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OLIGO + MER =
POLY
! Polymers # Plastics
4
POLYMERS
FUNCTIONAL
PLASTICS ELASTOMERS
POLYMERS
THERMO- THERMOPLASTIC
THERMOSETS
PLASTICS ELASTOMERS
1D : FIBERS
FIBERS
2D : FILMS
3D : OBJECTS 3D : OBJECTS 5
Thermoplastics, thermosets,
elastomers, thermoplastics elastomers
Thermoplastic materials.
Long chain molecules are held together by weak Van der Waals
forces. When heated, intermolecular forces are weakened, material
becomes soft and flexible; eventually, at high temperatures, it is a
viscous melt which can be put into any desired shape, that will be
retained by cooling. This process is reversible.
Thermoset materials.
Reactive molecules of a pre-polymer are heated in a mould with an
initiator, react with each other through intensive cross-linking,
leading to a huge molecular network of a single giant molecule.
Material is hard and strong, but cannot be softened again.
6
Thermoplastics, thermosets,
elastomers, thermoplastics elastomers
Elastomer materials.
Flexible twisted long chains are anchored together by only a
moderate level of cross-linking. When material is stretched,
molecules unwind but cannot slide, allowing return to the
original shape when strain is released.
Thermoplastic elastomers.
Behave as elastomer at room temperature. But the cross-
linking bonds between molecules weaken at elevated
temperature, leading to a viscous melt just as for
thermoplastics.
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FUNCTIONAL POLYMERS
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Polymers : some historical milestones.
Coal
Hydroelectricity
Nuclear Energy
Natural Gas
Significant volumes of
plastics usage started
only after World War
II, but already over-
passed steel in the
80s.
ALUMINUM
STEEL
200 8000
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Quantitative growth, but also an astonishing
qualitative diversity
PRICE/PERFORMANCE
HIGH PERFORMANCE POLYMERS
ENGINEERING POLYMERS
COMMODITY POLYMERS
MARKET SIZE
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PLASTIC PYRAMID
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A BRIEF INTRODUCTION to
THE DIVERSITY OF
POLYMER CHEMISTRY and
STRUCTURE
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Mer = unit Mono = single Oligo = some Poly = many
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The extraordinary diversity of polymers derives first from
the wide diversity of possible mono mers
all alkenes can be
Starting from the simple
polymerized one way or
ethylene
another,
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VF4 ? VF2 ? VDC ? Butadiene ?
Monomers with two (or more) reactive end groups lead to many
polymer families through step growth polymerization. Varying the
ends groups and the backbones yields a near infinity of polymers
Polyamides (containing amide functional groups in their main chain), , from di-acids
and di-amines, or from amino acids, or from lactams. Example :
Polyesters (containing ester functional groups in their main chain), from di-
alcohols (or epoxides) and di-acids (or di-chlorides). Example :
25
Some of the most important polymers
made by step polymerization
Acid Polyimide
anhydride
Isocyanate Polyurethane
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COMBINING DIFFERENT MONOMERS in the SAME
POLYMER MOLECULE ADDS ANOTHER DIMENSION TO
THE ART OF POLYMER TAILOR MAKING
Homopolymers are made up of only one monomer.
Copolymers make use of two or more monomers; the way these are
distributed in the copolymer chain will influence polymer properties.
Random, alternate, block, or grafted are the most usual distributions.
-B-B
-B-B-B-B
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FOR HOMOPOLYMER (and copolymers as well), VERY
DIFFERENT PROPERTIES CAN BE OBTAINED BY VARYING
THE SHAPE OF THE MOLECULES OF THE POLYMER
LINEAR -A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-T
-A-A-A-A-A-A-A-A-A-A-A-
A-
BRANCHED (short and long) -A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-T
--A-A-A
-A-A
CROSS LINKED -A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-T
--A-A-A-
--A-A-A-
-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-T
Same
Alternate
Random 29
Example of 1,3-butadiene polymerization
Three different
ways for the
The remaining
butadiene
double bond
molecule to be
can be within
inserted within
the chain, or on
the chain
the side of 30it.
Example of 1,3-butadiene polymerization
q = 0 M = Mn q = 1 M = Mw q = 2 M = Mz
Mn < Mw < Mz
The higher averages are increasingly more sensitive to the high
molecular weight fraction of the polymer.
In the solid state, the polymer molecules can get organized into an
organized crystalline structure, only if molecules have a regular
chain structure, and if forces holding chains together are strong
enough to overcome disordering effect of thermal energy.
In practice, no polymer can exhibit a 100% crystalline structure,
hence the name of semi-crystalline. PE, PP, PA are examples of
semi-crystalline polymers.
Free radical polymerization uses an initiator (e.g. peroxyde), which will generate
free radicals. Overall kinetics governed by initiation, propagation,and
termination rates.
1)Initiation I2R R + M M1 ki
2)Propagation M1 + M M2 .. Mn + M Mn+1 kp
3) Termination Mi + Mi Mi+j (or disproportionation) kt
But polymer quality will essentially be fixed by the various chain transfer
reactions that will determine the molecular weight distribution.
Mi + M Mi+ M1 Mi + S Mi+ S Mi + Mj Mi+
Mj Transfer to : Monomer Solvent or telogen Polymer
Controlled termination
enables to yield various
shapes of polymer
molecules and
controlled end groups.
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Example of anionic polymerization : SBS block copolymers
THERMOPLASTICS or THERMOPLASTIC ELASTOMERS (TPE) tri-block S-B-S
taylor-made by ANIONIC LIVING POLYMERIZATION (linear or star-shaped)
Asphalt Modification,
Footwear,
Adhesives,
Plastics
modifier
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Chain growth polymerization can proceed through different
chemical routes: Free radical, Anionic, Cationic, Co-ordination
~ -100C for
reaction control
PP Bumpers
Ethylene-Propylene-
Diene monomer Rubber HDPE films
Bi-oriented film PP
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Step Polymerization
Main
application
is textile
Thermoformed
packaging
Excellent
aptitude to
recycling
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Polyamides (containing amide functional groups in their main chain), from di-acids
and di-amines, or from amino acids, or from lactams. Example :
Actuator
injected
piece
Textiles
Colson
tier
Castor oil
PA11 Dish
washer 50
basket
Polyurethanes (containing amide functional groups in their main chain), from di-
isocyanates and diols. Example :
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Optimizing the polymer properties
52
Free Radical Copolymerization kinetics
- M1-M2-M2-M1-M1-M1-M2-M2-M2-M1-M2-M1-M1-M2-M1-M2-M1-
Is it really random ?
~~~~~~~~M1. + M1 M1. k11
~~~~~~~~M1. + M2 M2. k11
~~~~~~~~M2. + M1 M1. k21
~~~~~~~~M2. + M2 M2. k22
Simplified but realistic model assumes reactivity only dependent on the last
monomer unit (independent of penultimate monomer).
If k11 >> k12 and k22 >> k21 block copolymer
If k11 << k12 and k22 << k21 alternating copolymer
If k11 ~ k12 and k22 ~ k21 true random copolymer 53
Free Radical Copolymerization kinetics
Pseudo steady state hypothesis states that [M1.] and [M2.] can
be considered as constant in any time interval small compared to the
overall reaction time, M1. and M2. are being consumed and
produced at the same rate . dM dM 0
1
2
dt dt
It is a standard practice to
define:
and to use mole fractions :
F1 and F2 in the copolymer
being produced
instantaneously,
f1 and f2 in the reactive media.
Methyl acrylates /
Vinyl acetate
r1= 9 , r2= 0.1
Ethylene /
Vinyl acetate
r1=0.97 , r2= 1.02
Vinyl acetate /
Vinyl chloride
r1= 0.23 , r2= 1.68
Acrylonitrile /
1-3 Butadiene
r1=0.02 , r2= 0.28
Styrene /
Maleic Anhydride
r1= 0.01 , r2= 0.0
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A few examples of benefit from copolymerization
Modifying the Glass Transition temperature. Polyacrylonitrile could be an
exceptional wonderful polymer (e.g. barrier properties), but its Tg is so high that
material would degrade rather than soften at high temperature: not a thermoplastic.
Copolymerizing with acrylates (70%AN, 30%AM) leads to a reasonably good
barrier material which can be thermoprocessed.
Polystyrene is an easy to process polymer, but its Tg does not allow high usage
temperatures. Copolymerizing with Acrylonitrile (70% St, 30%AN) will lead to a
polymer (SAN) with improved mechanical properties.
Ideal plug flow reactors are continuous reactors (typically tubular type
of reactor) with flat velocity profile ; all volume elements have the
same residence time and the distribution is a Dirac function at
time = V/Q (V volume of reactor, Q volumetric flow rate through reactor).
Continuously Stirred Tank Reactors (CSTR) are continuous
reactors with an ideal agitation. Concentration of the various
chemicals are uniform throughout the reaction medium. All volume
elements in the reactor have the same probability to get out of it,
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independently of their age in the reactor.
Residence time distribution. CSTR
Let f(t) be the residence time distribution. This means that the probability of a
volume element to get out of the reactor between time t and t+dt is equal to
f(t).dt
The cumulative residence time distribution, F(t), is the probability that an
element of volume has a residence time between 0 and t.
F(t) = f(t) dt from 0 to t
In a CSTR, the probability for an element inside the reactor to get out of it
during the next time interval dt is equal to dV/V= Q.dt/V= dt/ ( = V/Q)
The probability for an element to get out of the reactor between time t and t+dt
is equal to the probability that it did not go out before time t, multiplied by the
probability to get out of it during the next time interval dt.
f(t).dt = [1-F(t)]. dt/ leading to a differential equation for F(t)
dF/dt = (1/).[1-F(t)] Ln[1-F(t)] = - t/
Example of
MITSUI PP
Process
Other
Chemicals Monomer(s) Product engineer
preferred domain
Polymerization Polymer
Additives
Technology Structure
Plastic
Properties Application End of life
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Analytical methods of characterization are important tools for the
proper understanding of the whole chain towards the right plastic.
Length of the chain requires a sophisticated traceability system:
the completeness of the information about every step in the process
chain. (Example of Jeanneau polyester boats: wrong pexyde premature aging
of the boat structure after some years).
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OTHER MECHANICAL TESTS
IMPACT RESISTANCE
Charpy test
Standard: ISO 179
Impact
Strength
Instrumented
impact test
Standard: ISO 66-03/2
Temp
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Mechanical Properties. POLYMER DEGRADATION
Degradation of plastics occur through
breakdown of its chemical structure. Not
only acids or solvents, but also water
(hydrolysis), oxygen, heat, stress,
radiation, or combination of those can
contribute to the degradation. Semi-
crystalline polymers usually offer better
environment resistance.
But one should not forget that, before entering the plastic phase, the
polymer needs to be stored, conveyed, dosed, fed, molten. And after
it has been shaped into a plastic, it has to go through cooling,
crystallizing, demolding stages. All of these operations are part of
the processing phase.
Size, shape and homogeneity of
pellets, content of fines or of angels
hair, crystallizing speed, content of
demolding agent, etc., have to be Lenticular and cylindrical pellets do
measured and controlled in the not behave in the same way in the
feeding zone of an extruder
polymerization plant. 73
Processing Properties. Rheology
Optical properties
Structure characterization, G.P.C.
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PROCESSING PROPERTIES MELT FLOW INDEX
Very simple, unsophisticated piece of
equipment, used to characterize
Weight
Masse
fluidity of a molten polymer. It
measures the flow rate of a molten
polymer (in g per 10 mn) through a
Heating
Chauffage
die.
It decreases when increasing the
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average molecular weight.
Cylinder
Cylindre Standards: ISO1133, ASTM1238, DIN53735
Molten
Polymre Polymer
fondu
Using two different weights (typically 2.16 and 21.6 kg) can give
an idea of the non-newtonian character of the polymer.
Melt Flow Ratio (MFR) = MI21.6/MI2.16 76
PROCESSING PROPERTIES MELT FLOW INDEX
Molecular weight / MFI relationship
Example of non plasticized PS
Linear relationship
between Log(MFI) and
Mw of polymer.
Note.
For certain polymers (PA, PET), the melt viscosity measurement is highly
sensitive to moisture regain Consequently, the preferred test method is the
solution viscosity measurement.
Standard for PA: ISO 307 - for PET: ISO 1628/5
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OPTICAL PROPERTIES