Journal of Polymers and the Environment (2020) 28:794–802

https://doi.org/10.1007/s10924-019-01642-5

ORIGINAL PAPER

Mechanical–Chemical Recycling of Low‑Density Polyethylene Waste

with Polypropylene
Rayane Veloso de Camargo1 · Clodoaldo Saron1

Published online: 23 December 2019

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
The global increasing consumption of thermoplastic such as polyethylene and polypropylene has caused the generation of
enormous amount of polymeric waste that are a challenge for solid waste management and represents a severe polluting
agent, mainly for the marine life. Mechanical recycling is an important alternative to decrease the volume of polymeric
waste. However, the mixture of different thermoplastic and other materials on the same object depreciates the properties of
the recycled polymer due to the formation of immiscible blends. The aim of this study has been to evaluate the recycling
of the post-industrial low-density polyethylene waste (LDPE waste) in presence of polypropylene using thermomechani-
cal processing and thermochemical treatment of the material. For it, blends of LDPE waste and virgin polypropylene (PP)
containing until 30 wt% of PP has been prepared with incorporation of zeolite ZSM-5 and Ziegler–Natta catalysts and sub-
mitted to the thermal treatment under controlled conditions of temperature and nitrogen flow. The results show the action of
zeolite catalyst as modifier of the polymeric structure during step of the thermomechanical processing of the material. The
catalysts have caused considerable changes on properties of the LDPE/PP blends, depending of the experimental conditions.
The treatment of polymeric waste in presence of catalyst presents potential for recycling of polymeric materials with high
contamination by other polymers and can generate recycled materials with improved properties.

Keywords LDPE · PP · Recycling · Zeolite ZSM-5 · Ziegler–Natta catalyst

Introduction Recycling is appointed as one of the best ways to mini-

In the last few decades, there has been an extreme increase
in the production and consumption of the polymers, lead-
ing to environmental, social and economic consequences.
Polymers have become villains given the large amount of
waste that ends up in the ocean, about 8 million tons per year
[1, 2]. Polyolefins like polyethylene (PE) and polypropylene
(PP) are the most widely consumed plastic commodities in
the world and have a great recycling potential [3]. Only in
2015, the global primary production of the PP was around
68 million metric tons (Mt) with primary waste generation
of 55 Mt. Not very far was the production and waste genera-
tion of LDPE, reaching 64 Mt and 57 Mt, respectively [4].
* Clodoaldo Saron
saron@usp.br
1
Department of Materials Engineering, Engineering
School of Lorena, University of São Paulo - LOM-EEL/
USP, Polo Urbo Industrial, Gleba AI‑6, s/n, Lorena,
SP CEP: 12602‑810, Brazil
mize the residues accumulation. When it comes to poly-
mers, four main types of recycling are known nowadays: the
primary, secondary, tertiary and quaternary recycling. The
primary and secondary recycling are equivalent to the same
kind of recycling, the mechanical, which is a thermome-
chanical process of mixing and remolding it into the same or
another product. Primary recycling consists in processing of
a known and uncontaminated material, usually a scrap from
the industrial processes. This recycling process leads to a
product very similar to the virgin one when performance is
required. The secondary recycling has a similar processing
of the materials except for previous steps such as separation
and washing, since the material is a post-consume waste
and it is contaminated with many kinds of residues, such as
organic compounds and other polymeric materials. As a con-
sequence of the secondary treatment, the material properties
decay in a cascade effect, what means that are depreciated
every time that the material is reprocessed [5, 6]. The chemi-
cal or tertiary recycling corresponds to the depolymerization
of the polymer chains, and thus the recovery of the original

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Journal of Polymers and the Environment (2020) 28:794–802
monomers and oligomers of various molar masses. In this
way, thermoplastics can again be obtained [7]. The quater-
nary or energy recycling is an energy recovery process based
on the combustion of polymeric waste [8].
Among the methods for chemical recycling of polyole-
fin, thermal and catalytic cracking are the most viable in
large scales [9, 10]. In the thermal cracking, a wide range
of products with variable molar mass can be obtained at
temperatures around 500 °C or higher. Catalytic cracking
offers the same result in lower temperatures and reaction
time [11]. Zeolite ZSM-5 is an example of catalyst that acts
promoting a narrow distribution on the molar mass for poly-
mers and reducing the energy consumed on the heating. De
Marco et al. used a proportion of zeolite ZSM-5 at 10 wt%
and temperature at 460 °C to obtain a pyrolysis yield around
90 wt% as liquid and gas products [12]. Pacheco Filho et al.
used zeolite catalyst at 10, 30 and 50 wt% for polypropylene
recycling to increase the conversion rates for formation of
pyrolyzed products [13].
Another known catalyst in the chemical industry is Zie-
gler–Natta, widely used in polymer and copolymers synthe-
ses [3]. On the other hand, it can also be used for cracking
reactions. The ­TiCl4 compound, the most common active
agent, has good cracking properties in reprocessing of poly-
mers by lowering the pyrolysis temperature to 350 °C with
conversions reaching 80% and producing mainly light liquid
fraction [14].
The advantage of using a commercial Ziegler–Natta
(Z–N) catalyst, as proposed by Donaj et al. is that the active
agent ­(TiCl4), when sustained by M­ gCl2, can be readily dis-
solved in molten polymers, protected against the decom-
position of ­TiCl4 at higher temperatures and extending its
residence time to cracking properties [15]. Thus, the appli-
cation of commercial Z–N catalysts allows the use at higher
temperatures, opening new possibilities in the catalytic
pyrolysis. Donaj et al. applied a Ziegler–Natta catalyst and
obtained an increase in the production of gaseous olefins,
unsaturated and aromatic hydrocarbons, in addition to the
remarkable production of propylene [15]. According to stud-
ies conducted by Donaj et al. the Ziegler–Natta under high
temperatures catalyzes the decomposition of the polyeth-
ylene, while at lower temperatures leads to the growth of
polymer chains [15]. The catalyst is expected to be activated
at a temperature around 120 °C [16].
The separation of post-consume polymeric waste is
other difficult found for polyolefin recycling. Thus, studies
have been performed on polyolefin recycling as polymeric
blends [17, 18]. Gu et al. [17, 18] evaluated the effect of
the incorporation of benzoyl peroxide on mechanical and
rheological properties of recycled polyolefin blends and
verified that blends of recycled HDPE/PP were modified
with the benzoyl peroxide, which lowered their melt flow
rate and increased the impact resistance. Mourad [17, 18]
795
has studied the thermo-mechanical performance of the low-
density polyethylene/isotactic polypropylene blends (LDPE/
iPP) thermally aged and verified that thermal stability of
the iPP is affected by the presence of the LDPE. Graziano
et al. wrote an important review on modification strategies
of polyethylene/polypropylene for enhancing their mechani-
cal behavior, emphasizing the importance of the interface
interactions between polymeric components [19].
The aim of this study was to associate the great mixture
potential of the mechanical recycling and a soft chain-break
attributed to the chemical recycling possessing, followed
by chain recombination using ZSM-5 and Ziegler–Natta
catalysts, in order to obtain a polyethylene-polypropylene
copolymer with low crystallinity and rubbery properties.
Materials and Methods
Materials
Scraps of low-density polyethylene films (LDPE waste) and
polypropylene pellets were donated by Valfim S.A-Brazil.
and Braskem-Brazil, respectively. LDPE waste contains
thermal stabilizer at 0.15 wt%. As catalysts to the semi-
decomposition and recombination reactions were used the
zeolite ZSM-5, donated by the Fábrica Carioca de Catalisa-
dores-Brazil and the Ziegler–Natta acquired from the Sigma-
Aldrich. The antioxidant SONGNOX 21 B FF was also used
as thermal stabilizer during thermomechanical processing
of the materials.
Methods
Processing and Thermal Treatment
LDPE waste was initially submitted to agglutination pro-
cess in equipment with rotary knives KIE, model AK-45
20CV to generate granules (pellets) with diameter around
5 mm. Then, the material was dried for 14 h at 80 °C in an
oven with forced air circulation QUIMIS, model BG 4000,
according to previous studies performed by Moreno et al.
[20]. After drying, LDPE waste and PP were mixed by tam-
bouring at a ratio of 70/30 wt% together with the antioxi-
dant SONGNOX 21 B FF at 0.15 wt%. On a fraction of the
mixture was also incorporated the zeolite ZSM-5 catalyst
at 5 wt%. After pre-mixture, the materials were submitted
to the extrusion in a single-screw extruder IMACOM with
screw rotation at 40 rpm, using a temperature profile of 110,
160, 160 and 180 °C from the feed to the array. Immediately
after extrusion, the materials were pelletized (granulates) by
use of a rotary knife device coupled to the extruder.
The LDPE/PP blends produced by extrusion were submit-
ted to injection molding in equipment DIPLOMAT, model
13
796
DW-130, using screw speed at 100 RPM, injection pressure
at 130 MPa and a temperature profile of 180, 190, 200 and
200 °C from the feed to the nozzle to produce tensile test and
impact specimens, according to the standard practices ASTM
D638 [21] and ASTM D256 [22].
Thermal treatment was carried out on the LDPE/PP blend
containing ZSM-5 catalyst at 5 wt% prepared by extrusion
and on the LDPE/PP blend containing both ZSM-5 and Zie-
gler–Natta catalysts at 5 wt%. Due to the corrosive character-
istic of the Ziegler–Natta catalyst, it was not incorporated to
the material by extrusion. Their incorporation has been carried
out by direct addition at 5 wt% in the blend previously con-
taining the ZSM-5 catalyst. The content of the Ziegler–Natta
catalyst was chosen by previous studies performed by Donaj
et al. [15], respectively. Table 1 presents the identification of
the materials based on presence of the catalyst and use of the
thermal treatment.
The thermal treatment was performed in tubular oven
FENIX, model FT 1200/H/3Z/GÁS/CLP on nitrogen flow,
using a heating rate at 20 °C min−1 from room temperature to
415 °C, following by additional isotherm by 10 min at 415 °C.
After thermal treatment, the material was quickly cooled in
a water tank at room temperature. Then, the materials was
ground and molded by injection for confection of tensile test
specimens on the same conditions previously reported.
Properties Characterization
Thermogravimetric analysis (TGA) and exploratory differen-
tial calorimetry (DSC) were performed using an equipment
NETZSCH, model STA 449 Jupiter. For TGA, it was used a
heating rate of 10 °C min−1 from 30 to 700 °C under nitrogen
flow at 100 mL min−1, while for DSC analysis the follow-
ing steps have been applied: cooling to − 150 °C using liquid
nitrogen; heating to 300 °C at a rate of 20 °C min−1; isotherm
by 10 min; cooling to − 150 °C at a rate of − 20 °C min−1;
isotherm by 5 min and second heating to 300 °C at a rate of
20 °C min−1.
Crystallinity degree (χc) was calculated by using Eq. 1 [23]:
ΔH
( )
𝜒c = × 100 (1)
ΔH ◦
where ∆H is the melting enthalpy for LDPE or PP experi-
mentally determined by DSC and ∆H0 is the theoretical
Table 1  Identification of the Material LDPE waste con-
materials tent (wt%)
Blend 1 70
Blend 2 66.5
Blend 3 66.5
Blend 4 63
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Journal of Polymers and the Environment (2020) 28:794–802
melting enthalpy, considering a full crystalline polymer.
For LDPE, ∆H0 have been 140 J g−1 [20], while for PP have
been used 209 J g−1 [24]. In the LDPE/PP blends, χc has
been calculated by considering the weight fraction (wt%) of
the components LDPE and PP.
Tensile tests were performed in equipment EMIC, model
DL 3000, using a load cell of 5 kN. Ten specimens measur-
ing 9.6 cm in length of each composition were tested with
deformation speed at 50 mm min−1, according to the stand-
ard practice ASTM D638 [21]. Impact tests were performed
according to ASTM D256 [22] at room temperature by the
Izod method using a XJU-22 Beam Impact Tester. Speci-
mens were injected in width of 12.5 mm, thickness of 3 mm
and length of 60.5 mm. A 2.75 Joules hammer was used to
test 10 specimens of each composition.
The melt flow rate (MFR) was determined following
the procedures stipulated by ASTM D1238 [25] in CEAST
plastometer, model 702100, using a load of 2.16 kg and a
temperature at 190 °C. To perform the tests, the material
was previously ground and dried. The MFR was obtained
from the arithmetic mean of ten specimens for each sample.
Fourier transform infrared (FTIR) spectroscopy was used
to identify functional groups and evaluating the chemical
changes in the materials. The spectra were determined in
the wavenumber range from 600 to 4500 cm−1 at 64 scans
and resolution at 4 cm−1, using a spectrometer SHIMADZU,
model IR PRESTIGE-21. The samples were obtained from
the injected specimens and the spectra were normalized from
the band at 1465 cm−1.
Results and Discussion
Thermal Analysis (TGA and DSC)
TGA and DSC curves of the materials are presented in
Figs. 1 and 2. Values related to these analyses are showed
in Table 2.
Thermal decomposition of LDPE waste is observed on
a temperature interval of 391 to 495 °C with a maximum
rate of weight loss (MRWL) at 470 °C. However, PP is less
thermically stable than LDPE, showing thermal decom-
position between 314 and 460 °C and MRWL at 435 °C
(Fig. 1a). The smaller thermal stability of PP is related to
Virgin PP content ZSM-5 content Ziegler–Natta Thermal
(wt%) (wt%) content (wt%) treatment
30 – – No
28.5 5 – No
28.5 5 – Yes
27 5 5 Yes
Journal of Polymers and the Environment (2020) 28:794–802 797

Fig. 1  TGA curves of the materials a PP and LDPE waste; b LDPE/PP blends (zoom); c LDPE/PP blends (full thermograms)

Fig. 2  DSC curves of the materials a PP and LDPE; b LDPE/PP blends

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Table 2  Thermal properties of Material Temperature of Thermal decomposi- Tm1 (°C) Tm2 (°C) Crystal-
the recycled LDPE/PP blends MRWL (°C) tion range (°C) linity
(%)

LDPE 470 391 495 125 – 76

PP 435 314 460 – 168 60
Blend1 464 380 495 124 163 63
Blend2 458 389 492 125 163 83
Blend3 468 408 488 124 163 55
Blend4 472 386 486 122 163 46

the presence of the methyl groups linked to the polymeric
chain, forming tertiary carbons in the chemical structure that
favor the formation of free radicals and thermal decomposi-
tion of the material [26]. Both LDPE waste and PP present
defined endothermic signals related to the melting at 125
and 168 °C, respectively (Fig. 2a). The shouder in endo-
thermic signals of the LDPE is attributed to the presence of
branching in their polymeric chains [27]. For LDPE waste
the crystallinity (χc) is 76%, while for PP is 60% (Table 2).
The LDPE/PP blend without catalyst or thermal treatment
(Blend 1) presents only one step of thermal decomposition
between 380 and 495 °C that lead to the total weight loss
(Fig. 1b). Thus, the thermal decomposition of the blend is
intermediate to the pure polymers. DSC curve for Blend 1
present two endothermic signals with no significant shift-
ing of temperature when compared to the individual LDPE
waste and PP (Fig. 2b), denoting immiscibility of the poly-
meric components in the blend. Considering the weight frac-
tion of the blend components and its partial crystallinity, the
overall crystallinity of the Blend 1 was 63%.
The incorporation of the ZSM-5 catalyst during material
processing by extrusion (Blend 2) causes a narrowing of
the thermal decomposition range of the material as well as
the decrease in temperature of maximum rate of weight loss
(MRWL) when compared to the Blend 1, shifting of 464 to
458 °C. This effect indicates the action of zeolite ZSM-5 as
a catalyst in the thermal decomposition mechanism of the
material. A residual weight of 5 wt% at high temperature
(700 °C) has been observed, corresponding to the amount
of zeolite ZSM-5 initially incorporated to the material that
shows the thermal stability of the zeolite ZSM-5 at referred
temperature (Fig. 1c). It is also verified a significant change
in the DSC curve profile of the Blend 2 with decrease of the
endothermic signal related to the PP phase and broadening
of the LDPE signal, which suggests the higher fragmentation
of the PP component and modification in LDPE chemical
structure that can be related, for example, to the copolymers
formation. The changes in endothermic signal related to the
LDPE cause a considerable increase in overall crystallinity
of the blend to 83%. However, this value may not be real
since the crystallinity calculation has been performed using
∆H0 of the LDPE for signal at 125 °C and the modifications
in the LDPE phase of the blend 2 can also cause enthalpy
changes.
In the blend containing zeolite ZSM-5 and submitted to
both extrusion processing and thermal treatment (Blend 3)
has been noted a higher narrowing of the thermal decom-
position range that occurs between 408 and 488 °C. The
temperature of MRWL is also increased to 468 °C. In DSC
signal related to the LDPE phase is noted the formation of
a shoulder, while the overall crystallinity has decreased to
55%. It is indicates that the treatment in the Blend 3 has
caused severe structural changes.
The presence of both zeolite ZSM-5 and Ziegler–Natta
catalysts in the thermically treated material (Blend 4) causes
mainly increase in the temperature of MRWL, arriving
472 °C, while the thermal decomposition range is verified
between 386 and 486 °C. For this blend, it was verified a
residual weight of around 8 wt% at 700 °C, denoting that a
fraction of Ziegler–Natta catalysts can be decomposed dur-
ing thermal treatment or in TGA analysis. A severe decreas-
ing of the endothermic signals of PP and LDPE waste is
also noted, leading to a crystallinity of 46%. Therefore, the
thermal treatment and the presence of zeolite ZSM-5 and
Ziegler–Natta catalysts is highly effective to cause structural
changes in LDPE/PP blends.
TGA and DSC have showed that both zeolite ZSM-5 and
Ziegler–Natta catalysts induce to changes on the thermal
properties of the LDPE/PP blends such as thermal stability
and melting enthalpy attributed to the components LDPE
waste and PP. These thermal changes should be related to
modifications in the polymeric structures that can involve
molecular fragmentation of the polymeric chains with sub-
sequent recombination in the form of copolymers LDPE-PP
and crosslink formation as well as degradation reactions.
Mechanical Properties
Mechanical testing have been carried out using materials
specimens produced by injection molding. Table 3 presents
the value of mechanical properties obtained by tensile and
impact testing.

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Journal of Polymers and the Environment (2020) 28:794–802 799

Table 3  Mechanical properties of the recycled blends results, foresee an increase in the material tenacity. However,
Material Tensile Young’s Elongation Impact resist- the behavior of the tensile strength and Young’s modulus
strength Modulus at break ance (kJ m−2) shows increase in the material hardness. Thus, the structural
(MPa) (MPa) (%) changes related to the crosslink formation and degradation
can be prevailing. The results of elongation at break and
LDPE waste 15.4 ± 0.2 90 ± 12 527 ± 8 8±1
impact resistance are illustrated in Fig. 4.
Blend 1 20.0 ± 0.5 168 ± 34 736 ± 14 12.0 ± 0.9
Both elongation at break and impact resistance present
Blend 2 17.0 ± 0.3 286 ± 10 98 ± 39 5.1 ± 0.3
decrease with the incorporation of the zeolite ZSM-5 and
Blend 3 13.0 ± 0.6 293 ± 8 7.2 ± 0.5 1.4 ± 0.1
thermal treatment. Elongation at break presents a drastic
Blend 4 15.0 ± 0.4 300 ± 8 10 ± 1 1.5 ± 0.3
decrease from 736 to 98% with the incorporation of the zeo-
lite ZSM-5 at 5 wt% (Blend 2). The thermal treatment on
this material lead to other decrease in elongation at break,
The incorporation of PP in LDPE waste (Blend 1) achieving 7% (Blend 3), while is not verified considerable
improves the mechanical performance of the material, changes with the additional presence of the Ziegler–Natta
increasing tensile strength, Young’s modulus, elongation at catalyst (Blend 4). For impact resistance, the presence of
break and impact resistance (Table 3). On the other hand, the zeolite ZSM-5 catalyst cause a decrease from 12 to 5 kJ m−2
presence of the catalysts ZSM-5 and Ziegler–Natta causes in the LDPE/PP blend (Blend 2), while the thermal treat-
changes on mechanical properties of the material. ment in presence of the zeolite ZSM-5 lead to the impact
Figure 3 presents a comparison between tensile strength resistance at 1.4 kJ m−2 (Blend 3). The additional presence
and Young’s modulus of the LDPE/PP blends. of Ziegler–Natta catalyst again causes insignificant change
There is a progressive decrease of tensile strength of the on impact resistance. These results shows the severe effects
blends with the presence of the zeolite ZSM-5 catalyst after on the mechanical properties of the LDPE/PP blends due to
thermomechanical processing (Blend 2) and thermome- the incorporation of the zeolite ZSM-5 catalyst in the mate-
chanical processing followed by thermal treatment (Blend rial. Elongation at break and impact resistance are properties
3), while in Blend 4, that contains both zeolite ZSM-5 and strongly affected by structural changes of the material such
Ziegler–Natta catalysts, there is not considerable property as crosslink formation and molar mass decrease, further evi-
change when compared to the Blend 3. dencing the hypothesis of occurrence of these modifications
Young’s modulus shows an inverse behavior than the ten- in the material.
sile strength, practically doubling in value when the zeolite
ZSM-5 catalyst is present in the Blend. The thermal treat- Melt Flow Rate (MFR)
ment and simultaneous presence of zeolite ZSM-5 and Zie-
gler–Natta catalyst causes a small and progressive increase Melt flow rate is directly dependent of the structural and
in Young’s modulus. Obviously, the changes verified in ten- molecular arrangement of the polymer and represents an
sile strength and Young’s modulus of the LDPE/PP blends important qualitative measure of the processability of the
are caused by action of the catalysts and thermal treatment material [28]. Figure 5 illustrates the results of MFR for the
on the chemical or physical structure of the material. LDPE/PP blends.
The decrease in crystallinity and possible copolymers
formation, which have been indicate by thermal analysis

Fig. 4  Elongation at break and impact resistance for the LDPE/PP

Fig. 3  Tensile strength and Young’s modulus for the LDPE/PP blends blends

13
800
Fig. 5  Melt flow rate for the LDPE/PP blends
LDPE/PP blend without catalysts or thermal treatment
(Blend 1) presents MFR at 0.98 ± 0.01 g 10 min−1. The
presence of zeolite ZSM-5 catalyst in Blend 2 lead to the
decrease in MFR to 0.65 ± 0.01 g 10 min−1. The increase of
the molar mass of the polymer causes respective decrease
in MFR. Thus, the hypothesis of crosslink formation veri-
fied in the results of mechanical properties and consequent
increase of molar mass of the polymer can be corroborated.
On the other hand, the Blend 3 and Blend 4 present increase
of MFR to 1.55 ± 0.01 and 2.48 ± 0.07 g 10 min−1, respec-
tively. For these materials, mainly for Blend 4, an intense
process of molecular fragmentation and consequent decrease
of molar mass can prevail.
Fourier‑Transform Infrared (FTIR)
FTIR analysis was used to evaluate the presence of func-
tional groups in the blends as well as to verify the chemical
changes that occurred in the materials as a function of the
catalysts and thermal treatment. The spectra of all materials
obtained by FTIR are shown in Fig. 6. For all blends, mainly
for Blend 1, characteristic bands of alkanes were observed
between 3000 and 2840 cm−1 (attributed to the symmetrical
and asymmetrical stretching of CH bonds), at approximately
1460 cm−1 (representing angular bending of CH groups) and
narrow bands around 720 cm−1 (related to the angular bend-
ing of CH). In addition, it is also noted bands at 1360 cm−1
(characteristic of the methyl groups).
In presence of zeolite ZSM-5 catalyst (Blend 2) appears
a double band around 1700 cm−1, changes in the profile of
the bands around 2900 cm−1 and the emergence of other
band at 670 cm−1. Bands at 1700 cm−1 are attributed to
carbonyl groups and denotes some oxidation of the poly-
meric material, while the modification in spectrum at 2900
and 670 cm−1 can be related to the chemical and struc-
tural changes that influence on the thermal, mechanical
13
Journal of Polymers and the Environment (2020) 28:794–802
Fig. 6  FTIR for the LDPE/PP blends
and rheological properties of the material as previously
discussed.
The thermal treatment in presence of the zeolite ZSM-5
(Blend 3) lead to decrease in band around 1700 cm−1 and
disappearance of the of the band at 670 cm−1. It is possible
that the thermal treatment can have caused the volatiliza-
tion of the compounds initially formed, which are responsi-
ble by respective bands in FTIR spectrum. Other important
change in FTIR of the Blend 3 is the decrease of the band at
1360 cm−1 that is related to the methyl groups of the poly-
propylene phase. Thus, the polypropylene should be prefer-
ably consumed during the process, causing the modification
on the material structure such as suggested from thermo-
gravimetric analysis results.
Drastic changes in FTIR spectrum of the material con-
taining both Ziegler–Natta and zeolite ZSM-5 catalysts are
noted after thermal treatment, mainly related to the intense
bands around 1700 cm−1 and at 3425 cm−1 attributed to the
carbonyl and hydroxyl groups, respectively. These bands
denote a high oxidation degree of the material and corrobo-
rate with high melt flow rate values due to the molecular
fragmentation and degradation of the material. According
to the results previously discussed, it is possible to suggest
the chemical changes that must happen within system when
the material is processed and thermally treated in presence
of the zeolite and Ziegler–Natta catalysts (Fig. 7).
Thus, the simple thermal processing by extrusion and
injection molding lead to the formation of LDPE/PP blend
(Blend 1). Additionally, when the thermal processing is car-
ried out in presence of zeolite ZSM-5 catalyst, copolymers
and crosslink of LDPE and PP chain can be formed, caus-
ing changes on the material properties. Some oxidation can
also occur in this process. The additional thermal treatment
(Blend 3) lead to an intensification of the chemical reactions,
Journal of Polymers and the Environment (2020) 28:794–802
Fig. 7  Action of the catalysts on chemical structure of the LDPE/PP blends
causing chain scission and molar mass decrease. The pres-
ence of both zeolite and Ziegler–Natta catalysts produces
additional and severe changes in the material that result in
intense chain scission and molecular oxidation.
Conclusions
The incorporation of zeolite ZSM-5 catalyst causes struc-
tural changes in the blends during thermomechanical pro-
cessing, which lead to changes in the crystallinity and ther-
mal stability of the material. The increase of the rigidity of
the material, accompanied by the decrease in the deforma-
tion and flow of the material in the molten state, indicates
that the structural changes must be related mainly to the
increase of molar mass due to molecular recombination with
formation of copolymers and crosslinks.
The thermal treatment of the polymer blends in the pres-
ence of both zeolite ZSM-5 and Ziegler–Natta catalysts
has caused severe changes in the properties of the mate-
rial, which includes abrupt decrease in deformation ability,
increased hardness and flow of the material in the molten
state, as well as unwanted reactions of oxidative degradation
of the polymer. Thus, even at low temperatures and reduced
treatment times in the presence of the catalysts, there is
already high fragmentation of the polymer chains.
In the conditions used for the study, the low intrin-
sic mobility of the polymer system in the molten state,
accompanied by the difficulty of dispersion of the catalysts
may have hindered molecular recombination reactions.
Thus, the conduction of studies under lower temperature
801
conditions and the use of mechanical shear could be an
alternative for the generation of recycled materials with
better properties.
The work showed that it is possible chemically to modify
the structure of polymer blends from the recycling process,
through the use of catalysts to generate materials with modi-
fied properties and that can be submitted to different types
of processing.
Acknowledgements The authors would like to thank the Fábrica Cari-
oca de Catalisadores and Valfilm Ltda for supplying the materials as
well as the Coordenação de Aperfeiçoamento de Pessoal de Nível
Superior-CAPES and Fundação de Amparo à Pesquisa do Estado de
São Paulo-FAPESP (Proc. 2017/05851-0) for their financial support.
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