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Increasing the IV value by Polycondensation

First, what in the hell does this means ?

Here what books are saying:
Polycondensation:
A polymerization in which the growth of polymer chains proceeds by
condensation reactions between molecules of all degrees of
polymerization.
Now, there are quite many publication on the subject but here we like only to
make you understand what this process does in relation to recycling process.
As written before, Polycondensation put together molecules to re-form the
polymer chain.
Doing this, it does transform also some contaminants into part of the polymer
chain with undesirable side effects and here are the most common:
Diethylene glycol (DEG)
DEG is one of the most important side products of the polycondensation
process.
PET which is directly produced by esterification of Terephthalic acid usually
contains more DEG than PET produced by transesterification of DMT (Chen,
1998 a). Most of the DEG is formed during the preheating of the melt-
polycondensation by intermolecular dehydration of Ethylene glycol. The
dehydration of Ethylene glycol is catalysed by acids and therefore promoted
by a high concentration of carboxyl end-groups.
In the course of polycondensation DEG is also co-polymerised in the
polyester chain causing a decrease in melting temperature of PET.
In general, the melting point of PET decreases by about 5 °C for each percent
increase in DEG concentration.
The incorporation of DEG in the polymer PET also deteriorates mechanical
properties, the hydrolytic and light stability as well as the thermal and
oxidative degradation behaviour of the material ).
There are other possibilities for the formation of DEG during the
polycondensation and manufacturing process of PET.
Carboxyl and Vinyl end groups
Another important side reaction during the production of the polyester
PET is the degradation of polymer chains by random thermal cleavage
of ester links forming carboxyl end groups and vinyl end groups
respectively.
The amount of carboxyl end groups is an important factor due to the
susceptibility to hydrolysis of the polymer since these end-groups have
a catalytic effect in the process as already mentioned above.
Vinyl end-groups may also polymerise to polyvinyl esters which are
responsible for the (dis)coloration of PET.
Acetaldehyde
The vinylester end group of PET can be transesterified under the formation of
Acetaldehyde.
The Acetaldehyde concentration of PET granules is of great importance when
manufacturing PET bottles for soft drinks especially when used for carbonated
mineral water.
Migrating to the beverage, retained Acetaldehyde can cause an intensive off-
flavour.
Formation of Acetaldehyde as a by-product of the polycondensation process
of PET.
Acetaldehyde is not only formed during the polycondensation process but also
occurs during blow molding of PET bottles from PET resin.

All this means it is not only a solid contamination matter but a chemical one.
That's why not a single washing line manufacturer has the FDA approval; he
just cannot have it
SSP Solid State Polycondensation is a step further Melt State
Polycondensation and can achieve an higher molecular weight and increase
the IV up to over 1.
The longer the chain, the higher the molecular weight and thus the IV with
which is measured.

The different SSP systems available.

SSP can be done in two different ways; first is the continuous one, normally
used with high production rates, and the batch process.
Both systems are using only heat and time so no chemical additives are
necessary for the process.
We like continuous system much better than batch processing but, like any
other case, there is a good and a bad part on both.
Continuous process is absolutely perfect if starting point (the IV value) is
constant; in fact according to heat and time IV will increase of the same value
but if the value is not constant, the final one will not be as well.
On the batch process instead, you can change the time for each batch
depending on what you put inside the machine; the cost per Kg is a little bit
higher but the result is absolutely constant, doesn't matter which IV you
did start with.
 Side Reactions in melt PET polymerization and their influence on PET
properties

In order to meet the stringent product specifications it is required that the molecular weight and side product concentration is
strictly controlled in the polymer. The important side products, which critically control the product quality, are acetaldehyde,
diethylene glycol, acid end groups, vinyl end groups and cyclic oligomers. The rate of formation of these side products depends
on the operating conditions and also on the type and concentration of the catalysts used in PET manufacture .

In addition, PET may undergo degradation reactions. The catalysts used in the transesterification and polycondensation stages
are also known to catalyze the degradation reactions.

Formation of Diethylene Glycol (DEG) and Dioxane

DEG (Diethylene glycol) is the most important side product in PET synthesis. DEG and dioxane can be regarded as condensation
products of EG formed according to the following stoichiometric as shown in reactions [42-44].

----[42]

------[43]

------[44]

Reaction for the formation of DEG and DIOXANE

PET made by direct esterification of TPA generally contains more DEG than PET made by transesterification of DMT. Alkaline
compounds of alkali metals, alkaline earth metals, amines or ammonium compounds of the fourth group are effective catalysts for
reducing DEG formation. It is reported that most of the DEG (70%) is formed during the preheating and low vacuum stage of
polycondensation. Only about 20% is formed during the transesterification stage and about 10% is formed in the final stages of
polycondensation.
Dioxane, which is formed from DEG, has a high vapour pressure (i.e. is quite volatile) and is removed from the process as
column top product. However, DEG is less volatile (boiling point 215°C) and, since it is a diol, it gets incorporated into the PET
chain as comonomer. This alters the crystallization behaviour of PET.

The quantity of DEG in PET molecules influences many important properties of the polymer; e.g., density, thermal, oxidative and
hydrolytic degradation, light-stability, and thermal transitions. Incorporation of DEG is known to increase the dyeability, though the
dye take-up of PET is not uniform. DEG content in the polymer decreases the melting point and thermal stability of the polymer.
The melting point of the polymer is depressed by approximately 2.5-5°C for each 1% of DEG incorporated in the polymer chain. It
is therefore important to control DEG formation in PET manufacture.

(ii) Thermal degradation of Repeat units

Thermal degradation of PET polymer chains is a major problem at temperatures above the melting point and occurs during the
melt polycondensation because of high temperature and residence time required for obtaining high molecular weight. The major
consequences of these on the PET quality are: drop in intrinsic viscosity, formation of carboxyl end groups and acetaldehyde, and
yellowing of polymer.

--------[45]
 Mechanism of Thermal Degradation of PET

The mechanism of thermal degradation of PET is shown in reaction [45] .Carboxyl end groups reduce the hydrolytic and thermal
stability, and in standard PET grades, their concentration should not exceed 25 mmol/kg. Acetaldehyde migrates into the contents
of food packaging, so causing flavour problem of the products. For bottle-grade PET, often acetaldehyde content below 1 ppm is
specified. By-products of thermal degradation are light gases, being mainly CO, CO , ethene, methane, and benzene, together
2

with PTA, BHET and short-chain oligomers.

The thermal degradation of PET is strongly influenced by metal catalysts. The acetates of Na and Mg have little activity, whereas
the acetates of Co, Cu and Zn accelerate the thermal degradation, with Zn being the most active.

The addition of stabilizers such as triarylphosphites or triarylphosphates blocking the metal ions has been recommended for
providing control of thermal degradation reactions.

(iii) Thermo-oxidative degradation

Presence of oxygen and traces of water/moisture, during the synthesis and processing stage of PET results in thermo-oxidative
degradation and hydrolysis take place, which cause a drop in molecular weight. Therefore, it is very critical to maintain moisture
free inert atmosphere during synthesis and processing by application of high vacuum.

iv) Formation of oligomers

During the process of melt polycondensation of PET, about 2-3 % of short chain oligomers are also formed as shown in
. Oligomers can occur as linear or cyclic molecules; however the cyclic trimer has been postulated to be
predominant (60 to 80% of the total amount of cyclic oligomers). The structure of cyclic Trimer as shown below in

---[47]

Cyclic dimers

It has been shown that during thermal processing, 98% of trimer primarily migrates to surface and cause serious problems in
spinning, dyeing, and subsequent processing steps. It exudes to the hot polymeric surface and coats spinneret plate on the melt
spinning unit leading to frequent filament breakages. During dyeing process it causes the coating of dyeing equipment and
interferes with the process.

-----[48]
Cyclic Trimer