Polymer Reviews

ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/lmsc20

A Review on Multifunctional Epoxy-Based Joncryl®

ADR Chain Extended Thermoplastics

Tobias Standau, Mohammadreza Nofar, Dominik Dörr, Holger Ruckdäschel

& Volker Altstädt

To cite this article: Tobias Standau, Mohammadreza Nofar, Dominik Dörr, Holger Ruckdäschel &
Volker Altstädt (2021): A Review on Multifunctional Epoxy-Based Joncryl® ADR Chain Extended
Thermoplastics, Polymer Reviews, DOI: 10.1080/15583724.2021.1918710

To link to this article: https://doi.org/10.1080/15583724.2021.1918710

Published online: 05 May 2021.

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POLYMER REVIEWS
https://doi.org/10.1080/15583724.2021.1918710

REVIEW

A Review on Multifunctional Epoxy-Based JoncrylV

R ADR

Chain Extended Thermoplastics

€rra, Holger Ruckd€aschela,
Tobias Standaua, Mohammadreza Nofarb,c, Dominik Do
and Volker Altst€adt a,d

a
Department of Polymer Engineering, University of Bayreuth, Bayreuth, Germany; bMetallurgical and
Materials Engineering, Department Faculty of Chemical and Metallurgical Engineering, Istanbul
Technical University, Maslak, Istanbul, Turkey; cPolymer Science and Technology Program, Institute of
Science and Technology, Istanbul Technical University, Maslak, Istanbul, Turkey; dBavarian Polymer
Institute and Bayreuth Institute of Macromolecular Research, University of Bayreuth, Bayreuth, Germany

ABSTRACT ARTICLE HISTORY

Reactive additives allow to adapt the properties of thermoplastic pol- Received 7 October 2020
ymers during processing and for their later use. The chemical modifi- Accepted 1 April 2021
cation using multifunctional epoxide styrene-acrylic chain extenders
KEYWORDS
(CE) in reactive processes is by now an established method to pre-
Chain extender; JoncrylV R;
vent degradation and to improve the process ability as well as the reactive extrusion; chemical
final properties of thermoplastics. One of the most common repre- modification; branching;
sentatives of these CE is better known under its trade name rheology; crystallization;
JoncrylV R . Since several years ago, JoncrylVR ADR owes an ever-grow- recycling; foaming; blending
ing importance in industry and academia. It can be applied as react-
ive melt modifier for numerous polymers, mainly polyesters, where it
largely affects the rheological properties and the thermal behavior.
This review focuses on the reactive behavior of JoncrylV R ADR as well

as the induced changes in the rheological behavior of the polymers

caused by this modification. The JoncrylV R ADR incorporation leads to

an increased shear viscosity, a higher melt strength and induces

strain hardening due to the formation of branched chains and/or
even crosslinking. The crystallization is also directly influenced by the
changed chain topology. Eventually, this review article extensively
addresses the benefits of using JoncrylV R for processing such as sta-

bilization, recycling, foaming, and polymer blending.

CONTACT Mohammadreza Nofar nofar@itu.edu.tr Metallurgical and Materials Engineering, Department Faculty
of Chemical and Metallurgical Engineering, Istanbul Technical University, Maslak, Istanbul, Turkey.
ß 2021 Taylor & Francis Group, LLC
2 T. STANDAU ET AL.

GRAPHICAL ABSTRACT

1. Introduction
1.1. General information about JoncrylV
R

A quite convenient method to individually adjust the rheological properties of poly-

mers for certain purposes is the reactive melt modification with appropriate chemical
agents. The most popular of these so-called chain extenders (CE) is the multifunc-
tional styrene–acrylic oligomeric chain extender sold under the trade name of
[1]
JoncrylVR ADR. It was first patented by the company Johnson Polymer LLC, which
was then acquired by BASF SE. Furthermore, masterbatches, which are Food and
Drug Administration (FDA) approved for food packaging, containing this CE are
available from Clariant AG[2] under the trade name “CESAV R -extend.” Originally the

chain extender JoncrylV ADR was supposed for the use in injection molding and
R

extrusion processes with virgin, post-industrial recycled and/or post-consumer

recycled polyesters such as polyethylene terephthalate (PET) and polybutylene tereph-
thalate (PBT), as well as polyamides (PA), bisphenol A-based polycarbonates (PC),
thermoplastic polyurethanes (TPU), polyoxymethylene (POM) and blends made out
of it to counteract degradation effects.[3,4] Yet, it is also widely used with other poly-
ester polymers such as polylactide (PLA) which is not vastly developed as a common
commodity polymeric product.[5]
 POLYMER REVIEWS 3

R —ADR/ADF/ADP/ADD
1.2. The different classes of JoncrylV
Interestingly, JoncrylVR is often used as a synonym for chain extenders; yet, the JoncrylV
R

portfolio offered by BASF SE consists not only out of some styrene-/acrylic-based

oligomers and is further subdivided in several classes applied in different functions.
Namely, there are flow modifiers (ADF), plasticizers (ADP), dispersants (ADD), and the
well-known reactive chain extenders (ADR). According to the supplier, one main inten-
tion of all these additives is the improvement of process ability and properties of
recycled polymers.[6] In Table 1, common representatives of JoncrylV R and their proper-

ties are given.

The ADF grades are flow additives mainly for styrene polymers [e.g., polystyrene
(PS), styrene-acrylonitrile resin (SAN), acrylonitrile butadiene styrene (ABS)]. The sup-
posed usage of these processing aids is to decrease the melt viscosity and thereby to
improve the melt flow under high additive loading such as flame retardants, reinforcing
agents, colorants or mineral fillers and simultaneously maintain the temperature resist-
ance and toughness. This enables faster molding in injection molding process that is
shorter cycle times, fewer ports, and thinner parts.[8]
A permanent plasticization can be achieved by JoncrylV R ADP grades. This allows the

reduction of filling pressure and times in the injection molding process. According to
the data sheet, it is supposed to be used in concentrations of 1–5 wt. % with PC and
PC/ABS blends. Properties that are affected are increased impact resistance, high surface
quality (i.e., higher gloss) and improved clarity.[9]
The acid-functional JoncrylV R ADD can enhance dispersion and compatibilization of

polar additives (e.g., glass fibers, mineral fillers, flame retardants, and inorganic pig-
ments) and consequently can improve their effects on the final part properties.[10]
Most works, however, focus on the use of the reactive and chain extending grades
JoncrylVR ADR, which is the subject of this review. Several grades of JoncrylV R ADR can

be found. The most common one is ADR 4368, which is by now upgraded as ADR
4468. According to the data sheet, it is supposed for the use with PA, PC, polyesters
like PET, PBT, PLA, and other polycondensation polymers such as TPU and POM. The
recommended dosage is between 0.1 and 1.5 wt. % depending on the process and poly-
mer. However, higher contents are also often reported in the literature. A peculiarity is
the grade ADR 3400, which is mentioned in the work of Tuna et al.,[7] as it is an
anhydride while all the other ADR grades are multifunctional epoxides.

1.3. Different grades of JoncrylV

R ADR

Figure 1 illustrates the general formula of the multifunctional epoxide styrene-acrylic

chain extender (i.e., JoncrylVR ADR). It is an oligomer with a low molecular weight (Mn

< 3,000, PDI > 3) and a number average functionality of fn > 4.[3]
Due to the multiple epoxy groups, the JoncrylV R ADR chain extenders are very react-

ive. These epoxy groups can react with hydroxyl and more efficiently with carboxyl
groups of different polymers.[11–13] While a bifunctional reactant would result in linear
chain extension,[14] JoncrylVR ADR is a multifunctional molecule (cf. Figure 1, the index

z can be up to 20) and a much wider variety of structures after reaction with the poly-
mer chains can occur. Hence, besides linear extension, branching is more likely to
 [6]
4

R -Types and their properties (based on data sheets and manufacturer brochure ).
Table 1. Commonly used JoncrylV
Molecular weight Glass transition Epoxy equivalent
Grade Class average Mw /g/mol Temperature /
C weight /g/mol Functionality (Efw) Supposed polymers
ADR 3400 Chain extender 10,000 N/A N/A N/A PA[7]
ADR 4300 Chain extender 5,500 56 445 12 (recycled) PET,
PETG,
PC, PA, PLA,
PBT, TPU
(and other
T. STANDAU ET AL.

polycondensation
polymers)
ADR 4318 Reactive plasticizer 7,500 40 1,900 4 Polyurethanes (PUR), silicones,
acrylics, butyl rubber,
polysulfide, epoxy, styrene-
butadiene, Polyvinyl
chloride (PVC), Neopren
ADR 4368 Chain extender 6,800 54 285 24 (recycled) PET,
ADR 4370 Chain extender 6,800 54 285 24 PETG,
ADR 4380 Chain extender 3,300 41 450 7 PC, PA, PLA,
ADR 4385 Chain extender 6,000 37 450 13 PBT, TPU
ADR 4468 Chain extender 7,250 59 310 24 (and other
ADR 4400 Chain extender 7,100 65 485 14 polycondensation
polymers)
ADF 1200 Flow aid 1,700 70 – – PS, HIPS, SAN, ABS, PC/
ABS, PVC
ADF 1300 Flow aid 2,800 56 – – PS, HIPS, SAN, ABS, PC,
3,000 PC/ABS
ADF 1350 Flow aid 4,000 54 – – PS, HIPS, SAN, ABS, PC, PC/
ABS, PBT, polyesters
ADP 1200 Plasticizer 1,500–2,000 70 – – PUR, silicones, acrylics, butyl
rubber, epoxy, styrene-
butadiene, PVC, Neopren
ADP 1230 Plasticizer 19,000 65 – – PUR, silicones, acrylics, epoxy,
styrene-butadiene, PVC,
ADD 3300 Dispersant 2,700 87 – – ABS, poly(methyl
ADD 3310 Dispersant 3,000 69 – – methacrylate) (PMMA), PS,
3,100 SAN, ABS, PBT, polyesters
 POLYMER REVIEWS 5

Figure 1. General chemical structure of multifunctional epoxy-based chain extender under the trade
[3]
name of JoncrylV
R ADR by BASF SE, based on Villalobos et al.

happen. Even cross-linking can happen. The extent of branching mainly depends on the
amount of reactive groups, that is, functionality and concentration of the CE.[12,15]
Currently, two different JoncrylVR ADR types are commonly purchased: ADR 4400

and ADR 4468. Both types were introduced in 2014, replacing the previous ADR 4300
and ADR 4368, respectively, which are often used in literature. According to the manu-
facturer, the upgraded types are particularly characterized by improved thermal stabil-
ity.[16] The main properties of the different ADR types are shown in Table 1[4,16,17].
Based on the stated data, the weight average functionality Efw of each type (number of
reactive epoxy groups) can be calculated according to Eq. (1)[18]:
Mw Joncryl
Efw ¼ Weight Average Functionality ¼ (1)
Epoxy Equivalent
For comparison reasons, the weight average functionality based on the weight average
molar mass and the epoxy equivalent weight are shown in Table 1, as these values can
be commonly found in the data sheets. Alternatively, it is possible to calculate the num-
ber average functionality Efn. This leads to lower values. For example JoncrylV R ADR

4368 has a weight average functionality Efw of around 24 but a number average func-
tionality Efn of around 9.[1,19]
Table 1 shows that the two currently available types (i.e., ADR 4400 and ADR 4468)
differ only in their functionality. The type ADR 4400 can be expected to result in a less
branched structure than ADR 4468 at the same concentrations because of its lower
functionality.

1.4. Alternatives
Generally, for the chemical modification in reactive processing, two kinds of reactions
can be distinguished as there are (i) reactive functional group reaction and (ii) free-rad-
ical reaction.[5] Just like the epoxy-based chain extender JoncrylV R ADR, isocyanates,

anhydrides, oxazolines, imides, and phosphites belong to the first group as they possess
reactive functional groups. Peroxides, which decompose and form reactive radicals,
belong to the second group. It should be mentioned that the chain structures obtained
6 T. STANDAU ET AL.

from free-radical reactions are less controlled due to the higher randomness of the reac-
tion compared to the functional group chain extender modification.[11,20]

1.4.1. Other epoxy-based chain extenders

Early works from Japon et al.[21–23] deal with multi-functional epoxies to improve the
melt properties of PET for foam extrusion prior JoncrylV R was established. In this con-

text tri-, tetra-, and octo-functional epoxies were investigated and it was concluded
among others that (i) the reaction of epoxy groups with carboxyl groups is more effi-
cient than with the hydroxyl groups and (ii) the tetra-functional epoxy increased the
rheological properties most efficiently. It could be shown that a mixture of linear, star-
shaped and randomly branched chains is formed, resulting in an increased elongational
viscosity and consequently improving the foamability.[22] Another study by Xanthos
et al.[24] compared anhydrides and epoxies with different functionalities as chemical
modifiers for PET, revealing that tri- and tetra-functional epoxies and pyromellitic
anhydride (PMDA) were the most reactive types. Hence, the molecular weight could be
increased and the molecular weight distribution was broadened. However, even the less
reactive modifiers investigated in this study were sufficient enough to allow successful
extrusion of low density foams.

1.5. Isocyanates
Isocyanates are very reactive species. Since they are at least bifunctional molecules like
MDI (4,4-methylene-diphenyl diisocyanate), HDI (1,6-hexamethylene diisocyanate), or
BDI (1,4-butane diisocyanate), they are suitable to be used either in suspension to mod-
ify prepolymers[25–27] or in the melt processing[28,29] to increase the molecular weight.
For instance, the NCO groups of diisocyantes are very reactive with PLA and PET end
groups.[30] Here, the isocyanate group can react with carboxyl and hydroxyl groups to
form ester-urethane linkages. However, the reactivity with the hydroxyl groups is
reported to be higher than that with the carboxyl groups.[31,32] The chemical modifica-
tion of recycled PET with several types of diisocyanates was reported by Torres et al.[32]
showing an increase in molecular weight and intrinsic viscosity. Also, the elongation at
break can be remarkably raised from 5 up to 300% converting PET from a brittle to a
very ductile material. Furthermore, it was claimed, that the diisocyanates are more
reactive with PETs end groups than diepoxides and anhydrides. It is also possible that
isocyanates can act as coupling agent in polymer blends.[33–35]

1.6. Anhydrides
Pyromellitic dianhydride (PMDA) can form reactive species by ring-opening reaction of
the anhydride group. Those can react, for example, with the hydroxyl group of PLA,
resulting in chain extension and consequently an increased melt strength.[36] However,
the reactivity with the hydroxyl group is reported to be rather low.[20] The efficiency of
PMDA can be increased by combination with other modifiers. Liu et al.[11,37] showed
that the addition of PMDA and triglycidyl isocyanurate (TGIC) can lead to different
chain structures such as linear chains, star-like structures with three arms and tree-like
 POLYMER REVIEWS 7

structures. Due to its hygroscopic character, PMDA tends to absorb water, which can
favor hydrolysis and consequently promote degradation during the processing.[38] An
early work of Incarnato et al.[39] it is reported that PET modified with PMDA in con-
centrations between 0.25 and 1 wt. % exhibit an obvious shear thinning behavior, a
reduced crystallinity and a significant increase of the melt strength which was attributed
to the increased molecular weight and broadened molecular weight distribution as well
as the occurring branching.
Furthermore, it was reported by Forsythe et al.[40] that the combination of PMDA
and the polyol pentaerythritol leads to an increased melt strengths and higher viscosities
due to the formation of long chain branches. H€arth et al.[41] conclude that PET reacting
with PMDA leads to a treelike branch-on-branch structure. Also strain hardening could
be shown as a result of PMDA modification. Similar findings were published in the
works of Kruse et al.[42,43] that report LCB-PET as a result of the modification with
PMDA exhibiting an increased dynamic viscosity and increased strain hardening behav-
ior with increased modifier concentration. It was furthermore observed that the zero
shear viscosity raised by two decades and the onset of the shear thinning got shifted to
lower shear rates.[42] The extent of long-chain branching is related to the concentration
of the end groups (i.e., hydroxyl and carboxyl groups, respectively) and the concentra-
tion of the PMDA.[43] Generally, a significant improvement of melt strength can be
attributed to the modification with PMDA already at concentrations below 1 wt. %
which is beneficial for the processability in processes involving any kind of stretching of
the material such as foaming[44] or blow molding.[39,45]
Another well-known anhydride is styrene maleic anhydride (SMA). It could be shown
in the work of G€ ottermann et al.[28] that for PLA a modification with SMA did not lead
to an increase in molecular weight but the use of JoncrylV R did as an increase of 50%

was noted.

1.7. Oxazolines
Oxazolines can react with carboxyl groups via ring-opening and form ester-amide link-
ages to achieve chain extension. Commonly, oxazolines are used with the oligomers in
solution reaction[46–48] but also melt processing was reported leading to an increased
molecular weight and higher melt strength.[28,36] Oxazolines can be effect chain extend-
ers for PET.[49] Inata et al.[50,51] made some comprehensive studies using oxazolines to
modify polyesters (i.e., PET and PBT). For PET a linear extension can be expected from
2,20 -Bis(2-oxazoline)[51] counteracting downgrading effects in recycled PET as thermal
and hydrolytic degradation can be partially compensated.[52]

1.8. Carbodiimides
Polycarbodiimides (PCDI) can react with hydroxyl and carboxyl groups[53] while the
reactivity with the latter is higher.[54,55] In the case of PLA, it can be used as a stabilizer
as it also reacts with moisture/water and consequently reduces hydrolysis.[54,56] In the
comparison with epoxide-based CE (i.e., JoncrylV R ADR 4368), in the study of Najafi
[57]
et al., it was shown that PCDI is less efficient to increase the molecular weight and
8 T. STANDAU ET AL.

viscosity of PLA. Furthermore, it was shown that by the modification with PCDI, only
linear extended chains can be achieved.

1.9. Phosphites
Phosphites are used as stabilizer for polyesters such as PLA[58,59] and PET[60] to coun-
teract degradation. Furthermore, it was reported that phosphites can react with the
hydroxyl and the carboxyl groups leading to chain extension.[61,62] For instance tris(-
nonyl-phenyl) phosphite (TNPP) can react with PLA in the melt, inducing chain relink-
ing but will not lead to the formation of branched structures.[40] Meng et al.[62,63]
showed that 2 wt. % of triphenylphosphite (TPP) can increase the molecular weight of
PLA by a factor of 1.5 and that even a higher concentration would have negative effect
as byproducts will favor degradation processes.
Chain extension effects in PET was proved for triphenyl phosphite (TPP) by
Cavalcanti et al..[64] However, simultaneously occurring chemical degradation (i.e., chain
scission) dominates at higher temperatures of 280 and 300
C, respectively. For PET
and PBT cross-linking was reported for the reaction with TPP.[65–67]
Bimestre et al.[68] published a study about the comparison of PMDA and the phos-
phite Irgafos 126 which reacts with the hydroxyl groups of PET, revealing similar chain
extending effects than the anhydride.

1.10. Peroxides
Peroxides can mainly lead to cross-linking of polymers.[69–71] The peroxide decomposes
under heat and forms primary radicals (RO). These primary radicals are highly reactive
species which cause hydrogen abstraction on the polymer chain. Consequently, polymer
macroradicals are formed. Two polymer macroradicals can recombine with each other
under the formation of a C-C bonding.[69,70] The degree of cross-linking depends on
the type and concentration of the peroxide and the radical formation but also on the
reaction conditions. During the melt processing, the balance of simultaneously happen-
ing chain combination (i.e., branching and/or cross-linking) and chain scission of the
polymer is guided by the processing conditions (temperature, residence time) and per-
oxide concentration.[70,72–74] Peroxides can also act as compatibilizers.[73,75,76] Generally,
it can be said that the free radical reaction of peroxides is much more random[11,20]
compared to the reaction of JoncrylV R.

2. Processing
2.1. Reactive processing
Polycondensates can be degraded during extrusion by hydrolysis, alcoholysis, and ther-
mal cleavage.[3] These reactions are even forced by the applied high processing tempera-
tures and shear forces.[77] Generally, during the recycling of polymers, the thermal load
and shear forces are even applied several times and will consequently lead to reduced
molecular weight, which results in a decrease of the viscosity[78] and hence a loss in
mechanical performance.[79] The main approach to overcome the property loss was the
 POLYMER REVIEWS 9

Figure 2. Schematic reaction mechanism of epoxy-based modifier with a degraded polymer.

According to Villalobos et al.[3] and Japon et al.[23]

solid-state polymerization process.[80] This established process has a huge disadvantage

compared to other techniques as it is very costly.[3] Hence, different more processes
were developed and nowadays the reactive extrusion is established as a low-cost, con-
tinuous, and diverse process for different polymers.[3] It is used for recycling, modifica-
tion, foaming or blending of polymers with chain extenders. The extrusion process can
be done even on single-screw extruders, but twin-screw extruders are more common to
be used.
The processing is significantly affected by the incorporation of JoncrylV R notable in

changed processing parameters, such as varied torques or temperatures. Yang et al.[81]

showed that the addition of JoncrylV R leads to an increased torque during the extrusion

process, which consequently results in higher shear forces and in turn can promote fur-
ther chain degradation.[82] Similar effects were also described by Cailloux et al.[15] while
using PLA. They mixed PLA with JoncrylV R ADR 4300 first showing an increase in tor-

que because of the starting reaction followed by a significant decrease as shear induced
degradation starts to take over.
Though, an investigation[83] with different concentrations of JoncrylV R ADR 4368

ranging from 0.5 up to 4 wt. % confirmed that a too high concentration would have
negative effects. While a viscosity increase was noted up to a concentration of 2 wt. %, a
significant decrease can be seen with a modification of 4 wt. %. Reason for this is that
molecular weight upbuilt resulted in higher torques and the occurring shear forces lead
to a dominating degradation.
Looking at torque rheometer experiments reveal that JoncrylV R modified PET shows a

reactive peak compared to untreated PET, which shows a decreasing torque curve as a
result of disentanglement and orientation in flow direction. Furthermore, with increas-
ing concentration of JoncrylV R the reactive peak is shifted upwards as the reaction rates

and molecular weights are believed to be increased as described in the work of Xiao
et al.[84] Similar was shown by Jaszkiewicz et al.[85] for JoncrylV
R modified PLA, adding


that the reaction is most efficient at temperatures above 200 C. By varying the melt
10 T. STANDAU ET AL.

Figure 3. Possible reaction between polyesters and epoxy groups of JoncrylV

R ADR: (a) End group

reaction and (b) reaction with a degraded chain. Adapted from Ref.[13].

temperature in torque rheometer experiments it was shown that the reactive peak
appears earlier and is more narrow at higher melt temperatures as the reaction kinetics
is promoted. From such experiments Arruda et al.[86] further noted, that PLA must
have a higher reactivity with JoncrylV R than PBAT has, as the torque increase is

more pronounced.
As stated before, the reactive parts of JoncrylV
R are the multiple epoxy-functional

groups, which can react with the functional groups of the polymers. Some proposed
reaction mechanisms during the reactive extrusion of JoncrylV
R ADR with different poly-

mers are shown more in detail in the following section.

2.2. Reaction mechanism

From the introduction and Table 1, it is clear that the reactive types of JoncrylV
R ADR

can be used in different polymers to induce an up build of the molecular weight. The
main application is the recycling of PET (cf. Section 5.2.) but it is also used in other
condensation thermoplastics. Villalobos et al.[3] schematically showed the general reac-
tion mechanism between a degraded polymer chain and the chain extender (cf.
Figure 2).
The semicircles mark the reactive chain ends of the degraded polymer, which react
with the epoxy groups (black dots) via epoxy ring-opening reaction.[13] Finally, a
 POLYMER REVIEWS 11

Figure 4. Reaction mechanism of JoncrylV

R ADR and PLA leading to a long chain branched structure.
[57,89]
Adapted from Ref. .

Figure 5. Possible reactions of the epoxy group and PA12. According to Ref.[92,94].
12 T. STANDAU ET AL.

Figure 6. Possible reaction of JoncrylV

R with ether- and ester-based TPUs according to Ref.
[89]
.

branched polymer with increased molecular weight is achieved. Generally, the reaction
of the epoxy groups can be with the carboxyl- and the hydroxyl group as described by
Japon et al.[23]
A more detailed investigation was done by Ghanbari et al.[87] During the extrusion of
PET, 1 wt. % JoncrylV R was added, which was totally consumed according to FTIR meas-
[38]
urements. Here the amount of JoncrylV R should be considered as Meng et al. showed
that the system can still be reactive after compounding with higher concentrations. The
consumption of epoxy groups is traced back to transesterification reactions with both
carboxyl and hydroxyl end groups of the PET. This reaction built new hydroxyl groups,
which can react with other epoxy groups.[88] Different researchers proposed that the
reaction between the PET carboxyl end group is more favorable than with hydroxyl end
groups.[3,88] Al-Itry et al.[13] predicted the reaction between polyesters and epoxy func-
tions in general, which is shown in Figure 3.
Besides the usage during the recycling of PET, JoncrylV R is used to increase both the

molecular weight and the melt strength of other polymers. One of the most used poly-
[57]
mers in combination with JoncrylV R is PLA. Najafi et al. investigated the reaction
between PLA and JoncrylV R and was able to transfer the results made for PET to PLA

(cf. Figure 4).

After the reaction a long chain branched PLA is achieved, which was confirmed by
other researchers.[89–91] Najafi et al.[57] noted a decreased zero-shear viscosity of a PLA
 POLYMER REVIEWS 13

Figure 7. (a) Viscosity of PLA mixed at different temperatures with 0.5 wt. % JoncrylV
R and (b)
[38]
Viscosity of PLA mixed with different concentrations of JoncrylV
R.

with 2 wt. % JoncrylV R in comparison to the PLA with 1 wt. % JoncrylV R . This was

explained possibly due to shifted condensation equilibrium by the reaction of hydroxyl

groups with the chain extender. In order to balance the system, the decomposition of
ester bonds in the backbone occurs and new hydroxyl groups are built, thus reducing
the molecular weight of the polymer. It can be assumed that there is an optimum con-
centration of JoncrylV R for every polymer. This observation was also confirmed
for PBT.[83]
JoncrylVR is also used in PAs. The multifunctional epoxy can possibly react with the

carboxyl group (cf. Figure 5(a)), amine groups (cf. Figure 5(b,c)), and imide groups
(after coupling reaction between amine and epoxy) in a PA.[92] Though, with a high
amounts of chain extender cross-linking is induced.[92,93]
Depending on the used PA type (e.g., PA12 or PA66) and therefore the degree of
functional groups, the branching density as well as the tendency of cross-linking is vary-
ing. D€ orr et al.[94] showed that the tendency of cross-linking of a PA12 with 5 wt. %
JoncrylV R ADR 4468 depends on the test temperature. Even at 250
C, it takes about

30 minutes until full cross-linking occurs.

Kahraman et al.[89] investigated the reactivity of JoncrylV R ADR 4468 with ether- and

ester-based TPU. It was shown that the ester-based TPU could better react with
JoncrylV R due to the higher reactivity of CE with the carboxylic acid end groups in the

ester-based TPU than that with the hydroxyl end groups in the ether-based TPU. The
possible reaction mechanism of both ether- and ester-based TPUs are depicted in
Figure 6.
Moreover, the reaction kinetics was investigated by different researchers. Corre
et al.[12] showed that the JoncrylV R does not react with itself at temperatures below

250
C. More detailed investigations were performed by Meng et al.[38] As shown in

Figure 7(a), the processing temperature has a huge influence. It is clearly recognizable
that the reactivity of JoncrylV R increases significantly with rising temperature most likely

due to the increased molecular kinetics that could facilitate the chain reaction.
Figure 7(b) shows the influence of the concentration and how the complex viscosity
of PLA could be enhanced with up to only 0.5 wt. % JoncrylV R after melt processing
14 T. STANDAU ET AL.

Figure 8. MFR values of r-PET samples without and with JoncrylV

R (here denoted as CE).
[98]

using a twin-screw extruder. Noteworthy, already a small amount of 0.1 wt. % increased
the viscosity of the polymer melt. This suggests that the reactivity and finally, the degree
of branching or molecular weight can be controlled by the concentration.
It can be concluded that JoncrylV R is highly reactive with different polymers and is

mainly used for polyesters. The reaction of a polymer with JoncrylV R leads to an increase

in molecular weight and both, the reactivity itself and the final polymer topology can be
analyzed through rheological measurements. This topic is discussed in the next section.

3. Rheological properties
3.1. Shear and elongational rheology
In order to improve the melt strength and the viscoelastic properties of polymers such as
PLA, PET, PBT, and PA, series of studies have been conducted to investigate their rheo-
logical properties affected by the chain extender JoncrylV R ; specifically, with the grade

ADR 4368. Noteworthy, not much amount of JoncrylV R is required to reach the desired

enhanced rheological properties as the studies reveal that the addition of only less than
1 wt. % JoncrylVR could dramatically enhance the melt properties of polymers and mostly

polyesters. Since the concentration of gel content within the cross-linked polymer is
dependent on the amount of chain extender, with the increase in JoncrylV R content, the

gel-like behavior and elongational viscosity of the cross-linked polymer would increase
due to the increased molecular weight and broader molecular weight distribution.[95]
However, it has been reported that the addition of JoncrylV R beyond 1.5 wt. % could

change the structure of polymer toward the sol–gel transition point.[84] The use of
JoncrylVR as a chain extender and chain branching additive could also improve the shear

thinning behavior of the polymers. Therefore, the Newtonian behavior of the polymers
originated from their low melt strength would be shifted toward more non-Newtonian.
 POLYMER REVIEWS 15

Figure 9. Shear and elongational rheological properties of PET with JoncrylV

R (here denoted as J-CE)

and PMDA.[81]

This behavior is indeed due to the increased molecular entanglement of the branched
structure. Thereby, the increase in shear rate could disentangle these branched molecules
more severely and cause shear thinning behavior. Such enhancements of shear thinning
behavior could eventually significantly improve the process ability of the noted polymers.
The enhanced melt strength and viscoelastic features could also lead to the improvements
of the foam ability of the noted polymers as the increased melt strength would hinder the
cell coalescence and cell wall rupture.[96,97]
It should be noted that during rheological experiments, the polymers should be ther-
mally stable at the testing temperature to minimize the thermal degradation effect on
the rheological behavior. Such thermal degradation sensitivity more severely exists in
polymers such as PLA and PET. It has been depicted that, thermal stability of PLA
improves when the testing temperature decreases. On the other hand, PBAT, which is
known as a thermally stable polymer, could also become thermally unstable when the
frequency sweep rheological testing temperature increases up to 200
C. Note that such
testing temperature is too high beyond the melting temperature of PBAT (120
C). In
this context, the use of JoncrylVR could meanwhile improve the thermal stability of poly-

mers that are sensitive to thermal degradation.[13,86]

16 T. STANDAU ET AL.

Figure 10. Frequency sweeps of processed PBT with and without JoncrylV
R (here denoted as CE)

at 250
C.[83]

In this context, the use of JoncrylV

R as a chain extender has also been observed to be a

promising solution to enhance the rheological properties of recycled polyesters and

thereby their process ability and shape ability. Figure 8 shows how the melt flow rate
(MFR) of recycled PET (r-PET) could be enhanced with the addition of up to 0.8 wt. %
JoncrylVR ADR 4368. As observed, PET is highly sensitive to thermal degradation and the

melt processing through the extruder could cause the molecular degradation of r-PET. In
this context, the addition of 0.25 wt. % JoncrylVR could compensate such degradation and
[98]
further JoncrylVR addition could noticeably decrease the MFR of the r-PET samples.

Although the majority of the studies have shown that JoncrylV R seems to be one of

the most efficient chain modifiers to generate branched structures, Yang et al.[81]
revealed that PMDA could similarly enhance the rheological properties of PET as both
JoncrylVR and PMDA could react with PET chains and could cause the formation of

branched structure. It should, however, be kept in mind that the molecular weight of
PMDA used in this study was much smaller than that of the used JoncrylV R . While the

weight-average molar mass of the used JoncrylV was 6800 g/mol, that of PMDA was
R

around 218 g/mol. The much lower molecular weight of PMDA could significantly
enhance its reactivity with the PET molecules and that could be why PMDA also
seemed to be as highly reactive as JoncrylV R . Figure 9 reveals that the incorporation of

JoncrylVR ADR 4368 and PMDA up to, respectively, 1.0 and 0.5 wt. % could dramatically

improve the complex viscosity, shear thinning, melt strength and strain hardening of
PET. Figure 9 also clearly shows that the increase in JoncrylV R content dramatically

enhances the elongational viscosity and the strain hardening behavior of the PET sam-
ples which are crucial parameters in polymer processing.
The steady and dynamic shear rheological properties of PBT with JoncrylV R has also

been explored in few studies and severe shear thinning behavior has been reported with
 POLYMER REVIEWS 17

Figure 11. Complex viscosity vs. time and frequency of PA6 and PA6-1 wt. % JoncrylV
R (here denoted

as JC).[10,100]

[3,83]
the increase in the JoncrylV R content. Figure 10 shows the small amplitude oscilla-
[83]
tory shear rheological experiments of PBT with JoncrylV R ADR 4368. It has been
reported that the shear thinning behavior of the PBT becomes more dominant when
using JoncrylVR and the viscosity of the PBT dramatically enhances specifically at low

frequencies when using JoncrylV R up to 2 wt. %.

Similar improvements in the rheological properties have also been reported when PA
[7,99]
was melt mixed with JoncrylV R. Figure 11 illustrates the complex viscosity versus
[7,99]
time and frequency for PA6 with JoncrylV R ADR 4368. Tuna et al. illustrated that
processing reduced the complex viscosity of PA6 due to its thermal and mechanical
degradation. This reduction was more serious when the processing temperature
increased from 260 to 300
C due to the more severe thermal degradation. The increase
in screw speed also further expedited the mechanical and thermal degradation of PA6.
When mixed with 1 wt. % JoncrylV R , they showed that the increase in processing tem-


perature from 260 to 300 C was not very effective in chain extension of PA6 molecules
whereas the decrease in screw speed from 200 to 100 rpm at processing temperature of
260
C provided more time for the chain extension between the PA6 and JoncrylV R mol-

ecules. Thereby, higher complex viscosity and shear thinning behavior was observed in
frequency sweep experiments after such processing. In samples prepared at screw speed
of 200 rpm, the unreacted JoncrylV R molecules have the potential to continue the chain

extension with the PA6 molecules and hence the reaction could continue during the
time sweep experiments. As seen in Figure 11, the complex viscosity increased over
time due to such chain extension continuation.
As depicted, although the JoncrylV R has high reactivity with polyesters and PA, the

processing parameters such as processing temperature, screw speed, and processing time
could play a determinative role on chain branching and hence enhancements in rheo-
logical properties and process ability of polyesters and PA.
One of the polyesters that has extensively been explored with JoncrylV R is PLA. JoncrylV R

ADR 4368 has been demonstrated as the most effective chain extender that does not only
improve the viscoelastic and rheological properties of PLA[96] but could also improve
the PLAs slow crystallization rate.[100–102] The high reactivity and the chain extension
between the JoncrylVR molecule and PLA chains were schematically shown in Figure 4.
18 T. STANDAU ET AL.

Figure 12. Elongation viscosity of (a) neat PLA at 170
C and branched PLAs at 180
C with (b)
[106]
0.4 wt. % and (c) 0.7 wt. % JoncrylV
R while using different strain rates.

JoncrylVR ADR 4368 could provide significant improvements in shear thinning, zero

shear viscosity, melt elasticity, storage modulus, and melt strength of PLA[96] while
inducing longer relaxation time in the terminal zone for branched PLA compared to
the linear PLA.[103] The efficiency of chain extension and branching of PLA with
JoncrylV R ADR 4368 has been demonstrated in several studies. Due to its much higher

reactivity, JoncrylVR could even more effectively cause the chain extension and branching

of PLA than other modifiers and chain extenders such as PMDA, HDI, PCDI, TNPP,
trimethylolpropane tris(2-methyl-1-aziridinepropionate) (TTMAP), and
TGIC.[20,38,57,104,105]
Several studies have also revealed that the addition of JoncrylV R ADR 4368 could also

significantly increase the elongation viscosity of PLA with remarkable strain hardening
behavior.[105,106] Such enhancements could thereby improve the melt strength, process
ability, and also the foam ability of PLA.[106] Figure 12 illustrates how the addition of
0.4 and 0.7 wt. % of JoncrylV R ADR 4368 could induce the strain hardening and enhance

the elongation viscosity of PLA at different strain rates.

Cailloux et al.[15,107] has also illustrated that using JoncrylV R ADR 4300 F could
[108]
enhance the melt rheological properties of PLA. Eslami et al. also melt processed
PLA with up to 2 wt. % of CESAV R -extend and showed that the neat PLA with CESAV R-

extend exhibits strong strain hardening behavior although long processing time seemed
to be required to have the chain extender be fully reacted with PLA. Figure 13 shows
the extensional viscosity behavior of PLA with CESAV R -extend after processing in an
 POLYMER REVIEWS 19

Figure 13. Elongation viscosity values of PLA with 2 wt. % CESAV

R -extend at various mixing times.
[109]

Figure 14. Dynamic shear viscosity behavior of semi crystalline PLA (scPLA) and amorphous
[89]
PLA(aPLA) with 0, 0.5, and 1.0 wt. % JoncrylV
R (here denoted as CE).
20 T. STANDAU ET AL.

Figure 15. Complex viscosity changes versus frequency of ether- and ester-based TPUs with JoncrylV
R

ADR4368 (here denoted as CE).[89]

internal mixer at various mixing times. As seen, it took almost 20 min to have the chain
extender be reacted with PLA as the strain hardening and elongation viscosity were dra-
matically enhanced when the processing time was over 10 min.[108]
Recently, Kahraman et al.[89] depicted that while the use of JoncrylV
R ADR 4368 could

highly react with two different grades of PLA with similar molecular weights that pos-
sessed various D-lactic acid contents, the semi crystalline one with low D-content of
0.5 mol % (scPLA) seemed to be slightly higher reactive with JoncrylVR than the amorph-

ous PLA grade with high D-content of around 12 mol% (aPLA). As Figure 14 shows,
the addition of JoncrylVR to both neat PLAs dramatically increased the complex viscosity

values throughout the whole frequency range and more dramatically at low frequencies
due to the formation of branched structures. However, although the reactivity of
JoncrylVR with PLA and the enhancements in the viscoelastic properties were relatively

similar in both PLAs, scPLA seemed to be reacted slightly more effectively with
JoncrylVR . This could be due to the possible higher molecular regularities of the scPLA

with much lower D-lactic acid content, which could have better interacted with the
JoncrylVR molecules during the melt mixing.

While JoncrylV R has been revealed to be highly reactive with polyesters and PA, the

reactivity of JoncrylVR ADR 4368 with ether-based and ester-based TPUs have recently

been reported[89] (cf. 2-2- Reaction mechanism). According to the small amplitude
oscillatory shear rheological experiments shown in Figure 15, JoncrylV R was not very

reactive with the TPU samples as is with PLA shown in Figure 14. The rheological
results of TPU samples with JoncrylV R (Figure 15) showed that the complex viscosity

upturn at low frequencies could mainly be observed in the ester-based TPU with the
JoncrylVR addition. In ether-based TPU with JoncrylV R , however, only a negligible

increase was observed in complex viscosity values. As seen, the reactivity of JoncrylV R

with ester-based TPU was somewhat better than that with the ether-based TPU as the
reactivity of JoncrylV
R with the carboxylic acid end groups in ester-based TPU could be
 POLYMER REVIEWS 21

Figure 16. Sketch of capillary rheometer and Rheotens apparatus to measure the melt strength.

higher than that with the hydroxyl end groups in ether-based TPU. The possible
reactivity of JoncrylV
R with end groups of ether- and ester-based TPUs were schematic-

ally shown in Figure 6.[89]

Therefore, it could be concluded that while JoncrylV R is highly reactive with mainly

polyesters, and while the processing parameters such as processing temperature and
time could play important roles on the enhancements of chain extension of the poly-
mers with the JoncrylV R (Figures 11 and 13), the molecular configuration such as como-

nomer content (Figure 14) and the type of the reactive end groups of the polymers
(Figure 15) could also identify the reactivity of JoncrylVR with polymer chains. These

could, thereby, differently affect the final rheological and viscoelastic properties and
hence the process ability and the final properties of the chain extended poly-
meric products.

3.2. Determination of melt strength—Rheotens

Aside from the above-mentioned rheological methods, Rheotens is another—less often
performed—method to gain knowledge of the melt behavior under strain forces. The
measurement is carried out with a capillary rheometer and a special Rheotens apparatus
fixed underneath the die of the rheometer as shown in Figure 16. The pushed out melt
strand is pulled down from the die by two accelerated, counter-rotating pairs of wheels
while the draw-down force is measured simultaneously. Due to the acceleration of the
wheels the draw-down force increases steadily; until the strand ruptures. This method
mainly allows statements on the draw ability and melt strength of a polymer melt.
Mainly the latter is an important factor to evaluate the process ability in processes that
involve any kind of stretching of the melt such as blow molding (films) or foaming.[109]
Yet, it is stated for many polyesters that they owe a rather low melt strength making
them unfavorable for these processes and the chemical modification to enhance their
molecular weight and change the chain topology is a way to overcome this issue. It is
22 T. STANDAU ET AL.

Table 2. Overview of publications that quantify the melt strength.

Polymer Chem. modifier Process Year [reference]
PLA Peroxides Reactive extrusion 2012[109]
PLA Luperox, lauroyl peroxide, PMDA, oxazoline Batch foaming 2012[113]
PLA CESAVR- Reactive extrusion / batch foaming 2013[114]
extend BL 10069 N
PLA JoncrylV
R ADR 4368, Foam extrusion 2019[115]
Dicumyl peroxide
PLA None Batch foaming 2020[116]
PLA POSS Batch foaming 2020[117]
PA Anhydride – 2009[118]
PA None Melt spinning 2015[119]
PBT JoncrylV
R ADR 4468 Bead foaming 2018[83]
PET PMDA Reactive extrusion 2006[40]
PET JoncrylV
R ADR 4380 Recycling 2014[95]
PET JoncrylV
R ADR 4368, PMDA Film blowing 2020[120]

plausible that longer and especially chains that are non-linear (i.e., short- or long-chain
branched or even cross-linked) possess a higher melt strength as they tend to entangle
more easily resulting in a higher resistance against the stretching forces that results in
higher melt strength.
Early and fundamental works including Rheotens experiments were carried out by
Wagner et al.,[110] Lin et al.,[111] and R€atzsch,[112] mainly on polyolefins (i.e., LDPE,
HDPE, and PP) revealing that higher molecular weights and branching leads to
increased drawability and melt strength.
Though, it is interesting, in literature melt strength is often mentioned as a key factor
for foaming, melt spinning, and blow film molding, however, it is rarely measured as
the Rheotens devices are not widely used and consequently not many results are pub-
lished. Only few studies that quantify the melt strength of such polymers that can be
modified with JoncrylV R were found as summarized in Table 2.

The work of Dean et al.[109] clearly reveals that increased chain length and the
branching due to the chemical modification (i.e., lauroyl peroxide) can lead to a three-
fold increase in melt strength of PLA. A further study of this group[113] compared sev-
eral chemical modifiers such as anhydride, peroxide and oxazoline regarding the impact
on the melt strength and the expand ability in batch foam experiments. They revealed
that the cell structure becomes more uniform and cell density increases with increasing
melt strength. This was while the foaming window was also broadened.
For the JoncrylV R chain extender, it was shown that 1 wt. % concentration can signifi-

cantly increase the molecular weight and consequently the melt strength gets higher
resulting in much finer foam structure and higher compression strength of extrusion
foams.[115] Liu et al.[117] used POSS (octa(epoxycyclohexyl) polyhedral oligomeric silses-
quioxanes) with an epoxy equivalent of 177 from Hybrid Plastics to chain extend PLA/
CNT composites. Here it was shown that with increasing POSS/CNT concentration, the
melt strength and the draw ability could be increased resulting in batch foams with
higher expansion ratios and very homogeneous fine cells.
Polyamides were barely investigated by Rheotens measurement.[118,119] The work of
Sailer et al.[118] reveals the very low melt strength of PA 6 and that it can be increased
by the use of styrene- acrylonitrile maleic anhydride (SANMA). However, even though
it was shown above that PA can efficiently be modified with JoncrylV R there is currently

no scientific work with Rheotens results published.

 POLYMER REVIEWS 23

Figure 17. Cooling thermograms of PLA grades with various branching degrees (JoncrylV
R is denoted

as CE here).[101]

Makkam et al. investigated the influence of JoncrylV R ADR 4380 on the melt behavior

of recycled PET. While the melt strength of recycled PET is too low to be measured, it
can be increased by the addition of 0.3 wt. % CE. With CE concentrations of 0.6 and
0.9 wt. % the melt strength of recycled PET exceeds the melt strength of virgin PET.
The work of H€arth et al.[120,121] compared JoncrylV R ADR 4368 and PMDA to improve

the melt properties to allow film blowing, showing that both modifiers are able to
increase the melt strength at low concentrations of 0.1 up to 0.4 wt. % but that PMDA
is more efficient in terms of increasing melt strength and drawability in the Rheotens
experiment. Gel formation is named as reason for the lesser drawability of the JoncrylV R

modified PET and increases with the concentration of JoncrylV R . However, the modifica-

tion with JoncrylV R was more efficient to create a branched structure. It was found that

for the film blowing the JoncrylV R induced molar mass increase, the broadened molar

mass distribution, and the formation of long-chain branches were beneficial for the pro-
cess as (i) the extrusion pressure is reduced due to the shear thinning, (ii) the bubble
stability is improved and (iii) the film thickness stays more uniform.
It can be concluded that the few works that quantify the melt strength of neat and
chemically modified polymers clearly prove the fact that an increased melt strength is
beneficial for (i) recycling as the melt properties can be maintained like the virgin
material, (ii) blow molding as the film uniformity gets improved, and (iii) foaming as it
results in lower densities, finer cells and broader processing windows. This will be fur-
ther discussed more in details in Section 5.3.

4. Crystallization behavior
Generally, chain extension or chain branching hinders the molecular mobility and
increases the molecular entanglement in thermoplastic polymers. Hence, such increased
24 T. STANDAU ET AL.

Figure 18. Isothermal melt crystallization of linear and branched (with 0.7% CE) PLAs at various tem-
peratures (a, b) and the crystallization half-time and degree of crystallinity of the isothermally treated
[101]
PLAs with various branching degrees (c,d) (JoncrylV R is denoted as CE here).

molecular entanglement reduces the crystallization rate, the degree of crystallinity, the
crystallite size, and closed packing density of the formed crystals. Nevertheless, despite
what theoretically is expected, in thermoplastic polymers such as PLA and PET that pos-
sess slow crystallization kinetics, the induction of branched structure when using JoncrylV R

has shown improvements in their crystallization rate. This has been demonstrated when
using JoncrylV R up to an optimum content beyond which the hindrance of the molecular

mobility would suppress the crystallization. In PLA with intrinsically slow crystallization, it
has been illustrated that the use of up to less than 1.0 wt. % JoncrylV R ADR 4368 could

expedite both the melt and cold crystallization of PLA. This has been elucidated as the
branched points could behave as crystal nucleating sites in PLA. Figure 17 shows the cool-
ing curves of a PLA with 4.5 mol % D-lactic acid content with and without JoncrylV R at the

cooling rate of 2
C/min. As shown, the melt crystallization rate and the degree of crystal-
linity increased dramatically with the use of 0.35 and 0.70 wt. % of JoncrylV R . The further

increase in degree of branching would, however, hinder the molecular mobility and hence
the branching could suppress the crystallization of PLA.[100–102]
Figure 18(a,b) also compares the isothermal melt crystallization of the linear PLA and
branched PLA with 0.70 wt. % JoncrylV R at various temperatures. It is shown how branch-

ing expedited the isothermal crystallization of PLA at a wider isothermal crystallization

range. The crystallization half-time and the degree of crystallinity of the isothermally
 POLYMER REVIEWS 25

Figure 19. Normalized complex viscosity, gr, of (a) PLA 2003 D and (b) PLA 3001 D with various con-
tents of JoncrylVR prepared using different strategies, as a function of time at 130
C (The S1 and S2

in the Figure is related to the different preparation strategies).[123]

Figure 20. Polarized optical micrographs of crystal morphologies of (a) a linear PLA 3001 D and (b)
long chain branched PLA 3001 D (LCBPLA) under quiescent conditions at 130
C.[123]

treated PLA samples without and with the use of 0.35 and 0.70 wt. % of JoncrylV R are also

revealed in Figure 18(c,d). It is obvious that the isothermal melt crystallization occurred
much faster in the branched PLA with 0.70 wt. % JoncrylV R . The critical temperature

(Tcritical) at which the crystallization is the fastest in almost all PLA grades is similarly
around 105–110
C although the isothermal temperature range within which the crystal-
[100,101]
lization could be accomplished is wider in PLA grades with JoncrylV R.

The shear induced crystallization behavior of linear and branched PLA grades when
using JoncrylV R has demonstrated that the use of JoncrylV R below 1 wt. % could further
[103,122,123]
expedite the crystallization when exposed to shear flows. Figure 19 shows the
shear induced crystallization of two different PLA grades, i.e., 2003 D and 3001 D with D-
contents of, respectively, 4.5 and 1.5 mol%, without and with 0.4 and 0.7 wt. % JoncrylV R

ADR 4368. As seen, the induction of branching in PLA dramatically enhanced the shear
induced crystallization even in PLA 2003 D that possesses a very slow crystallization rate.
26 T. STANDAU ET AL.

Figure 21. Cooling thermograms of r-PET grades with various branching degrees.[98]

According to what has been discussed, it is seen that the slow crystallization of PLA
could noticeably be improved when using certain content of JoncrylV R as chain extender.

Figure 20 shows that the spherulitic crystal nucleation in PLA could be improved
with the use of JoncrylV R as the branched points could behave as crystal nucleating sites

and this could be effective up to a certain content of JoncrylV R beyond which the hin-

drance of the molecular mobility would be more dominant in determining the crystal-
lization behavior of PLA.
As noted, the enhancements in the crystallization rate when using JoncrylV R as the

chain extender has been observed in the thermoplastics with a very slow crystallization
kinetics including PLA. Similar behavior to what was discussed has also been reported
for PET which, similar to PLA, has also a very slow crystallization rate. Figure 21
reveals the cooling thermograms of r-PET that possessed a very low molecular weight
without and with up to 0.8 wt. % JoncrylV R ADR 4368. As seen, the addition of 0.4 wt.

% of JoncrylV R could expedite the crystallization rate and the degree of crystallinity of

the r-PET. Similarly, such enhancements could have been because the branched molecu-
lar structures could act as crystal nucleating points that could promote the crystalliza-
tion of PET with slow crystallization rate. As seen in Figure 21, with the addition of
0.8 wt. % of JoncrylVR , both the crystallization rate and degree of crystallinity of r-PET

were hindered due to the hindrance of molecular mobility.[98]

5. Benefits and application

The use of JoncrylVR during the polymer processing is widely known in academia as

well as in the industry. The following sections will show some typical applications of
JoncrylV
R . These include from the easiest application as stabilization agent during
 POLYMER REVIEWS 27

Figure 22. Viscosity of PLA with 0.5 wt. % of different chain extenders.[38]

Figure 23. (a) Thermal stability of PLA incorporating with 1.5% wt. of JoncrylV
R (PLA-J) in comparison

to unmodified PLA (PLA-C) during processing and (b) water uptake of modified and unmodi-
fied PLA.[126]

processing to the applications such as recycling and foaming where enhanced rheo-
logical and melt properties are required to the possibility the use of JoncrylV
R as a com-

patibilizer during compounding of immiscible polymers.

5.1. Stabilization
During the processing of polymers, especially polycondensation polymers, the molecular
weight can decrease due to the thermal degradation. As already shown in Figure 7,
JoncrylV
R can be used during the processing to obtain a stable process with no change

in the viscosity over time. Depending on the concentration of JoncrylV R , the reaction
28 T. STANDAU ET AL.

Figure 24. Viscosity of (a) PA6[127] and (b) PET nanocomposites[87] stabilized with JoncrylV
R (here

denoted as J).

can be adjusted. The efficiency of JoncrylV R at the same concentration compared to

other chain extenders was demonstrated by Meng et al.[38] and can be seen in
Figure 22.
In comparison to HDI and PMDA, the usage of JoncrylV R can prevent strong degrad-

ation and stabilize the system. Nearly some results were obtained by G€ ottermann
[28,124]
et al. V
where they show the high efficiency of Joncryl in comparison to other
R

chain extenders and peroxides.

niguez-Franco et al.[125] also showed the stabilization effect of JoncrylV
I~ R during the

processing of PLA. After an increase in molecular weight, they could process PLA over
16 minutes without any further degradation (c.f. Figure 23(a)). In Figure 23(b) the sta-
bilization effect of JoncrylV R and PLA regarding the water uptake is illustrated. JoncrylV R

cannot only be used as a process stabilizer, but it also leads to a stabilization of the
properties of PLA because it absorbs less water.
[126]
Besides the usage in PLA, JoncrylV R could also stabilize the processing of PA and
[87] [126] [87]
PET. As illustrated in Figure 24, Tuna et al. and Ghanbari et al. showed that
the incorporation of nanoclay (C30B) could, respectively, cause the degradation of PA
and PET during the melt processing. However, with the use of JoncrylV R such molecular

degradation could be compensated and hence the melt properties of the nanocomposites
could be improved. Similar behavior has also been reported in the PLA/C30B nanocom-
posites where JoncrylV R could compensate the molecular degradation of PLA induced in

the presence of C30B nanoclay.[32,40]

5.2. Recycling
Nowadays, the recycling of plastics is increasingly becoming the focus of the world. The
sustainability of the material is increased by recycling by conserve fossil resources like
oil and gas.[127] Different methods and processes for plastics recycling can be distin-
guished. In addition to combustion (thermal energy recovery), disposal in landfills and
depolymerization into monomers, mechanical recycling is the main focus of modern
times.[128,129] Here, either directly uncontaminated material (primary mechanical
 POLYMER REVIEWS 29

Figure 25. Comparison of the relative increase in molar mass of PET and rPET at different JoncrylV
R

concentrations.[138]

recycling) or waste (secondary mechanical recycling) is used. In both processes, how-

ever, obtaining pure material is absolutely necessary to obtain high-quality
recyclate.[128,130]
Today mechanical recycling is the most commonly used method[129,130] and mainly
used for polypropylene (PP), polyethylene (PE), and PET.[129] Furthermore, other
thermoplastic materials, like PLA, PS, and its copolymers (e.g., ABS), PMMA, PC, and
PA are mechanically recycled nowadays.[130]
Mechanical recycling consists of different steps, like washing, grinding and separ-
ation. Details about these steps can be found in the literature.[129,131] During the last
step of polymer melt processing, notable thermal-mechanical degradation occurs.[131]
Based on the reprocessed material, chain scission, cross-linking, and branching could
occur introduced by the heating and shearing of the material during the process-
ing.[128,130,131] This particularly affects polycondensates. Here the reduction of
molecular weight (Mw) is very pronounced and thus the mechanical properties are
significantly lower compared to non-recycled material.[128,132] To overcome this issue,
chain extenders are introduced during the melt processing to either stabilize or
increase the molecular weight.[131]
In the following paragraphs, the use of JoncrylV
R ADR as a chain extender during the

mechanical recycling is focused. As already shown in a previous section (cf. Section 2),
JoncrylVR is mainly used for polycondensation thermoplastics.
30 T. STANDAU ET AL.

5.2.1. PET
Recycling rate of PET in Europe is, in comparison to other thermoplastics, with 57%
(2014) very high.[131] On the one hand, this high recycling rate is governed by the
European Union (2004/12/EC). On the other hand, used PET bottles are collected either
by pledge system (e.g., in Germany) or an established loop system (e.g., in Swiss) as
post-consumer PET (r-PET),[130] where nearly pure and unmixed material is gathered.
This makes the recycling easier and cheaper.
Besides the usage of JoncrylV R , different methods and processes are described in the

literature for the recycling of PET[133] such as: reprocessing under vacuum,[134] the use
of metal-based stabilizers,[135] and solid state polymerization.[136] Nevertheless, the use
of chain extenders is a less expensive and easier applicable extrusion process which can
be easily adapted to the given material.[3,133]
Villalobos et al.[3] investigated the influence of JoncrylV
R ADR 4368 and showed that

already low concentrations (< 1.5 wt. %) of JoncrylV can increase the molecular weight,
R

which is comparable to unprocessed PET. Furthermore, a large gel-free processing win-

dow could be observed, which is beneficial for a stable recycling process. Based on this
study, different groups investigated the influence of JoncrylV R ADR on the recy-

cling behavior.
The group of Tavares et al.[137] used a blend of JoncrylV R ADR 4368 and JoncrylV R

4370 (Polyad PR 002) with neat PET (nPET) and r-PET and investigated the process
ability during extrusion as well as the final product. They showed that JoncrylV R was

more efficient in r-PET than in virgin PET (see Figure 25) regarding the increase in
molecular weight, which could be traced back to more reactive groups in r-PET with
shorter chains. Furthermore, the addition of less than 1 wt. % JoncrylV R is enough to

compensate the PET degradation.

Fracture and mechanical properties of un- and modified r-PET with 1 wt. % JoncrylV R

ADR 4300 were investigated by Karsli et al..[138] The toughness and crack resistance
were reduced by the addition of chain extender, but the tensile strength was increased.

5.2.2. PA
Recycling of PA is less considered in the literature. This could have two reasons: On
one hand, there is no closed loop system for recycling PA as a pure, and on the other
hand, the separation of the different PA types, for example, PA12 and PA6 is not easy.
The mechanical recycling of PA6 was investigated by Su et al.[139] and it was shown
that the molecular weight is reduced as well as the molecular weight distribution is
broadened, whereby no chemical changes were observed. To obtain the reduction of
molecular weight, Tuna et al.[7] added 1 wt. % of JoncrylV R ADR 4300 (epoxy-based) or

JoncrylVR ADR 3400 (anhydride) to a self-recycled PA6. The complex viscosity was only

slightly increased by about 25% with the epoxy JoncrylV R 4300, whereby the viscosity

with the anhydride JoncrylV 3400 got increased by about 300%. They assumed that the
R

hydrolytic peptide scission degradation is not dominant during moisture free recycling
and the used chain extender should be adapted to the resulting degradation products.
Villalobos et al.[3] showed that already 0.25 wt. % of JoncrylV R ADR 4368 lead to an

increase in viscosity and furthermore in the tensile strength of a PA6 system. The exact
 POLYMER REVIEWS 31

Figure 26. Batch foams of neat and chain extended PLA at varying foaming temperatures.[146]

dosing of JoncrylVR is essential for a stable process and a good final product, hence over-

dosing of Joncryl R can lead to gelation.[3,94]

V

5.2.3. PLA
Although PLA is a biobased and biodegradable material, the recycling of PLA is of
interest in the literature. Nevertheless, JoncrylVR is mainly used in the modification of

PLA during its first extrusion and not during recycling, to obtain a stable molecular
weight.[140,141] Cosate de Andrade et al.[142] extruded PLA twice and added 0.6 wt. % of
JoncrylVR ADR 4368 before the second extrusion step. The addition of JoncrylV R also

increased the molecular weight but caused an increase in polydispersity. In comparison

to the neat material, the mechanical properties were nearly recovered.

5.2.4. Other polymers

JoncrylV R is rather less used in the recycling of other polymers. However, Villalobos

et al.[3] showed that JoncrylV

R ADR 4368 can be used to recycle degraded PC material at

concentrations below 1 wt. %, to reduce the melt flow index on the order of 50%.

5.3. Foaming
Often a too low melt strength is mentioned as a serious obstacle for foaming of thermo-
plastics in general and polyesters in specific. Therefore, the literature that can be found
32 T. STANDAU ET AL.

Figure 27. influence of the JoncrylVR concentration on the foam expansion and cell morphology of
[149]
PLA extrusion foams at different die temperatures (here JoncrylV
R is denoted as CE).

on foaming with JoncrylV

R is mostly about PLA. A smaller number of publications also

deals with PET and PA, respectively.

5.3.1. PLA
To improve the foam ability of PLA several approaches are known including (i) the
increase in the molecular weight, (ii) the variation of L/D-ratio, (iii) controlling the
crystallization behavior, (iv) the incorporation of additives, or (v) the use of chemical
modification that induce chain extension, branching and/or cross-linking.[97,143,144]
Using JoncrylV R belongs to the latter mentioned option. Publications on all foaming

methods (i.e., batch foaming, foam extrusion, bead foaming and foam injection mold-
ing) using PLA modified with JoncrylV R can be found. Commonly, it is reported that

JoncrylV is used in a reactive melt processing to induce chain build up and, depending
R

on the concentration and processing conditions, cause chain branching or even cross-
linking. As a consequence of the increased molecular weight and the change in chain
topology, a higher viscosity is measured. Hence, often it is stated that the melt strength
as well as melt elasticity increases and that strain hardening can be observed, which is
 POLYMER REVIEWS 33

Figure 28. Foam morphology and compression behavior of PLA extrusion foams (adapted
from Ref.[116]).

both beneficial for foam processes. In general the addition of JoncrylV R leads to wider

processing windows, higher expansion rates, finer foam morphologies, a changed crys-
tallization behavior and different mechanical properties.[5]
An early work on the modification of PLA with CESAV R -extend was done by Corre
[145]
et al. on batch foaming confirming a widened processing window after the modi-
fication. Furthermore, it was remarked that the different crystallization behavior of
neat and highly chain extended PLA influences the foam morphology at low foaming
temperatures. Aside from the rheological properties, the crystallization behavior con-
trols the nucleation and the growth of the cells. In Figure 26, the influence of the
foaming temperature on rising degrees of chain extension can be seen. The chain
extension mainly causes an increase in expansion and a shift from macro- to micro-
scaled cells.
Ren et al.[146] showed that the crystallization induced during the saturation phase
with CO2 can be almost as efficient as a modification with JoncrylV R in terms of expan-

sion and achieving a high cell density for batch foams. This is because the formed crys-
tal domains act as nucleating sites and physical cross-linking points that stabilize the
cell structure. However, the integrity of the cells get enhanced while the cell density and
expansion can be increased due to the so-called strain hardening effect, which is caused
[105,147]
by the non-linear chain structure when modifying PLA with JoncrylV R.

One of the first publications on the effect of JoncrylV R on PLA extrusion foams was
[148]
done by Pilla et al. As Figure 27 shows the expansion was promoted by JoncrylV R as

well as the foam cells got finer and more evenly distributed. The open cell content was
also increased while the crystallinity decreased at higher JoncrylV R concentrations.

Though, the crystallization of extrusion foams also depends on the residence time.[106]
Commonly, relative high CO2 concentrations around 7 to 9 wt. % are reported for the
production of low density PLA extrusion foams. Mihai et al.[149] recognized that the use
of JoncrylV R can lead to low density foams even at lower CO2 concentrations of 5 wt. %.
34 T. STANDAU ET AL.

Figure 29. Improvement of cell morphology of foam injection molded PLA with nanoclay. (a–d)
Foam morphology of linear PLA with 0, 0.25, 0.5 and 1.0% nano clay. (e–h) Foam morphology of
[160]
JoncrylV
R modified PLA with same nanoclay contents.

When using JoncrylV R during the extrusion, higher torques and pressures at the die can
[12,148]
be noted.
Interestingly, Larsen and Neldin[150] stated that the use of JoncrylV R not necessarily

brings a further decrease in density but lowering the die temperature, which can also
result in low density foams. However, most works report that the cell integrity of the
low density foams can be improved due to higher melt strength and elasticity.[106] Due
to the occurring strain, foaming can result in significant higher crystallinities.[115]
Crystallinity can also be controlled by the residence time in the die channel,[106] the
[151]
concentration of JoncrylV R and by the additional incorporation of nucleation agents
[152]
such as talc. However, recently published studies show that the presence of CO2
[141]
inhibits the reactivity of JoncrylV R which has to be considered during the foam
extrusion process.
Bocz et al.[152] showed that foamed PLA modified with JoncrylV R and talc owes an

improved mechanical behavior due to the more uniform cell structure compared to
neat PLA. Yet, it can be concluded that the foam morphology is improved by chemical
modifications and finer cells can enhance the compression strength of extruded PLA
foams[115] as it becomes also evident from Figure 28.
Due to the complex thermal behavior of PLA, it is possible to produce bead foams
via very different routes, as summarized in a previous review.[5] One way is to impreg-
nate micro granules in a water filled stirring autoclave at temperatures close to the melt-
ing point with the blowing agent over an isothermal saturation phase as it is also
common for the production of expanded PP.[153–156] However, hydrolysis that is for
sure an issue under this harsh condition can be counteracted using JoncrylV R . Even

though significant loss in molecular weight can be monitored after up to 60 minutes,

foaming is still possible with up to 31 fold expansion.[157] Also, in a patent of BASF SE
[158]
on the production of expandable PLA bead foams the use of JoncrylV R is mentioned.

For foam injection molding (FIM), it is noticeable that the most works are carried
out without any chemical modification and grades that usually possess lower molecular
weight were used. This can ensure a good melt flow during processing.[5] In a work of
 POLYMER REVIEWS 35

Figure 30. Foam morphology of a bead foam made from chemically modified PA.[168]

Najafi et al.[159] on FIM, linear PLA was compared with JoncrylV R modified long chain

branched PLA (LCB). Both were further additivated with different amounts of nanoclay.
While for the linear PLA the crystallinity increases with increasing nanoclay content, an
opposite effect was noted for the LCB PLA, as crystallization is sterically less favorable.
Furthermore, the LCB exhibits a higher cell density with finer and more uniform cell
morphology as it can be seen from Figure 29. While larger gas pockets appear in the
linear PLA, this is not the case in the JoncrylV
R modified LCB PLA. This is explained by

the accelerated gas diffusion rate enabled by the higher melt strength[105] and larger
shear forces resulting from the branching. Hence, this promotes a more uniform poly-
mer-gas solution, which in turn minimizes the formation of large pockets from undis-
solved gas.

5.3.2. PET
PET is a polyester with rather unfavorable rheological properties for foaming. Namely,
the low intrinsic viscosity (IV) is often mentioned as an issue. Also, the use of r-PET
with less consistent properties is addressed in the literature. The work of Yan et al.[160]
deals with chemical modification of fiber grade PET and r-PET. A combination of
PMDA and TGIC were used in this study and compared with JoncrylV R ADR 4370. The

study revealed that the IV can be increased but especially a too long reaction time will
lead to gelation effects which are negatively affecting the expansion in the batch foam
experiment. Expansion ratios of 15 and cell sizes down to 30 mm were achieved. In the
work of Yang et al.[81] PMDA was compared with JoncrylV R ADR 4368 and by compar-

ing of the torque data it was shown that JoncrylV R reacts much faster. Furthermore, it is

stated that the modification with JoncrylVR leads to less viscous behavior but higher elas-

ticity than the modification with PMDA. In turn, this increased elastic properties result
in an improved expansion in batch foaming experiments. While neat PET could not be
foamed, the modified PET could be foamed with homogeneous foam morphology and
cell sizes down to 60 mm.
As described by Bethke et al.,[161] PMDA can be used as chain extender in foam
extrusion processes to obtain a stable process with fine celled foams of a bottle grade
36 T. STANDAU ET AL.

Figure 31. Neat and JoncrylV

R modified PBT bead foams made in a continuous process.
[83]

PET with different flame retardants. It was clear that chemical modification was neces-
sary. Yao et al.[162] used a combination of PMDA and JoncrylV R ADR 4368 in different

ratios. They attributed a (linear) chain extension reaction when using PMDA while the
JoncrylV R led to chain branching. It was concluded that the chain extension which is

attributed to the PMDA is beneficial for the rheological properties, however, the crystal-
lization gets hindered as the molecular movement was impeded. On the other hand, the
long-branched structures, which are created by JoncrylV R have positive effects on crystal-

lization kinetics and melt strength. The branched structures increased the isothermal
and non-isothermal crystallization rates. Furthermore, smaller and denser crystals were
observed. During foam extrusion an expansion ratio of 17 was achieved and shear and
strain during the process promoted the crystallization of the branched structures. The
crystals act as dispersed phase and heterogeneously nucleated the foam resulting in
much finer cells with average diameters of 120 mm (compared to 160 mm of the neat
PET). Another work dealing with foam extrusion of PET was published by Bocz
et al.[163] Here, JoncrylV R was used to increase the intrinsic viscosity of r-PET. Foams

with densities below 35 kg/m3 and cell sizes between 213 and 360 mm were achieved.
During foaming r-PET, the occurring scission of the reprocessing typically results in
a remarkable viscosity decrease but as it was shown in the work of Szabo et al.[164] the
addition of CESAV R -extend reduces the cell coalescence which in turn results in

enhanced mechanical properties of the foamed injection molded parts even at high
loading of a flame retardant additive.

5.3.3. PA
Only few works on foaming of JoncrylV R -modified PAs can be found. Two studies were
[165]
carried out with PA6 and JoncrylVR ADR 4368. In the work of Xu et al., batch foam-
ing experiments were carried out with JoncrylV R and maleic anhydride grafted polypro-

pylene (MAH), respectively. The virgin PA could not be foamed but with the addition
of the JoncrylV
R a significant expansion was achieved. The volume expansion ratio was

7. In comparison with MAH, even higher expansion ratios of up to 16 were reported.

 POLYMER REVIEWS 37

Also, the processing window is stated to be wider. However, both modifiers allowed
small celled foams with average diameters between 7 and 22 mm. In the works of Yeh
et al.,[166] PA6 was modified with JoncrylV R and SMA, respectively, to increase the melt

strength and reduce the crystallinity. Here, JoncrylV R was found to be more effective to

induce chain extension. Furthermore, the degradation during the foaming process could
be minimized. Yet, they achieved foams with expansion rations around 4. Also, it was
claimed that a bimodal and even a nanocellular cell structure appeared.
Another work, carried out by D€ orr et al.[167] showed that the use of a chain extender
is also essential for the expand ability of PA12 in continuous bead foam process done
on a foam extrusion line coupled to an under-water granulator. The produced bead
foams exhibit a higher thermal resistance and possess low densities of down to 66 kg/m3
with very fine and homogeneous cell structure were achieved as clearly visible in Figure
30. Noteworthy, the use of the JoncrylV R for the production of bead foams from PA6,

PA66, PA12, and PEBA, respectively, is mentioned in patents to increase the molecular
weight and to stabilize the process.[168–172]

5.3.4. PBT
PBT is a polymer which is rarely investigated regarding its foam ability. Only a few
works exist. First works were published by Jeong et al.[173,174] on foam extrusion. With
a chemical blowing agent only a limited expansion was achieved; with foam densities
ranging between 600 and 1200 kg/m3. However, the addition of chemical modifier (i.e.,
TGIC) to increase the complex viscosity and the use of an organic blowing agent (i.e.,
isobutane) enhanced the foam ability and yet intermediate foam densities down to
330 kg/m3 were reported. A recent work of Aksit et al.[175] showed that the use of
JoncrylVR to improve expandability in combination with supramolecular additives to

promote finer cell morphology can lead to PBT extrusion foams improved compression
strength at densities down to 80 kg/m3. It is well-known that a higher viscosity can lead
to improved cell structure as it also can be seen in the study on continuously produced
PBT bead foams by K€ oppl et al..[176] Here, it is clearly shown that the cell morphology
turns out much finer with an increased viscosity. This attempt was followed in further
works,[83,177] and PBT was modified with JoncrylV R to improve the expansion. The opti-

mum concentration regarding the expansion and morphology was found to be 1 wt. %
as can be seen in Figure 31. Interestingly, only JoncrylV R -modified PBT bead foams were

weldable in the steam chest molding process showing superb bead fusion.[178] It was
hypothesized that this is possibly due to unreacted JoncrylV R which is reactivated while

steaming and/or (more likely) due to the reduction of crystallinity on the surface lead-
ing to a bead skin with high amorphous content.

5.3.5. Others
Polyhydroxyalkanoates (PHAs) are a relatively new group of polymers slightly turning
into the focus of the scientific research. Polyhydroxybutyrate (PHB) and Poly(3-hydrox-
ybutyrate-co-3-hydroxyvalerate) (PHBV) belong to this group. These polymers can be
derived from bacterial fermentation and are classified as biodegradable. As stated by
Duangphet et al.[179] the use of JoncrylV R is a helpful tool to overcome the issue with
38 T. STANDAU ET AL.

the intrinsically high brittleness and the sensitivity to thermal and hydrolytic degrad-
ation. It was shown that the activation energy for the thermal decomposition increases
with increasing JoncrylV R concentration which enhances the residence time. Ventura
[180,181]
et al. studied the foaming behavior of PHB. It was shown that during the foam
extrusion process the use of JoncrylV R can decrease the degradation rate of this sensitive

polymer which leads to better expansion and even slightly better mechanical proper-
ties.[180] A later work of this group deals with cellular PHB which is flax fiber reinforced
obtained from batch foaming process. Here it was found that the addition of JoncrylV R

lead to an increase in the matrix stiffness.

Also in the batch foaming of polybutylene succinate (PBS), the use of JoncrylV R is
[182]
beneficial. Zhou et al. described that at a JoncrylV concentration of 0.75 phr cross-
R

linking occurred and the expansion ratio increased up to 15. Again, same behavior in
terms of rheological and thermal behavior was observed compared to the other poly-
mers as the viscosity increased and the degree of crystallization decreased.
Furthermore, the use of JoncrylV R as a nucleating agent in polystyrene extrusion

foams is mentioned in some patents.[183,184] It is claimed that the morphology of foam

extruded PS and bead foams can be improved by the use of JoncrylV R . These foams fur-

ther exhibit an improved mechanical behavior compared to the reference samples with
similar densities (i.e., increased Youngs modulus and compression strength,
respectively).

5.4. Compatibilization in polymer blends

In immiscible polymer blends, the lack of sufficient interfacial interaction between the
phases would even suppress the final properties of the blends to much lower than the
average or even the individual components. To be able to develop these blends and
make them applicable for various applications, the dispersed phase morphology or the
co-continuous structure of the blends with low compatibility or completely immiscible
blends could be improved by interfacial modification via the incorporation of compati-
bilizers.[185] The major effect of compatibilization is to increase the compatibility
between two polymer phases, reduce the droplet size of the dispersed phase and narrow
its distribution, and also to stabilize the blend morphology against coalescence when
exposed to various shear flows or annealing. The decreased droplet size is indeed a con-
sequence of the decreased interfacial tension and reduced coalescence during processing.
This is while the processing type and processing temperature influence the final blend
morphology and the interfacial interactions.[186–191] All these occur while increasing the
interfacial adhesion and interfacial interaction between the dispersed phase and
the matrix either through chemical or physical bonding. In emulsion blend types, the
Palierne model could be used to estimate the interfacial tension between the two phases
in a polymer blend while fitting the experimentally obtained melt dynamic rheological
properties of the blends.[192] Hence, it could predict how the use of compatibilizers
could influence the interfacial tension values between the matrix and the dispersed
phase. This model is simplified as Eqs. (2) and (3) by assuming that the droplet size dis-
tribution is narrow having polydispersity index lower than 2 and the interfacial tension
is not dependent on shear and interfacial area variations.
 POLYMER REVIEWS 39

1 þ 3/H  ðxÞ
Gb ðxÞ ¼ Gm ðxÞ (2)
1  2/H  ðxÞ
     
4 Rcv 2Gm ðxÞ þ 5Gd ðxÞ þ Gd ðxÞ  Gm ðxÞ 16Gm ðxÞ þ 19Gd ðxÞ
H  ðxÞ ¼       (3)
40 Rcv Gm ðxÞ þ Gd ðxÞ þ 2Gd ðxÞ þ 3Gm ðxÞ 16Gm ðxÞ þ 19Gd ðxÞ

where /, x, and c denote the volume fraction of droplets of volume average radius Rv,
the angular frequency and the interfacial tension, respectively. Gb ðxÞ, Gm ðxÞ, and
Gd ðxÞ are the norms of the complex modulus of the blend, matrix, and the dispersed
phase, respectively. The dispersed phase size, Rv, and distribution, PDI, should be calcu-
lated from the real SEM micrograph images of the processed blends.
In this context, physical or chemical compatibilizers could be used into the blends as
a third component. The physical compatibilizers, such as block or graft copolymers,
could be small molecules that are compatible with both phases and hence could reduce
the interfacial tension between the separated phases. The chemical compatibilizers, how-
ever, could go through in situ reactive compatibilization between the two phases during
the processing as they are molecules that is highly reactive with both phases. Therefore,
the compatibilized blends with sufficient interface and interfacial interaction would offer
promising polymeric blend systems that could be used in various applications while
their properties (i.e., mechanical and rheological) and morphological stability (i.e.,
against coalescence and coarsening under various shear flows and annealing) are
enhanced significantly with the presence of a reasonably strong interface. In this con-
text, despite the block or graft copolymers that generate a physical bonding between the
domains, these compatibilizers create a strong chemical bonding with the blend compo-
nents during the processing. Therefore, chemical reactive compatibilizers could be con-
sidered much more effective at reaching the interface and stabilizing the morphology
than the physical compatibilizers.
The use of multifunctional styrene acrylic JoncrylV R chain extender has been offered

as an effective compatibilizer in blends that consist of mainly polyesters. This chain

extender has been mainly reported as a compatibilizer in PLA-based blends and more
extensively in PLA/PBAT blend systems that are highly demanded for packaging and
similar commodity applications. Other PLA-based blends that the JoncrylV R chain

extender has been attempted as a reactive compatibilizer could be named as: PLA/
PBSA,[108,193] PLA/PBS,[194] PLA/PA,[195–199] PLA/ABS,[200,201] PLA/thermoplastic starch
(TPS),[202,203] and PLA/TPU.[89] Moreover, few numbers of blends have been melt
blended with JoncrylV R chain extender to explore its effect on phase compatibility

enhancements. These limited numbers of blends could be listed as: PET/PBT,[98] PBAT/
TPS,[204] and TPU/POM.[205]
As noted, JoncrylV R as a reactive compatibilizer has been extensively used in blends of

PLA with PBAT. Al-Itry et al.[13,104,140,206,207] comprehensively examined the effect of

JoncrylVR in PLA/PBAT blends. Through rheological measurements they revealed that

the compatibility between the PLA and PBAT was dramatically increased and conse-
quently the melt strength, strain hardening, and process ability to produce uniform
PLA/PBAT film and bottle products were enhanced. They also show that the strain at
break of PLA blends was increased up to around 135%. Arruda et al.[86] also showed
40 T. STANDAU ET AL.

that JoncrylV R reduced the PLA dispersed phase size within the PBAT matrix and

increased the melt strength of the blend while noticeably improved the quality of the
produced blown films. Dong et al.[208] also confirmed that the compatibility between
PLA and PBAT were significantly increased with adding JoncrylV R , and the strain at

break was enhanced up to 500%, while not sacrificing too much from the strength. It
has further been confirmed that the melt strength, toughness, and strain at break values
of PLA/PBAT blends could be enhanced profoundly with the use of 0.5% of JoncrylV R

due to the increased phase compatibility and reduced droplet size of PBAT dispersed
phase in PLA matrix while the tensile strength and stiffness were not sacrificed
much.[209] In all these attempts it has been demonstrated that JoncrylV R could be consid-

ered as a promising compatibilizer as it could dramatically enhance the rheological and

melt properties and hence the process ability and uniformity of the final product. This
was while the ductility, impact, and toughness of the final product were also enhanced
favorably with not much loss in the strength and stiffness values were recorded.
It has also been reported that the use of JoncrylV R could be highly efficient to improve

the phase compatibility of PLA with PBSA and PBS and hence the melt strength and
process ability of their blends with enhanced mechanical properties of their final prod-
ucts.[108] It has been shown that while JoncrylV R enhances the phase compatibility, it

could dramatically improve the melt strength and strain hardening of PLA/PBSA blends
(70/30).[108] It has also been illustrated that toughened PLA/PBSA blends could be man-
ufactured through in situ reactive compatibilization using JoncrylV R . The elongation at

break of the PLA/PBSA blends increased up to 200% while the impact strength
[193]
increased 8 times when using 0.6% JoncrylV R in their PLA-based blends.

The compatibility between PLA and PA and the final properties of their blends have
also been explored while using JoncrylV R as the reactive compatibilizers. Khanukra
[195]
et al. demonstrated that the use of 5.0 phr of JoncrylV R chain extenders in PLA/PA6

(70/30) blends increased the melt strength although the droplet morphology did not
vary with the addition of chain extender. They also showed that JoncrylV R remarkably

increased the impact strength and elongation at break of the blends while also increas-
ing the tensile modulus and strength. These results were partially confirmed else-
where.[196] The compatibility of PLA with biodegradable PA11 was also of the great
interest of researchers in recent years.[197–199] It has also been illustrated that although
the compatibility between phases and melt rheological properties of blends increased,
the final mechanical properties were not influenced much and further modifications
need to be performed to reach meaningful enhancements in mechanical properties such
as impact strength of the PLA/PA11 blends.
JoncrylV R has also showed to have toughening effect in the PLA/ABS blends due to

possibly its compatibilization role in these blends.[200,201] It has also been observed that
the JoncrylV R could increase the PLA/TPS blend viscosity and its melt strength and

hence its process ability while improving the ductility of the blend systems.[202,203]
Kahraman et al.[89] also revealed that the ester-based TPU had a better compatibility
with PLA and hence the mechanical properties of the blends were improved more
remarkably. This was while the JoncrylV R also showed a better reactivity with ester-based

TPU than with ether-based TPU. Therefore, while the PLA and ester-based TPU pos-
sessed better compatibility, the JoncrylV R addition further enhanced the interfacial
 POLYMER REVIEWS 41

compatibility of their blends. This dramatically caused the enhancements of the final
properties such as morphological, rheological, impact strength, and ductility.
Few other attempts have been made to explore the compatibilization effect of
JoncrylV R in few other blends and to find possible enhancements in the processing or

the final properties.[70,162,163] In blends of PBAT with TPS, it was found that while
the incorporation of TPS up to 30 wt. % promoted the thermal degradation during
[204]
the processing, the use of 1 wt. % JoncrylV R reverted such degradation. Nofar
[98]
et al. also examined the use of JoncrylVR in blends of PET/PBT that are miscible in

their amorphous phases while the miscibility of their crystalline phase varies depend-
ing on the cooling rate. While they explored the phase miscibility behavior of the
blends, the JoncrylV R mainly increased the melt viscosity of PET and its blend with

PBT and at the low contents, increased the PETs crystallization rate. The strain at
break values of the blends were also increased with the use of only 0.2 wt.
% JoncrylV R.

As discussed, the use of JoncrylV R chain extender has not extensively been used as a

compatibilizer in polymer blends and mainly PLA-based blends with limited numbers
of polymers have been investigated so far. Considering the high capability of JoncrylV R

and its high reactivity with polyesters, it could widely be used in variety of polymer
blends not only as a phase compatibilizer in immiscible blends but also as a melt viscos-
ity modifier to enhance the process ability, form ability, and even foam ability of the
immiscible and miscible polymer blend systems. Therefore, a huge research potential
exists in this area.

5.5. Injection molding, fibers, sheet, and film applications

To control the thermo-mechanical degradation Jaszkiewicz et al.[210] used JoncrylV R with

PLA in injection molding. It was found that the occurrence of branched chains result in
a different flow behavior. Here, flow spirals and MFI investigation revealed a significant
decrease in flow ability. Consequently, the process parameters (i.e., melt temperature
and injection pressure) need to be adjusted. However, in terms of mechanical perform-
ance the PLA can benefit from the modification with JoncrylV R as toughness increased

and the enhanced ductility could effectively stop propagating cracks.

Furthermore, by the addition of JoncrylV R the fiber surface of electrospun fibers can
[211]
be improved as Selatile et al. reported. They mention smooth and bead free fibers
for PLA additivated with 0.5 and 1 wt. % JoncrylV R . Also for melt spinning the use of

JoncrylVR is mentioned as an additive; for example for the production of yarns from

PA 6.6.[212]
Raffa et al.[213] investigated several multifunctional epoxy-based chain extenders to
make r-PET suitable for extrusion of thermoformable sheets. It was found that 1.5 wt. %
of JoncrylVR result in a sufficiently high melt viscosity and elongation at break.

The poor shear and elongational properties of PLA were mentioned as a drawback of
PLA for blow film extrusion by Mallet et al..[214] In their study they used JoncrylV R to

enhance the process ability. The film blowing process is more stable with JoncrylV R

modified PLA and a more flexible and ductile material was achieved as product com-
pared to the neat and brittle PLA.[214,215]
42 T. STANDAU ET AL.

Stretch films from PLA/PBAT were produced by Al-Itry et al.[206] using JoncrylV R.

Here, the modifier mainly acts as compatibilizer. It was concluded that by this compati-
bilization and/or the modification of the composition it is possible to adjust the stretch
ability and the microstructure evolution. Arruda et al.[86] also investigated PLA/PBAT
blends modified with JoncrylV R for film blowing. It was found that the thermal stability

is increased due to the modification and that PLA has a higher reactivity with JoncrylV R

than PBAT. Due to the change of viscosity ratio and the reduction of the interfacial ten-
sion (e.g., formation of PLA/PBAT copolymers) the morphology got changed. As a con-
sequence, the blend gets reinforced and the ductility is increased.
In some current studies H€arth et al.[120,121] investigated the use of JoncrylV
R for blow

films from PET. It was revealed that the very pronounced strain hardening effect of the
long-chain branched chains results in a more homogeneous film thickness.
Sun et al.[216] prepared cast films from PLA and PPC modified with JoncrylV R and

investigated its influence on the mechanical, thermal and barrier properties. With FTIR
it was shown that reaction with PLA and PPC took place. As a PLA-chain extender-
PPC copolymer was formed, the compatibility and the interfacial adhesion of both poly-
mers was drastically increased. With the addition of JoncrylV R a tremendous increase of

elongation at break (up to 1940%) was noted. Also, the crystallization could be hindered
which influences the barrier properties against water and oxygen.

6. Summary and outlook

In this review article, the properties of JoncrylV R ADR aided thermoplastics were com-

prehensively studied. It has been observed that the use of JoncrylV R ADR as a very effi-

cient chain extender could generate branched structures during the reactive melt
processing. This is while its interaction with polyesters is more pronounced due to its
high reactivity with hydroxyl and more efficiently with carboxylic acid end groups of
the polymer chains. Such efficient chain branching could dramatically enhance the pro-
cess ability of the wide range of polyesters and also PAs. The enhanced process ability
is mainly because JoncrylV R ADR could provide significant improvements in shear thin-

ning, shear and elongation viscosity, melt elasticity, storage modulus, melt strength, and
strain hardening behaviors of the noted polymers. It should also be noted that the use
of JoncrylVR up to a certain limit could improve the crystallization rate of the thermo-

plastics with very slow crystallization, specifically those of PLA and PET.
With such improvements, JoncrylV R ADR could be introduced in vast applications

where stabilization and recycling are required. The enhanced melt rheological properties
could also dramatically enhance the foaming ability of the polyesters where the
improved melt strength could stabilize the cell nucleation and growth with minimized
cell coalescence and cell wall rupture. Moreover, JoncrylV R ADR could also be utilized as

a reactive compatibilizer in immiscible polymer blends where the used phases possess
high reactivity with JoncrylV R ADR. Thereby, the interfacial tension between the phases

could be reduced while the interfacial interaction could be improved. These modifica-
tions would eventually significantly influence the final properties of the blends.
So far, series of studies have explored the effects of using JoncrylV R ADR in various

polymers, however, the most common cases that have successfully practiced with
 POLYMER REVIEWS 43

JoncrylV R could be listed as: PLA, PET, PBT, and PA. This is because the process ability

of these polymers are poor due to their inferior melt properties and require molecular
modification during processing. Moreover, due to the environmental concerns, the
vastly used PET and PA as commodity polymers need to be recycled and JoncrylV R has

turned to be a promising candidate to make them reusable.

The research on the use of JoncrylV R in various polymeric systems during melt mixing

is still continued. This is to make it more applicable in processing stabilization, recycling,

foaming, and polymer blending. Still, the complete reaction of the added JoncrylV R with

the polymer melt during the very short melt processing period could be considered as one
of the major challenges in the use of JoncrylV R . To further expand the use of JoncrylVR in

various applications, the effects of processing parameters, molecular configuration of the

polymers, or the use of a catalyzer on stimulating the reactivity of JoncrylV R could be of

the future research perspectives. Thereby, the foaming behavior of the noted polymers
and the compatibilization of the immiscible blends could be more efficiently be examined.
The fast reaction of JoncrylV R could also make significant progresses in the recycling of the

commodity thermoplastics and stabilization of polymers during melt processes.

Acknowledgements
The authors would further like to thank Kathrin Hilgert for researching and refining the litera-
ture as well for graphical works. Also, we would like to acknowledge the Laboratory at Bavarian
Polymer Institute (BPI) and Polymers and Nanocomposites Laboratory at Istanbul Technical
University (ITU).

Funding
This research was funded by the German Research Foundation (DFG), grant numbers AL474/34-
1, AL474/42-1 and by the Istanbul Technical University-Scientific Research Project (ITU-BAP) -
General Research Projects (GAP) with the project number of 42573. The authors would further
like to thank Kathrin Hilgert for researching and refining the literature as well for graphical
works. Also, we would like to acknowledge the Laboratory at Bavarian Polymer Institute (BPI)
and Polymers and Nanocomposites Laboratory at Istanbul Technical University (ITU)..

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