1338 DOI: 10.1002/mame.

200600243 Full Paper

Summary: In the framework of chemical recycling of poly- POM and DSC. Thermal polymerization of this monomer
mers, leading to the generation of secondary value-added was carried out at 80 8C in the presence of benzoyl peroxide
products, PET flakes taken from post-consumer soft drink as initiator. A UV-curable formulation was also prepared on
bottles, were glycolyzed with DEG. The oligomers obtained the basis of neat PET-GLY-DMA, as well as by mixing PET-
were analyzed for their molecular weight and characterized GLY-DMA with styrene, using DMPA as photoinitiator.
by FT-IR and POM. Subsequently, dimethacrylated oligo- Nanoparticles of SiO2 were dispersed into PET-GLY-
esters of PET glycolysate (PET-GLY-DMA) were synthes- DMA/styrene copolymers as reinforcing agents and the
ized by methacrylation of the glycolyzed PET product. The mechanical properties of resins formed were studied.
resulted monomer PET-GLY-DMA was studied by FT-IR,

Preparation of methacrylated PET glycolysate.

Chemical Recycling of PET by Glycolysis:

Polymerization and Characterization of the
Dimethacrylated Glycolysate
George P. Karayannidis,* Alexandros K. Nikolaidis, Irini D. Sideridou, Dimitris N. Bikiaris, Dimitris S. Achilias
Laboratory of Organic Chemical Technology, Department of Chemistry, Aristotle University of Thessaloniki,
GR-541 24, Thessaloniki, Macedonia, Greece
E-mail: [email protected]

Received: June 19, 2006; Revised: September 8, 2006; Accepted: September 8, 2006; DOI: 10.1002/mame.200600243
Keywords: chemical recycling; dimethacrylated oligoesters; glycolysis; poly(ethylene terephthalate); UV-curable formulations

Introduction dous quantities of this material are consumed in the

manufacture of video and audio tapes, X-ray films, food
Poly(ethylene terephthalate) (PET) is a semi-crystalline packaging and especially of soft-drink bottles. PET does
thermoplastic polyester showing excellent tensile and not create a direct hazard to the environment, but due to its
impact strength, chemical resistance, clarity, process- substantial fraction volume in the plastics waste stream and
ability and reasonable thermal stability.[1] Although its its high resistance to atmospheric and biological agents, it
main application was by far the textile industry, tremen- could be considered as a noxious material.[2] PET accounts

Macromol. Mater. Eng. 2006, 291, 1338–1347 ß 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Chemical Recycling of PET by Glycolysis: Polymerization and Characterization . . . 1339

for 8% by weight and 12% by volume of the world’s solid In our previous work,[18] PET was depolymerized with
waste.[3] DEG at different DEG/PET molar ratios and the oligomers
PET recycling represents one of the most successful and obtained were identified and subsequently used as raw
widespread examples of polymer recycling. The main materials for the synthesis of alkyd resins.
driving force responsible for this extremely increased re- Farahat and Nikles[23–25] provided results on the glyco-
cycling of post-consumer PET is its widespread use, lysis of PET with DEG and a new application for the
particularly in the beverage and food industry. PET bottles obtained oligoester diols/polyols, by converting the hydro-
are characterized by high strength, low weight and xyl terminals into acrylate/methacrylate groups. These new
permeability of gasses (mainly CO2) as well as by their acrylated/methacrylated oligoesters were tested as UV
aesthetic appearance (good light transmittance, smooth curable monomers, either alone or as mixtures with other
surface), while they do not have any side effect on the commercially available diacrylate/dimethacrylate mono-
human organism.[2] Many attempts are currently directed mers. They gave promising results, from the point of view
toward recycling of PET waste, because of the interests in of their curability by UV and their mechanical properties,
environmental protection, energy preservation and eco- in order to work as novel binder systems for solventless
nomic benefits.[4] PET bottle collection in Europe (Euro- magnetic tape manufacturing.
pean Union member states plus Norway, Iceland, Switzer- Atta et al.[3,26] performed the glycolysis of PET with
land, and all EU candidate countries) is growing steadily. DEG or tetraethylene glycol (TEG); an epoxy resin was
In 2004, 665 000 t were collected, an 8.4% increase in then prepared by the reaction of glycolyzed products with
comparison with 2003. By 2009, it is forecast that Euro- epichlorohydrin. New diacrylate and dimethacrylate vinyl
pean PET collection will increase to more than 1 Mt.[5] esters were also synthesized by the reaction of the terminal
Among the different recycling techniques (primary, epoxy groups with acrylic and methacrylic acid. These
mechanical, chemical recycling and energy recovery), vinyl esters were used as cross-linking agents for unsatu-
the only one acceptable according to the principles of rated polyester resin diluted with styrene and the resulted
‘‘Sustainable Development’’ is chemical recycling, since it resins were evaluated in coating applications of steel.
leads to the formation of the raw materials from which the The aim of the present investigation was to apply the
polymer is made, as well as of other secondary value-added dimethacrylated oligoesters, produced from PET chemical
products.[6] Chemical recycling has been defined as the recycling, as potential raw materials for the production of
process leading to total depolymerization of PET into UV-curable formulations, used as enamel paints or coat-
monomers, or partial depolymerization into oligomers and ings for metallic surfaces in the automotive industry. For
other chemical substances. The main methods used for this this purpose, depolymerization of PET was firstly conduc-
purpose are glycolysis, methanolysis, hydrolysis (alkaline, ted using DEG and the oligomers produced were then
acidic and neutral) and other processes such as aminolysis and characterized. Then the hydroxyl end-groups of the glyco-
ammonolysis.[7] Glycolysis makes it possible to employ very lyzed PET product (PET-GLY) were converted into meth-
low amounts of reactants, as well as applying lower acrylate groups and the dimethacrylated oligoesters of PET
temperatures and pressures, in contrast with other methods glycolysate (PET-GLY-DMA) obtained were studied.
such as supercritical methanolysis and thermal degrada- UV-polymerization was chosen for the resulted monomer,
tion,[8–12] while hydrolysis under acidic or basic conditions to give solvent-free systems and allow rapid curing, as well
may cause corrosion and pollution problems.[13,14] Recently, as a low curing temperature for in-line production. Finally,
a growing interest has been observed in PET glycolysis for nanoparticles of SiO2 were dispersed into PET-GLY-DMA/
the manufacture of specialized products such as un- styrene copolymers as reinforcing agents and the mechan-
saturated polyesters,[15–18] polyurethanes,[19–22] vinyl ical properties of the final resins were studied.
esters,[23–25] epoxy resins,[26] and polymer concretes.[27,28]
Baliga et al.[29] carried out the glycolysis of PET with
ethylene glycol (EG) using various catalysts. They found
that glycolyzed products had 1–3 repeating units, depending Experimental Part
on the catalyst used. Halacheva and Novakov[30] have Materials
investigated the chemical structure of the oligoesters pro-
duced from PET glycolysis with diethylene glycol (DEG) PET flakes were prepared from post-consumer clear PET
bottles, after the removal of polyethylene caps and the
and they have pointed out the existence of secondary
poly(propylene) label. The bottles were cut and fed to a rotary
hydroxyl groups of the products obtained at a large excess of
cutter with a maximum size of 6 mm. Diethylene glycol
DEG. Glycolysis of recycled PET was also investigated by (DEG), acetic anhydride, triethylamine (TEA) and styrene
Chen et al.,[31,32] Mansour and Ikladius,[33] Michel et al.[34] monomer were all supplied by Fluka AG. Methacryloylchlor-
and Troev et al.[35] Moreover, the mechanism of formation ide (MAcCl), and manganese acetate [Mn(CH3COO)2
4H2O]
and applications of PET glycolysates have also been studied with a purity of 99% were obtained from Aldrich and used
in the literature.[36–39] without further purification. Fumed hydrophobic nanoparticles

Macromol. Mater. Eng. 2006, 291, 1338–1347 www.mme-journal.de ß 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1340 G. P. Karayannidis, A. K. Nikolaidis, I. D. Sideridou, D. N. Bikiaris, D. S. Achilias

of silica (SiO2) were supplied by Degussa AG (Hanau, 2.5 wt.-% SiO2) were also copolymerized. Films were obtained
Germany) under the trade name AEROSIL1 R 974. The by spreading the monomer or the mixture of monomers on a
photoinitiator used was 2,2-dimethoxy-2-phenylacetophenone glass surface for a thickness of about 1 mm, controlled by using
(DMPA) from Aldrich, while the initiator for the thermal a doctor’s knife. Curing was performed by the addition of 1
polymerization was benzoyl peroxide (BPO) from Fluka AG. wt.-% of DMPA in each case (lmax ¼ 253.7 nm) and UV
Tetrahydrofuran (THF), used as a solvent in gel permeation irradiation using a Hanovia high-pressure quartz mercury-
chromatography (GPC), was obtained from Riedel-de-Haen. vapor lamp (Model L 679A-36) at the output intensity of 450 W.
All other chemicals used were reagent grade. The distance chosen between films and lamp was 10 cm, while
the irradiation time was 30 min per side of the film. In addition,
films of pure PET-GLY-DMA were obtained as mentioned
Glycolysis of PET above by thermal polymerization at 80 8C for 2 h, in the
presence of BPO as initiator.
A continuously stirred 500 mL round-bottom four-necked
flask was charged with 150 g (0.781 mol per repeating unit) of
PET waste flakes and 84.6 g of diethylene glycol (correspond- Characterization of the Glycolyzed PET,
ing to a DEG/PET molar ratio of 1.02). Manganese acetate, PET-GLY-DMA Resins
0.6 wt.-% based on weight of PET, was added as trans-
esterification catalyst. The flask was immersed in an oil bath The molecular weight distribution and the average molecular
and heated for 4 h at 210 8C. The reaction was carried out weight of the glycolyzed PET product were determined by Gel
under reflux in an argon atmosphere. After the 4 h period, the Permeation Chromatography (GPC). The instrument used was
reaction product was allowed to cool at room temperature, from Polymer Laboratories and included a pump (Marathon
dissolved in a suitable amount of dichloromethane and fil- III HPLC pump), an Evaporative Mass Detector (PL-EMD
tered. The filtrate was washed several times with distilled 950) and a Plgel 5m MIXED-D column. The sample was
water in order to remove traces of unreacted DEG, the dissolved in THF at a constant concentration of 0.2 wt.-%.
produced EG and the remaining catalyst. After phase sepa- After filtration, 25 mL of the sample was injected into the
ration, the organic layer was collected and dried over an- chromatograph. The elution solvent was also THF at a
hydrous Na2SO4. Finally, purified oligoesters were obtained constant flow rate of 1 mL
min1. Calibration of GPC was
after removal of the solvent by rotary evaporation. carried out with standard polystyrene samples (Polymer
Laboratories).
The content of hydroxy end-groups (hydroxyl number, HN)
Synthesis of PET-GLY-DMA of the oligoester diols obtained was determined by titration
with 1 N KOH solution. About 1.5 g sample was accurately
In this procedure, 69 g of PET glycolysate were dissolved in weighted and added to 10 ml acetylating solution, containing
300 mL CH2Cl2 in a 500 mL round-bottom four-necked flask, 10 vol.-% acetic anhydride in pyridine, in a round-bottomed
equipped with a magnetic stirrer, inlet to inert gas (argon), flask. The flask was fitted with a vertical reflux condenser and
thermometer and a 100 mL additional funnel. After cooling heated to 80 8C for 2 h. Afterwards, 10 ml of water were added
the content under an argon purge to 0 8C with an ice bath, and the heating was continued for 10 min at 100 8C. The
35 mL of TEA were introduced and 25 mL (0.254 mol, 5% mixture was then cooled at room temperature and 10 ml of
excess) of MAcCl were added dropwise through the funnel methanol were added from the top of the condenser. The
over a 50 min time span. The mixture was kept at 0 8C for 3 h, resulting solution was titrated against 1 N KOH standard using
allowed to reach room temperature and remain there for an phenolphthalein as indicator. A blank run was also performed.
additional 18 h. The insoluble TEA salt was then filtered and The values obtained provide a measure of the number average
the filtrate was washed twice with 300 mL of 1 M aqueous molecular weight.
NaOH saturated with NaCl and several times with distilled The chemical structure of the glycolyzed PET product, as
water. After phase separation, the organic layer was collected well as the extent of the methacrylation reaction were
and centrifuged. The synthesized product was then isolated, confirmed using a Perkin-Elmer spectrophotometer (Model
dissolved in 300 mL of a CH3OH/CH2Cl2 (50:50 v/v) mixture Spectrum One).
and dried over anhydrous CaSO4. The purified PET-GLY- Phase identification of the glycolyzed PET product and
DMA was obtained after removal of the solvents by rotary PET-GLY-DMA was performed by polarized optical micro-
evaporation. scopy using a Nikon OPTIPHOT-2 polarizing microscope,
equipped with a Linkam THMS 600 heating stage and a TP 91
control unit. Heating rates were 10 8C
min1.
Homopolymerization and Copolymerization of the Tg measurement and thermal polymerization study of
Prepared Monomer PET-GLY-DMA in the absence of initiator were performed
using a differential scanning calorimeter of Perkin-Elmer
PET-GLY-DMA was homopolymerized in order to produce (Pyris 1) equipped with the Pyris software for Windows and
UV-curable films. Mixtures containing PET-GLY-DMA and calibrated for temperature and enthalpy with indium.
styrene (50:50 w/w), as well as a series of mixtures containing Tensile tests were performed using an Instron 3344
PET-GLY-DMA and styrene (50:50 w/w) and silica nano- dynamometer, in accordance to the ASTM D638 method at
particles in several ratios (corresponding to 0.5, 1 and room temperature. Prior to measurements the samples were

Macromol. Mater. Eng. 2006, 291, 1338–1347 www.mme-journal.de ß 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Chemical Recycling of PET by Glycolysis: Polymerization and Characterization . . . 1341

conditioned at 50  5% relative humidity for 36 h, placed in cross-linked structures, leading to improved mechanical
a closed chamber containing a saturated Ca(NO3)2
properties.[23,24]
4H2O solution in distilled water (ASTM E-104). Tensile tests The number average molecular weight, M n , of the
were performed under the condition that the crosshead speed obtained glycolysate was calculated by determining the
of tensile tester was set at 5 mm
min1 and the initial gauge
hydroxyl number (HN), which was found to be 196.2 mg
length was fixed at 22 mm. Five measurements were con-
KOH/g of the sample. Based on this value the M n calcu-
ducted for each sample, and the results were averaged to
obtain a mean value. lated was found to be 572. The number (M n ) and weight
(M w ) average molecular weights of the polyester oligomers
produced and the polydispersity of the molecular weight
Results and Discussion distribution obtained from GPC were 880, 990 and 1.13,
respectively. It was noticed that the number average
Glycolysis of PET and Characterization of the
molecular weight measured by GPC was higher than that
Glycolyzed Product
obtained from the hydroxyl number. If it is considered that
The alcoholysis of PET with diethylene glycol proceeds the oligoester produced is a trihydroxy-compound,[23,24]
according to the reaction shown in Scheme 1. The alcoho- the M n estimated based on the HN, becomes equal to 858,
lysis consists of the transesterification of PET and the that is very near with that obtained from GPC (880). The
depolymerization of its polymer chain, resulting in the greater than one polydispersity of the molecular weight
decrease of its molecular weight. Using a small excess of distribution revealed that the distribution was not uni-
glycol in the depolymerization of PET, the oligoesters modal. Actually, three distinct peaks (trimodal shape) were
obtained have mainly two hydroxyl end-groups, that is, identified (Figure 1). That means that PET glycolysis using
mixtures of oligoester diols are formed.[30] The choice of DEG results mainly in three kinds of oligoesters. On trying
DEG to carry out the glycolysis is usually determined by to identify the oligoester diols produced, the structure in
the necessity of having good flexural properties in the Scheme 2 was proposed,[30] According to this structure, if
UV-cured resin, since the long chains containing this gly- one replaces m with 0, 1 and 2 the following molecular
col improve flexibility. weights are obtained: 342, 534 and 726, respectively. By
In the present study, the glycolysis of PET was carried comparing these values with the values obtained by GPC, it
out using an initial DEG/PET molar ratio of 1.02, to obtain can be concluded that the above structure is confirmed with
a small degree of depolymerization and, as a consequence, m ¼ 0, 1 and 2.
oligomers of relatively high molecular weights. These The FT-IR transmission spectrum (Figure 2) confirms
could partly maintain the primary features of PET and the proposed chemical structure for the glycolyzed PET
impart improved mechanical properties to the cured film of product. The characteristic peaks for the PET glycolysate
the final dimethacrylated product. This means that the as shown in Figure 2 are the following:
presence of more terephthalate repeating units between the 3 429 cm1 ( –OH), 3 030 cm1 ( –H arom.), 2 953 cm1
cross-links can result in the existence of harder domains ( –CH2 –), 1 718 cm1 ( –C –– O –ester), 1 612 and 1 506 cm1
and better separation between the cross-links in the packed ( –C –– C – arom.), 1 274 cm1 ( –C –O –C –ether).

Scheme 1. The alcoholysis of PET with diethylene glycol.

Macromol. Mater. Eng. 2006, 291, 1338–1347 www.mme-journal.de ß 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1342 G. P. Karayannidis, A. K. Nikolaidis, I. D. Sideridou, D. N. Bikiaris, D. S. Achilias

Figure 1. Molecular weight distribution of the glycolyzed PET Figure 2. FT-IR spectrum of the PET-GLY.
product.

By using a hot-stage polarizing optical microscope to both UV and thermal oxidations, while increasing the Tg
(POM), a significant amount of crystallites dispersed in the of the final product.[40] Furthermore, the direct esterifica-
viscous amorphous phase was observed at room tempera- tion reaction with methacrylic acid, in the presence of
ture. So the glycolyzed PET product could be characterized methanesulfonic acid or p-toluenesulfonic acid as ester-
as a semi-crystalline substance. That is probably why the ification catalysts, was avoided, because the M n values of
glycolysate performs as a semi-solid and opaque material. the methacrylated products by these methods were report-
Crystallization might be related to the molecular species of ed to be slightly lower than that of the starting oligomers,
lower molecular weight, namely the oligomers correspond- indicating the occurrence of an acidic degradation reaction,
ing to the proposed structure for m ¼ 0 and 1. By increasing which does not affect the methacrylic functionality.[41–43]
the temperature to 37 8C, a movement of the crystallites The excess of MAcCl was intended to cause the meth-
into the liquid amorphous phase was detected, due to its acrylation of as many hydroxyl end-groups of PET
fluidization. At 65 8C these crystallites were shown to be glycolysate as possible. Dichloromethane was proved to
melted or dissolved in the amorphous phase. Furthermore, be a more effective solvent of the glycolyzed PET product
the above changes were completed at 80 8C. Up to 120 8C for the methacrylation reaction than THF, without resulting
no other change was observed. During the slow cooling of in by-products. In our first effort using THF as solvent
the sample, new spherulites appeared possessing a dark some oligomers of polytetrahydrofurane were produced,
Maltese cross pattern. which did not separate from the reaction mixture by the
rotary evaporator. Triethylamine was used as a basic
scavenger, in order to remove the HCl as triethylamine salt,
(C2H5)3NþH Cl. To avoid the hydrolysis of MAcCl and
Synthesis and Characterization of PET-GLY-DMA
the polymerization of the corresponding acid, as well as to
The methacrylation reaction of PET glycolysate could be control the temperature of the reactant mixture, meth-
represented by Scheme 3. MAcCl was chosen as the acrylation was conducted at 0 8C, because it is an exo-
methacrylation agent instead of acryloylchloride (AcCl), thermic reaction. The washes with the aqueous solution
because the presence of methyl groups at the a-carbon of 1 M NaOH aimed at the hydrolysis of the MAcCl excess,
atom of the ester chain generally imparts higher resistance dissolved in the organic phase, to the corresponding acid

Scheme 2. Proposed structure of the oligoester diols resulting from PET glycolysis using DEG.
m ¼ 1–3.

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 Chemical Recycling of PET by Glycolysis: Polymerization and Characterization . . . 1343

Scheme 3. Preparation of methacrylated PET glycolysate. m ¼ 1–3.

Figure 3. FT-IR spectrum of the PET-GLY-DMA. Figure 4. DSC traces of the PET-GLY-DMA.

Macromol. Mater. Eng. 2006, 291, 1338–1347 www.mme-journal.de ß 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1344 G. P. Karayannidis, A. K. Nikolaidis, I. D. Sideridou, D. N. Bikiaris, D. S. Achilias

and hence at the removal of the latter as methacrylic salt in 1 722 and 1 271 cm1 against the intensity of the peak at
the aqueous phase. 1 637 cm1, reveals a larger ratio of methylene, ester and
As shown by the FT-IR transmission spectrum (Figure 3), ether groups against the methacrylate groups in the chemical
the progress of the methacrylation reaction is confirmed by structure of PET-GLY-DMA.
the reduction of the broad band at 3 535 cm1, corres- Similarly to the glycolysate, PET-GLY-DMA was found
ponding to the –OH group (against the FT-IR spectrum of by POM to consist of a significant amount of a crystalline
the glycolysate), and the appearance of a new band at phase dispersed in the viscous amorphous phase at room
1 637 cm1, corresponding to the newly formed meth- temperature (semi-crystalline substance) and consequently
acrylate group. The higher intensity of the peaks at 2 957, giving a semi-solid and opaque material. By heating the

Scheme 4. Photochemical homopolymerization of PET-GLY-DMA by UV irradiation.

Macromol. Mater. Eng. 2006, 291, 1338–1347 www.mme-journal.de ß 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Chemical Recycling of PET by Glycolysis: Polymerization and Characterization . . . 1345

sample up to 120 8C and cooling it slowly to room tem- The DSC thermogram (Figure 4) shows that by a first
perature, a behavior similar to that of the glycolysate was heating of the PET-GLY-DMA from 50 to 120 8C, the Tg
observed. Heating PET-GLY-DMA again up to 220 8C, no of the sample appeared at 30 8C.
movement of the amorphous phase was detected, while the This rather low value of Tg could be attributed to the
little crystallites did not change. This attitude could be flexibility that the segments of ether and methylene groups
attributed to thermal polymerization of the substance, impart to the oligomer chains. Despite the low value of
which might have been initiated at the end of the first Tg, the material performed as a semi-solid mass at room
heating (120 8C) and led to a cross-linked structure and a temperature, perhaps due to the presence of crystals
trap of the two phases. During cooling the sample again to detected by using POM into the amorphous phase, which
room temperature, no change was observed, obviously due retained the stiffness of the material. In addition, the broad
to its polymerization. endothermic peak at the temperature area of 40–90 8C

Scheme 5. Photochemical copolymerization of PET-GLY-DMA with styrene by UV irradiation.

Macromol. Mater. Eng. 2006, 291, 1338–1347 www.mme-journal.de ß 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1346 G. P. Karayannidis, A. K. Nikolaidis, I. D. Sideridou, D. N. Bikiaris, D. S. Achilias

maybe confirms the total fluidization of the amorphous

phase, as well as the total melting or dissolution of the
crystals, effects which were also observed by POM. By a
second heating of the same sample from 50 to 220 8C, the
Tg was found to be increased to 23 8C, while the exo-
thermic peak recorded at 130 8C supports the possibility of
a thermal polymerization of PET-GLY-DMA at the
particular temperature. The additional increase of Tg from
23 to 12 8C, as well as the loss of the exothermic peak at
130 8C observed by a third heating of the same sample
(from 50 to 150 8C), just confirms the above claim.

Homopolymerization and Copolymerization of the

Prepared Monomer
Figure 6. Young’s modulus of PET-GLY-DMA/styrene copoly-
The UV-homopolymerization of the PET-GLY-DMA mers containing different amounts of SiO2.
monomer with DMPA as photoinitiator is shown in
Scheme 4. The dispersion of DMPA in the semi-solid
monomer was achieved by using methanol-dichloromethane
50:50 v/v mixture as diluent. After the casting of this mechanical properties. In both cases, the polymerization
formulation on a glass plate and the evaporation of the of the films was macroscopically confirmed by the fact
diluent the photopolymerization followed. that they hardened after the UV-irradiation. The UV-
The above homopolymer did not harden enough even copolymerization reaction of the PET-GLY-DMA mono-
after 30 min of irradiation. This behavior could be attri- mer with styrene is shown in Scheme 5,
buted to the relatively low concentration of double bonds in Nanoparticles of SiO2 were used as a reinforcing agent.
the structure of the monomer. Furthermore, the films that These fine inorganic particles exhibit huge surface areas
were produced by this homopolymerization were rather due to their small size. For this reason a satisfactory
flexible, due probably to the flexible methylene– and ether dispersion and adhesion in the copolymer matrix and thus
groups in the structure of the PET-GLY-DMA. So, styrene an improvement in the mechanical properties were ex-
was used as the co-monomer of the PET-GLY-DMA in pected. This adhesion could be also attributed to the pre-
order to act as a reactive diluent; on the one hand, aiding sence of hydrophobic methyl groups at the SiO2 surface,
the dispersion of DMPA and SiO2 into the semi-solid which are quite friendly to the organic material.
PET-GLY-DMA monomer, as well as the molding of the The thermal polymerization of PET-GLY-DMA at 80 8C
material into film; and on the other hand participating in a for 2 h in the presence of benzoylperoxide (BPO) was
copolymerization process with PET-GLY-DMA, leading to considered to be adequate, as the polymerized material
the formulation of cross-linked films with improved yielded a quite hardened and brittle film.

Figure 5. Stress-strain curves of PET-GLY-DMA/styrene copo- Figure 7. Tensile strength at break of PET-GLY-DMA/styrene
lymers containing different amounts of SiO2. copolymers containing different amounts of SiO2.

Macromol. Mater. Eng. 2006, 291, 1338–1347 www.mme-journal.de ß 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Chemical Recycling of PET by Glycolysis: Polymerization and Characterization . . . 1347

Mechanical Properties of the Resin [10] S. Takeshi, O. Idzumi, S. Tsutomu, O. Katsuto, Y. Satoshi,
Films Produced T. Yoshihiro, Polym. J. 2000, 32, 178.
[11] S. J. Chiu, W. H. Cheng, Polym. Degrad. Stab. 1999, 63, 407.
PET-GLY-DMA/styrene and PET-GLY-DMA/styrene/ [12] S. J. Chiu, W. H. Cheng, J. Anal. Appl. Pyrolysis 2000, 56,
SiO2 specimens performed as tough and brittle materials 131.
by their fracture in the dynamometer (Figure 5). Especially, [13] C. Y. Kao, W. H. Cheng, B. Z. Wan, J. Appl. Polym. Sci.
1998, 70, 1939.
the samples containing SiO2 exhibited a slightly lower [14] G. Gamze, Y. Tuncer, O. Saadet, O. Murat, Thermochim.
Young’s modulus than the specimens of PET-GLY-DMA/ Acta 2003, 404, 193.
styrene copolymer (Figure 6), perhaps due to the presence [15] U. R. Vaidya, V. M. Nadkarni, J. Appl. Polym. Sci. 1987, 34,
of nanoparticle agglomerates and their inefficient disper- 235.
sion into the copolymer matrix. A similar behavior can be [16] D. J. Suh, O. O. Park, K. H. Yoon, Polymer 2000, 41, 461.
[17] C. Kawamura, K. Ito, R. Nishida, I. Yoshihara, N. Numa,
seen in Figure 7, where the tensile strength at break of Prog. Org. Coat. 2002, 45, 185.
PET-GLY-DMA/styrene copolymers containing different [18] G. P. Karayannidis, D. S. Achilias, I. D. Sideridou, D. N.
amounts of SiO2 is shown. Bikiaris, Eur. Polym. J. 2005, 41, 201.
[19] U. R. Vaidya, V. M. Nadkarni, J. Appl. Polym. Sci. 1988, 35,
775.
[20] U. R. Vaidya, V. M. Nadkarni, J. Appl. Polym. Sci. 1989, 38,
Conclusion 1179.
In this work, PET glycolysis for the production of the [21] S. C. Lee, Y. W. Sze, C. C. Lin, J. Appl. Polym. Sci. 1994, 52,
869.
dimethacrylated glycolysate PET-GLY-DMA was carried [22] O. Saravari, B. Vessabutr, V. Pimpan, J. Appl. Polym. Sci.
out. By finding the M n of the PET glycolysate according to 2004, 92, 3040.
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