangements or decomposition of the PCs
Lee [68]
structural unit are observed:
Achilias et al. [71]
H2C Nam Jang [43] (i) a disproportionation reaction of the BPA isopropyli-
Puglishi et al. [48] dene bridges of PC to yield phenyl and isopropenyl
OH
Bozi et al. [52] end groups (Scheme 2d);
H3C
Lee [68] (ii) the formation of dibenzofuran units by the dehydro-
Other substituted phenols Chiu et al. [3] genation of ether units (Scheme 2c);
Nam Jang [43] (iii) the formation of compounds containing xanthone and
Bozi et al. [52]
fluorenone units, most likely generated by isomeriza-
Achilias et al. [71]
tion of the aromatic carbonate functional groups and
Chiu et al. [3]
successive condensation (Scheme 2e) [42, 48].
CH 3

OH
Nam Jang et al. [43] Analytical limitations and more specifically the limited
CH 3
Puglishi et al. [48] ability of the GC–MS technique to record peaks of high
Davis et al. [50] molecular mass structures did not allow for the conduction
Bozi et al. [52] of a complete pattern of the thermal decomposition pro-
Achilias et al. [71] cesses occurring in the pyrolysis of PC. More recently
Montaudo et al. [42] used a more advanced method of
Matrix assisted laser description ionization time of flight
Pyrolysis Mechanism (MALDI-TOF) and FAB mass spectroscopic technique
which allowed the detection of oligomers up to 30,000 Da
Non-Catalytic to verify the above suggested mechanistic scheme. Nam
Jang et al. [49], in a more recent study reported the iden-
Most of the researchers describe the pyrolysis degradation tification of products by using TGA/FTIR and they sug-
to follow a typical radical chain mechanism, nevertheless gested the main degradation pathways of PC to be are
the order and type of the reaction mechanism varies. classified into two categories: chain scission of

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16 Waste Biomass Valor (2013) 4:9–21

Scheme 2 Thermal
degradation processes occurring
during pyrolysis of PC [48]

isopropylidene linkages and hydrolysis/alcoholysis of car- decomposition in a nitrogen atmosphere was calculated to be
bonate linkages. 133.2 kcal mol-1, whereas Ea for oxidative thermal
It is interesting to mention that many of the above decomposition was calculated to be 86.5 kcal mol-1.
described reactions lead to the formation of oligomers
which can act as char precursors. For this reason, but Catalytic
mainly because of the low selectivity of the process in the
monomer production and the large amount of additional Gobin et al. [55] have studied the catalytic action of zeo-
byproducts, pyrolysis has not been considered appropriate lites in polymers’ pyrolysis and suggest that the acidic
for polymers recycling. What should also be stressed is the properties of the solid catalyst are the active catalytic sites
potential of catalytic pyrolysis in terms of tailoring the responsible for the polymer degradation reaction. Catalytic
reaction products and making the process a more attractive activity in cracking reactions is due to their acidity, with
alternative. the number and strength of the acid sites being the most
The literature concerning the kinetics of the thermal important factors determining conversion and yield of
degradation of PC is also limited. Kitahara et al. [73] specific products. They also state that the catalyst particle
investigated the kinetics of the thermal decomposition of PC, size plays a large role, as smaller particles have a higher
and the subsequent decomposition of BPA, under pyrolysis external surface and hence a higher fraction of their acid
conditions and in the presence of oxygen. The decomposition sites is on the external surface [55].
of PC obeyed Arrhenius kinetics, which allowed the deter- Concerning the catalytic action of the basic catalysts
mination of the activation energy (Ea) for thermal decom- Grause et al. [9] suggest that degradation reactions in the
position to BPA from Arrhenius plots. Ea for thermal presence of these catalysts follow two alternative

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Waste Biomass Valor (2013) 4:9–21 17

mechanisms, elimination (E) and nucleophilic substitution hydrogen bonding with serine and histidine and polar
(SN), depending on the reaction conditions. The alkaline interactions with aminoacids such as aspartate, glutamate
earths oxides and hydroxides act as nucleophiles (or bases and threonine [74].
in the case of elimination reactions) attacking the carbonate
carbon; and in a second step the oxides are released by the
addition of water. The higher activity of some oxides/
hydroxides compared to others in the same study reported Recycling of Waste Electric and Electronic Equipments
could also be caused by their stronger basic character [9]. (WEEEs) and PC Blends

WEEEs
Novel Recycling Methods
Production of electric and electronic equipment (EEE) is
Recently, a novel method for the recycling of PC has been one of the fastest growing areas of our days. For this rea-
proposed based on biodegradation. Degradation reactions son, but also due to their sort life cycle (15–20 years), the
in the presence of enzymes can be promising alternative research on the area of their disposal is of increasing
methods, since they use milder conditions, that is lower interest. The main polymers that can be found in the WEEE
temperatures and pressures. The more recent study was are thermoplastics and thermosets such as acrylonitrile–
carried out by Artham et al. [74] using three different butadiene–styrene terpolymer (ABS), high impact poly-
enzymes (lipases): Candida antarctica (CAL), Candida styrene (HIPS) and PC [47, 71].
rugosa (CRL) and porcine pancreas (PPL) in water-mis- Advanced thermo-chemical treatments of WEEEs pro-
cible (tetrahydrofuran) and water-immiscible (chloroform) vide a viable and promising engineering solution since, not
solvents at 50 °C for 10 days. It was found that maximum only have they recovered healthy monomer fractions up to
degradation (60 % reduction in Mn) of the polymers was 60 % in past reports, but they produce valuable petro-
observed in tetrahydrofuran with PPL, compared to the chemicals such as gases (low molar mass hydrocarbons),
experiments without the enzyme. The degradation products tars (waxes and liquids very high in aromatic content) and
in all the experiments were bisphenol-A and 4-a-cumyl char (carbon black and/or activated carbon). Methods of
phenol suggesting that the lipases act through an end-chain chemical recycling (such as mechanical recycling or sol-
scission on the polymer. The authors suggest that, to make volysis) could be feasible alternatives, but they are not able
this process ‘‘greener’’ more work needs to be done on the to deal with high contents of additives, or polymer blends
solvent front [74]. The same research group reported in usually present in used PC [9].
another study that biodegradation of PC can be enhanced The process of pyrolysis seems as a promising alterna-
by pretreatment, such as UV radiation [75], c-irradiation, tive for the degradation of WEEEs since it can, under
addition of biosurfactants, and thermal pretreatment of the controlled conditions, deal with a number of organic
polymer [76]. The aim in all pretreatment techniques is to macromolecules and decompose them into useful products
enhance the accessibility of the polymer to the active site (usually the polymers’ monomer and other organic com-
of the enzyme. pounds, some of which, of a commercial value). Significant
levels of lead, mercury, cadmium, chromium (VI), poly-
Mechanism brominated biphenyls and polybrominated diphenylethers
can be found in electrical and electronic waste [75]. Most
Artham et al. [76] suggest that because of the presence of of the inorganic material included (which in some cases is
the carbonate bond, PCs undergo a hydrolytic degradation. or can be related to a catalytic activity in the polymer’s
This type of degradation leads to the formation of low- degradation) is located in the solid residue after the pyro-
molecular-weight oligomers, which are easier assimilated lysis process, with a problematic exception in the case of
by microorganisms. halogenated compounds which usually lead to the forma-
The same authors suggest that the mechanism of bio- tion of undesirable organo-halogenated compounds in all
degradation of PC is quite similar to the ester hydrolysis by fractions. The problem becomes more demanding when the
serine proteases. It seems that a catalytic triad of amino- halogen atoms come from halogenated aromatic com-
acids (Ser, His, Asp/Glu) is involved in the hydrolysis of pounds (such as in the case of PC) since they require more
carbonate bond leading to release of bisphenol-A. Since the energy in order for the bonds to break, not only because of
model PC contains aromatic rings it has the ability to stack the bond energy of the Caromatic–X bond which is higher
with phenyl alanine, tyrosine and histidine. This interaction compared to Caliphatic–X bond, but also because of the lack
occurs because of strong van der Waals bonding between of favorable geometry which will have as a result an
the surface of aromatic rings. The PC material also forms increase in the activation energy of the reaction [47].

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18 Waste Biomass Valor (2013) 4:9–21

Williams [77] in a recent review paper reported the use volatilisation analysis and differential scanning calorimetry.
of pyrolysis to treat waste printed circuit boards as a means They have reported that during the degradation of the blend,
to recover valuable materials, including the recovery of no change was observed in the nature of the volatile prod-
metals, the oil and gaseous product as well as the glass fibre. ucts, but the rate of the PC depolymerisation reaction was
He also stressed that printed circuit boards contain signifi- increased and the PMMA depolymerisation was retarded.
cant concentrations of bromine in the form of brominated This was attributed to PMMA radicals attacking PC mac-
fire retardants, so several parts of the oil product become romolecules leading to chain scission in the PC at lower
contaminated by organic bromine containing compounds temperatures than required for homolysis in pure PC. In
which could affect the potential use options of the oil. It another of the first attempts to understand the degradation
seems that effective debromination routes would be a mechanism of PC blends, Osawa et al. [80] examined the
determining step in order to increase the economic viability extend of photo-degradation of PC/PMMA blends with
of the process. The role and potential of PC recycling in the various ratios, by changes in IR and UV spectra and
process is not reported in this extended study. molecular weight. They reported that photo-degradation of
Vasile et al. [47] attempted an upgrade of pyrolysis PC was not inhibited in the blend with PMMA, while
liquid produced from WEEE by catalytic hydrogenation in blending with PC retarded the photo-degradation of the
order to find applications as fuels or chemicals. Apart from PMMA component. Based on the experimental results
dehalogenation, denitrification and desulfuration were also obtained, a model of the photodegradation mechanism of the
the aims of the current study. The authors introduced a polymer blends was proposed. More recently, Uyar et al.
conventional acidic catalyst (DHC-8), and a neutral cata- [81] investigated the direct pyrolysis mass spectrometry
lyst in the hydrogenation process and they found that both analyses of poly(vinyl acetate) (PVAc), PC, and the binary
catalysts improved the quality of the pyrolysis oil by PVAc/PC blend and their thermal behaviors and degradation
eliminating compounds containing oxygen, nitrogen, hal- mechanisms were reported. They found that the presence of
ogens and sulphur and by increasing its stability. The main the second polymer in the blend affects the degradation
drawback of the catalytic process is that the amount of mechanism. Results indicated that CH3COOH formed by
aromatics remained high, and this will affect a future deacetylation of PVAc above 300 °C reacts with PC chains
potential application of the oil as a fuel. decreasing their thermal stability. Fraisse et al. [82] worked
Balart et al. [6] investigated the thermal properties of PC- in order to find a suitable way of recycling PET and PC
ABS mixtures obtained from WEEE by using thermo- which should enable production of their blends with
gravimetric analysis (TGA). Kinetic parameters, such as mechanical properties which can replace PVC in several
apparent activation energies were calculated by the appli- applications. They reported that blending of PET and PC
cation of the autocatalytic method, which has been suc- limited the degradation extend caused by mechanical and
cessfully applied to other polymer systems. Activation thermal processing during recycling, so PET and PC blends
energies determined from TGA data were practically exhibited mechanical properties comparable to the proper-
independent of heating rates in the case of ABS-based ties of PVC.
mixtures, while there seems to be some influence of the In another study of PC blends it was suggested that when
heating rates in the PC-based mixtures. The authors suggest PC is mixed with PVC and pyrolyzed at 700 °C an inter-
that the thermal degradation mechanism of these samples is esting situation arises. The presence of PVC with PC is
composed of several complex processes, and that the use of resulting in an increased yield of volatile degradation
a complex stabilizing system will be necessary for an effi- products, 5.3 % when co-pyrolyzed and 25 % when pyro-
cient stabilization of these mixtures and also a limitation of lyzed as a blend. These represent significant increases, since
the action of the main degradation processes. The same the degradation of PC is only expected to show a 0.15 %
authors [78] reported a decrease on mechanical properties mass loss at 700 °C. The presence of copper also appears to
of the PC-ABS blends when compared to the original cause a ten-fold increase in mass loss at 700 °C [67].
polymers in compositions in the range 20–80 wt% PC.

PC Blends Conclusion

A research area of particular recent interest is the study of This article outlines the recent advances in the area of PC, its
polymer blends mainly due to their significant industrial blends and WEEEs recycling and also attempts a review of
applications and improved characteristics. One of the first the degradation reactions mechanisms. The two main
studies in the literature has been the work of Rincon et al. methods employed are chemical degradation and pyrolysis.
[79] who studied the degradation of PC/poly(methyl meth- Drawbacks of the first method are related to the use of an
acrylate) (PC/PMMA) blends by thermogravimetry, thermal appropriate solvent system in terms of separation of the

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Waste Biomass Valor (2013) 4:9–21 19

monomer, as well as environmental and safety issues. 14. Karayannidis, G.P., Achilias, D.S.: Chemical recycling of
Pyrolysis seems to be a promising alternative, but it suffers poly(ethylene terephthalate). Macromol Mater Eng 292(2),
128–146 (2007)
from low selectivity and high separation cost. Further 15. Al-Salem, S.M., Lettieri, P., Baeyens, J.: The valorization of
research in the area of the designing and scaling up pyrolysis plastic solid waste (PSW) by primary to quaternary routes: from
reactors suitable for polymers degradation, as well as the re-use to energy and chemicals. Prog Energy Combust Sci 36,
implementation of suitable catalytic systems are expected to 103–129 (2010)
16. Pan, Z.Y., Zhen, B., Chen, Y.X.: Depolymerization of Poly(Bi-
increase the process applications in PC recycling. A suitable sphenol A Carbonate) in Subcritical and Supercritical Toluene.
and effective separation scheme seems to be a common Chin Chem Lett 17, 545–548 (2006)
place for both PC recycling processes, which becomes even 17. Pinero, R., Garcia, J., Cocero, M.J.: Chemical recycling of
more crucial in WEEEs and PC blends applications. polycarbonate in a semicontinuous lab-plant: a green route with
methanol and methanol-water mixtures. Green Chem 7, 380–387
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funds through the Operational Program ‘‘Education and Lifelong 19. Shaffer, S.J.: Method for recovering bis hydroxy aromatic organic
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