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Gel Formation in Low Pressure Slurry Process of High

Density Polyethylene
Subhasish Mitra
Manager (Process), HDPE plant
Reliance Industries Ltd, Gujarat, India

Introduction: Meanwhile, the polymer undergoes


mixing, pelletization, and packaging.
Gel formation on the all types of
polyethylene (PE) film i.e. HDPE, LDPE Gel formation:
and LLDPE is reported to be a much Generically all types of polyethylene
common phenomenon and experienced (PE) process has two distinguished
almost everywhere. The problem is sections i.e. Powder production
learnt owing to various operational (Polymer production) and Powder
features of the concerned process. Origin processing (Additive dosing and
as well as probable measures to Extrusion) and problem of gels
overcome this particular problem is formation can be attributed to the
discussed in this note based on the operating conditions in both sections.
experience in Low Pressure Slurry
Process of High Density Polyethylene Polyethylene is very reactive before
(Licensor: M/s Basell Polyolefins, stabilization. In presence of radical,
Germany) engaged in production of Polyethylene generates macro-radicals
blow molding grade, pipe grade and film having tendency to recombine generally
grade product. - but not always - to branching and even
gelling. With the influence of heat,
Brief description of Bassel Polyolefins shear, oxygen or light, the polymer
- HDPE process: backbone can react via free radicals
reactions. These reactions are very
Slurry process (Fig1) utilizes continuous complex and can lead to numerous
stirred-tank reactors (CSTRs), the species depending on the nature of the
monomers, chain-transfer agent, solvent, radicals and the polymer structure. In
and catalyst species enter the reactors for film extrusion, where optical properties
polymerization. The vaporization of the are important, this phenomena is called
solvent removes a large portion of the "fish eyes" or unmelts.
highly exothermic heat of
polymerization. The resulting slurry Gel particles in PE product may result
undergoes separation, removing from several sources.
unreacted monomer, solvent, and
oligomeric species from the polymer. • Unmelted particles that resulted
Solvent is separated from the oligomer from insufficient melting and
and recycled to the reactor inlets, and the mixing, such as undispersed
oligomer is processed and packaged. additives
• Gels generated during extrusion, polymer reactor play a very crucial role
such as cross-linked particles to prevent gel formation. Generically,
• Recycled plastics reactor temperature, hydrogen flow and
• Carbonized resin on screw root co monomer flow are the critical
of extruder parameters that govern the MFI of
• Extruder-die fouling product. If MFI goes low than specified
limit due to fluctuation in these
Gels or unmelted particles may originate operating parameters, then higher
in the resin, due to the plasticization molecular weight polymer may form
technology and quality control. The gels which may not melt at extruder and
may be in form of extremely high appear as gels.
molecular weight polymer chains
aggregated dispersed in the regular In Powder Processing section, gels
polymeric matrix, or different grades or formation is reported to occur due to
types of plastic (in recycling case and oxidation and thermal deterioration of
wide spec. resin) in a major plastic. Such PE powder. When PE powder gets
a system can be viewed as a small oxidized or thermally deteriorated,
percentage of high molecular weight cross-linking takes place in between PE
polymers blended in a low molecular molecules, which makes the resultant
weight matrix, or a blend of two product very hard. This hard degraded
different plastics. oxidized polymer, which does not melt
in extruder, comes out as “Gels”.
Origination of gels in polymer
production section may be significant if Oxidation of PE powder may take place
the reactor is used for different grades of due to ingression of air in powder
product and comparatively higher storage and subsequent processing
molecular weight polymer of previous sections or exposure to humid
run mixes with lower molecular weight environment if adequate Nitrogen
blanketing is not maintained. In the
context of LDPE synthesis under two-
phase conditions, the process has been
reported to be sensitive to gel formation,
and this can be more easily seen when
the melt index is low. Gel formation is
also found to increase with increasing
melt temperature and increasing mixing
time. The effect of mixing efficiency is
minor. When the polymer contained
BHT (Butylated Hydroxy Toluene -- anti
oxidant agent) there is a decrease in gel
Fig1. Block diagram of low pressure content. Based on the similar kind of
slurry HDPE process experience in the above-mentioned
HDPE process the following suggestions
polymer of next run as there is no scope may be considered to avoid the problem
for reactor cleaning in between. of gel formation.
Maintaining operating conditions of
1. Stable operating conditions in aid is able to reduce die build up
reactor are required to be because as the coating layer
maintained ensuring no excess develops any degraded material
dosing of initiator in reactor. clinging to the die is displaced
and also stagnation in the
2. Adequate nitrogen blanketing i.e. extrusion process is minimized
positive nitrogen pressure in reducing the production of
polyethylene powder storage and thermal degradation products.
subsequent processing units is to The low energy surface provided
be ensured. On line Oxygen by the coating reduces internal
analyzer should be accurate build up and subsequent
enough to indicate the oxygen degradation leading to cross-
volume%. If oxygen content in linked and oxidized gels.
the system (should be in the Reducing unmelted/unmixed gels
order of 10 – 50 ppm) increases effects the prevention of solid
then nitrogen pressure in the bed break-up and the process aid
respective system is to be may prevent premature melting
increased as well. in the feed section thus helping to
maintain a coherent solid bed.
3. Non-exposure of PE powder to
direct sunlight is to be ensured. 7. Die plate temperature is to be
maintained to avoid over heating
4. Proper dosing and mixing of of polymer.
master batch with PE powder is
to be ensured if gel count is more 8. Periodical cleaning/purging of
than usual. extruder die plate holes may be
planned after planned shutdown
5. If gels keep on coming in film to remove degraded polymers.
sample then Extruder barrel
temperature controller’s set 9. Fluoropolymer process aids have
points may be increased by few been widely reported to be quite
degrees to ensure sufficient useful to improve the
temperature for melting along processability of various types of
with reduction in Extruder polymers in a great range of
throttle valve opening to ensure extrusion processes. These aids
more residence time inside for contribute to improve extrusion
better homogeneity. melt stability, reduce melt
fracture, increase extrusion
6. During processing, deposits of throughput, reduce die swell, or
low molecular weight polymer, die build-up. This process aid
additives and degradation concentrate is particularly
products can build up on the die effective in polymer systems
and extruder surfaces. Such containing silica & talc
deposits when released can make antiblocks, pigments and other
defects on the extrudate. A additives. When used in LLDPE
commercially available process & HDPE films, it is reported
elsewhere to reduce melt fracture orifice. Even low level addition
and significantly limit die lip can increase production
build-up. In blow molding throughput significantly and
applications, it can improve reduce gel formation in most
surface gloss and reduce extrusion applications.
oxidative build-up at the parison

Reference:

1. K.R.Slusarz, J.P.Cristiano, Stephen E Amos, An Experimental Investigation of the


effect of polymer processing Additives on the Melting and Gel Formation
Mechanism in a Single Screw Extruder (1998).

2. Susan Woods, Stephen E Amos, The Use of Polymer Processing Aids to Reduce
Gel Formation in Polyolefin Plastomer Extrusion (1998).

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