POLYMER 2 -Reaction between at least two molecules

containing functional groups, with liberation of

POLYMERIZATION: High Polymer Synthesis a by product
Two steps: Two types:
1. Synthesis of polymer  AA + BB = AABBAABBAABBAABB
2. Synthesis of high polymer  AB = ABABABABABABABABABAB
Types:

 Polycondensation – Step Growth - As DP increases, [M] decreases

 Polyaddition – Chain Growth - Number ave. DP <Xn> = Total number
 Insertion – Coordination Polymerization of molecules originally present/ Total
number of molecules after the
POLYCONDENSATION polymerization has stopped.
- Carother’s equation = Xn = 1/(1-p); p =
Steps:
Monomer + Monomer fractional monomer conversion
Step growth: Monomer>Dimer>Polymer
Branching and cross linking : w/ crosslinking
Grows slowly
agent
Examples :
polyamides (nylon 6,6) POLYADDITION
polyesters (PET)
Steps:
polyurethane
Initiation : Monomer + Initiator, formation of
Polycarbonates (Lexan)
growth center
Resin
Propagation : Growth of polymer chain, living
polyimide
chain
Termination : Elimination of free radical, dead
Polymerization example: esterification
chain, initiator is not eliminated
R-C=O-OH + HO-R = R-C=O-OR + H2O
:amidation (nylon 6,6)->
Characteristics:
Hexamethylene diamine + adipic acid = nylon
High MW
6,6 + H2O
Exothermic
:Polyester (PET) ->
No change of composition (only 2 electrons in
Ethylene glycol + terephthalic acid = PET + H2O
the pi-bonding)
:Polyamide (Amino acid) ->
Diamine + Diacid = Amino acids
Initiators :
:Polycarbonates
Radical
From carbonic acids and dihydroxy compounds
Cationic
(diol)
Anionic
-Monomers with a functionalgroup
From unsaturated monomers – alpha - olefins
 -OH, -C=OOH, -C=OOR, -NH2, -C=OCl,
-C=O-O-O=C-R
Polymer examples:
polyethylene/polypropylene, polystyrene,
polydiene, polyvinyl chloride
Types of growth centers: depends on R
- Cationic = e- donating group
- Anionic = e- withdrawing group
- Radical = compatible for radical
formation
1. Radical polymerization
Conditions: low conc. of initiator to prevent
frequent recomination (termination)
Steps:
a. Initiation
Initiator + Heat -> Initiator
Initiator + Monomer> +Monomer>
b. Propagation
Fast reactionlong chain for short time
Kinetic does not depend on chain length
c. Termination
- Recombination
- Dismutation – H transfer
Interrupt chain growth
Produce inactive species
Inhibitors : stop growth, give non reactive
species
Monomer – substitute R should be electron
withdrawing
Initiator: Base, organometallic (-OH, -OR, C-)
Solvent: Polar and aprotic , ex. THF, DMF, dried
solvent
Application: control of molar mass and small
polydispersity(because no termination)
:control of chain extremity
:conception of particular architecture(ex.
grafting)
:anionic polymer can be a initiator
3. Cationic Polymerization
Ex. isobutylene
Monomer- substitute R should be e-
donating/releasing group
Iniator: Bronsted acid (H+ donor), Lewis acid (e-
acceptor)

Kinetic schema
-Homolytic decomposition of initiator (slow)
-Activation by primary radical (fast)
-Propagation
-Transfer (Fast)
-Termination

Trommsdorf effect: undersired

- High propagation, high T, auto-
acceleration, formation of solid (gel)
- Hotspot
2. Anionic Polymerization
Attack of nucleophile monomer on electrophile
active site
No termination, because of same signs
COORDINATION POLYMERIZATION
Between Transition metal (Ti, V, etc) and C
*Polyethylene (LDPE) – atactic – radical polymer
*Polyethylene (HDPE) (LLDPE) – linear low –
coordination polymerization – few short
branches
Branch in LDPE occurs by Chain Transfer –
Backbiting
PE and PP production: could not produced by
radical polymerization. Only low MW and not
rigid are produced
Coordination:
- Ti based
- Insertion of monomer between TI and C
- No side reaction such as chain transfer
or back biting
- For alpha – olefins such as ethylene and
propylene
- Linear polymer – (very few branch)
- Catalyst – initiator
- Final reaction is chain transfer
Ziegler- Natta catalyst
-can produce linear and low-branch HDPE at
low pressure
-can produce isotactic PP
-control tacticity
-control direction of methyl branch
-temperature and time effect MW
-length and MW depend on the competition
between rate of propagation and rate of
termination
-control of MW – control termination step
POLYMERIZATION PRACTICE
Systems:
 Homogeneous : Bulk/ Solution
 Heterogeneous : Precipitation/
Dispersion/ Suspension/ Emulsion
Homogeneous
1. Bulk ( Mass)
-from undiluted monomer
-viscosity increases
-adv : pure product, simple, no solvent
-disadv: heat control, disperse MW
-apps : step rxns, nylon 6
2. Solution
-monomer dissolved in solvent
-polymer still dissolved
- not increase in viscosity
-adv: directly usable, controlled heat
-disadv: contamination, chain transfer,
recycling (solvent)
-apps: acrylic coating, fiberspinning,
film casting
Heterogeneous
1. Precipitation
-homogeneous at first then polymer
precipitates
-polymerization in solution and in solid
phase
-monomer + solvent + initiator (soluble)
2. Dispersion
-polymer not soluble in monomer or
solvent
-polymer formed is stabilized particles,
swollen by monomer
-polymerization in particles
-monomer + initiator + stabilizer (all
soluble)
-particle formation:
homogeneous/coagulative nucleation
-apps: polystyrene or PMMA
3. Suspension
-monomer + initiator in droplets in a
continous phase (water)
-prevents coalescing by agitation and
stabilizer
-stabilization of droplets of polymer
with non-ionic stabilizers
-polymer are polydisperse or
monodisperse ( filtrate)
-particle formation: droplets nucleation
-monomer (disc phase, insoluble) +
continous phase (water) + initiator
(soluble in monomer) + stabilizer (non-
ionic)
-adv: heat control, directly usable easy
handling
-disadv: contamination w/ stabilizers,
coagulation
-apps: ion-exchange resins, polystyrene
foam, PVC
4. Emulsion
-polymerization is propagated in
micelles (stable stabilizer)
 -monomer (disc phase, insoluble) +
continous phase (water) + initiator
(soluble in water) + surfactant
(emulsifier, creates micelles)
-particles are monodisperse
-particle formation: homogeneous/
micellar/ coagulative/ no nucleation
inside droplets
-product : latex (SBR, PVA, PAN, PS,
PVAL)
Techniques : Core-shell particle
A. Batch
B. Semicontinous:
I : production of defined number of
reaction sites (seeds)
II: addition of second monomer (starved
feed)
Applications : coating, painting, adhesives,
cosmetics, pharmaceutical, super-absorber,
paper coating

-Emusifiers, Stabilizers, Surfactant Products of emulsion polymerization:

-reduce the interfacial tension between
phases forming a barrier
-w/ hydrophobic and hydrophilic part
Emusifiers (soaps) – small amphiphilic
molecules that form nanometer micelles after
CMC conc (Critical Micelle Conc)
Stabilizers (suspension agents) – polymeric/
oligomeric molecules (PVA), cant form regularly
shaped micelles
- Styrene Butadiene Rubber (SBR)
- Butadiene Acrylonitrile (nitrile rubber)
- Acrylonitrile-Butadiene-Styrene (ABS)
- Polyacrylates
Adv: low viscosity even at high solid, ind control
of MW, direct application
Disadv: contamination with additives, more
complicated in case of water soluble

Emulsion mechanism: Heterogeneous adv: efficient heat transfer, low

Initiator diffuse into micelle and polymerize, viscosity, high conv, high rate, can high MW,
more monomer diffuse over, particle increases direct app of product, high area
Empty micelle>w/monomer>large Disadv: contamination not easy to control
hydrophilic monomers
Emusion Mechanism stages (Smith-Ewart-
Harkins Theory)
Stage I : (2-15 % conv) monomer from droplet
diffuse to micelle, polymerization initiated
: rate increases, particle absorbs more
surfactant, inactive micelles dissolve
Stage II : no more available surfactant, no new
particles, monomer diffuses to maintain
equilibrium
: slight rate increase due to Trommsdorf
effect, finsih when droplets disappear
Stage III : (40-60 %) monomer exist in particles
: particle size constant
: can reach to 100%, rate decreases

Phases : nucleation (surfactant> cmc)

, stationary phase (surfactant < cmc)
final step ( no monomer) ( no droplets)
 POLYMERIZATION IN INDUSTRY
Polyethylene and polypropylene: most
important polyolefins (plastics)
POLYETHYLENE
Types
- LDPE (branched)
High P
Radical polyaddtion
H/ chain transfer
- LLDPE/VLDPE/HDPE (linear)
Low P
Ziegler-Natta (no branch)
w/ comonomer (short branch)
Industrial Polymerization
1. High P
2. Low P *solution*
3. Low P *slurry*
4. Low P *gas*
>High P
Feed : ethylene gas (monomer)
Initiator : peroxide (injection)
Fast reaction
Small autoclave, small
production, high cost
From auto clave : polymer melt> then
purified> then extruded
>Low P (slurry)
Feed in CSTR : monomer (ethylene),
comonomer ( 1-butane, control
density), solvent (hexane), catalyst (Zi-
N, Ti, Al), H2 gas (control MW,
terminator)
Then cake (wet polymer) into
centrifuge> liquid (oligomers +hexane)
+ powder (poltethylene precipitates in
hexane), into dryer->extrusion
“Hoeschst process”
-suspension process
-hexane as solvent
“Philips Process (LLDPE)”
-Cr-based catalyst
-copolymerization by higher a-olefin
(isopentane, isobutane)
-Loop reactor
>Low P (solution)
-ethylene-octene: high T
-solvent : cyclohexane
-CSTR, w/ solvent recycle
-can control MW,
-homogeneous, FLASH DISTILLATION
>Low P (gas)
-fluidized bed reactor
-bottom : monomer gas feed
-middle : inert gas + catalyst
-top : disengagement zone, prevents
entrainment of liquid particles,
decrease velocity gas due to bigger
diameter
-with gas recycle and heat exchanger
-adv: homogeneous mixing and T,
continous
-disadv: difficult scale up, regular pump,
loss of solid, corrosion
“Union Carbide FBR” – Low P
-Comonomer : 1- butene
-No polymer separation, diluent
recovery, drying
-Problem: exothermic, hot spot
(powder melts due to high T, melt
inside the reactor, gel formation, need
shut down)
“ BP Process”
-solution to union carbide
-injection of ‘prepolymer feed’ to FBR
(catalyst + monomer + H2 in CSTR)
-reacts slower, lower T
Properties and Characteristics of PE
Density:
-Direct: stiffness, strength, resistance,
hardness, shrinkage
-Inverse : transparecy, stress crack
resistance, flexibility, impact strangth
-No effect: weatherability
Melt Index (inv. Of MW)
-Direct: fluidity, distortion resistance,
optical
-Inverse : impact strength, crack
resistance, elongation, tensile strength
elasticity
-No effect: weatherability
Summary POLYPROPYLENE
1. Density -do not focus on density but on comonomer
-inverse to branching - Tacticity: isotactic, syndiotactic, atactic
-direct to comonomer
-inverse to comonomer/ethylene Types
2. MW 1. PP Homopolymer
-inverse to MFI -propene monomer
-direct to viscosity -stiff, high thermal resistance
-inverse to H2 (induce termination) - limited app, low impact resistance,
-MFI is direct to H2/ethylene low flexibility
*adjust density before MI 2. PP Random Coplymer
-propene w/ 2- % ethylene
Challenge and Opportunities (PE) -low heat dealing, high transparency,
1. minimize off-spec during grade changeover flexible, high impact, lower strength
2. heat removal control -rubber properties
3. removal of reaction poisons (adsorber) 3. Block Copolymer
4. static control (accumulation of particles due -ethylene-propylene rubber (EPR)
to charge) -sequential feed
5. gel formation (hetero result, high T) -2 TG , lower transparency
-Ti, Al are very sensitive inject carbon 4. High Impact PP
oxide to calm high T -homopolymer + random copolymer
6. film clarity -high impact strength
-Zn cannot produce transparent pdts - 2 series reactor
-New catalyst: Metallocene (for -50% EPR
aesthetic problem) -isotactic PP (porous, w/ still active
catalyst matrix) +
Hybrid Technologies (PP+ethylene/propylene) feed (gas
1. Combination of loop reactor and FBR phase reactor) = EPR copolymer mixed
2. 2 FBRs in series (produce bimodal PE, plastic w/ PP matrix (polymer blend)
film) -amorphous, low crystallanity
-no elimination of Zn catalyst
Processes
1. Bulk (liquid pool)
2. Liquid Slurry (suspension)
3. gas phase

>Bulk Process
-no solvent
-stirred or loop reactor ( higher heat
transfer)
-two reactors give higher yield
-High P to pressurize PP and high
crystallanity
-similar to slurry (but slurry needs
isobutane)
“Himont Spheripol Process”
Homopolymerization (loop reactors) >
 Impact copolymerization(fbr)
>compounding
>Solution
-Solvent: hexane/heptane
-stirred reactor
-terminate by H2
-w/ separation step, solvent recovery
>Slurry + gas
>Gas phase
-between solid catalyst and polymer
containing monomer
-cheaper than bulk
-Easy with low P
-eg. Union Carbide (w/ FBR) , BASF
(CSTR)
“Unipol- Shell Process”
-2 FBRs for High Impact PP
Synthesis of Copolymer PP and PE
-homopolymers: high stiff, high chemical T,
lower impact resistance, low T
-same feed time
-EPR random copolymer has higher
transparency, flexibility, high impact resistance,
low Tg
-sequential : block copolymer, 2Tg
Elementary stress/strain and rheological
behaviors of polymers
Tensile test:
Stress-strain relationship (Young mod)
Toughness
Brittleness and Ductility
Formability
Yield point>elongation>break
point(ultimate strength)
Stress-strain behavior
Brittle: high stress, very low strain
Plastic: moderate stress, moderate strain
Highly elastic: low stress, high strain
Rigid plastic>Fiber>Fiberplastic>Elastomer
Tensile response: Brittle and plastic
-Brittle failure
“aligned, cross linked networked
-(amorphous elongate)>onset of necking
(crystalline align)>unload/reload (crystalline
regions slide)> plastic failure
“semi-crystalline case”
Tensile response : Elastomer
-(cross-linked)>reversible deformation>
(straight chains, still crosslinked)

Synthesis of High Impact PP Mechanical properties: (factors)

-santropene (ex) -MW : increase MW, increase tensile strength
-2 reactors in series -Degree of crystallinity: increase, increase
-PP w/ 50 % EPR tensile
-predeformation (necking)
-heat treating (annealing)

Rheology
Flow types: Newtonian and non-newtonian
Newtonian : linear relationship of shear rate
and shear stress

Viscolelasticity
Elastic> Viscous liquid> Viscoelastic
*Polymer exhibits vicoelasticity in liquid state
(viscous and elastic).
Elastic characteristics
1. Rod climbing
2. Die swell (high modulud and elongation at
break for HDPE)
Newtonian : vortex formation

Example: polyacrylamide solution :

Weissenberg effect

Flow curve of polymer melt

Zero shear viscosity> power law region>
viscosity at ultimate high shear

Forming method:
Compressive molding
Extrusion (cylindrical die)
blow molding
injection molding
Four-roll calendar (wad of plastic)

MFI of Polymer melt

-grams per 10mn pushed out of a die
-low melt index: high MW: highly viscous

-MI<5; film injection

-MI- 5-100; injection molding

Capillary viscometer
Shear stress: pressure drop/capillary L/R
Apparent shear rate: 4Q(volume flow
ratw)/piR^3

Cone and plate viscometer:

-with rotating cone, no contact on plate
Viscosity = shear stress/ shear rate

Structure and rheological behavior

Viscosity
-direct to pressure
-direct to filler
-inverse to temperature
-inverse to additive
Zero shear viscosity
-direct to MW

*LLDPE is stiffer than LDPE in shear