Reactive Extrusion

1. INTRODUCTION

As we are aware of the material called polymer and also knows that these

are macromolecules which are form by linking together a much smaller molecules i.e.

monomer and product called as polymer.

The polymers/plastics are widely used in different fields as diverse as

defense, radars and communications. These has been increasing acceptance of plastic for

housing, electrical and electronics equipments leading to increased use of more general

purpose plastics.

Plastic has been widely accepted as packaging materials. The use of

plastic films for wrapping bags and sacks is well known. The automobile industry is the

major user of plastic and which is increasing year by year.

In general area of medicine user range from spare parts of surgery such as

hip-joints, syringe etc.

We use this material in various forms in our daily life. Sheets, tubes,

pipes, households, foams and many more. The different conventional processes are

required for converting these polymeric materials into finished and shaped product.

Major techniques are injection molding, compression molding, transfer molding,

extrusion and so on.

This seminar covers a special processing technique called as Reactive

Extrusion.

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2. STATISTICAL DATA

The consumption of plastic worldwide data is given as follows:

WORLDWIDE PLASTIC CONSUMPTION

Year Quantity (million tons )

1995-96 112
1997-98 130
1999-2000 146
2001-2002 160

Following table represents the data regarding plastic consumption in India

year wise.

PLASTIC CONSUMPTION IN INDIA

Year Quantity(million tones)

1995-96 1.88
1997-98 2.3
1999-2000 3.1
2001-2002 4.3
2006-2007 8

Following table represent the individual consumption of plastic in the country (India).

INDIVIDUAL PLASTIC CONSUMPTION IN INDIA

(In Metric tons)

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Material Year
1999-2000 2000-2001
HDPE 515,496 540,000
PVC 649,000 700,000
PP 789,480 905,000
PS 175,382 193,300
LDPE/LLDPE 723,860 820,000

The table below will gives percentage/data of processing techniques which

has been used for converting the plastic into desired shape.

GLOBAL SCENARIO PLASTIC

PROCESSING INDUSTRY.

PROCESS PERCENTAGE
Extrusion 36%
Injection molding 32%
Blow molding 10%
Calendaring 6%
Coating 5%
Compression molding 3%
Powder form 2%
Other process 6%
Total 100

3. GENERAL EXTRUSION
This is the oldest techniques developed from aluminium extrusion, which

is a continuous process in which the plastic or polymer material is fed from a

hopper into heated cylinder. The screw inside the cylinder forces the molten

material through a dia-orifice by means of pressure and gives required shape to

molten material.

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Extrusion is one of the method available which comprises the

forcing of plastic or molten material through a shape die by using pressure. The

range of products produced by extrusion process includes pipes, films, sheets,

filaments, wire coating, profiles and blow molded products.

In the extrusion process the compounded plastic material is fed

through the hopper of the extrusion machine as either powder or granules into a

cylinder having provisions for electrical heating for softening of material. The hot

plastic charge is further worked through the cylinder by a helically flighted

revolving screw. The temperature of the plastic material rises owing to the

frictional heat produced by the compression of charge between the rotating screw

and the cylinder surface. During its journey from hopper to die the plastic

material passes through distinct zone named feed zone, compression zone and

metering zone. The final action of screw is to force the melted polymer through a

die which determines its final size.

The general extruder design consist of hopper, screw, nozzle, barrel

and heating arrangements. There are three zones named as feed zone, compression

zone, metering zone.

Feed zone:

This is the first zone where the raw material is fed to the extruder

from hopper, from figure it is clear that maximum clearance is provided by screw

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Hopper
Hopper
 Reactive Extrusion

to accept the raw material or granules. In this zone, preheating is done and with

the help of screw movement the feed is conveyed to the compression zone.

Barrel
Barrel Heater

Screw

Die
Compression Feed
Metering zone zone
zone
Compression zone:

At this zone material is heated and melt stream is formed by means

of electrical heating on the surface of barrel, and by shearing heat which is

provided by keeping minimum clearance between screw flight and internal surface

of barrel. The material is melted by compression in this zone.

Metering zone:

Another zone is metering zone. In this zone molten material from

compression zone conveyed to the nozzle and die. The molten material is

plasticized for final product of die.

Different types of extruder designs are available namely single screw

extrusion, twin screw extrusion, co-extrusion and vented extrusion.

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CO-EXTRUSION :

In this technique two or more polymers are extruded simultaneously

to form a single layer which makes a combination of properties with economics of

that product.

VENTED EXTRUSION :

This is equipped with vent port to remove moisture and other

volatile harmful materials. Since some of the plastic materials are hygroscopic in

nature and this tendency is removed by vented extrusion.

4. REACTIVE EXTRUSION

This is a recent development of extrusion technique in which the

extruder is used as mini reactor. “ Reactive extrusion is the name given to the

process where by the plastic is manufactured in the extruder from base chemicals

and once produced it passes through a die of the desire shape, which gives shape

to the material.”

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Reactive processing Technology has now been established as an

effective method for producing new polymer and polymer alloys. This system

enable us to give various kinds of products from thermoplastic polymers alloys; as

well as highly reactive material which are generally difficult to handle with

conventional processing method such as injecting molding.

This system is well suitable for many kinds of thermoplastic alloys,

particularly for small lot production. The main reason lays that the continuous and

low volume production and chemical composition control of polymers, their micro

structure, physical properties are readily possible with this method. On the other

hand, there are many plastic, currently being developed possessing excellent

qualities in terms of functionality and reactivity, but having the difficulty to

extrude/process them or else showing the poor fluidity necessary for processing

due to the highly cross linking characteristics at molding temperature, Some kinds

of polymeric material with significant thermo degradability requires to be quickly

shaped after extrusion.

These disadvantages leads the difficulties in commercial production

using the conventional methods.

Under these circumstances newly developed reactive extrusion and

molding system can efficiently handle such materials as well as the conventional

materials.

PROCESS:

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In a typical reactive extrusion process the reactants are fed into the

extruder feed throat were the material is usually heated to initiate reaction or

increase the reaction rate. The reactant mixer is conveyed through sequential

barrel segments. Where degree of mixing and specific energy input bring the

reaction to the desired degree of completion within the limit of residence time in

the extruder. At this stage the reaction may be quenched or addition of catalyst

quencher may be done where applicable. Volatile by- products or excess reactants

may be removed.

Feed Vent

Polymerisation Devolatization Processing

Fig. REACTIVE EXTRUDER

Then molten polymer is extruded through the die and rapidly cooled

by contact with a fluid medium such as water. After cooling and solidification

quencher has been added to restrict further reaction.

The mixing devices recently employed for both single and twin

screw extruders are adequate for most reactive extrusion processes but some

reaction for e.g. the co-polymerisation of two monomer of unequal reactivity, it is

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beneficial for a high degree of back mixing of the sort typically found in a well

stirred batch reactor.

Such mixing can be provided in reactive extrusion by employing a

tangential counter-rotating twin screw extruder. Mixing enhances desired

reactions and minimized side reactions.

MATERIALS

1. POLYETHEREMIDES :

These materials can be manufactured in an extruder reactor by the

condensation of Bis-phenol A dianhydride with different aromatic amines.

Chemistry :

The condensation reaction of bisphenol-A dianhydride with a diamine

such as phenylenediamine. The reaction can be shown as follows:

Chemical Reaction:

O O NH2
|| |
CH3
O | O +
O C O
|| | NH2
O CH3 O

O O
||
CH3
N | N
O C O

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|| |
O CH3 O

+ 2 H2O

Processing :

The reactor design consists of a twin-screw extruder with

intermeshing screws and barrel length, Such that the average material. Residence

time is 4.5 minute. A solid mixture of bisphenol-A-dianhydride, a diamine such as

m-phenylenediamine, and a pthalicanhydride chain stopper is fed to the extruder

throat, where the material melt in zone 2 and begins polymerisation. Zone 2 is

only partially filled so that surface renewal allows removal of some of the water of

reaction through the first vent maintained at atmospheric pressure. A vacuum vent

at zone 4 removes the rest of the water. Fig. 2 shows the screw geometry in zone 3,

which promotes melt sealing to prevent Back mixing of material between zone 2

and 4. Here a right handed (forward-conveying) screw element is followed by left

handed (backward-conveying) screw element to retard the flow of material

between zones.

Fig.1 Twin-screw extruder reactor for polyetherimide synthesis

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Fig. 2 Diagram of screw elements in zone 3 to promote melt sealing.

In procedure with better stoichiometry control the dianhydride and

diamine are fed to extruder as separate melt streams via a concentric tube feed

inlet fig. 3. Diamine melt

Dianhydride melt

Fig.3 Concentric feed pipe for feeding molten reactants to extruder

Keeping the two molten reactants separate untill they can be mixed

properly in the extruder promotes product homogeneity.

2. POLYURETHANE :-

Both polyurethane and polyurethaneureas have been prepared in

extruder reactors. The chemical required as 9 parts butane 1,4 diol chain extender

and 91 parts low molecular weight polyesters.

Chemistry :

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As these reactions proceed by step growth polymerisation. The

stoichiometry control of the reactants is important for high molecular wt.

polymers. The reaction is as follows

Chemical Reaction:

O O
|| ||
H – { O – C – (CH2)4 – C – O –(CH2)4 } OH

+ HO – (CH2)4 – OH + OCN – – CH2 – – NCO

O H H O
|| | | ||
{O–C–N– – CH2 – – N – C – O – (CH2)4 etc.

Polyurethane

The reactants are often fed to extruder as melts or liquids. The

functional groups – CN – and – OH – combines with each other through steps and

tends to consume all the groups present in that molecule or reaction mixture.

Processing :

In this process 53mm twin screw extruder with co-rotating, self-

wiping screws and 1855 mm in length is used as a reactor. A mixture of 9 parts

Butane – 1, 4 diol chain extender and 91 parts low mol. wt. Polyester (OH number

= 51.9) prepared from Adipic acid and butane – 1, 4 – diol and 35 parts 4, 4’- di-

isocynatodiphenylmethane are pumped separately as melts into the extruder entry

Zone at 90-1200C.

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The middle section of extruder is held at 180-2600C and the last

section of the extruder it 100-1800C. Operating at 70-300 rpm, the extruder

produces polyurethane sheet through a sheet die at 30-100 kg/h throughput and

2.5 – 0.8 min residence time.

The specific net energy requirement is 180-540 KJ/Kg of material.

The key to the success of this process is the presence of at-least two or at-most

three kneading zones each 240 mm long preceded by short metering segment. As

shown in fig.4

Fig. 4 Extruder reactor design for polyurethane synthesis

5. COMPARISON

GENERAL EXTRUSION REACTIVE EXTRUSION

It requires granules or pellets as raw No granules or pellets are required as raw

material or feed i.e. polymeric material i.e. monomer is fed to the

material in the granules form. extruder

It leads to high heating history in a It leads to less heating history as there is

polymer-polymer alloy as compare to no remelting

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Reactive.
Processing for a heat sensitive or Processing of a heat sensitive/highly

highly reactive material is quite reactive raw material can be done

difficult. efficiently and smoothly.

These type of technique is used It’s not in global use for manufacturing

universally. process.
Morphology control is difficult or it No morphology changes. Obtained by

may change during the process. this to the min level.

Manufacturing process are more Manufacturing process are simplified and

costly comparatively cost reduction can be realized.

It can be used for large production of It posses many advantage is research and

thermo plastic product. development activities on new plastic

material.
6. ADVANTAGES

The main advantages of the Reactive extrusion techniques are as

follows.

1) Enclosed Tubular Reactor :-

An extruder may be considered to be horizontal reactor with one or

two internal screws conveying reactant polymer/monomer in the form of solid or

slurry, melt or liquid.

2) Product Purity :-

The most common reactant are polymers or polymers melts and

gaseous liquid or molten low mol. Wt. compound. A particular advantages of the

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extruder as a chemical reactor in this context is the absence of solvent as the

reaction medium. No solvent, stripping or recovery process is required and

product contamination by solvent impurities is avoided.

3) Easy Control of Process:-

Because of their versatility, most extruder reactors are twin screw

extruders, which posses a segmented barrel, each segment can be individually

cooled or heated externally. In addition to external heating shear heat is develop

by motion of screw.

4) Temperature and Residence time :-

The entire range of temperature may extend over the length of an

extruder, the temperature differential between adjacent barrels segment is often <

1000C because of slow heat transfer to and from reactant material. Typical

extruder residence time 10-600 sec. These values will vary for different reactions

and reactants as well.

5) Flexible Design of Reactor or Extruder :-

By providing individual barrel segment with external opening its

possible to introduce solid, liquid or gaseous reactants at specific point in the

chemical process. Volatile bi-products from chemical reactions or excess reactant

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may be removed easily by applying a vacuum to the appropriate barrel segment

and providing the appropriate screw segment with proper flight depth and

geometry to ensure efficient surface renewal and exposure of the reaction mixture

to low pressure. The individual reaction zones at different pressure may be

segregated from one another by melt seals formed by restricting the flow of

material both before and after the zone. Melt seals are commonly formed by using

reverse flight and/or shallow screw flight segment that prevent back mixing of

materials in adjacent zone, such technique used for high pressure differential

between adjacent zones. Typical pressure encountered in reactive extrusion

process are 50 mpa (500 atmp, i.e. 7250 psi ).

6) Efficient mixing:

As it is possible to arrange the kneaders in reactive extruder for

better mixing and high heat transfer for viscous material. Running of two or more

extruder is possible in this technique , which increases the rate of reaction and

process.

7) Continuous/ one line process:

As we know without remelting/ palletizing one pass molding is

done. So it reduces the time, heat losses requirement and leads to the economy.

This Process/ technique increases product quality respectively.

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7. DISADVANTAGES

Some of the disadvantages of this process are as follows:

1) Limited residence time:

The limited residence time available in an extruder is often a

disadvantage, although when applicable, catalysis frequently shortens the time

required for reaction, but a large number of reactions are not rapid enough to be

performed in extruders on commercial scale.

2) Parameter stability:

The beneficial effect on rate and outcome of reaction often observed

in organics and polymers reactions by changing solvent polarity, hydrogen

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bonding stability, boiling point and other parameter are not duplicated in a melt

process.

3) Inefficient heat transfer:

Most reactive extrusion processes may make heat transfer inefficient

and difficult to control in exothermic chemical reactions, because most polymer

melts have low thermal conductivity especially when limited amounts of valuable

starting materials are involved most commercial reactive extruder involve simple

one step chemical reaction between inexpensive and Readily available starting

material.

4)Process limitation:

Small commercial continuous extruder requires a minimum of 100-

1000gm of material for a typical experiment, such extruder reactions may not be

convenient for running a large matrix of screening experiment. to optimize

processing conditions especially when limited amounts of valuable starting

materials are involved. Most commercial reactive extruder involve simple one step

chemical reaction between inexpensive and readily available starting material.

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8. APPLICATIONS

The important applications where the reactive extrusion technique can be used are

as follows.

Stampable sheet fabrication:

If inorganic fillers or glass fibre are fed into a twin screw extruder or

a fabricated fibre material is inserted into the mold, fiber reinforced composites

can be obtained from this result this system can be applicable to more complicated

polymer alloy composite.

Online monitoring device:

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This system is not only suitable for research and development but

also utilized as a useful in online-monitoring device for quality assurance as well

as for evaluation of processability and flow character of a product.

Large size products manufacturing:

It can also be applied to special kinds of processing methods such as

large size products and hybridized composites.

Also to form a polymer alloy of thermoset material like unsaturated

polyester by micro dispersion of elastomeric compound to improve its low impact

strength can be easily possible by this method.

New material for special application:

‘Innovative Polytetraflouroethylene’ polyamide material. A new

material has been developed by reactive extrusion combining the excellent sliding

properties of PTFE with the very good material and processing properties of

polyamides. During the melt modification reaction, the coupling between

polyamide and PTFE was realized by a transmidation reaction as a result

polyamide – PTFE block copolymers were founded.

Starch foam products:

It is used to develop and manufacture starch foam products having

the resilience and compressibility of foam polystyrene, using water as the

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plasticizer and blowing agent. Which are commercialized through one of

company, KTM for arts and crafts and for toy application.

9. SCOPE AND CONCLUSION

The reactive extrusion processing and manufacturing can be used not

only for highly reactive materials but also for thermally unstable materials to the

development of new thermoplastic polymers and alloys, and to the recycling of

used plastic product.

In future it could be the part of commercial and mass, production

line. As it is economical as compared to other extrusion techniques. It is also used

in research and development areas. So in future the manufacturing of new

materials can be possible at comparatively lower cost.

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BIBLIOGRAPHY

1) Mark,Bikales, Overberger, Menges. “Encyclopedia of Polymer science and

Engineering”, Second Edition, Volume 14, Wiley Inter-science

Publication,1991, Page no. 169-177.

2) Michael L. Berins, “SPI Plastic Engineering Handbook”, Fifth Edition, Chapman and

Hall,Newyork and London,1991, Page no. 79-93.

3) Allan L. Griff, “Extrusion Technology”, Second Edition, Robert E. Krieger Publication

Co.,1981, Page no. 1-13.

4) A. S. Athaley , “Handbook of Packaging”, 1995, Page no. 28-35.

5) Dr. J. S. Anand, “International Plastic Engineering and Technology”, Volume 2 No.1,

New Age International Limited Publication, Nov.1995, Page no.33-44.

6) Popular plastic and packaging , July 2001. Page no. 51-52.

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7) www.nap.edu

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