Visual Encyclopedia of Chemical Engineering

Reactive Polymer Processing

General Information

For thermoset polymer compounds, cross-linking between the growing polymer chains
occurs during the polymerization reaction, so the production and processing steps need
to be combined when working with these compounds. For some thermoplastic polymers
it is also more economical to combine the production and processing steps. Fiber spin-
ning, extrusion, and injection molding are some of the most common forms of reactive
polymer processing.

(Source: Coperion GmbH, Stuttgart, Germany)

Process Map

Reaction Fiber Spinning

In reaction fiber spinning, monomers are continuously bonded and cross-linked together
in simultaneous chain extension reactions as they are drawn into their fiber form. For
more information on the processing of polymers into fibers and threads, see the Fiber
Spinning [a] page of the polymer processing section.

Equipment Design

Reaction spinning is similar to dry spinning, where the material is dissolved and then
extruded through a spinneret to create fine fibers, but with an additional polymerization
step. During polymerization, the shorter monomer chains react and cross-link to create
the new enhanced polymer fiber.

Usage Examples

Reaction spinning is not very widely used for fiber spinning, but its most common prod-
uct is spandex. Reaction spinning is used to crosslink a flexible and a stiff pre-polymer.
The resulting enhanced fiber is the strong, durable, stretchy, material we know as Span-
dex.

Advantages

Disadvantages

• Creates enhanced fibers with unique qualities.

• Limited by reaction conditions.

• Not commonly used in industry
• Generally more expensive than other reactive polymer processing methods.

Reaction Extrusion

Polymer products with viscosities of 10 to 1,000 poise can be formed using reaction
extrusion, as the torque from the screw provides ample force to move the material
through the barrel despite the high viscous resistance. Typically, twin barrel extruders
are used for polymerization reactions due to their excellent mixing abilities. The melt-
state of the feed components is induced by the shearing action of the tightly-intermesh-
ing twin screws fighting against viscous forces as well as by the heating action provided
by heating elements outside the barrel. Read more at the Extruders [b] page.
Equipment Design

The feed monomer can enter the reactor in numerous phases, such as solid pellets or
granules; dissolved in a volatile solvent; or as a liquid. In order for the reaction to occur,
the feed must reach a fluid melt-state. The barrel of the extruder is often broken up into
hypothetical sections, each serving a specific purpose. The first portion of the barrel
length is dedicated to heating the feed to the temperature required to achieve melt. The
second section of the barrel allows for the complete mixing of all now-fluid components.
After the feed has been melted and mixed, the polymerization reaction occurs in the
third section. A devolatilization separation process typically occurs in the remaining
length of barrel that removes any volatile byproducts of the polymerization reaction.

Furthermore, it is possible to further designate sections of the barrel to allow for heating
and cooling within different regions. This additional segmentation also allows for differ-
ent zones of the barrel to be operated at different pressures. Sample ports can also be
installed in these different barrel regions so polymer properties such as average molecu-
lar weight can be tested at different points in the reaction. The r esidence tim e, or the
time a given quantity of material remains within the extruder, is dependent on the
length of the barrel and the rotation speed of the screw. All things considered, higher
residence times lead to longer chain lengths in the product polymer.

Usage Examples

Reaction extruders are used to produce a majority of some thermoplastic polyurethanes.

To do this, liquid reactants are fed in stoichiometric ratios to a twin screw extruder.
Constant mixing and kneading action is applied by the rotating screws. Any reaction heat
can be dissipated through the walls of the barrel and removed using cooling water. The
product is forced through a die and cooled and pelletized, to be further processed later.
Thermoplastic polyurethane created in this fashion is used to make ski boots and medical
hose, among other products.
(Source: Coperion GmbH, Stuttgart, Germany)

Advantages

Disadvantages

• Excellent control over residence time distribution by adjusting screw speed

• Allows for high-pressure reactions
• Can handle extremely viscous polymer products
• High level of radial mixing and dispersion

• High costs for longer reaction times

• Difficult to remove heat from polymerization without unwanted side effects

Reaction Injection Molding

Reaction injection molding (RIM) was developed in the late 1950s at General Motors Cor-
poration for the production of the bumper cover for the Corvette. RIM is a batch process
similar to injection molding, but the polymer itself is not directly injected into the mold.
Instead two or more monomers are injected into the mold and polymerized within the
mold, so that the mold acts as a chemical reactor. To read more about injection molding,
see the Molding [c] page in the polymer processing section.
(Copyright Graco Inc. and Subsidiaries)

Equipment Design

The reactants are kept in overhead feed tanks. A loop that includes circulation pumps
and heat exchangers ensures that the reactants are maintained near the reaction temper-
ature. Melting pumps provide additional heating and deliver the reactants to the mixing
head. There the reactants are mixed and pushed into the mold, where the mixture can
react and be molded simultaneously.

(Copyright Graco Inc. and Subsidiaries)

The mixing head shown on the left below is typical of those used in reaction injection
molding. The picture on the right shows a reaction injection process to make polyure-
thane roofing tile.
(Copyright Nonferrous Products, Inc.,

Franklin, IN)

(Copyright EPW, Inc., Elkhart, IN)

The following animation depicts the reaction injection molding process. The hot reac-
tants are injected into the mixing head, where they are forced to mix by impingement .
The monomer mixture is then injected into the mold. There it reacts to form a polymer,
while being molded into the desired shape. Once the product cools, the mold is emptied
and the process is repeated.
Usage Examples

Reaction injection molding is used to make products in wide range of fields, from sports
equipment to home constructions and biomedical applications , as well as the production
of several kinds of structural foams in a process called Foam Injection Molding (FIM).
RIM foams are produced by introducing a blowing agent, such as nitrogen gas, to the
monomer mix. The blowing agent helps make the foam more flexible than other RIM
plastics. The bike seat shown below is made of polyurethane integral skin foam, meaning
it has a high-density outer skin and low-density inner core.

(Copyright Bayer MaterialScience AG, Fribourg, Switzerland)

Structural reaction injection molding (SRIM) is similar to RIM except for the addition of
a reinforcement to the mold prior to monomer injection. The monomers are infused into
the reinforcement, made of fabric, metal, or plastic, to produce a more rigid structure
than those of RIM products. Shown below is a picture of a mold for a SRIM truck door
panel.
(Copyright EPW, Inc., Elkhart, IN)

SRIM was developed by General Motors Corporation and used to make spare tire well
covers. SRIM has since been used to produce many other car parts, such as door panels,
instrument panels, and sunshades. In addition to automotive parts, SRIM is commonly
used to produce satellite dishes and door panels, such as the one pictured below.

(Copyright EPW, Inc., Elkhart, IN)

Advantages

Disadvantages

• Lower energy requirements to pump monomers rather than polymers.

• Relatively inexpensive.
• Process can be repeated as many as 1 million times on the same mold.
• Can produce a variety of different products.
• Hardness and other physical properties can be adjusted.
• Produces low weight products.
• RIM parts are more paintable than parts produced through other methods.

• Inconsistent moldings.
• Reactants must be fast reacting.
• Rates of reaction must be synchronized with molding times.
• Requires high pressures.
 • Temperature must be precisely controlled throughout process.
• Poor performance at high humidity.

Acknowledgements
Bayer MaterialScience AG , Fribourg, Switzerland

EPW , Elkhart, IN

Graco Inc. and Subsidiaries , Minneapolis, MN

Nonferrous Products, Inc. , Franklin, IN

References
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Moncrieff, R. W. Artificial Fibres . New York: John Wiley & Sons, Inc., 1954.

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Whelan, A. Injection Molding Machines . Elsevier Applied Science Publishers Ltd., 1984.
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Wigotsky, Victor. "Injection Molding Machinery: on to 2000." Plastics Engineering

December 1997: 24-30. Print.

Xanthos, M. Reactive Extrusion: Principles and Practices, 1st ed. New York: Oxford Uni-
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Zhang, Xiangwu. Fundamentals of Fiber Science. Lancaster, Pa.: Destech Publications,

Inc., 2014

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