Solid-State Modification (SSM)

Therefore, there is a growing interest in developing efficient techniques to

modify thermoplastic materials by adding desired functionalities using low-
content additives and avoiding detrimental reactions during their processing
[18,19]. Such a technique relies on solid-state modification (SSM) of
polymeric materials, which exploits the mobility of the amorphous phase
within semi-crystalline polymers [20]. This method involves using mechanical
forces to drive through the incorporation of monomers or oligomers into the
amorphous phase of the polymer through multiple exchange reactions [21].
The temperature plays a critical role during this process as it needs to be
above the Tg of the semi-crystalline polymer and close to its Tm. The
exchange reactions mainly occur in the amorphous phase, which means that
the main crystalline phase and its associated properties remain unaffected.
This technique can be considered a post-synthetic modification method that
allows for the preservation and/or modulation of desired properties.

SSM holds the key to adding functionalities to thermoplastics with minimal

additives and avoiding adverse reactions during processing. SSM is
increasingly recognized for its potential to enhance material performance
from catalysts to composites. These developments have covered some
polymers, including thermoplastic and thermosets.
SSM has expanded to different contemporary peaks research issues, such as catalysts and
composites, often serving as a tool to investigate compositional effects and materials
behavior, as well as to improve end-product performance.

In this respect, this review will focus on describing the current perspective of using pre-
formed
thermoplastic polymers with solid-state modification (SSM) methodologies to modify
thermoplastic
polymers with desired functionalities.

By contrast with solid-state polymerization (SSP), which relies

on a kind of bulk polymerization technique, SSM goes beyond by encompassing the concept
of
thermomechanochemistry. Thermomechanochemistry is a highly specialized field of
chemistry that
delves into the interaction between thermal (heat), mechanical (force or pressure), and
chemical
factors in material reactions and transformations [22,23].

This study area is particularly significant

for understanding and designing materials that undergo chemical changes due to
mechanical stress
or thermal conditions.

It combines the principles of thermodynamics, mechanical engineering, and

chemistry to analyze and manipulate the behavior of materials.The aim is to provide the
reader with information not only to understand the relevant solid-state modification
technique but also to encourage future research, as we believe that SSM methodologies are
a continuously thrilling field.

Thermo-Mechanochemistry: A Scientific Field that can be Focused on Solid-State

Modification Through Mechanical Means
SSM is a technique that has not been widely explored in literature, despite being at the
forefront
of thermo-mechanochemistry. It involves modifying polymeric matrices after synthesis to
extend
their range of applications or improve a specific targeted property. This technique is related
to solidstate
polymerization (SSP), which increases the molecular weight of semi-crystalline
polycondensates. SSP is commonly used in the production of glass fiber-reinforced PET
grades. [28].
This technique enables the formation of copolymers without requiring a high-temperature
melt
polycondensation reaction. This process demands precise control of reaction parameters
and
significant thermal stability. SSM involves heating the starting material in an inert
atmosphere or
vacuum to a temperature below its melting point. This temperature is high enough to initiate
and
propagate the exchange reaction in the presence of a comonomer. However, the material
must be
above its glass transition temperature to ensure enough mobility of the end groups in the
amorphous
phase. It is also essential to prevent the crystalline phase from participating in the reaction.
The image
of Figure 2 illustrates this basic principle [29].

Figure 2. Schematic representation of solid-state modification.

The reaction mechanisms involved in SSM are similar to those in melt modification (Figure 3)
[30]. However, a solid-state matrix is utilized as the reaction medium instead of a melt
polymeric
matrix. It is important to note that SSM has limitations on end-group diffusion due to
restricted
mobility. This is not an issue in melt or dissolution technology. These limitations become
more severe
over long reaction times when nearby functional groups already react. As a result, the
concentration
and distribution of these groups are reduced locally, making the migration of unreactive
chain ends
crucial for the reaction to continue. Removing condensate effectively through diffusion is
crucial for
achieving high SSM rates and extents. Although internal and surface diffusion are
theoretically
different, they are related and influenced by similar parameters. This is because both
internal and
surface diffusion eliminates concentration gradients of by-products in the reaction zone. This
eliminates depolymerization and promotes a shift in the reaction equilibrium towards the
desired
products [29].
Figure 3. Schematic representation of how the same reagent can modify a polymer both in its melted
and solid-state forms.
In SSM processes, the removal of by-products is accomplished by either applying a vacuum
or
through the convection caused by an inert gas at atmospheric pressure. The oligomers that
are formed
during the reaction can sublimate into the gas phase along with the condensate. This
process can
also involve heating the mixture under a continuous flow of inert gas (open system), which
promotes
the removal of by-products. During SSM (Solid State Polymerization) processes, the
elimination of
by-products is achieved either by using vacuum or the convection created by an inert gas at
atmospheric pressure. The oligomers that are produced during the reaction can vaporize
into the gas
phase alongside the condensate. The primary objectives of using an inert gas are to remove
the
condensate, prevent polymer oxidation by excluding oxygen from the reactor atmosphere,
and to
heat the reaction mixture. The most used inert gases include nitrogen, carbon dioxide,
helium,
superheated steam, and supercritical carbon dioxide. This process can also involve heating
the
mixture under a continuous flow of inert gas (open system), which helps to remove by-
products.
4. Parameters that Affect the Solid-State Modification Technique
Solid-state modification (SSM) is a complex process, and several parameters can be
controlled
to attain the desired polymer material. These parameters include temperature, gas flow,
vacuum
applied, crystallinity, catalysts, and others. The factors that impact the SSM technique are
listed below
[21]:

4.1. Temperature
The temperature at which the solid-state modification (SSM) process occurs is a crucial
factor
that impacts almost all other process stages [29]. The reaction temperature mainly affects
the reaction
kinetics [31]. Maintaining a temperature range optimal for maximizing the reaction rate
while
avoiding undesired reactions such as partial melting, sticking, or cyclization is crucial.
However, if
the monomer has a high melting temperature, the temperature range can be broader, and
the impact
of temperature on the process rate is minimized. It is not feasible to carry out SSM on
polymers with
a melting temperature that is too low [32]. Raising the temperature of a process quickens its
overall
rate, the chemical reaction, and the movement of terminal functional groups and mass
transport
[27,29,30]. However, the temperature shouldn't be too close to the melting temperature to
avoid
particle agglomeration. In summary, the reaction should be conducted above the glass
transition
temperature and between 10°C to 40°C below the melting temperature of the crystalline
phase of the
prepolymer to prevent particle agglomeration [31]. [31,33,34].
4.2. Atmosphere
SSM can be carried out using either a vacuum or an inert gas, such as nitrogen. The main
objectives of these reaction conditions are to remove by-products, inhibit polymer oxidation
by
excluding oxygen from the reactor atmosphere, and heat the reaction mass (in the case of
gas flow
only). The difference between these two methods is that for vacuum, the rapid removal of
byproducts
is affected by the applied pressure, while for gas flow, it depends on the flow rate of the
inert gas used. In SSM processes, the commonly used inert gases include nitrogen, carbon
dioxide,
helium, and superheated steam [35]. When performing the Solid-State Polymerization (SSM)
process,
it is important to take into account the characteristics of the inert gas being used, since they
may have
an impact on the process. SSM can be carried out in two different ways: either under a
continuous
flow of inert gas, which is referred to as an open system and is primarily focused on
removing byproducts,
or under a stagnant inert gas atmosphere, which is known as a closed system and helps to
limit the loss of monomers and oligomers [36,37].
4.3. Crystallinity
Crystallinity plays a crucial role in SSM as it impacts the movement of chain end groups and
the
diffusion of by-products. The effect of crystallinity on the rate of SSM is two-fold. Higher
crystallinity
levels result in an increased concentration of end groups released into the amorphous
phase, which
in turn leads to an acceleration of the reaction rate. [28]. The polymer chains become less
mobile as
the reaction progresses due to increased crystallinity. This decrease in mobility slows down
the rate
of SSM. When reactions are limited by by-product diffusion, high crystallinity also reduces
the rate
of SSM. However, in processes controlled by chemical reactions, high crystallinity actually
increases
the rate of SSM due to the concentration of end groups in the amorphous phase [38]. In
order to
prevent particles from sticking together, it is necessary for them to have a high level of
crystallinity.
the particle agglomeration, particles must have sufficiently high crystallinity [39].
Furthermore, it has
been shown for many years that semi-crystalline polymers can be described using a 3-phase
model.
This means that they contain a crystalline phase and an amorphous phase. However, the
amorphous
phase is divided into two zones: a mobile and a rigid amorphous zone, as shown in Figure 3
[40]. The
exchange reactions should occur in the more mobile zones that can better tolerate changes
[41].
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doi:10.20944/preprints202401.0197.v1

Figure 4. Schematic representation of 3-phase model, i.e., mobile amorphous fraction (MAF), the rigid
amorphous fraction (RAF) and the crystalline fraction (CF).

4.4. Catalysts
Catalysts are crucial for the rate of polymerization and modification reactions. Their role
extends beyond simply accelerating reactions. They also contribute to the quality and
properties of
the final polymer product by influencing the chain initiation and growth, as well as the
interactions
among the polymer constituents. Additionally, catalysts can lead to complete conversions of
specific
groups, significantly impacting the polymerization rate, as observed with phase-transfer
catalysts
[42]. This ability to control reaction rates is crucial, especially in processes where removing
byproducts
like water is necessary for the desired reaction outcomes [20]. The incorporation of catalysts
into the polymerization process can be done at different stages. They can be added during
the
production of the prepolymer or while melting the prepolymer, providing flexibility in
controlling
the polymerization process. This versatility allows for a tailored approach to achieve specific
properties and characteristics in the final thermoplastic polymer product [36].
5. Thermoplastic Polymers Modified Through Solid-State Modification Technique
Solid-state modification (SSM) of post-synthetic thermoplastic polymers is a rapidly evolving
technique with numerous advantages and potential applications. This approach is
particularly
attractive because it allows adding new functionalities to existing polymer matrices, thereby
extending their utility or assigning new purposes [43]. One of the main benefits of SSM is its
ability
to overcome solubility issues often encountered with certain polymers. Additionally, it offers
a more
environmentally friendly alternative to traditional methods, featuring greater selectivity and
the
potential for scalability [44]. SSM in thermoplastic polymers is cost-effective and allows for
more
significant creative variability and reduced degradation reactions compared to solutions or
melts. It
has been applied effectively to reprocess and recycle condensation plastics, enhancing their
properties without needing solid-state re-polymerization. This makes high-end recycling
economically attractive, especially for high-value-added engineering applications like
manufacturing
higher-performance fibers and films with high tensile properties [45]. SSM is especially
beneficial due
to its compatibility with a wider range of monomers, including those that are fragile or have
a low
degradation temperature, thanks to the milder conditions it employs, particularly in terms of
temperature control. This expands the scope of modifications that can be made to
thermoplastic
polymers. Several research groups are exploring various modifications of polymers using
SSM
techniques. This includes mechanochemistry, which allows for the physical blending and
alteration
of polymer structures without the need for solvents or high temperatures, as typically
required in
other polymer processing methods. However, it is important to note that, to date, only a few
thermoplastic polymers have been effectively modified using these techniques.
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doi:10.20944/preprints202401.0197.v1
7
5.1. Polypropylene
The study conducted by Qiu et al. in 2004 on grafting maleic anhydride onto polypropylene
presented several significant benefits. This process, known for its efficiency and eco-
friendliness,
particularly in the absence of solvents, has been shown to enhance the properties of
polypropylene
in various ways [46]. While the exact study by Qiu et al. (2004) is not directly cited in the
available
literature, similar studies provide insights into the benefits of this methodology. Among its
advantages it is possible to highlight: (1) the improved mechanical properties that includes
better
mixing in blends and composites with other polymers and fillers, as well as improved impact
resistance and low-temperature brittleness in blends [47]. (2) the process is energy-efficient,
particularly important in industrial applications where cost and energy consumption are
critical
factors. On the other hand, the process to carry out the modification is quite complex due to
achieving
the optimal degree of grafting requires careful control of various parameters, which can be
complex
and challenging. Additionally, this methodology requires specialized equipment since the
process
may require specific equipment for effective grafting, potentially increasing the investment
and
operational costs. Finally, maintaining consistent quality in the grafting process can be
challenging,
especially at a larger industrial scale.
Jain at all, (2005) employed SSM for the preparation of polypropylene/silica nanocomposites
with varying degrees of adhesion between the filler and matrix [48]. The methodology
combines
solid-state modification with a sol-gel method to create nanocomposites with varying
degrees of
adhesion between the filler (silica) and the matrix (polypropylene). Interestingly, the use of
solidstate
modification and sol-gel reactions can enhance the mechanical and thermal properties of
the
resulting polypropylene-silica nanocomposites, moreover, the methodology allows for the
adjustment of the degree of adhesion between the silica filler and the polypropylene matrix,
enabling
customization of the composite properties. However, the combination of solid-state
modification and
sol-gel methods can be more complex and challenging to optimize compared to more
straightforward
composite fabrication methods. Additionally, the complexity and potential scalability issues
need to
be considered when applying this method on an industrial scale.
Finally, Both reported methodologies involve combining mechanochemistry with external
energy sources, which is critical for controlling local heating and enabling chemical reactions
that
overcome activation energy barriers unsuitable for conventional mechanochemical
syntheses [49].
5.2. Poly(butylene terephthalate) (PBT)
PBT has been effectively modified using solid-state modification, a user-friendly technique
that
has led to various changes in its properties. In the field of SSM, this is he thermoplastic
polymer that
has been widely reported [15,50–54]. The research groups of C. Koning and S. Muñoz-Guerra
show
only examples involving poly(butylene terephthalate) (PBT) and biobased monomers, e.g.,
sugar or
fatty acid derivatives [50,51,54]. These studies are focused on the microstructure of
the copolyesters obtained and their morphology, emphasizing the influence of structures
and
compositions on thermal properties and crystallinity [54]. C. Lavilla also studied the
comparison of
copolymers obtained in SSM with those obtained in conventional polycondensation and
showed that
these methods appeared to be equivalent [53]. Although these modifications are typically
carried out
using batch processes on a small scale, there is great potential for continuous processes to
be used for
this purpose, such as reactive extrusion, as shown by several recent studies on
mechanochemistry
[55,56].
Recently, Gerbehaye et al. has advanced this field by designing a new process that
transitions
polyester SSM from batch to continuous, using PBT and 1,12-dodecanediol (DDO) as model
compounds [15]. Initially, a calorimetric method was developed to investigate the key
characteristics
of the reaction on a small scale. This helped with the selection of the appropriate catalyst
using the
differential scanning calorimetry (DSC) technique. In the next step, a qualitative kinetic
discussion
was conducted to confirm the results obtained from the calorimetric study. The study also
shed light
on the influence of the reaction time on the molecular and thermal features of the
copolymers
produced. After optimizing the reaction conditions, they were transferred to a gram-scale
batch
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