General Approaches to Polymer Synthesis

• 1. Addition Chain Growth

Polymerization of Vinyl Monomers

Ring Opening Polymerization

Heterocylics
Metathesis of Cyclic Olefins
2. Condensation Step Growth
Polymerization of A-B or AA/BB Monomers
3. Modification of Preformed Polymers
Polysaccharides
Peptides and Proteins
Synthetic Precursors
Current Strategies in Polymer Synthesis

• Objectives: Precise Macromolecular Design

• 1 . Control of: Molecular Weight
– Molecular Weight Distribution
– Composition
– Sequence of repeat units
– Stereochemistry
• 2. Versatility

–
 Free Radical Initiated Polymerization
• Classical Free Radical Process
• Applied to wide range of monomers
• Broad scope of experimental conditions
• Molecular weight can be controlled
• Mw/Mn > 1.5  2.0 
• Statistical compositions and sequences
• Little stereochemical control
 Anatomy of Addition Polymerizations
• Initiation
– Generation of active initiator
– Reaction with monomer to form growing chains
• Propagation
– Chain extension by incremental monomer addition
• Termination
– Conversion of active growing chains to inert polymer
• Chain Transfer
– Transfer of active growing site by terminating one
chain and reinitiating a new chain.
 Polymerizability of Vinyl Monomers

Active Centers must be stable enough to persist

though multiple monomer additions

X X X
radical cationic anionic

• Typical vinyl monomers

CN

R O
O CH3
O O
OEt
Polymerizability of Vinyl Monomers
Monomers Radical Cationic Anionic Complex
Metal
Ethylene + - + +
Propylene - +/- - +
1,1-Dialkyl - + - -
olefins
1,2-Dialkyl - + - +
olefins
1,3-Dienes + + + +
Styrenes + + + +
Polymerizability of Vinyl Monomers
Monomers Radical Cationic Anionic Complex
Metal
VCl + - - +/-
Vinyl esters + - - -
Acylates/ + - + -
methacrylates
Acrylonitriles + - + -
/ Acrylamides
Vinyl ethers - + - -
Substituted + +/- +/- +/-
Styrenes
 Types of Vinyl Polymerization
Method Advantages Disadvantages
Bulk (Neat) Simple equipment Heat buildup
Rapid reaction Gel effect
Pure polymer isolated Branched or crosslinked product

Solution Good mixing Lower mol. Wt.

Ready for application Low Rpoly
Solvent Recovery
Suspension Low viscosity Removal of additives
(Pearl) Direct bead formation
Emulsion High Rpoly Removal of additives
Low Temperatures Coagulation needed
High Mol. Wt. Latex stability
High surface area latex

Inverse Emulsion Water in oil latex

formed
Inversion promotes
dissolution in water
Thermodynamics of Polymerization

X X X X
Thermodynamics of Polymerization
Monomer -Hp, -Sp, Tc, K (C)
kJ/mole J/K-mole Observed
Ethylene 93 155 600 (327)
400
MMA 56 104 478(205)
220

-Methyl 35 110 318 (45)

styrene 61
Isobutylene 48 121 326 ( 123)
50
 Suspension Polymerization

Equivalent to a "mini-bulk" polymerization

Advantages
• Aqueous (hydrocarbon) media provides good heat transfer
• Good particle size control through agitation and dispersion agents
• Control of porosity with proper additives and process conditions
• Product easy to recover and transfer
Disadvantages
• Suspending Agents contaminate product
• Removal of residual monomer necessary
Suspension (Pearl) Polymerization
Process Type Aqueous Phase Monomers Used Product

BEAD  1% Sol. Polymer Styrene Clear Beads

Polymer Soluble in Suspending Agents Methyl Methacrylate
Monomer Cu++ Inhibitors Vinyl Acetate

POWDER Suspending Agents Vinyl Chloride Opaque Beads or

Polmer Insoluble in Electrolytes Acrylonitrile Powders
Monomer Fluoroethylene

INVERSE Monomer Acrylamide Beads

Hydrocarbon Media Initiator Acrylic Acids 
Emulsions
 Suspension Polymerization of Styrene
Monomer Phase
16.6 Kg. Styrene
Temp (0.5 kg Methacrylic Acid)
0.012 kg AIBN
0.006 kg Benzoyl Peroxide
0.015 kg tert-Butyl Perbenzoate

Aqueous Phase: 16.6 Kg of H2O

0.24 kg Ca3PO4
0.14 kg Na+ Naphthalene sulfonate
0.077 kg. 15% Sodium Polyacrylate

Polymerization Time. Hours

 EMULSION POLYMERIZATION

• Advantages:
• High rate of polymerization
• High molecular weights
• Few side reactions High Conversion achieved
• Efficient heat transfer
• Low viscosity medium Polymer never in solution
• Low tendancy to agglomerate
• Emulsified polymer may be stabilized and used directly
Disadvantages:
Polymer surface contaminatedby surface active agents
Coagulation introduces salts;Poor electrical properties
Components of Emulsion Polymerization

Monomer

Polymer
Monomer
Droplet
500-2000 A
Monomer Micelle 20 -30 A

R.

Water soluble initiator

Monomer Droplet
10,000 A (1 )
 POLYMERS PRODUCED USING
EMULSION PROCESSES
Polymer
Styrene-Butadiene Rubber
(SBR)
Butadiene-Acrylonitrile (nitrile
rubber)
Applications
Tires, Belting, Flooring,
Molded goods, Shoe soles, Electrical
insulation
Fuel tanks, Gasoline hoses, Adhesives,
Impregnated paper, leather and textiles

Acrylonitrile-Butadiene-Styrene Engineering plastics, household appliances,

(ABS) Automobile parts, Luggage

Polyacrylates Water based latex paints

 Major Developments in the 1950-60's

Living Polymerization (Anionic)

• Mw/Mn  1
• Blocks, telechelics and stars available
(Controlled molecular architecture)
• Statistical Stereochemical Control
• Statistical Compositions and Sequences
• Severe functional group restrictions
 Ziegler-Natta (Metal-Coordinated)
Polymerization

• Stereochemical Control
• Polydisperse products
• Statistical Compositions and Sequences
• Limited set of useful monomers, i.e. olefins

• SINGLE SITE CATALYSTS

 Polyolefins

• Polypropylene (1954)
•

• PP
• dishwasher safe plastic ware, carpet
yarn, fibers and ropes, webbing, auto parts
 H
Tacticity
H

Isotactic H X
X X X X X
All asymmetric carbons have same configuration
• Methylene hydrogens are meso
• Polymer forms helix to minimize substituent interaction

Syndiotactic

• H haveX
Asymmetric carbons X configuration X
alternate X X X
• Methylene hydrogens are racemic
• Polymer stays in planar zig-zag conformation

Heterotactic (Atactic)
• Asymmetric carbons have statistical variation of configuration
 Additional Developments in the 1980's

• "Immortal" Polymerization (Cationic)

– Mw/Mn  1.05
– Blocks, telechelics, stars
– (Controlled molecular architecture)
– Statistical Compositions and Sequences
– Severe functional group restrictions
 Free Radical Initiated Polymerization
• Controlled Free Radical Polymerization
• Broad range of monomers available
• Accurate control of molecular weight
• Mw/Mn  1.05 --Almost monodisperse
• Blocks, telechelics, stars
• (Controlled molecular architecture)
• Statistical Compositions and Sequences
 Genetic Approaches via Modified
Microorganisms
• Monodisperse in MW
• Monodisperse in Composition
• Sequentially Uniform
• Stereochemically Pure
• Diverse set of functional groups possible
through synthesis of novel amino acids
 Commodity Polyolefins
Polyethylene
High Density (1954)
HDPE
Bottles, drums, pipe, conduit, sheet, film

Low Density (1939-1945)

LDPE
Packaging Film, wire and cable coating, toys, flexible
bottles, house wares, coatings
Linear Low Density (1975)
Shirt bags, high strength films LLDE
 Commodity Polyolefins

Polypropylene (1954)
PP

dishwasher safe plastic ware, carpet yarn, fibers and ropes,

webbing, auto parts

Polyisobutylene (1940)

PIB
inner tubes, flexible adhesives, raincoats
 Commodity Vinyl Polymers

Polystyrene (1920)

PS
Styrofoam, clear plastic cups
envelop windows, toys
Cl

Poly(vinyl chloride) (1927) Cl Cl Cl

PVC
garden hose, pipe, car trim, seat covers, records,
floor tiles
 Semi-Commodity Polymers
CO2CH3 CO2CH3
CO2CH3

Poly(methyl methacrylate) (1931) CO2CH3 CO2CH3

PMMA
plexiglas, embedding resin, resist for X-ray applications

F F F F
F F F F

F F F F
Polytetrafluoroethylene. (1943) F F F F

teflon, non stick cookware, no grease bearings,

pipe-seal tape
 Commodity Condensation Polymers
O
H O
C N C
N N C
H H O

Nylon 6 / Nylon 66 (1939)

bearings, molded parts Fibers, tire cord, fishing line
carpet yarn
marine rope
cooking/boiling bags
 Commodity Condensation Polymers

O
O C
O C
O
Polyester (1941)
PET, dacron, mylar, kodel
fibers, film-backing, magnetic tapes, soft drink bottles, tire
cord, moldings
O O
Polycarbonate (1957)
O

PC, Lexan
shatter proof glass, cd-disks, car doors and roofs,
appliance housings