General Approaches to Polymer Synthesis

1. Addition Chain Growth

Polymerization of Vinyl Monomers Ring Opening Polymerization Heterocylics Metathesis of Cyclic Olefins

Current Strategies in Polymer Synthesis

Objectives: Precise Macromolecular Design

. Control of: Molecular Weight

Molecular Weight Distribution Composition Sequence of repeat units Stereochemistry

2. Condensation

Step Growth

Polymerization of A-B or AA/BB Monomers

3. Modification of Preformed Polymers

Polysaccharides Peptides and Proteins Synthetic Precursors

2. Versatility

Anatomy of Addition Polymerizations

Initiation
Generation of active initiator Reaction with monomer to form growing chains

Polymerizability of Vinyl Monomers

Active Centers must be stable enough to persist though multiple monomer additions
radical X cationic X X anionic

Propagation
Chain extension by incremental monomer addition

Termination
Conversion of active growing chains to inert polymer

Typical vinyl monomers

CN O O CH3 O R O OEt

Chain Transfer
Transfer of active growing site by terminating one chain and reinitiating a new chain.

Polymerizability of Vinyl Monomers

Monomers
Ethylene Propylene 1,1-Dialkyl olefins 1,2-Dialkyl olefins 1,3-Dienes Styrenes

Polymerizability of Vinyl Monomers

Monomers
VCl Vinyl esters Acylates/ methacrylates Acrylonitriles / Acrylamides Vinyl ethers Substituted Styrenes

Radical Cationic + + + +/+ + + +

Anionic Complex Metal + + + + + + + +

Radical Cationic + + + + + + +/-

Anionic Complex Metal +/+ + +/+/-

Thermodynamics of Polymerization
X X X X

Thermodynamics of Polymerization
Monomer
Ethylene

Gp = Hp-TSp Hp < 0 Sp < 0 -bond -bond Loss of translational entropy

MMA -Methyl styrene Isobutylene

-Hp, kJ/mole
93 56 35 48

-Sp, J/K-mole
155 104 110 121

Tc, K (C) Observed

600 (327) 400 478(205) 220 318 (45) 61 326 ( 123) 50

Polymerization favored below a ceiling temperature, Tc

Tc = S

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

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

Types of Radical Initiators Application Temperatures, T1/2 = 10 hr.

150C Hydroperoxides and Alkyl peresters 80C Benzoyl Peroxide, AIBN, Persulfates 25C AIBN + Light, Percarbonates, Photoinitiators 05C Redox Systems, ROOH + Me++

Thermal Free Radical Initiators

Rate of Decomposition
Rd = kd [I] where k = A e -Ea/RT and A 1015 sec-1

To produce 10-7 to 10-6 radicals mole/l.sec, Ea 30-40 kcal/mole (115-140 kJ/mole) For 1st order reactions, half-live, = ln 2/k

Temperatures giving half lives of 10 hr considered optimum use temperatures

Fate of Initiator Radicals

Radical reactions
Recombination in solvent cage Recombination in media Reaction with polymer radicals (kt) Reaction with initiator (MIH) Radical abstraction from polymer chains Reaction with solvent or inhibitor

Kinetics of Polymerization
Initiation steps Rd = kd[I]
O R O O O R + X R ki X R heat 2 R O O -CO2 R

Chain initiation, Ri = 2 f kd [I]

R + X ki R X

Ri = ki [I.] [M] Where [I.] = 2 kd [I]

Efficiency factor, f = 0.1 - 0.9

Add efficiency factor, Ri = 2 f ki [I] [M}

Propagation Steps
Sequential monomer addition
R X R + M R kp1 R M X M M X Rp = kp1[M ][M]

Termination Steps
Termination by coupling, Rtc = 2 ktc [RPM.]2
2 R X P M R ktc X P M M P R X

M + M kp2 X

Rp = kp2[MM ][M]

R X

P M

+ M

R kp X

P M

Termination by disproportionation Rtd = 2 ktd [RPM.]2

2R H P C H X R X ktd P X R H C X H P C H X + H C H X

Assume rate of addition is independent of radical size, Rp = kp [M.][M]

Chain Transfer
Hydrogen transfer to growing polymer chain
R H P C H X X + R S H ktr R P C H X + R S H H X

Rate Expressions for Radical Polymerization

Overall growth of polymer
Rpoly = Ri + Rp Rt Rpoly ~ Rp Rp= kp [M.][M] Assumptions: Contribution of Ri and Rt negligible for high degrees of polymerization Radical concentration based upon Steady State concentration of radicals, i.e. Ri = Rt 2 ki f [I][M] = 2 (ktc + ktd) [M.]2 [M.] = {(ki f)/ (ktc + ktd)}1/2 [I]1/2 [M]
Assume [M] on initiation is negligible [M.] = {(ki f)/ (ktc + ktd)}1/2 [I]1/2

Reinitiation of growing chain using transferred radical

R S + X ka R S X kp

Rate Expressions for Radical Polymerization Overall rate of polymerization

Rp= kp [M.][M] [M.] = {(ki f)/ (ktc + ktd)}1/2 [I]1/2

Control of Molecular Weight

Impact of initiator concentration
DP = Rp / Rt where is the kinetic chain length
DP = =
DP =

Then Rpoly = kp {(ki f)/ (ktc + ktd)}1/2[I]1/2[M]

Rate of polymerization is proportional to:
square root of initiator concentration First order in monomer concentration

Rp Ri

Rp Rt

kp [M.] [M] kt [M.]2

1 = DP

kt [M.]2 kp [M.] [M]

kd(f kd)1/2 [I]1/2 kp [M]

For termination by coupling DP = 2 For termination by disproportionation, DP =

Control by Chain Transfer

Add chain transfer processes to termination processes
1 = DP kt [M.]2 + ktr[SH][M.] + ktm[M][M.] + kti[I][M.] kp [M.] [M]

Calculation of Ctr
Ctr

1/DP
kt[M.] kp[M] + ktr[SH] kp[M]

Assume chain transfer to monomer and initiator are small

1 = DP kt [M ] + ktr[SH][M.] kp [M.] [M]
. 2

1 = DP

1 [SH] + Ctr [M] DPo

Where Ctr is the chain transfer constant

1/DPo [SH]/[M]

Types of Vinyl Polymerization

Method Bulk (Neat) Advantages Simple equipment Rapid reaction Pure polymer isolated Good mixing Ready for application Low viscosity Direct bead formation High Rpoly Low Temperatures High Mol. Wt. High surface area latex Disadvantages Heat buildup Gel effect Branched or crosslinked product Lower mol. Wt. Low Rpoly Solvent Recovery Removal of additives Removal of additives Coagulation needed Latex stability

Solution

Suspension (Pearl) Emulsion

Inverse Emulsion Water in oil latex formed Inversion promotes dissolution in water