Thermoplastic Elastomers

CORPORATE TRAINING AND PLANNING

 Thermoplastic Elastomers
By Dr.B.Ramaraj
 Important Thermoplastic Polyurethane
Elastomers
 POLYURETHANE ELASTOMERS
 POLYOLEFIN ELASTOMERS
 POLYESTER ELASTOMERS
 STYRENE ELASTOMERS
 POLYAMIDE ELASTOMERS
 ELASTOMER- THERMOPLASTIC BLENDS

CORPORATE TRAINING AND PLANNING

 Introduction
Thermoplastic Elastomers are made by
copolymerising two or more monomers.
TPE’s contains hard and soft segments.
TPE’s properties can be controlled by
varying monomer ratios and length of the hard soft
segments.
TPE’s can be reclaimed and recycled.

CORPORATE TRAINING AND PLANNING

 Thermoplastic Polyurethane
Elastomers (TPU)
 Polyurethanes are characterized by the presence of
urethane linkages
 - CO-NH-(R)-NH-CO-O- (R’)-O-
Urethanes are reaction product of a diisocyanate and
diols
Abrasion resistance of the urethane is outstanding
among elastomers

CORPORATE TRAINING AND PLANNING

 TPU-Structure and properties
• Polyurethane consist of hard and soft segments
• The hard segments control the rigidity and strength -
Diisocyantes- MDI, HMDI
• The soft segment controls low temperature
properties solvent resistance and weathering -
polyesters, polyethers

CORPORATE TRAINING AND PLANNING

 TPU-Additives
• Mold release agents are the most commonly
employed additives
• Polyester based TPUs are stabilized by aromatic
carbodiimides
• Sterically hindered phenols, amines are used against
degradation by light, oxidation
• Friction can be reduced by the addition of graphite's,
silicone oil, fluorinated hydrocarbons
• Calcium carbonate, organic fibers and glass fibers
are used as reinforcing fillers

CORPORATE TRAINING AND PLANNING

 TPU-Synthesis
• Thermoplastic polyurethanes are made by mixing
the isocyantes and alcohols at temperatures above
80 C. for optimum results, the ratio of isocyanate
groups and alcohol's ,should be close to one.

CORPORATE TRAINING AND PLANNING

 TPU-General characteristics
• High tensile strength • Good chemical resistance
• Excellent tear resistance • Low gas permeability
• Excellent flex life • Excellent low temperature
• Excellent abrasion resistance
resistance • Good migration resistance
• High scratch resistance • good ozone resistance
• Easy printability
• Good thermal properties

CORPORATE TRAINING AND PLANNING

 Properties table

S.No Properties Unit values

1 Speicific gravity --- 1.11-1.28

2 Tensile strength MPa 10.3 - 76

3 Tensile modulus MPa 2.3 - 10

4 Flexural modulus MPa 69 - 690

5 Elongation at break % 110 - 1000

6 Hardness-Shore D - 46 - 80

7 Water absorption % 0.30

24 hrs

8 Glass transition 0C -51

temperature

CORPORATE TRAINING AND PLANNING

 5. PROCESSING

Thermoplastic polyurethanes are normally supplied as granule in

moisture proof containers. They can be processed by usual methods for

thermoplastic materials such as injection moulding, extrusion, blow

moulding and clendering.

CORPORATE TRAINING AND PLANNING

 TPU blends
• TPU as a minor component with Poly(butylene
terephthalate), polyoxymethylene, epoxy resin and
unsaturated polyester resin
• TPU as equal component with polycarbonate and
ABS
• TPU as major component with ABS

CORPORATE TRAINING AND PLANNING

 TPU applications
• Automotive- exterior body parts, automobile
interiors, body side mouldings, fender extensions
etc.,
• Electrical/electronics - wire and cable jacketing,
hose jackets, sheets, cable cores & seals etc.,
• films and sheets- adhesive film fro garment labels,
conveyor belts, gaskets etc.,
• Tubings - air instrument tubing, blood tubing, dental
tubing, fuel hose jackets etc.,

CORPORATE TRAINING AND PLANNING

 TPU-availability
Trade name Manufacturer

ESTANE B.F.Goodrich

ROYLAR Uniroyal

TEXIN Mobay

PELLETHANE Upjhon

RUCOTHANE Hooker

PLASTOTHANE Thiokol

CORPORATE TRAINING AND PLANNING

 Polyolefin elastomers(PoE)
A number of investigation have tried to synthesis polyolefin block

copolymers with molcular structure similar to the S-B-S triblock

copolymer with S and B Blocks replaced with crystallisable, elastomeric,

poluolefin segments respectively.

[ (E) - (E/P)]3 - (E)

[ (E/P)1 - (E/P)2]3 - (E/P)1

[ (E) - (P)]3 - (E)

where the polyolefin blocks are ethylene (E), Propylene (P) and

ethylene/propylene (E/P) sequences

CORPORATE TRAINING AND PLANNING

 Polyolefin elastomers
• Propylene/ α -olefin copolymers
• high molecular weight stereoblock polypropylene
• Graft copolymer of EPDM

CORPORATE TRAINING AND PLANNING

Propylene/ -olefin copolymer -
synthesis
Direct co polymerization
of -olefins A and B
produces a copolymer
with a structure of (A
By)n, x and  denotes
the monomer sequence
length in a particular
segment n of a chain
molecule.
CORPORATE TRAINING AND PLANNING
 Elastomeric characteristics of propylene/hexene-1 and
propylene/decene-1 copolymer
Properties P/Hexene-1 P/Decene-1

% -olefin (mole) 26 22

Crystalline index 28 37

Stress (MPa)

At 100% elongation 2.76 1.52

At 300% elongation 8.28 3.31

Tensile strength (MPa) 18.27 6.62

Ultimate elongation(%) 495 480

Permanent set (%) 80 32

Hardness, Shore A 71 49

CORPORATE TRAINING AND PLANNING

 High molecular weight stereo-block
polypropylene
The most recent and interesting development of
-olefin TPE is a composition derived from a
homopolymer of polypropylene. The key factor
which enables the production of an elastic
propylene homopolymer or elastmeric
polypropylene is the discovery of a class of
stable catalyst based on absorption of transition
metal organometallic compound on Al2 O3 . The
polymerisation can be carried out in either batch
or continuous process. in hydrocarbon medium
or in liquid polypropylene.

CORPORATE TRAINING AND PLANNING

 Graft copolymer of EPDM
• An EPDM backbone grafted with a chemically
dissimilar crystalline polypivalolactone is the only
known exception where the crystalline phase is
distinctly separated from the amorphous phase and
the polypivalolactone crystals are dispsersed into
smaller discreet domains over a wide composition
range.

CORPORATE TRAINING AND PLANNING

 PoE- Applications
• Automotive - filler panels, bumper covers, fender
extensions, flexible front and rear panels, corner
panels, sight shields
• wire and cable- box gaskets, transformer
encapsulation, cable ties, sleeving, caps, plugs,
grommets and connectors.
• Miscellaneous- belting, hose, fabric coating, seals,
and various industrial molded goods

CORPORATE TRAINING AND PLANNING

 Polyolefin Elastomers(PoE)- General properties
 Being based on polyolefins, have the lowest specific
gravities of all thermoplastic elastomers.
 PoE’s are compatible with most olefinic materials
 PoE’s are an excellent impact modifier
 PoE’s are available in several grades having room
temperature hardness ranging from 60 shore A to 60
shore D.
 PoE’s have emerged as a leading material for
automotive interior and exterior applications.

CORPORATE TRAINING AND PLANNING

 Polyester elastomers
• Multi-block copolymers with formula (-A-B-)n
• Related structurally to polyurethane and polyamide
elastomers
• Hard segments composed of tetramethylene
terephthalate units
• Soft segments composed of aliphatic polyether or
polyester glycols

CORPORATE TRAINING AND PLANNING

 Polyester elastomer - synthesis
• The copolyesters are prepared by transesterification
of dimethyl terephthalate polytetramethylene ether
glycol (PTMEG) and 1,4-butanediol
• ( -O - (CH2)4 -OOC- C6H5 - CO-)

CORPORATE TRAINING AND PLANNING

 Polyester elastomer- General properties
• Resilience, high resistance to deformation,
outstanding flex resistance, good abrasion
resistance,
• Good retention of properties at low and elevated
temperatures
• High modulus, good elongation and tear strength
• resistant to non-oxidizing acids, some aliphatic
hydrocarbons, aromatic fuels, grease, alkaline
solutions, hydraulic fluids and hot oils.
• Weathering resistance is low, but can be improved
by additives CORPORATE TRAINING AND PLANNING
 Polyester elastomer- Mechanical properties
Property Units ASTM Hardness grades
Method
40D 70D

Tensile strength PSI D-638 3700 5700

Ultimate % D-638 450 350
elongation
Flexural Modulus PSI D -790 7000 75000
at 24 oC
Notched impact Ft-lb/in D-256A No break 3.9
strength at 24 oC
Taber abrasion Mg loss/ D - 1044 3 13
CS-17, 1kg load 1000
cyles
Heat deflection oF D-648 No 330
temperature at deformation
66PSI
CORPORATE TRAINING AND PLANNING
 Polyester elastomer - Processing
• Polyester elastomers are generally tougher over a
broader temperature range than the urethanes
• can be processed by injection , extrusion, rotational
and blow molding and casting process

CORPORATE TRAINING AND PLANNING

 Polyester elastomer- Applications
• Applications of copolyester elastomers include
hydraulic hose, fire hose, power transmission belts,
flexible couplings, diaphram, gears, protective
boots, seals, oil field parts, sports shoe soles, wire
and cable insulation, fiber optic jacketing, electrical
connectors, fastner knobs and bushings

CORPORATE TRAINING AND PLANNING

Polyester elastomer - availability
Trade name Manufacturer

HYTREL Dupont

GAFLEX GAF

LOMOD GE

CORPORATE TRAINING AND PLANNING

 Styrene Elastomers
Triblock copolymers based on polystyrene and
polybutadiene are the largest in terms of commercial
production
Styrenics are the lowest priced elastomers.
 Styrenics are block co-polymers with
hard(Styrene) and soft segments
(polybutadiene, polyisoprene, ethylene-
propylene).

CORPORATE TRAINING AND PLANNING

 Styrene elastomers- Structure and synthesis
• Most of the polystyrene/polybutadiene block
copolymers have the basic structure of Poly(styrene-
b-butadiene-b-styrene) or poly(styrene-b-isoprene-b-
styrene).
• This is a phase separated system and retain their
basic properties.
• These block copolymers are prepared in inert
hydrocarbon solvent by anionic polymerization

CORPORATE TRAINING AND PLANNING

 Styrene elastomers - General properties
• Tensile strength is lower and elongation is higher
than SBR or natural rubber
• resistant against alcohol's, dilute alkalis and acids.
• Soluble in chlorinated solvents, esters and ketones
• weather resistance is same as that of SBR and
natural rubber

CORPORATE TRAINING AND PLANNING

 Styrene Elastomers - Applications
• Applications of styrene-butandiene copolymer
blocks include disposable medical products, food
packaging, tubing, sheet, belting, mallet heads and
shoe soles.
• These materials also used as sealants, hot melt
adhesives, coatings for wire and cable insulation

CORPORATE TRAINING AND PLANNING

 Styrene Elastomers - Availability

Trade name Manufacturer

KRATON D, KRATON G, Shell

CARIFLEX TR, ELEXAR
SOLPRENE 400 Philips

FINAPRENE Fina

STEREON Firestone

TUFPRENE, ASAPRENE Ashahi

CORPORATE TRAINING AND PLANNING

 Polyamide Elastomers
The reaction of dicarboxylic acid polyamide blocks
with diamide polyether blocks or diamine polyamide
block with dicarboxylic polyether blocks in molten
state give polyamide ether block elastomer
• HOOC-PA-COOH + H2N-PE-NH2
• HO - CO-PA-CO-NH-PE-NH- H
• H2N-PA-NH2 + HOOC-PE-COOH
• H - NH-PA-NH-CO-PE-CO- OH
The reaction of poly(oxyethylene) diisocyanate with
a diamine aromatic polyamide to form polyamide
polyether block copolymers with urea linkages.

CORPORATE TRAINING AND PLANNING

 Polyamide Elastomers –
Chemistry & Structure
• The polyether amide block is obtained by the molten
state polycondensation of polyetherdiol blocks and
dicarboxylic amide blocks.
• HO - CO-PA-CO-OPE-O-H
• Dicarboxylic polyamide blocks are produced by the
reaction of polyamide with dicarboxylic chain.
• The structure of polyether block amide comprises
linear and regular chains of rigid polyamide segment
and flexible polyether segments

CORPORATE TRAINING AND PLANNING

 Polyamide elastomers –
General properties
• The polyamide elastomers are low density, high
elongation materials with solvent and abrasion
resistance
• polyamide elastomers are characterized for high
abrasion and excellent fluid resistance
• available in wide range of hardness by
copolymerising with flexible polyethers or
polyether- esters

CORPORATE TRAINING AND PLANNING

 Polyamide elastomers - Processing
• All grades of thermoplastic polyamide must be
adequately dried before the use (80 C for 4 hrs).

• During processing upto 20% regrind materials can

be used.

• These materials are easy to process and can be

processed by extrusion moulding, rotational
moulding and thermoforming etc.,

CORPORATE TRAINING AND PLANNING

 Polyamide elastomers –
Applications
• End use for polyamide elastomers include sporting
goods, automotive applications, hydraulic and
pneumatic equipments, polymer modification, cable
jacketing and tubing, medical applications and
miscellaneous consumer products

• automotive applications are limited to items that are

not under the hood because of the materials low
heat stability

CORPORATE TRAINING AND PLANNING

Polyamide elastomer - Availability

Trade name Manufacturer

PEBAX, OREVAC Atochem

MONTAC Monsanto

ESTAMD Upjohn

CORPORATE TRAINING AND PLANNING

 Elastomer-Thermoplastic Blends
• The elastomer-Thermoplastic blends are prepared by
blending elastomers with thermoplastics

• They are two categories -

•
• Elastomer with amorphous plastics(PVC),

• Elastomer with crystalline plastics (PE, iPP)

CORPORATE TRAINING AND PLANNING

 Elastomer - PVC blends
• Nitrile elastomer with PVC- the use of nitrile
elastomer as plasticizer improved the swelling
resistance. These blends have one phase or multi
phase depending on the acrylonitrile content
• Polyester with PVC - polyesters are used in PVC as
plasticizer and impact modifiers. Oligomeric
polyesters are used as plasticizers and high
molecular weight copolymers are used as impact
modifiers.
• Ethylene copolymers with PVC - EVA copolymers
were used as impact modifiers, and its compatibility
is stated to increase with increase in vinyl acetate
content
CORPORATE TRAINING AND PLANNING
 Polyolefin blends
• Thermoplastic elastomers based on mixtures of
polyolefin elastomers with polyolefin thermoplastics
• Ethylene/propylene copolymers and terpolymers
with polyethylene and propylene: various grades of
these materials are available with shore A hardness
from 65 - 92.
• Natural rubber with polyethylene and
polypropylene: various grades of these materials are
available with shore A hardness from 34 - 68.

CORPORATE TRAINING AND PLANNING