Classes of Polymeric Materials

Elastomers
Professor Joe Greene
CSU, CHICO

Elastomers
Elastomers are rubber like polymers that are thermoset
or thermoplastic
butyl rubber: natural rubber
thermoset: polyurethane, silicone
thermoplastic: thermoplastic urethanes (TPU), thermoplastic
elastomers (TPE), thermoplastic olefins (TPO), thermoplastic
rubbers (TPR)

Elastomers exhibit more elastic properties versus plastics

which plastically deform and have a lower elastic limit.
Rubbers have the distinction of being stretched 200%
and returned to original shape. Elastic limit is 200%
2

Rubbers

Rubbers have the distinction of being stretched 200% and

returned to original shape. Elastic limit is 200%
Natural rubber (isoprene) is produced from gum resin of
certain trees and plants that grow in southeast Asia, Ceylon,
Liberia, and the Congo.
The sap is an emulsion containing 40% water & 60% rubber particles

Vulcanization occurs with the addition of sulfur (4%).

Sulfur produces cross-links to make the rubber stiffer and harder.
The cross-linkages reduce the slippage between chains and results in higher
elasticity.
Some of the double covalent bonds between molecules are broken, allowing the
sulfur atoms to form cross-links.
Soft rubber has 4% sulfur and is 10% cross-linked.
Hard rubber (ebonite) has 45% sulfur and is highly cross-linked.

Rubber Additives and Modifiers

Fillers can comprise half of the volume of the rubber

Silica and carbon black.

Reduce cost of material.
Increase tensile strength and modulus.
Improve abrasion resistance.
Improve tear resistance.
Improve resistance to light and weathering.
Example,
Tires produced from Latex contains 30% carbon black which improves the body
and abrasion resistance in tires.

Additives
Antioxidants, antiozonants, oil extenders to reduce cost and
soften rubber, fillers, reinforcement
4

Vulcanizable
Elastomeric
Compounds
Rubbers are compounded into practical elastomers
The rubber (elastomer) is the major component and other components are given as weight per
hundred weight rubber (phr)
Sulfur is added in less than 10 phr
Accelerators and activators with the sulfur
hexamethylene tetramine (HMTA)
zinc oxide as activators

Protective agents are used to suppress the effects of oxygen and ozone
phenyl betabaphthylamine and alkyl paraphenylene diamine (APPD)

Reinforcing filler
carbon black
silica when light colors are required
calcium carbonate, clay, kaoilin

Processing aids which reduce stiffness and cost

Plasticizers, lubricants, mineral oils, paraffin waxes,

Vulcanizable Rubber
Typical tire tread
Natural rubber smoked sheet (100),
sulfur (2.5) sulfenamide (0.5), MBTS (0.1), strearic acid (3), zinc
oxide (3), PNBA (2), HAF carbon black (45), and mineral oil (3)

Typical shoe sole compound

SBR (styrene-butadiene-rubber) (100) and clay (90)

Typical electrical cable cover

polychloroprene (100), kaolin (120), FEF carbon black (15) and
mineral oil (12), vulcanization agent

Synthetic Rubber

Reactive system elastomers

Low molecular weight monomers are reacted in a polymerization step with very little cross-linking.
Reaction is triggered by heat, catalyst, and mixing
Urethanes processed with Reaction Injection Molding (RIM)
Silicones processed with injection molding or extrusion

Thermoplastic Elastomers
Processing involves melting of polymers, not thermoset reaction
Processed by injection molding, extrusion, blow molding, film blowing, or rotational molding.
Injection molded soles for footwear

Advantages of thermoplastic elastomers

Less expensive due to fast cycle times
More complex designs are possible
Wider range of properties due to copolymerization

Disadvantage of thermoplastic elastomers

Higher creep

Thermoplastic Elastomers
Four types of elastomers
Olefinics and Styrenics
Polyurethanes and Polyesters

Olefinics (TPOs are used for bumper covers on cars)

Produced by
Blending copolymers of ethylene and propylene (EPR) or ter polymer of ethylene-propylene diene
(EPDM) with
PP in ratios that determine the stiffness of the elastomer
A 80/20 EPDM/PP ratio gives a soft elastomer (TPO)

Styrenic thermoplastic elastomers (STPE)

Long triblock copolymer molecules with
an elastomeric central block (butadiene, isoprene, ethylene-butene, etc.) and
end blocks (styrene, etc.) which form hard segments

Other elastomers have varying amounts of soft and hard blocks

Thermoplastic Elastomers
Polyurethanes
Have a hard block segment and soft block segment
Soft block corresponds to polyol involved in polymerization in ether based
Hard blocks involve the isocyanates and chain extenders

Polyesters are etheresters or copolyester thermoplastic

elastomer
Soft blocks contain ether groups are amorpous and flexible
Hard blocks can consist of polybutylene terephthalate (PBT)

Polyertheramide or polyetherblockamide elastomer

Hard blocks consits of a crystallizing polyamide
Soft

Hard Soft
Hard Soft Hard
9

Commercial
Elastomers
Diene C=C double bonds and Related Elastomers
Polyisoprene- (C5H8)20,000

H H C H3 H
Cis [C C C C ]
H
H
H H
H
Trans is major component of gutta percha, the first plastic
Trans [C C C C ]
Natural rubber was first crosslinked into highly elastic network by Charles Goodyear
(vulcanization
with
H
H
CH
3
sulfur in 1837)

Basic structure of natural rubber

Can be produced as a synthetic polymer
Capable of very slow crystallization
Tm = 28C, Tg = -70C for cis polyisoprene
Tm = 68C, Tg = -70C for trans polyisoprene

Sulfur crosslinked with the unsaturations C=C

Natural rubber in unfilled form is widely used for products with

very large elastic deformations or very high resilience,
resistance to cold flow (low compression set) and
resistance to abrasion, wear, and fatigue.

Natural rubber does not have good intrinsic resistance to sunlight, oxygen, ozone, heat aging, oils, or
fuels.

10

Commercial ElastomersH

H H H
[C C C C ]
Polybutadiene
H
H
Basis for synthetic rubber as a major component in copolymers Styrene-Butadiene
Rubber (SBR, NBR) or in
Blends with other rubbers (NR, SBR)
Can improve low-temperature properties, resilence, and abrasion or wear resistance
Tg = -50C

Polychloroprene

H H Cl H
Polychloroprene or neoprene was the very first synthetic rubber [C C C C ]
H
H
Due to polar nature of molecule from Cl atom it has very good resistance
to oils and

is flame resistant (Cl gas coats surface)

Used for fuel lines, hoses, gaskets, cable covers, protective boots, bridge pads,
roofing materials, fabric coatings, and adhesives
Tg = -65C.

11

Commercial Elastomers
Butyl rubber- addition polymer of isobutylene.

H CH3
[C C ]
H C H3

Copolymer with a few isoprene units, Tg =-65C

Contains only a few percent double bonds from isoprene
Small extent of saturation are used for vulcanization
Good regularity of the polymer chain makes it possible for the elastomer to crystallize on
stretching
Soft polymer is usually compounded with carbon black to increase modulus

Nitrile rubber

Copolymer of butadiene and acrylonitrile

Solvent resistant rubber due to nitrile C:::N
Irregular chain structure will not crystallize on stretching, like SBR
vulcanization is achieved with sulfur like SBR and natural rubber

Thiokol- ethylene dichloride polymerized with sodium polysulfide. Sulfur makes

thiokol rubber self vulcanizing.

12

Thermoplastic Elastomers
Thermoplastic Elastomers result from copolymerization of
two or more monomers.
One monomer is used to provide the hard, crystalline features, whereas
the other monomer produces the soft, amorphous features.
Combined these form a thermoplastic material that exhibits properties
similar to the hard, vulcanized elastomers.

Thermoplastic Urethanes (TPU)

The first Thermoplastic Elastomer (TPE) used for seals gaskets,
etc.

Other TPEs

Copolyester for hydraulic hoses, couplings, and cable insulation.

Styrene copolymers are less expensive than TPU with lower strength
Styrene-butadiene (SBR) for medical products, tubing, packaging, etc.
Olefins (TPO) for tubing, seals, gaskets, electrical, and automotive.

13

Thermoplastic Elastomers
Styrene-butadiene rubber (SBR)
Developed during WWII
Germany under the name of BUNA-S.
North America as GR-S,Government rubber-styrene.

HH H H H H
C C [C C C C ]
H
H
H
n

Random copolymer of butadiene (67-85%) and styrene (15-33%)

Tg of typical 75/25 blend is 60C
Not capable of crystallizing under strain and thus requires reinforcing
filler, carbon black, to get good properties.
One of the least expensive rubbers and generally processes easily.
Inferior to natural rubber in mechanical properties
Superior to natural rubber in wear, heat aging, ozone resistance, and
resistance to oils.
Applications include tires, footwear, wire, cable insulation, industrial
rubber products, adhesives, paints (latex or emulsion)
More than half of the worlds synthetic rubber is SBR
World usage of SBR equals natural rubber

14

Acrylonitrile-butadiene rubber (NBR)

H H
Also called Nitrile rubber
Developed as an oil resistant rubber due to

C C
H C:::Nn

H H H H
[C C C C ]
H
Hm

the polar C:::N polar bond. Resistant to oils, fuels, and solvents.

Copolymer of acrylonitrile (20-50%) and butadiene(80-50%)

Moderate cost and a general purpose rubber.
Excellent properties for heat aging and abrasion resistance
Poor properties for ozone and weathering resistance.
Has high dielectric losses and limited low temperature flexibility
Applications include fuel and oil tubing; hose, gaskets, and seals; conveyer
belts, print rolls, and pads.
Carboxylated nitrile rubbers (COX-NBR) has carboxyl side groups
(COOH)which improve
Abrasion and wear resistance; ozone resistance; and low temperature flexibility

NBR and PVC for miscible, but distinct polymer blend or polyalloy
30% addition of PVC improves ozone and fire resistance

15

Ethylene-propylene rubber (EPR)

EPR and EPDM
Form a noncrystallizing copolymer
with a low Tg.

The % PP and PE units determines properties

Tg = -60C for PE/PP of 67/33 to 50/50

H H

H H

H H

C C

C C

C C

H H

Unsaturated polymer since PP and PE are saturated

Resistant to ozone, weathering, and heat aging
Does not allow for conventional vulcanization

H CH3
m
n

H CH2
CH m
CH
CH3

Terpolymer with addition of small amount of third monomer (Diene D) has

unsaturations referred to as EPDM

1,4, hexadiene (HD); 5-ethylidene-2-norbornene (ENB); diclopentadiene (DCPB)

feature unsaturations in a side (pendant) group
Feature excellent ozone and weathering resistance and good heat aging

Limitations include poor resistance to oils and fuels, poor adhesion to many
substrates and reinforcements
Applications include exterior automotive parts (TPO is PP/EPDM), construction
parts, weather strips, wire and cable insulation, hose and belt products, coated
fabrics.

16

Ethylene Related Elastomers

Chlorosulfonated Polyethylene (CSPE)

H H

Moderate random chlorination of PE (24-43%)

C
Infrequent chlorosulfonic groups (SO2Cl)
Sulfur content is 1-1.5%.
H
CSPE is noted for excellent weathering resistance

Cl

mO S Ok
Cl

Good resistance to ozones, heat, chemicals, solvents.

Good electrical properties, low gas permeability, good adhesion to substrates

Applications include hose products, roll covers, tank linings, wire and cable
covers, footwear, and building products

Chlorinated Polyethylene (CPE)

Moderate random chlorination
Suppresses crystallinity (rubber)
Can be crosslinked with peroxides
Cl range is 36-42% versus 56.8% for PVC

Properties include good heat, oil, and ozone resistance

Used as plasticizer for PVC

17

Ethylene Related Elastomers

Ethylene-vinylacetate Copolymer (EVA)
Random copolymer of E and VA
Amorphous and thus elastomeric
VA range is 40-60%
Can be crosslinked through organic peroxides

H H

H H

C C

C C

Properties include
Good heat, ozone, and weather resistance

Ethylene-acrylate copolymer (EAR)

Copolymer of Ethylene and methacrylate
Contains carboxylic side groups (COOH)

Properties include
Excellent resistance to ozone and
Excellent energy absorbers
Better than butyl rubbers

H H

n H O m
O=CCH3

H H

H H

C C

C C

H H

n H C OCH3
O m

18

FluoroElastomers
Polyvinylidene fluoride (PVDF)
Tg = -35C

Poly chloro tri fluoro ethylene (PCTFE)

Tg = 40C

Poly hexa fluoro propylene (PHFP)

Tg = 11C

Poly tetra fluoro ethylene (PTFE)

Tg = - 130C

Fluoroelastomers are produced by

random copolymerization that
suppresses the crystallinity and
provides a mechanism for cross linking by terpolymerization
Monomers include VDF, CTFE, HFP, and TFE

H F
C C
H F

F F
n

C C
F Cl

C C

n
F F

F F

C C

F F

F CF3

19

FluoroElastomers
Fluoroelastomers are expensive but have outstanding properties
Exceptional resistance to chemicals, especially oils, solvents
High temperature resistance, weathering and ozone resistance.
Good barrier properties with low permeability to gases and vapors

Applications
Mechanical seals, packaging, O-rings, gaskets, diaphrams, expansion joints, connectors, hose liners, roll covers, wire and cable insulation.

Previous fluoroelastomners are referred to as

Fluorohydrocarbon elastomers since they contain F, H, and C atoms with O sometimes

Two other classes of elastomers include fluorinated types

Fluorosilicone elastomers remain flexible at low temperatures
Fluorinated polyorganophosphazenes have good fuel resistance

20

Silicone Polymers
Silicone polymers or polysiloxanes (PDMS)
Polymeric chains featuring

CH3
Si O

Tg = -125C
3
Very stable alternating combination of
m
Silicone and oxygen, and a variety of organic side groups attached to Si
Two methyl, CH3, are very common side group generates polydimethylsiloxane (PDMS)
Unmodified PDMS has very flexible chains corresponding to low Tg
Modified PDMS has substitution of bulky side groups (5-10%)
Phenylmethlsiloxane or diphenylsiloxane suppress crystallization
Substituted side groups, e.g., vinyl groups (.5%) featuring double bonds (unsaturations ) enables
crosslinking to form vinylmethylsiloxane (VMS)
Degree of polymerization, DP, of polysiloxane = 200-1,000 for low consistency chains to 3,000-10,000
for high consistency resins.
Mechanism of crosslinking can be from a vinyl unsaturation or reactive end groups (alkoxy, acetoxy)

CH

21

Silicone Polymers
Silicone polymers or polysiloxanes (PDMS)
Properties

CH3
Si O
CH

3
Mediocre tear properties
m
High temperature resistance from -90C to 250C.
Surface properties are characterized by very low surface energy (surface
tension) giving good slip, lubricity, and release properties (antistick) nand
water repellency.
Excellent adhesion is obtained for curing compounds for caulk.

22

Silicones

Unmodified PDMS has very flexible chains with a low Tg.

Regular structure allows for crystallization below Tm
Addition of small amount of bulky side groups are used to
suppress crystallization
Trifluoropropyl side groups enhance the resistance to solvent swelling and
are called fluorosilicones
Linear form (uncrosslinked) polysiloxane corresponds to DP of 200-1000
for low consistency to 3,000-10,000 for high consistency resins
Mechanism for crosslinking (vulcanization) can be based upon vinyl
unsaturations or reactive end groups (alkoxy)

Silicone polymers are mostly elastomers with mediocre tear properties,

but with addition of silica can have outstanding properties unaffected by
a wide temp range from 90C to 250C
Surface properties have low surface energy, giving good slip, lubricity,
release properties, water repellency, excellent adhesion for caulks
Good chemical inertness but sensitive to swelling by hydrocarbons
Good resistance to oils and solvents, UV radiation, temperature
Electrical properties are excellent and stable for insulation and dielectric
23

 Properties

Silicones

Low index of reflection gives silicone contains useful combination of high

transmission and low reflectance
Can be biologically inert and with low toxicity are well tolerated by body
tissue
Polymers are normally crosslinked in the vulcanization stage. Four groups

Low consistency-room temperature curing resins (RTV)

Low consistency-high temperature curing resins (LIM,LSR)
High consistency-high temperature curing resins (HTV, HCE),
Rigid resins

RTV elastomers involve low molecular weight polysiloxanes and rely on

reactive end groups for crosslinking at room temperature.
One component, or one part, packages rely on atmospheric moisture for curing and
are used for thin parts or coatings
Two component systems have a catalyst and require a mixing stage and result in a
small exotherm where heat is given off.

24

 Properties

Silicones

LSR elastomers involve low molecular weight polysiloxanes but a different

curing system
Relatively high temperature (150C) for a faster cure (10-30s)
Mixed system is largely unreactive at room temp (long pot life)
Suitable for high speed liquid injection molding of small parts.

HTV elastomers contain unsaturations that are suitable for conventional

rubber processing.
Heat curable elastomers (HCE) are cross linked through high temperature vulcanization
(HTV) with the use of peroxides.

Rigid silicones are cross linked into tight networks.

Non-crosslinked systems are stable only in solutions that are limited to paints, varnishes,
coatings, and matrices for laminates
Cross-linking takes place when the solvent evaporates.
Post curing is recommended to complete reaction, e.g., silicone-epoxy systems for
electrical encapsulation.

25

Silicones Applications

Most applications involve elastomeric form.

Flexibility and hardness can be adjusted over a wide range

Electrical applications high voltage and high or low temperatures

Power cable insulation, high voltage leads and insulator boots, ignition cables,
spark plug boots, etc..
Semi-conductors are encapsulated in silicone resins for potting.

Mechanical applications requiring low and high-temperature flexibility

and chemical inertness
O-rings, gaskets, seals for aircraft doors and windows, freezers, ovens, and
appliances, diaphragms flapper valves, protective boots and bellows.

Casting molds and patterns for polyurethane, polyester, or epoxy

Sealants and caulking agents
Shock absorbers and vibration damping characteristics
Silly-Putty: Non-crosslinked, high molecular weight PDMS-based compound
modified with fillers and plasticizers.

Biomedical field for biological inertness include prosthetic devices

26

Miscellaneous Other Elastomers

Acrylic Rubber (AR)
Polyethylacrylate (PEA) copolymerized with a small amount (5%) of 2chloro-ethyl-vinyl-ether CEVE, which is a cure site.
The Tg of PEA is about -27C and acrylic rubber is not suitable for low
temperature applications.
Polybutylacrylate (PBR) has a Tg of -45C.
Applications
Resistant to high temperatures, lubricating oils, including sulfur-bearing
oils.
Include seals, gaskets, and hoses.

Epichlorohydrin Rubber (ECHR)

Polymerization of epichlorohydrin with a repeat unit of PECH.

Excellent resistant to oils, fuels and flame resistance. (Cl presence)
Copolymer with flexible ethyleneoxide (EO) provides Tg = -40C
Applications include seals, gaskets, diaphragms, wire covers

27

Miscellaneous Other Elastomers

H H
[C C S
Polysulfide Rubbers (SR)
H H S
One of the first synthetic rubbers. Tg =-27C, PES Thiokol A

S ]
S

Consists of adjacent ethylene and sulfide units giving a stiff chain.

Flexibility is increased with addition of ethylene oxide for polyethylene-ethersulfide (PEES), Thiokol B
Mechanical properties are not very good, but are used for outstanding resistance
to many oils, solvents and weathering.
H H
Applications include caulking, mastics, and putty.

Propylene rubber (PROR)

Does not crystallize in its atactic form and has a low Tg = -72C.
Has excellent dynamic properties

C C O
H CH3 n

28

Miscellaneous Other Elastomers

Polynorborene (PNB)
Norborene polymerizes into highly molecular weight PNB.
Tg = 35C but can be plasticized with oils and vulcanized into an
elastomer with lower Tg = -65C.
Excellent damping properties that can be adjusted.

Polyorgano-phosphazenes (PPZ)
Form an example of a new class of polymeric materials involving
inorganic chains.
Atoms of Nitrogen (azo) and Phosphorous form, the chain and a variety of organic
side groups, R1 and R2 can be attached to the phosphorous atom.
Side groups include halo (Cl or F), amino (NH2 or NHR), alkoxy (methoxy, ethoxy,
etc.) and fluoroalkoxy groups.
High molecular weight is flexible with a low Tg
Excellent inherent fire resistance, weatherability, and water & oil repellency
Applications
coatings, fibers, and biomedical materials

29

Commercial Elastomers
Characteristics
Name
Natural rubber
Polyisoprene
Polybutadiene
SBR
Nitrile
Butyl
EPR (EPDM)
Neoprene
Silicone
Thiokol
Urethanes

Chemical Name
cis polyisoprene
cis polyisoprene
Polybutadiene
Polybutadiene-styrene
Polybutadiene-acrylonitrile
Poly isobutylene-isoprene
Poly ethylene propylene- diene
Polychloroprene
Polydimethylsiloxane
Polyslkylenesulfide
Polyester or polyether urethanes

Vucanization agent
sulfur
sulfur
sulfur
sulfur
sulfur
sulfur
Peroxies or sulfur
MgO
peroxides
ZnO
Diisocycanates

30

Commercial Elastomers
Costs
Name
Consumption 1983 (metric tons)
Natural rubber
676,267
Polyisoprene
Polybutadiene
335,541
SBR
887,005
Nitrile
57,239
Butyl
EPR (EPDM)
141,490
Neoprene
85,096
Silicone
Thiokol Psulfides
Urethanes

$/lb
$0.44
$0.72
$0.74
$0.66
$1.10
$0.76
$1.01
$1.29
$4.40
$1.83
$3.70

Type
General Purpose
General Purpose
General Purpose
General Purpose
Solvent Resistant
General Purpose
General Purpose
Solvent Resistant
Heat Resistant
Solvent Resistant
Solvent Resistant

31

Polymerization Mechanisms
Step-wise (Condensation) Polymerization
Monomers combine to form blocks 2 units long
2 unit blocks form 4, which intern form 8 and son on
until the process is terminated.
Results in by-products (CO2, H2O, Acetic acid, HCl
etc.)

Chain Growth (Addition) Polymerization

Polymerization begins at one location on the monomer
by an initiator
Instantaneously, the polymer chain forms with no byproducts
32

Condensation Polymerization Example

Polyamides
Condensation Polymerization
Nylon 6/6 because both the acid and amine contain
6 carbon atoms
NH2(CH2)6NH2 + COOH(CH2)4COOH
Hexamethylene diamene

Adipic acid

n[NH2(CH2)6NH2 CO(CH2)4COOH] (heat)

Nylon salt

[NH(CH2)4NH CO(CH2)4CO]n + nH2O

Nylon 6,6 polymer chain

33

Condensation Polymerization Example

Polyurethane
Reaction of isocyanate and polyether-alcohol (polyol)

Polyester
Polymerization of acid and and alcohol

Polycarbonate
Polycarbonates are linear, amorphous polyesters because they contain esters of carbonic acid and an aromatic bisphenol (C 6H5OH)

OH

+ CH3

O
C CH2

Phenol + Acetone

CH2
OH
OH +
C
CH2
Bisphenol-A + water

H2O
34

Other Condensation Polymers

Thermoplastic Polyesters
Saturated polyesters (Dacron).
Linear polymers with high MW and no crosslinking.
Polyethylene Terephthalate (PET). Controlled crystallinity.
Polybutylene Terephthalate (PBT).

Aromatic polyesters (Mylar)

O
R

O C R

O
O C

R
35

Step-Growth Polymerization
Condensation Polymerizatio

Main feature is that all molecular species in the

system can react with each other to form higher
molecular weight species.
Step-growth polymerization reactions fall into two
classes
A-R1-A + B-R2-B
A-R1-A + B-R2-B

=> A-R1-R2-B + AB
=> A-R1-AB-R2-B

where A and B are repeat polymer groups which react with each other;
Example, for polyurethanes A = Isocyanate and B = Polyol and the
by-product is water.
and R1 and R2 are long chain polymers

36

Formation of Polymers
Condensation Polymerization
Step-growth polymerization proceeds by several steps which result
in by-products.

Step-wise (Condensation) Polymerization

Monomers combine to form blocks 2 units long
2 unit blocks form 4, which intern form 8 and son on until the
process is terminated.
Results in by-products (CO2, H2O, Acetic acid, HCl etc.)

37

Chain Growth (Addition)

Polymerization
Chain Growth (Addition) Polymerization by
Free Radical Mechanism
Involves three primary steps
Initiation- formation of free radicals through homolytic
dissociation of weak bonds (e.g., peroxides). Results in opening
up unsaturated (C=C) bonds to saturated (C-C) bonds)
Propagation- formation of long chain polymers of the now free
C-C bonds
Termination- reactions at the ends of the polymer cause C-C to
terminate with a functional group that does not have any free
electrons to bond with and results in unsaturated end group (CC=CX)
38

Chain Growth (Addition)

Polymerization
Special case of Diene polymerization
Very important in elastomers- mostly addition
Polydienes are the backbone of the synthetic
rubber are produced by free radical
polymerization
Early attempts of polymerization was slow and
produced low molecular weight polymers (oils)
Emulsion polymerization (1930s) was introduced
to speed up polymerization and higher Molecular
weights
39

Polymerization Methods
4 Methods to produce polymers
Some polymers have been produced by all four methods
PE, PP and PVC are can be produced by several of these
methods
The choice of method depends upon the final polymer form, the
intrinsic polymer arrangement (isotactic, atactic, etc), and the
yield and throughput of the polymer desired.

Bulk Polymerization
Solution Polymerization
Suspension Polymerization
Emulsion Polymerization
40

Formation of Polymers
Polymers from Addition reaction
LDPE

HDPE

PP

H H

H H

H H

C C

C C

C C

H H

PVC

H H

H CH3

PS

H H

H H

C C

C C

H Cl

41

Other Addition Polymers

Vinyl- Large group of addition
polymers with the formula:
Radicals (X,Y) may be attached to this repeating
vinyl group as side groups to form several related
polymers.

Polyvinyls

or

Polyvinyl chloride
Polyvinyl dichloride
(polyvinylidene chloride)

Cl

Polyvinyl Acetate (PVAc)

Cl

Cl

OCOCH3 42

Manufacturing of Emulsion SBR

Free-radical emulsion process
Developed in 1930s and still in use
Typical process (Figure)
Soap stabilized water emulsion of two monomers is converted in a train of
10 continuous reactors (4000 gallons each)
Water, butadiene, styrene, soaps, initiators, buffers, and modifier are fed
continuously
Temp is 5 to 10C and conversion proceeds until 60% of the reactants have
polymerized in the last reactor.
Shortstop is added in the emulsion to stop the conversion at 60%
Unreacted butadiene is flashed off with steam and recycled
Unreacted styrene is stripped off in a distillation column that separates liquid
rubber emulsion from the gas styrene.
Rubber is recovered from the latex in a series of operations.
Introduction of antioxidants, blending with oils, dilution with brine,
coagulation, dewatering, drying, and packaging the rubber

43

Manufacturing of Emulsion SBR

Polymerization
Cold SBR: at 5 to 10C is called the cold process,
Better abrasion resistant, treadwear, and dynamic properties.

Hot SBR: at about 50C is called the hot process.

Conversion is allowed to proceed to 70%
Higher branching occurs and incipient gelation.

Typical SBR recipes, Table from Mortons Rubber

technology

44

Manufacturing of Emulsion SBR

Compounding and Processing
Similar to natural rubber
Materials for large scale use, e.g., tires, based on
Rubber, fillers (carbon black), extending oils, zinc oxide, sulfur,
accelerators, antioxidants, antiozonants, and waxes.

Materials are mixed in a mill or twin rollers or calendered

Processing into smooth compounds that can be quickly
pressed, sheeted, calendered, or extruded

Recipes
Large parts, e.g., tires and hoses, are given in Tables 7.6,
7.7, 7.8, and 7.9
45

Polymerization of Elastomers
Butadiene-Acrylonitrile (Nitrile) Rubber
Produced by emulsion polymerization
Nitrile rubbers have nitrile contents from 10 to 40%.

Chloroprene rubber
Produced by emulsion polymerization
Produced as a homopolymer that has a high trans 1,4
chain structure and is susceptible to strain-induced
crystallization, much like natural rubber.
Leads to high tensile strength

Does not lead itself to copolymerization

46

Polymerization of Elastomers
Butyl Rubber Only important commercial rubber prepared by cationic
polymerization
Processes with AlCl at 98 to 90C

Copolymer of isobutene and isoprene with isoprene used

in 1.5 % quantities
The isoprene is introduced to provide sufficient unsaturations
for sulfur vulcanization.

MW is in the range of 300,000 to 500,000

47

Processing of Elastomers
Rubber Products
50% of all rubber produced goes into automobile tires;
50% goes into mechanical parts such as
mountings, gaskets, belts, and hoses, as well as
consumer products such as shoes, clothing, furniture, and toys

Elastomers and Rubbers

Thermoset rubbers
Compounding the ingredients in recipe into the raw rubber with a
mill, calender, or Banbury (internal) mixer
Compression molding of tires

Thermoplastic elastomers
Compression molding, extrusion, injection molding, casting.

48

Processing of Elastomers
Rubber Processors
Mills and Banbury mixers

49

Compression Molding Process

Materials

Elastomers:
Thermoplastic
Thermoplastic Olefin (TPO), Thermoplastic Elastomer (TPE),
Thermoplastic Rubber (TPR)
Thermoset rubbers
Styrene Butadiene Rubber, isoprene

Thermoplastic:
Heat Plastic
prior to molding

Thermosets:
Heat Mold
during molding

50

Polyurethane Processing
Polyurethane can be processed by
Slow process: Casting or foaming, or
Fast process: Reaction Injection Molding (RIM)

51

Injection Molding Glass Elastomers

Plastic pellets with copolymer elastomers.
Similar processing requirements as with injection
molding of commodity and engineering plastics
Injection pressures, tonnage, pack pressure, shrinkage

52

Transfer Molding of Rubbers

Transfer molding is a process by which uncured rubber
compound is transferred from a holding vessel (transfer pot) to
the mold cavities using a hydraulically operated piston.
Transfer molding is especially conducive to multicavity designs
and can produce nearly flashless parts.

53

Calendering of Rubbers
Calendering is the process for producing long runs of uniform
thickness sheets of rubber either unsupported or on a fabric
backing. A standard 3 or 4 roll calender with linear speed range
of 2 to 10 feet/minute is typical for silicone rubber. Firm
compound with good green strength and resistance to
overmilling works the best for calendering.

54

Curing of Rubbers
Extruded profile may be cured by hot air vulcanization (HAV),
steam vulcanization (CV) or liquid-medium cure. HAV consists
of a heated tunnel through which the profile is fed continuously
on a moving conveyor. Air temperature reaches 600F to
1200F, and cure times are usually short, on the order of 3 to 12
seconds. The recommended curing agents are DCBP-50 or
addition cure, both of which provide rapid cure with no
porosity.
Steam cure commonly refers to the steam curing systems used
by the wire and cable industry and consists of chambers 4
6 in diameter and 100 150 feet in length. Steam pressure
varies from 50 psig to 225 psig depending on wall thickness of
the insulation.
For liquid-medium cure, continuous lengths of extruded profile
are fed into a bath of moltenmaterial (salt or lead) which cures
the extrudate.
55

Polymer Length
Polymer Length
Polymer notation represents the repeating group
Example, -[A]-n where A is the repeating monomer and n represents the
number of repeating units.

Molecular Weight
Way to measure the average chain length of the polymer
Defined as sum of the atomic weights of each of the atoms in the
molecule.
Example,
Water (H2O) is 2 H (1g) and one O (16g) = 2*(1) + 1*(16)= 18g/mole
Methane CH4 is 1 C (12g) and 4 H (1g)= 1*(12) + 4 *(1) = 16g/mole
Polyethylene -(C2H4)-1000 = 2 C (12g) + 4H (1g) = 28g/mole * 1000 = 28,000
g/mole

56

Molecular Weight
Average Molecular Weight
Polymers are made up of many molecular weights or a
distribution of chain lengths.
The polymer is comprised of a bag of worms of the same
repeating unit, ethylene (C2H4) with different lengths; some
longer than others.
Example,
Polyethylene -(C2H4)-1000 has some chains (worms) with 1001 repeating
ethylene units, some with 1010 ethylene units, some with 999 repeating
units, and some with 990 repeating units.
The average number of repeating units or chain length is 1000 repeating
ethylene units for a molecular weight of 28*1000 or 28,000 g/mole .

57

Molecular Weight

Average Molecular Weight

Distribution of values is useful statistical way to

characterize polymers.
For example,
Value could be the heights of students in a room.
Distribution is determined by counting the number of students in the
class of each height.
The distribution can be visualized by plotting the number of students on
the x-axis and the various heights on the y-axis.

Frequency

Histogram of Heights of Students

25
20
15
10
5
0

Series1

60

70
Height, inches

80

58

Molecular Weight
Molecular Weight Distribution
Count the number of molecules of each molecular weight
The molecular weights are counted in values or groups that have similar lengths,
e.g., between 100,000 and 110,000
For example,
Group the heights of students between 65 and 70 inches in one group, 70 to 75
inches in another group, 75 and 80 inches in another group.

The groups are on the x-axis and the frequency on the y-axis.
The counting cells are rectangles with the width the spread of the cells and
the height is the frequency or number of molecules
Figure 3.1
A curve is drawn representing the overall shape of the plot by connecting
the tops of each of the cells at their midpoints.
The curve is called the Molecular Weight Distribution (MWD)

59

Molecular Weight
Average Molecular Weight
Determined by summing the weights of all of the chains
and then dividing by the total number of chains.
Average molecular weight is an important method of
characterizing polymers.
3 ways to represent Average molecular weight
Number average molecular weight
Weight average molecular weight
Z-average molecular weight

60

Gel Permeation Chromatography

GPC Used to measure Molecular Weights
form of size-exclusion chromatography
smallest molecules pass through bead pores, resulting in
a relatively long flow path
largest molecules flow around beads, resulting in a
relatively short flow path
chromatogram obtained shows intensity vs. elution
volume
correct pore sizes and solvent critical

61

Gel Permeation Chromatography

62

Number Average Molecular Weight, Mn

Mn

NM
N M N M N M ...

N
N N N ...

where Mi is the molecular weight of that species (on the x-axis)

i

where Ni is the number of molecules of a particular molecular species I (on

the y-axis).
Number Average Molecular Weight gives the same weight to all polymer
lengths, long and short.
Example, What is the molecular weight of a polymer sample in which the polymers

molecules are divided into 5 categories.

Group Frequency
50,000
1
100,000
4
200,000
5
N i M i N1 M 1 N 2 M 2 N 3 M 3 ...
M

n
500,000
3
N 1 N 2 N 3 ...
Ni
700,000
1
1(50 K ) 4(100 K ) 5(200 K ) 3(500 K ) 1(700 K )
Mn

(1 4 5 3 1)

M n 260,000

63

Molecular Weight

Number Average Molecular Weight. Figure 3.2

The data yields a nonsymmetrical curve (common)
The curve is skewed with a tail towards the high MW
The Mn is determined experimentally by analyzing the number of
end groups (which permit the determination of the number of
chains)
The number of repeating units, n, can be found by the ratio of the
Mn and the molecualr weight of the repeating unit, M 0, for example
for polyethylene, M0 = 28 g/mole
The number of repeating units, n, is often called the degree of
polymerization, DP.
DP relates the amount of
monomer that has been converted to polymer.

Mn
n
M0

64

Weight Average Molecular Weight, Mw

2
N
M
i i

N 1 M 12 N 2 M 22 N 3 M 32 ...
Mw

N i M i N1 M 1 N 2 M 2 N 3 M 3 ...

Weight Average Molecular Weight, Mw

Favors large molecules versus small ones
Useful for understanding polymer properties that relate to
the weight of the polymer, e.g., penetration through a
membrane or light scattering.
Example,
Same data as before would give a higher value for the
Molecular Weight. Or, Mw = 420,000 g/mole

65

Z- Average Molecular Weight

Mz

3
N
M
i i

2
N
M
i i

N 1 M 13 N 2 M 23 N 3 M 33 ...

N 1 M 12 N 2 M 22 N 3 M 32 ...

Emphasizes large molecules even more than Mw

Useful for some calculations involving mechanical
properties.
Method uses a centrifuge to separate the polymer

66

Molecular Weight Distribution

Molecular Weight Distribution represents the
frequency of the polymer lengths
The frequency can be Narrow or Broad, Fig 3.3
Narrow distribution represents polymers of about the
same length.
Broad distribution represents polymers with varying
lengths
MW distribution is controlled by the conditions
during polymerization
MW distributions can be symmetrical or skewed.
67

Physical and Mechanical Property

Implications of MW and MWD
Higher MW increases
Tensile Strength, impact toughness, creep resistance, and
melting temperature.

Due to entanglement, which is wrapping of polymer

chains around each other.
Higher MW implies higher entanglement which yields
higher mechanical properties.
Entanglement results in similar forces as secondary or
hydrogen bonding, which require lower energy to break
than crosslinks.
68

Physical and Mechanical Property Implications

of MW and MWD

Higher MW increases tensile strength

Resistance to an applied load pulling in opposite directions

Tension forces cause the polymers to align and reduce the number of
entanglements. If the polymer has many entanglements, the force would be
greater.

Broader MW Distribution decreases tensile strength

Broad MW distribution represents polymer with many shorter molecules
which are not as entangled and slide easily.

Higher MW increases impact strength

Impact toughness or impact strength are increased with longer polymer
chains because the energy is transmitted down chain.

Broader MW Distribution decreases impact strength

Shorter chains do not transmit as much energy during impact

69

Thermal Property Implications of MW & MWD

Higher MW increases Melting Point
Melting point is a measure of the amount of energy necessary
to have molecules slide freely past one another.
If the polymer has many entanglements, the energy required
would be greater.
Low molecular weights reduce melting point and increase ease
of processing.
Broad MW distribution represents polymer with many shorter
molecules which are not as entangled and melt sooner.
Broad MW distribution yields an easier processed polymer
Melting
Point

Mechanical
Properties

Broader MW Distribution decreases Melting Point

* Decomposition
70

Example of High Molecular Weight

Ultra High Molecular Weight Polyethylene (UHWMPE)
Modifying the MWD of Polyethylene yields a polymer with
Extremely long polymer chains with narrow distribution
Excellent strength
Excellent toughness and high melting point.

Material works well in injection molding (though high melt T)

Does not work well in extrusion or blow molding, which
require high melt strength.
Melt temperature range is narrow and tough to process.
Properties improved if lower MW polyethylene
Acts as a low-melting lubricant
Provides bimodal distributions, Figure 3.5
Provides a hybrid material with hybrid properties

71