Professional Documents
Culture Documents
Ch5 General Polymer Synthesis
Ch5 General Polymer Synthesis
–
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
X X X
radical cationic anionic
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
X X X X
Gp = Hp-TSp
Tc =
S
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
• 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 contaminatedby surface active agents
Coagulation introduces salts;Poor electrical properties
Components of Emulsion Polymerization
Mo no me r
Po lyme r
Mo no me r
Dro ple t
500-2000 A
Mo no me r Mic e lle 20 -30 A
R.
Mo no me r Dro ple t
10,000 A (1 )
POLYMERS PRODUCED USING
EMULSION PROCESSES
Polymer Applications
Styrene-Butadiene Rubber Tires, Belting, Flooring,
(SBR) Molded goods, Shoe soles, Electrical
insulation
Butadiene-Acrylonitrile (nitrile Fuel tanks, Gasoline hoses, Adhesives,
rubber) Impregnated paper, leather and textiles
• Stereochemical Control
• Polydisperse products
• Statistical Compositions and Sequences
• Limited set of useful monomers, i.e. olefins
• 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
Asymmetric carbons have Xalternate
X configuration X 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
Polypropylene (1954)
PP
Polyisobutylene (1940)
PIB
inner tubes, flexible adhesives, raincoats
Commodity Vinyl Polymers
Polystyrene (1920)
PS
Styrofoam, clear plastic cups
envelop windows, toys
Cl
PVC
garden hose, pipe, car trim, seat covers, records,
floor tiles
Semi-Commodity Polymers
CO2CH3 CO2CH3CO2CH3
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
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