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3 FreeRadical
3 FreeRadical
4. Coordination Polymerization
2/11/2018 1
Characteristics of Chain-Growth Polymerization
1. Only growth reaction adds repeating units one at a
time to the chain
2. Monomer concentration decreases steadily throughout
the reaction
3. High Molecular weight polymer is formed at once;
polymer molecular weight changes little throughout
the reaction.
4. Long reaction times give high yields but affect
molecular weight little.
5. Reaction mixture contains only monomer, high
polymer, and about 10-8 part of growing chains.
2/11/2018 2
The Chemistry of Free Radical Polymerization
Radical Generation R R 2R
-
Initiator Radicals
Initiation R +C C R C C
Monomers
Propagation R C C + nC C R (C C)n C C
Termination R C C + C C C R`
R C C C C C R`
2/11/2018 Polymer 3
Free Radical Polymerization Mechanisms
A. Initiation
1. Radical Formation (Generation)
D
In In In + In
h v , etc.
2. Initiation
In + M In M
2/11/2018 4
B. Propagation
In-M1 . + M2 In-M1M2.
In-M1M2. + M3 In-M1M2M3.
In-M1M2M3…MX. + MY In-M1M2M3…MXMY.
2/11/2018 5
C. Termination
1) Radical Coupling (Combination)
In + In In In
HH HH
In MxC C + C C My In
HH HH
In Mx CH CH2 + H3C CH2 My In
2/11/2018 6
D. Chain Transfer (sometimes) – An atom is transferred
to the growing chain, terminating the chain growth
and starting a new chain.
H X H F
H Y H F
Vinylidene fluoride
2/11/2018 8
B. Allyl Monomers
X Cl
Allyl Chloride
C. Ester Monomers
1) Acrylates
OH OR
O O
Acrylic Acid Acrylate Esters
2/11/2018 9
2) Methacrylates
OH OR
O O
Methacrylic Acid Methacrylate Esters
3) Vinyl Esters
O
Vinyl Acetate
O
D. Amide Monomers
NH2
O
2/11/2018 10
Acrylamide Methacrylamide
3. Monomers that are not susceptible to Free Radical
Addition
A. 1,2-a-olefins (Polymerize to oils only)
x
B. Vinyl ethers
R
O O
methyl vinyl ether
C. 1,2-disubstituted Ethylenes
Cl Cl
1,2-dichloroethylene
2/11/2018 11
H H
4. Initiation – “Getting the thing started!”
A. Radical Generators (Initiators)
1. Benzoyl Peroxide
O O
0
80-90 C
C O O C
O
C O 2 + 2 CO2
(continued)
2/11/2018 12
+
Initiator End-Group Ph
Ph
2) t-Butyl Peroxide
2/11/2018
(continued) 13
CH 3
O
H 3C C +
CH 3 O
O
3) Azobisisobutyronitrile (AIBN)
CH3 CH3
~60oC
H3C – C – N=N – C – CH3
CN CN or hn
2/11/2018
(continued) 14
CH3 CH3
Ph
H3C C + N2 H3C C C CH
H2
CN CN
4) Cumyl Hydroperoxide
CH3
C O OH + OH
Ph O
CH3
(continued)
2/11/2018 15
(continued)
O
+
Ph O O
O
Ph O
O
2/11/2018 16
Hydroperoxides can generate radicals by “induced
decomposition” from growing polymer chains:
P + H O O R
PH + O O R 2R OO
R-OO-OO-R 2 RO + O2
2+ 3+
H O O H + Fe HO + OH + Fe
OR
O 3S O O SO 3 + SO 32- SO 4- +
S-SO 3 - +
SO 42-
2/11/2018 18
6) Photoinitiators (Photocleavage – Norrish I)
O O
hv
C
HO +
OH
benzoin
C
H
H
C +
Ph
OH OH
2/11/2018 Ph Ph 19
H
(continued)
OR
O O
hv
C C
benzil O
2 C
2/11/2018 20
7) Photoinitiators (Photo-Abstraction)
O
Photosensitizer
O*
hv
Ph Ph
benzophenone excited state
R R
H C N OH R R
+ C N
Coinitiator R R
Ph Ph R R
2/11/2018 21
5. Propagation - “Keeping the thing going!”
A. The addition of monomer to an active center (free radical)
to generate a new active center.
H
R C CH2 X R C C C CH
H2 H2 H2
X X X
X X H
R C C C CH
etc. H2 nH2
etc.
X X
(continued)
2/11/2018 22
Examples: Polystyrene
Ph H
R C CH2 R C C C CH
H2 H2 nH2
Ph Ph Ph
O
R C C CH CH 3
H2 H2
C O O
Polymethyl O
Acrylate CH 3
H
R C C C C CH
H2 H2 H2
C O C O
O O
2/11/2018 CH 3 CH 3 23
B. Configuration in Chain-Growth Polymerization
1) Configuration Possibilities
favored
- H2C CH P C CH
H2 X
attack X
P
H .
HC CH2 X P C CH2
a-
attack X X
sterically
and electronically unfavored
2/11/2018 24
2) Radical Stability Considerations
Which possible new active center will have the greatest
stability?
.
P C CH2 P C CH
H2 H2
P C CH
-attack produces resonance H2
stabilized free radical
2/11/2018 25
H
P C CH2 X No resonance stabilization
______________________________________________
CH2
CH2O
a P CH
HC C O CH3 X
O C O CH3
P
H2C C C O CH3 P C CH
H H H2
O C O
P C CH
Secondary radical H H2 O CH3
is resonance stabilized C O
2/11/2018 26
O CH3
(more examples)
Cl H Cl
a
X P C CH2
Cl H Cl
P
H Cl Cl
P C C
H2
H Cl Cl
Cl Cl
P C C P C C
H2 H2
Cl Cl
Tertiary radical is
resonance stabilized
2/11/2018 27
3) Steric Hinderance Considerations
HC CH2 X
X
P
4) Radical Stability
3o > 2o > 1o
2/11/2018 28
5 ) “Bottom Line”
Resonance and steric hinderance considerations lead to the
conclusion that -substitution (head-to-tail) is strongly
preferred in chain-growth polymerization.
H H H H
C C C C C C C C
H2 H2 H2 H2
X X X X
Alternating configuration
2/11/2018 29
6. Termination - “Stopping the thing!”
A. Coupling (most common)
H H
Px C C + C C Py
H2 H2
X X
H H
Px C C C C Py
H2 H2
X X
- occurs head-to-head
- produces two initiator fragments (end-groups)
2/11/2018
per chain. 30
B. Disproportionation
HH HH
In MxC C + C C My In
HH HH
In Mx CH CH2 + H3C CH2 My In
2/11/2018 31
C. Factors affecting the type of termination that will take
place.
2/11/2018 (continued) 32
H H
Px C C C C Py
H2 H2
Ph Ph Ph =
PMMA CH3 H3 C
~~~PX – CH2-C. + . C-CH - P ~~~
2 Y
C=O O=C
1. Sterically
hindered O O
2. 5 -Hydrogens CH CH3
3
3. Disproportion-
ation dominates
2/11/2018 (continued) 33
CH3 H3 C
C=O O=C
O O
CH3 CH3
4) Electrostatic Repulsion Between Polar Groups –
Esters, Amides, etc.
2/11/2018 34
Polyacrylonitrile (PAN)
~~~PX – CH2-CH. + . HC-CH2- PY~~~
d+ CN d- d- NC d+
2/11/2018 35
D. Primary Radical Termination
~~~PX – CH2-CH. + . In
X
~~~PX – CH2-CH-In
More Likely at X
High [In.]
Y Y
B. Chain-transfer to solvent:
Y Y
2/11/2018 37
C. Chain-transfer to monomer:
OR
2/11/2018 38
H H
~~~PX – CH - C. + H2C =CH
2/11/2018 39
Propylene – Why won’t it polymerize with Free Radicals?
CH3 CH3
H2C-CH-CH2
Chain-transfer occurs so readily that propylene won’t polymerize
with free radicals.
2/11/2018 40
D. Chain-transfer to polymer:
2/11/2018 41
F. Chain-transfer to Chain-transfer Agent:
Definition – The transfer of reactivity from the
growing polymer chain to another species. An
atom is transferred to the growing chain,
terminating the chain and starting a new one.
Examples: R-OH; R-SH; R-Cl; R-Br
~~~PX – CH2-CH. + O= =O
para-Benzoquinone
Will Not
~~~PX – CH2-CH2-O- -O.
Propagate
Intiation:
Initiator
2/11/2018breaks down smoothly to generate a low, steady-state concentration of44
radicals.
Propagation:
Monomer adds quickly to the small number of growing chains present at any given time.
2/11/2018 45
Termination: