Propylene-ethylene copolymers with improved melt strength and

resistance to discoloration

Lucia N. Schmidt 1, Jorge Guapacha 1,2, Dahiana X. Haure 1,4, Lidia M. Quinzani
1, Marcelo D. Failla 1,3

1 Planta Piloto de Ingeniería Química (PLAPIQUI), UNS-CONICET - Camino La Carrindanga km 7,

(8000) Bahía Blanca, Argentina.
2 Departamento de Ingeniería Química, UNS - Av. Alem 1253, (8000) Bahía Blanca, Argentina
3 Departamento de Ingeniería, UNS - Av. Alem 1253, (8000) Bahía Blanca, Argentina
4 Departamento de Física, UNS - Av. Alem 1253, (8000) Bahía Blanca, Argentina
Corresponding e-mail address: lschmidt@plapiqui.edu.ar

ABSTRACT
Propylene-ethylene copolymer (PEC) with improved melt strength and resistance to discoloration is
produced by reactive processing in two consecutive steps. In the first one, a low level of anhydride
groups is grafted onto a commercial random PEC (PECg). Then, branched PEC (PECb) is obtained by
reactive mixing PECg with m-xylylenediamine (XDA) and Basic Fuchsin (BF), which act as crosslinking
agents (CA). Both CA have primary amines in their molecular structure. Before being added to the
molten polymer, BF is dispersed/dissolved in XDA. Changes in molecular structure are confirmed with
FTIR analysis following the evolution of anhydride, amine and amide/imide groups. Rotational and
extensional rheology is used to analyze the flow dynamic of the system. All results confirm the existence
of branched structure in PECb, which presents significant strain hardening. Fade resistance of colored
materials has also been analyzed by submerging thin films in ethanol and measuring dye concentration
in the solvent. PECb displays good colorfastness.

Keywords: Propylene copolymers. Organic dye. Crosslinking. Fade resistance.

1. INTRODUCTION
Propylene-ethylene copolymers (PEC) have good impact strength and very good chemical and abrasion
resistance. For these reasons, PEC is widely used in various industries, like packaging, automotive,
construction, and textile (Jubinville et al., 2020). However, PEC, as all polyolefins, is difficult to dye due
to its high crystallinity and non-polar molecular structure. Different methods are used to provide
coloration to polyolefins, like modification by grafting of polar groups or blending with dyable polymers
and/or nanoparticles, plasma treatment, and mass coloration via pigmentation (Shamey, 2017; Elmaaty
et al., 2019; Kuo and Chen, 2021). Use of organic dyes has several advantages over pigments, however
most dies do not dissolve in polyolefins, giving place to blooming and surface deposition of color
(Mahmud-Ali et al., 2018; Kuo et al., 2018, 2021). This shortcoming may be overcome by chemically
linking dye and polymer molecules.
In addition, the linear molecular structure of PEC limits its application, mainly in those that involve
processing dominated by extensional flow. To improve the extensional properties of linear polymers, it
is necessary to modify their molecular structure by introducing long-chain branches (LCB). The
presence of LCB gives place to strain hardening behavior under elongational deformation (Guapacha
et al., 2018, 2020). Branching can be done by applying two-step reactive processing: grafting of
anhydride groups (AG) followed by modification with polyfunctional substances that act as crosslinking
agents (CA).
In this work, chromophore groups and LCBs are simultaneously incorporated in the molecular structure
of PEC that has been previously modified with maleic anhydride. For that, m-xylylenediamine (XDA)
and basic fuchsin (BF) are used as CA. XDA has already been used as crosslinker of PP (Guapacha et
al., 2020). Changes in molecular structure are verified combining FT-IR and rheological characterization,
while color fastness is analyzed by exposure of colored PECbs to ethanol.
2. EXPERIMENTAL
2.1 Materials
A PEC with 4 w/w% of ethylene was provided by Petroquímica Cuyo S.A. (Mw = 695 kg/mol; Mn = 215
kg/mol; 0 = ~300 kPa.s). The other substances used are: maleic anhydride (MA, YPF S.A), organic
peroxide 2,5-dimethyl-2,5-di(tert-butyl peroxy) hexane (DBPH, Akzo Nobel), m-xylylenediamine (XDA,
Sigma Aldrich) and Basic Fuchsin (BF, Oxoid Ltd).
2.2 Modification of PEC
In a first step, a low level of anhydride groups (AG) is grafted onto PEC. Functionalization is done by
reactive extrusion considering 1 w/w% of MA and 480 ppm of DBPH, which is used as radical initiator.
Initially, MA is dissolved in methylethylketone (MEK) and poured over PEC pellets, which are then mixed
and placed on a current of air for solvent removal. DBPH was also previously dissolved in MEK before
being added to the pellets. The impregnated pellets were fed to a single-screw extruder with a mixing
section (Göttfert) using a temperature profile of 160–190–200–200–160 °C from hopper to die and 1
kg/h of mass flow rate (Guapacha et al., 2020).
The grafted PEC was purified by Soxhlet extraction with MEK to remove unreacted MA. This material
(PECg) is the one to be used to synthesize PECb by reactive mixing in a Brabender Plastograph
equipped with cam-blades. Conditions used are 30 rpm for 20 min, nitrogen atmosphere and 190°C.
BF was dissolved/dispersed in XDA before being added to the molten polymer. Figure 1 schematizes
the expected crosslinking reactions. Amide/imide groups should appear after the modification of PPg
with XDA and BF.
Table 1 lists the CA concentrations used in this work. XDA contents were selected according to previous
works (Guapacha et al., 2018, 2020), and those of BF to keep the molar ratio XDA:BF about 1:1. Table
1 also shows the ID code selected for synthesized PECbs. Number in the code refer to w/w% of XDA
employed, while letters X and F refer to the CA used, XDA and BF, respectively.

Figure 1. Scheme of the main reactions for the formation of PECb.

Table 1. Concentration of XDA and BF used in the synthesis of branched PEC. Molar concentrations
refer to the molar content of anhydride groups in CPEg.
XDA BF XDA BF
PECb
[w/w%] [w/w%] [mol/molAG0] [mol/molAG0]
PX5 0.05 - 0.09 -
PX5-F 0.05 0.12 0.09 0.08
PX15 0.15 - 0.26 -
PX15-F 0.15 0.35 0.26 0.24
PX30 0.30 - 0.51 -
PX30-F 0.30 0.70 0.51 0.48
PX40 0.40 - 0.69 -
PX40-F 0.40 1.0 0.69 0.69
3. CHARACTERIZATION
Chemical changes introduced by functionalization and crosslinking were verified by FT-IR spectroscopy.
A Nicolet Nexus spectrometer was used from 400-4000 cm-1 with a resolution of 2 cm-1 averaging 100
scans. Spectra were recorded on 100 µm films that were prepared by compression molding at 190°C.
Linear viscoelasticity of all materials was determined using small-amplitude oscillatory shear flow in an
AR-G2 rheometer from TA Instruments equipped with 25 mm diameter parallel plates and nitrogen
atmosphere. The rheometer was operated under stress-controlled conditions. The samples, 25 mm
diameter disks with a thickness of 1.5 mm, were prepared by compression molding at 190°C. Dynamic
frequency sweeps (from 0.04 to 100 s-1) were performed at 180°C. Stress sweeps were previously
applied to all materials to select the stress for the frequency sweeps assuring operating in the linear
viscoelastic regime.
The extensional behavior of the polymers was determined in the same rheometer equipped with a
SER2-G testing universal platform by Xpansion Instrument. Rectangular samples of 18×10×0.7 mm
were prepared by compression molding at 190°C. The transient extensional viscosity, 𝜂𝐸+ (𝜀̇, 𝑡), was
measured at 180 °C under nitrogen atmosphere using elongation rates, 𝜀̇, between 0.01 and 0.3 s−1.
Migration of colorants was analyzed in colored PECb samples by submerging 10×30×0.1 mm strips in
10 mL of ethanol (solvent of BF) up to 24 hours in the dark. Strips and solvent were analyzed using UV
spectroscopy (T60UV-VIS system from PG Instruments). Concentration of BF was determined in
ethanol using a previously built calibration curve based on solutions of known concentrations of the
colorant. Color parameters of the films were measured in a NR110 Precision Colorimeter using the CIE-
L*a*b* scale. Measurements were taken by viewing Geometry of 8/d and light source D65. The values
of L* (lightness), a* (red-green color coordinate), and b* (yellow-blue color coordinate) of each sample
were reported averaging ten measurements.
4. RESULTS AND DISCUSSION
Figure 2 presents a photograph of 100 µm thick films of PECg, colored PECbs and PX40, the PECg
modified with the largest concentration of just XDA. They are about 8×14 mm in size. Specimens have
been placed on top of a white sheet. PECg has the typical translucence of polypropylene films. PX40,
on the other hand, has a light sienna coloration due to the presence of XDA. Samples of colored PECbs
display the typical purplish coloration of BF. They also show a translucent character that indicates that
BF is homogeneously distributed in the polymer.
Color parameters of the films are listed in Table 2. PECg and PX40 is characterized by large lightness
(L*). Colored PECbs display a value of L* that decreases with BF concentration. Parameters a* and b*
approach red and blue coloration as BF increases slightly affected by the presence of XDA.

PECg PX5-F PX15-F PX30-F PX40-F PX40

Figure 2. Films of PECg and colored PECbs photographed on top of a white sheet with 1mm thick
black line.

Table 2. Color parameters (L*, a* and b*) of films in Figure 2.

Polymer PECg PX5-F PX15-F PX30-F PX40-F PX40
L* 99,4 82,3 55,9 53,9 42,6 99,4
a* -4,1 7,1 25,0 27,9 21,6 -6,1
b* 1,7 -12,6 -33,3 -26,8 -22,5 2,2

Figure 3.a) displays the 1900-1500 cm-1 range of the IR spectra of original PEC and the grafted PECg.
The spectra of the grafted PEC as it comes from the extruder (PECg-E) is included. They have been
normalized with the area of the absorption band at 2720 cm− 1, which corresponds to the stretching of
methine groups, and arbitrarily shifted along the y-axis. In particular, stretching of carbonyls from AG of
PECg gives place to a band centered at about 1790 cm-1, not present in PEC. Additionally, a band
centered at 1725 cm-1 can be appreciated, which can be associated to carbonyls from carboxyl groups
resulting from partial hydrolysis of AGs. Both bands decrease after Soxhlet extraction, as it can be seen
comparing the spectra of PECg and PECg-E. This indicates that a large proportion of MA has grafted
to PEC. The area of these bands can be used to quantify the degree of grafting of PECg by using a
calibration curve previously determined (Riechert et al., 2019). In this way an AG content of 0.71 w/w%
was determined.

a)

b)

Figure 3. Region of the FTIR spectra of: a) PEC and grafted PEC before and after Soxhlet extraction,
and b) PECg and the two PECb synthesized with the largest CA concentration.

As an example of the structure characterization of PECbs, the spectra of PX40 and PX40-F are shown
in Figure 3.b in comparison with that of PECg. As it can be appreciated, PECbs do not display the
absorbance band of AG at 1790 cm−1. The intensity of this band actually decreases gradually with CA
concentration. Spectra of PECbs also display a band at 1709 cm-1 ascribed to imide groups that increase
gradually with CA content. Additionally, PX40-F displays a set of bands at 1550, 1585, 1630 and 1655
cm-1 that can be linked to the aromatic groups of BF. The intensity of these bands also change according
to dye concentration (not shown here). All together, these results confirm the reaction between AGs of
PECg with the amine groups of the CAs. The incorporation of dye onto the polymer is suggested by the
lesser intensity of the 1720 cm-1 band in PX40-F compared to PX40 (associated to acid groups) and the
existence of a small band at about 1500cm-1 that can be ascribed to carboxylate groups. These last
groups would appear after a reaction where dye and acid groups in the polymer participate.
Linear viscoelastic behavior of polymers is very sensitive to structural changes in the topology of
macromolecules. Figure 4 displays the elastic modulus (G) and the dynamic viscosity ( = G/) of
PECg and colored PECbs at 180°. The rheological behavior of PECg is in agreement with the expected
decrease in molecular weight after functionalization, being this is a process that produces
macromoleuclar scission. In fact, the zero shear-rate viscosity of PECg (0 = 4 kPa.s) is about 75 times
lower than that of PEC (0 = ~300 kPa.s), which indicates a decrease of the molecular weight of about
3 times.

a) b)

Figure 4. Elastic modulus (a) and dynamic viscosity (b) of PECg and colored PECbs at 180 ºC as a
function of frequency.
The modification with CAs give place to moduli that increase with CA concentration, mainly at low
frequencies. This result suggests an augment in molecular size and/or complexity after modification with
CAs. The new molecules present structures with higher terminal relaxation times than PECg.
A parameter that is very affected by the presence of LCBs is the elongational viscosity. Figure 5
presents, as an example, the transient elongational viscosity, 𝜂+
𝐸
(𝜀̇, 𝑡), of PECg and PX40-F at 180ºC
determined at several elongation rates, 𝜀̇. The colored polymer displays clear and significant strain
hardening. The same qualitative behavior was observed in all PECbs. This result confirms the presence
of LCBs in the synthesized PECbs.

Figure 5. Transient elongational viscosity of PECg and one of the colored PECbs at 180ºC and
different elongation rates.

Finally, as described in the Experimental Section, color fastness of PECbs was analyzed by submerging
films in ethanol (Et) during 6,18 and 24 h. Table 3 displays BF concentration measured in the solvent
after treatment. The determined concentrations are very low. In fact the values after 24 hours correspond
to about 0.1 % of the total dye that would be present in the films. According to this result, colored PECbs
display good resistance to discoloration. An additional information (not shown here) that backups this
observation is that none of the films showed changes in IR and UV-visible spectra after treatment.

Table 3. Dye concentration in ethanol after migration tests.

BF concentration (10− 4 mg/ml) in ethanol
6h 18h 24h
PX5-F n/d ~0,1 ~0,1
PX15-F ~0,4 ~0,7 1,1
PX30-F 1,4 1,5 2,3
PX40-F 1,7 1,8 2,9

5. CONCLUSIONS
The results obtained so far from FT-IR spectroscopy and rheological characterization indicates that the
reactive mixing of PECg with XDA and BF is effective in generating LCBs in the polymer. Moreover, the
high melt strength polymers display good color fastness after up to 25 hours of ethanol exposure. Further
studies of molecular structure characterization and rheological and color properties are underway.
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