POLYMER CHEMISTRY

Polymer
Chemistry

Polymer Chemistry
As far back as 1839, Charles Goodyear first improved
the elastic properties of natural rubber by heating with
sulfur (vulcanization). It was not until the 1930s that the
macromolecule model of rubber was understood. After
World War II and through the 1950s rapid developments
in synthetic polymers were made. Most commercial highperformance elastomers trace their origins to the 1960s
and 1970s.
Polymers are long chains of repeating chemical units,
or monomers. The chemical skeletal structures may be
linear, cyclic or branched. When one monomer is polymerized, the resultant polymer is called a homopolymer.
Examples include polyethylene, polstyrene and polytetrafluoroethylene (PTFE). Copolymers (or dipolymers) are
derived from the polymerization of more than one type
of monomer. The distribution of monomers in these
copolymers can be statistical, random or alternating.
Examples include ethylene-propylene and fluorocarbon
elastomers (vinylidene fluoride and hexafluoropropylene).

Terpolymers are three-monomer-unit polymers, such as

ethylene-propylene-diene (EPDM) and specialty fluorocarbon grades.
Simrit/FreudenbergNOKs technology center, located in
Plymouth, Michigan, has capabilities ranging from basic
polymer research to applied material development which
continue to meet specific application and market needs.

Polymer chemistry is the backbone of our business. By carefully matching the customers needs with Simrits
polymer technology, the optimum sealing solution for both performance and economy can be chosen.

Types of Polymers
There are two general classes of polymers:
1. Thermoplastics
(can be melted with the
application of heat)
Crystalline
crystallize when cooled
Amorphous
no crystallization when cooled
Semicrystalline
polymers which contain both
crystalline and amorphous segments
2. Thermosets/Elastomers (Cross-Linked)
(degrade rather than melt with the
application of heat)

Plastics are rigid long-chain polymers

which are not usually connected or crosslinked. Plastics can either be thermoplasticmeaning they can be heated
and cooled without changing properties
or thermoset, where an increase in temperature
changes the chemical structure and properties. As a class,
plastics have low elongation and high elongation set.
Elastomers are flexible long-chain polymers which are
capable of cross-linking. Cross-linking chemically bonds
polymer chains, which can prevent
reversion to a non-cross-linked polymer
at elevated temperatures. The cross-link
is the key to the elastic, or rubbery,
properties of these materials. The
elasticity provides resiliency in sealing applications.
Thermoplastic elastomers (TPEs) often combine the
properties of elastomers with the ease of processability
of thermoplastics. They are the chemical
resultant of elastomers and thermal
plastics. Thermoplastic elastomers are
generally classified by their structure
rather than their chemical makeup.

Types of Polymerization Reactions

1. Condensation Polymerization: Yields polymers with
repeating units having fewer atoms than the monomers
from which they are formed. This reaction generally
involves the elimination of small molecules such as
H2O or HCl.
2. Addition Polymerization: Addition curing of
elastomers involves addition of SiH (silicone hydride)
across double bonds in the presence of platinum
complexes (although palladium and rhodium are also
suitable). The reaction proceeds gradually at room
temperature or rapidly at elevated temperatures.

There are no volatile by-products produced during

cure, so post-curing is not required.
3. Chain Polymerization/Free Radical Polymerization:
A. Initiation: Formation of free radicals by scission of
a single bond (homolysis), or by the transfer of a
single electron to or from an ion or molecule (redox).
B. Propagation: Growth of macromolecular structure.
C. Chain Transfer and Termination: Completing the
polymerization step.

Types of Chain Polymerization Methods

1. Bulk Polymerization: Involves only the monomer and
a monomer-soluble initiator.

particles are produced in the form of beads in the

range of 0.1 to 2 mm in diameter.

2. Solution Polymerization: A solvent lowers the viscosity,

assisting heat transfer and reducing the likelihood of
auto-acceleration.

4. Emulsion Polymerization: The initiator is not soluble

in the monomer but soluble only in the aqueous
dispersion medium. Polymer is produced in the form of
a latex with particles in the range of 0.05 to 1 micron.

3. Suspension Polymerization: Reaction mixture is

suspended as droplets in an inert medium. Polymer

Elastomer Process Diagram

The production of elastomeric components involves several steps. This diagram is a
basic schematic of the process flow from monomer to finished part.

UPDI

Cleaning
Extrusion

Molding & Curing

Finishing & Inspection

Polymerization

N2

Packaging

Compounding
Isolation

Flash Removal

Post-Curing

Elastomer Processing
Simrit Elastomer Production
Simrit/FreudenbergNOKs production facilities are
typically equipped to provide compounding-to-packaging
steps in elastomer processing. In select elastomer materials,
our capabilities begin at the polymerization stage.

Polymerization
The beginning step for elastomers is the polymerization
of the backbone and cure-site monomers. This is typically
done by large chemical companies such
as DuPont Dow (DDE), Bayer, GE,
Ausimont, Daikin and Dyneon. Common
techniques are emulsion, microemulsion,
and suspension polymerization.
Polymerization combines two or more process gases
(monomers) into an aqueous environment and, under

specific temperature and pressure conditions, connects

the individual monomers into the desired polymer.
Initiating agents, buffers and other chemicals may be
added to the polymer reactor to achieve the desired
chemical properties and polymerization dynamics.

Isolation
The backbone polymers are isolated (brought out of the
emulsion), cleaned and dried. Chemical agents may be
added at this step to isolate the polymer
latex into a more usable form.
Once the polymer is cleaned and dried,
the crumb polymer is shipped to
compounders or molders for mixing.

Elastomer Processingcontinued
Compounding (Mixing)
The crumb polymer is mixed with a cross-linking agent
and other functional fillers. The cross-linking agent allows
chemical bonds to form between the
polymer backbones, thus providing
resiliency to the material. Functional
fillers include reinforcing fillers, pigments,
anti-degradants, acid scavengers and
process aids. These ingredients are typically mixed
together on a 2-roll mill or other custom mixing machinery.

Molding and Curing

Most of the elastomeric o-rings used are compression
molded. A preshaped form is inserted into a multi-section
mold and transferred to a heated press.
Under heat and pressure, the elastomer
flows into the mold cavities and chemical
cross-linking takes place (or begins to
take place, depending on the specific
elastomer compound). This cross-linking is commonly
referred to as curing or vulcanization. After a period of
time ranging from several seconds to several minutes, the
Mill Mixing
Once the material is compounded, it is shaped into
sheets and then shipped to o-ring molders.

Extrusion
The sheet compound is extruded into a configuration
similar to the desired finished part.

Clean Extrusion
Compression Molding
parts are removed from the hot molds. Depending on the
compound, mold releases are often used. These diluted
spray coatings are often a derivative of fluoropolymers,
or silicone-based polymers.

Elastomer Processingcontinued
Flash Removal

Finishing and Inspection

After the parts are removed from the molds, they contain
thin flash as a result of the elastomer
flowing in the multi-section mold. This
flash is typically removed by exposing
the parts to a cryogenic tumbling process.
The elastomer is cooled and tumbled,
causing the thinner flash section to become brittle and
break away from the main part. Additional tumbling or
hand-deflashing may be required on some part designs
or compounds.

After the parts are removed from the curing ovens, they
are inspected to ensure that the parts
meet the material and dimensional
specifications.

Automatic
Inspection
Machine

Cryo-Deflash Unit

Post-Curing
Some high-performance elastomers are subjected to a
post-curing operation. Elastomer parts are
exposed to high temperatures in carefully
controlled environments for several hours
to complete the curing process. Additionally,
this post-curing step removes excess water
vapor and volatile process additives, thereby improving
vacuum and contamination performance.

Post-Cure Ovens

Elastomer Processingcontinued
Cleaning

Packaging

After the parts are inspected, they are thoroughly cleaned.

In the case of perfluoroelastomers, an ultrapure deionized
water (UPDI) rinsing cycle is used to
remove surface contamination from
the parts.

Parts are then counted and packaged, either individually

or in bulk. Shipping labels include a complete description
of the parts, lot number, the batch and cure
date, as well as any specific information,
including the customers part number,
when applicable.

Common Elastomers
ASTM

POLYMER

TRADE NAMES

MONOMERS

NBR

Nitrile (Buna-N)

PARACRIL, CHEMIGUM

-CH2CH=CH(CH2)2CHCH(CN)-

HNBR-HSN

Hydrogenated Nitrile/

THERBAN, ZETPOL

-CH2-CH(CN)-CH2-(CH2)2-CH2-

Highly Saturated Nitrile

EPDM

Ethylene-Propylene Diene

VISTALON, NORDEL

-CH2CH2-CH2CH(CH3)-

VMQ

Silicone

SILASTIC, SILPLUS

-OSi(CH3)2-OSi(CH3)(CH=CH2)-

FVMQ

Fluorosilicone

SILASTIC LS, FSE

-OSi(CH3)(CH=CH2)OSi(CH3)(CH2CH2CF3)-

FKM

FFKM

Fluoroelastomer A

VITON, FLUOREL

-CH2CF2-CF2CF(CF3)-

Fluoroelastomer B

-CH2CF2-CF2CF(CF3)-CF2CF2-

Fluoroelastomer GF

-CH2CF2-CF2CF(OCF3)-CF2CF2-

Fluoroelastomer ETP

VITON, VITON ETP

-CF2CF2-CF2CF(OCF3)-CH2CH2-

Fluoroelastomer TFE/P

AFLAS

-CF2CF2-CH2CH(CH3)-

Perfluoroelastomer

SIMRIZ, CHEMRAZ,

-CF2CF2-CF2CF(OCFnCF3)-

KALREZ

AFLAS is a registered trademark of Asahi Glass Co., Ltd.

SILASTIC and SILASTIC LS are registered trademarks of Dow Corning STI

CHEMIGUM is a registered trademark of Goodyear

SILPLUS is a registered trademark of General Electric

CHEMRAZ is a registered trademark of Greene, Tweed & Co.

SIMRIZ is a registered trademark of Simrit Division of Freudenberg-NOK

FLUOREL is a registered trademark of Dyneon

THERBAN is a registered trademark of Bayer

FSE is a registered trademark of General Electric

VISTALON is a registered trademark of Exxon Chemical Co.

KALREZ is a registered trademark of Du Pont Dow Elastomers, LLC

VITON and VITON ETP are registered trademarks of Du Pont Dow Elastomers, LLC

NORDEL

ZETPOL is a registered trademark of Zeon Chemical

is a registered trademark of Du Pont Dow Elastomers, LLC

PARACRIL is a registered trademark of Uniroyal

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Publication No. 2103