2 Chain-Growth Polymerization

1
Chai n- growth Pol ymeri zati on

by Dr . Wal ai por n Pr i ssanar oon- Ouaj ai
Dept . of I ndust r i al Chemi st r y KMUTNB
411317Polymer Chemistry(updated2/2552)
411317 by Dr. Walaiporn Prissanaroon-Ouajai (IC-KMUTNB)
2
Chain-growthpolymerization
formationof polymers viachainreaction
Key factors for chain-growth polymerization
monomers
initiator (to break -bond)
3
Monomers for chain-growthpolymerization
Aldehyde
or ketone
Alkene
(olefins & vinyl monomers)
except
Acetylene
H
2
C
C C
CH
2
H X
H
2
C
C C
CH
2
H H
H
2
C
C C
CH
2
H Cl
HC CH
Ring-opening polymerization
Diene
4
Mechanisms of chain-growthpolymerization
1. Initiation
2. Propagation
3. Termination(Dependent on type of active center)
Propagating chain
(polymer chain with activecenter)
Additionpolymerization
Activecenter = +
Active species (initiator fragment with active center, can be +,-or radical)
Activecenter =radical
Activecenter = -
Polymer
Chaintransferringagent
Dead chain
(polymer chain without activecenter)
Active center
5
Summary
Mechanisms of polymerizationfor polyethylene
R
R
Degreeof polymerization(DP, X
n
)
=number of monomer unit
inapolymer chain
6
Characteristics of Chain-growthPolymerization
1. ..n:a MW.:.:.!:a:
.......z...a:.: ..
.:a..a.!: MW.:.:a:..:a
.a:
2. MW time ..
....:.aa time
3. :.:.:.....: (10
-1
-10
-6
s)
.a: DP .:.n:.a:......
.z...:.: (High MWat low
conversion)
4. Monomer .:a: a.aa:z
5. !:: by-product
time
MW
Timetoreach10
6
MW
PS~7.6s , PMMA~1.5s, PVC ~0.13s
7
Somecomparisons betweenStep-growthandChain-growthpolymerizations
Step-growth Chain-growth
6. M
n
of polymer HighM
n
at highconversion
(M
n
time)
HighM
n
at lowconversion
(M
n
time but n time)
2. [M] withtime Immediatelydisappeared
1. Monomer type Containat least 2functionalities Containunsaturatedbond
Graduallydecrease
3. Reactivity Reactivityof functional endgroup
is independent onsize of polymer
Reactivityof active centre decreases
Withlonger polymer chain
5. Mixture composition
duringreaction
Dimer, oligomer, polymer
andtrace monomer (<1%)
Monomer andpolymer withhighM
n
time
M
n
o
r

X
n
Chain
S
t
e
p
X
n
X
n
W
t
.

f
r
a
c
t
i
o
n
W
t
.

f
r
a
c
t
i
o
n
PER
Step
Chain
4. Rate Growthof chains is usuallyslow
(minutes to days)
Chaingrowthis usuallyveryrapid
(<sec)
8
FreeRadical Polymerization
Monomer for freeradical polymerization
Most alkenes
where R =neutral group or some e-withdrawing character
9
Initiator for freeradical polymerization
sometimes called"catalysts"
asourceof freeradicals
radicals must beproducedat anacceptablerateat convenient
temperatures
havetherequiredsolubility behavior
transfer their activity to monomers efficiently
beamenableto analysis, preparation, purification
Requirements for aninitiator
10
1. Organic peroxides or hydroperoxides
Cumyl hydroperoxide
2. Azocompounds
Examples of freeradical initiationreactions
Benzoyl peroxide (BPO)
2,2'-Azobisisobutyronitrile (AIBN)
Lowdissociationenergy of the O-Obond
But reagents are unstable.
11
3. Redoxsystems
4. Electromagnetic radiation
Redoxinitiator = Initiator + Reducingagent
hydrogenperoxide
persulfate
Soluble inwater (canalso work inorganic
solvents)
Lowdissociationenergy thencanproceedat
relative lowTempreduce side effect
photochemical initiationinvolves the direct excitationof themonomer or photolytic
fragmentationof initiators
photochemical initiators include a wider varietyof compounds
12
FreeRadical Initiator Efficiency
reactive species can undergo as alternatives to adding to monomers to
commence the formation of polymer
two radicalsare trapped together in a solvent (cage) resulting in
direct recombination
2-cyanopropyl radicals fromAIBN acetoxyradicals fromacetyl peroxide
benzoyloxyradicals fromBPO
Solvent Cage
Reduce free radical efficiency
(the efficiency with which these radicals initiate polymerization)
13
Reactions betweentheinitiator radical andthesolvent
For example, carbon tetrachloride is quite reactive towards radicals because
of the resonance stabilizationof the solvent radical produced.
These species are less reactive than the initiator radicals
These species can be recombined with the initiator radicals
Reduce free radical efficiency
Terminate polymerization via chain transfer reaction
14
f depends on the conditions of the polymerization, including the solvent.
In many experimental situations, f =0.3-0.8.
FreeRadical Initiator Efficiency (f)
radicals incorporatedinto polymer
radicals formedby initiator
f =
Note:f shouldbemonitoredfor eachsystemstudied.
Evaluationof initiator efficiency
1. Direct method-End-groupanalysis
Limitation:difficult inadditionpolymers (veryhigher MWthancondensationpolymers)
R
R
n
2. Indirect method
Reactionwithscavengers
diphenylpicrylhydrazyl radicals
15
1. Initiation
Mechanismof Freeradical Polymerization
Step1:Dissociation of initiator
Step2:Reaction of radical
with 1st monomer
In case of asymmetry monomer Ex.
There are 2 possible ways for the reaction of radical to 1
st
monomer
Part I is higher possibility(lowE
a
)
andradical canresonance withX group
16
2. Propagation
Again! for
there are 2possible ways for the reactionof propagatingchainto next monomer
head-to-tail configuration, H-T
head-to-head configuration, H-H
head tail
Part I (H-T) is higher possibility andmorestable
17
3. Termination
two propagatingchains aredeactivated, resultingindeadpolymer
Two principal modes of termination
Little monomer is left
Lowefficiency of active centres
in long propagating chains
Reasons for termination
1) Combinationor Coupling(connect two active centers)
2) Disproportionation(transfer anatom(normallyH) fromone propagatingchainto another)
18
produce one polymer chainwith
single "head-to-head" linkage
a polymer chaincontains two
initiator fragments(R) per molecule
higheraverage MW
Comparisonof terminationby couplinganddisproportionation
Coupling Disproportionation
produce two polymer chains
one polymer chaincontains double bond
andanother contains onlysingle bond
eachpolymer chaincontains one initiator
fragments (R)
loweraverage MW
Note: -Since the disproportionationrequires bondbreaking, E
td
>E
tc
-Couplingoccurs at lower temperature.
Examples:At 60C polyacrylonitrile 100%coupling
poly(vinyl acetate) 100%disproportionation
PS andPMMA bothprocesses
H
19
Kinetics of Freeradical Polymerization
1. Initiation
Step1:Dissociation of initiator
Step2:Reaction of radical
with 1st monomer
where k
d
=Rate constant for dissociationof initiator
where k
a
=Rate constant forformationof active center
If f=free-radical efficiency
Rate determining step
1/2Rateof radical formation =Rateof initiator dissociation
Fromdifferential rate law
(for most initiators Ex. Peroxide, azo)
R
i
= d[ R
.
] = 2f k
d
[I]
dt
+1 d[R
.
] = -d[I] = k
d
[I]
2 dt dt
Rateof initiation(R
i
) = Rateof radical formation
20
k
d
andactivationenergies (E
d
) for someinitiator decompositionreactions.
Data fromJ. C. Masson
Effect of temperatureonR
i
k = Ae
(-E*/RT)
lnk =lnA (E*/RT)
lnk
d1
= E* 1 - 1
k
d2
RT T
1
T
2
Arrheniusequation
Evaluationof k
d
at different temperature
21
+1 d[R
.
] = -d[I] = k
d
[I]
0
2 dt dt
Evaluationof k
d
d [I] = -k
d
dt
[I]
0
d [I] = -k
d
dt
[I]
0

t=0
t=t
t=0
t=t
ln[I] = -k
d
t
[I]
0
where [I] =concentration of initiator at t =t
[I]
0
=concentration of initiator at t =0
time
ln[I]
[I]
0
Slope =-k
d
Assume f =1
22
2. Propagation
where k
p
=Rate constant for propagation
Assumption:k
p
is a constant independent of the size of the growing chain
(same k
p
for every propagation steps)
3. Termination
where k
tc
=Rate constant for terminationbycoupling
k
td
=Rate constant for terminationbydisproportionation
R
p
= d[RM
n
.
] = k
p
[RM
n-1
.
][M]= k
p
[RM
n
.
][M]
dt
23
3. Termination
where k
tc
=Rate constant for terminationbycoupling
k
td
=Rate constant for terminationbydisproportionation
wherek
t
=k
tc
+ k
td
Fromdifferential rate law
- 1 d[RM
n
.
] = k
t
[RM
n
.
]
2
2 dt
R
t
= d[RM
n
.
] = 2k
t
[RM
n
.
]
2
dt
Rateof termination(R
t
) = Rateof RM
n
.
reduction
24
R
p
= k
p
[RM
n
.
][M]
0
In propagation step
Stationary stateradical concentration[RM
n
.
]
At thebeginningof polymerization R
i
>> R
t
After aperiodof time
R
i
= R
t
Lots of RM
n
.
areformedinInitiationstepwhereas
lots of RM
n
.
aredisappearedinterminationstep
Total radical concentration[RM
n
.
] becomes constant
stationary state
2f k
d
[I] = 2k
t
[RM
n
.
]
2
[RM
n
.
] = [f k
d
[I]]
k
t
1/2
[RM
n
.
] = 0
25
R
p
= k
p
[RM
n
.
][M]
[RM
n
.
] = [f k
d
[I]]
k
t
1/2
but
therefore R
p
= k
p
f k
d
[I] [M]
k
t
1/2 1/2
Overall Rateof Polymerization(R
pol
) R
p
R
pol
= K[I]
0
[M]
0
1/2
Initial rateof polymerization
a) Effect of [I] onR
pol
; R
pol
[I]
1/2
b) Effect of [M] onR
pol
;
-if free radicals have very high efficiency (f!1) and do not depend on [M]
R
pol
[M]
-if free radicals have lowefficiency (f!1) and depend on [M]
R
pol
[M]
3/2
26
R
pol
= K[I] [M]
1/2
logR
pol
= logK + 1/2log[I] +log[M]
(b) [AIBN] inMMA (l )
[BPO] instyrene (n)
[BPO] inMMA (p )
at constant [M]
Log-logplots of R
p
versus concentrationwhichconfirmthekinetic order.
(a) [MMA] variedat constant [I]
a) DatafromT. SugimuraandY. Minoura, J. Polym. Sci. A-1, 2735(1966)
b) DatafromP. J. Flory, Principles of Polymer Chemistry, copyright 1953byCornell University,
Slope=1
Slope=1/2
a) logR
pol
=(logK+1/2log[I]) +log[M]
b) logR
pol
= (logK+log[M]) +1/2log[I])
27
Rateconstants at 60C andactivationenergies for somepropagationand
terminationreactions
DatafromR. Korus andK. F. ODriscoll
overall values
k
p
/(k
t
)
1/2
=polymerizability(or ability of monomer to bepolymerized)
R
p
= k
p
f k
d
[I] [M]
k
t
1/2 1/2
28
R
p
= k
p
f k
d
[I] [M]
k
t
1/2 1/2
R
p
=-d[M] = k
p
f k
d
[I] [M]
dt k
t
1/2 1/2
d[M] =-k
p
f k
d
[I] dt
[M] k
t
1/2 1/2
d[M] =-k
p
f k
d
[I] dt
[M] k
t
1/2 1/2
t=0
t=t
t=0
t=t
ln[M] =-k
p
f k
d
[I]
0
t
[M]
0
k
t
1/2 1/2
where[M]
0
and[I]
0
=[M] and[I] at t =0
Evaluationof [M] at any time
[RM
n
.
] = R
i
2k
t
1/2
R
i
= R
t
= 2k
t
[RM
n
.
]
2
At stationary state
R
p
= k
p
R
i
[M]
2k
t
1/2
R
p
= k
p
(R
i
) [M]
(2k
t
)
1/2
1/2
Evaluationof R
p
whenR
i
is known
R
pol
(R
i
)
1/2
29
Meankinetic chainlength:
=number of monomers addedinto activecenters = -d[M]/dt= R
p
number of activecenters -d[I]/dt R
i
number of monomer molecules
polymerized per chain initiated
At stationary-statecondition, R
i
=R
t
= R
p
=
R
t
Number-averagedegreeof polymerization(X
n
)
1. Coupling
2. Disproportionation
X
n
=2
X
n
=
Assumef =1andno chaintransfer reactions
30
Summary:Effect of [M], [I] andtheir natures onR
pol
and
Inthesamesystemof MandI
-highR
pol
andhighMWpolymer result fromhigh[M]
-highR
pol
andlowMWpolymer result fromhigh[I]
k
p
/(k
t
)
1/2
(polymerizability) tells theability of monomer to bepolymerized
At 60
o
C k
p
/(k
t
)
1/2
for MMA=0.678, k
p
/(k
t
)
1/2
for styrene=0.0213
of PMMA> of PS (32times)whensameI (samek
d
), [I] and[M] areused
Initial R
pol
and canbeevaluatedwhen[I]
0
and[M]
0
aregiven
31
AverageRadicallifetime,
Average time of radical exists in polymerization
Average time elapsing between formation and termination of active centers
= concentrationof activecenter = [RM
n
.
]
rateof loss of activecenters R
t
= [RM
n
.
] = 1
2k
t
[RM
n
.
]
2
2k
t
[RM
n
.
]
but R
p
= k
p
[RM
n
.
][M] or [RM
n
.
] = R
p
k
p
[M]
k
p
f k
d
[I] [M]
k
t
1/2 1/2
R
i
= 2f k
d
[I]
Evaluatek
p
by measuring andR
p
withknown[M]
= k
p
[M]
2k
t
R
p
depends onnatureof I (K
d
) and[I], not [M]
Evaluatek
t
by measuring andR
i
32
ExampleThe polymerizationof ethylene at 130 C and 1500 atmwas studied
using different concentrations of the initiator, 1-t-butylazo-1-
phenoxycyclohexane. The rate of initiation was measured directlyand radical
lifetime were determined using the rotating sector method. The following results
were obtained, Evaluate k
t
.
(data fromT. Takahashi andP. Ehrlich, Polym. Prepr., Am.
Chem. Soc. Polym. Chem. Div. 22, 203(1981)).
33
Trommsdorffeffect
Auto-acceleration
R
pol
[M]
0
R
pol
= k
p
f k
d
[I] [M]
k
t
1/2 1/2
ReprintedfromG. V. Schulz andG. Harborth, Makromol. Chem. 1, 106(1948).
Acceleration of the polymerization rate
for different [MMA]
0
in benzene at 50
o
C
Gel effect
At low[M]
0
Effect of [M]
0
onconversion 1
st
order
(
i
n
d
i
c
a
t
e
R
p
o
l
)
At high [M]
0
(>40%)
Effect of [M]
0
onconversion>1
st
order
high[M]
0
highinitial R
pol
highviscosity of mediumDifficult to terminate
(k
t
decreases)
Largeincreasein
bothR
pol
and
At lowconversion
Note: [M] =100%Bulkpolymerization
(no solvent)
34
Problemof auto-acceleration
generally, H=10-30kcal/mol
Most of freeradicalpolymerizations areexothermicreaction
Solving
1.stopreactionbeforegel effect
2.reducemediumviscosity by
addingsolvent
LargeR
pol
largereleasedheat
Explosionif poor ventingsystem
HighMWD
Mole fractionof i-mersas a functionof X
i
for
terminationbycombinationfor various values of p.
p =%conversion
X
i
M
o
l
e

f
r
a
c
t
i
o
n
35
1. Transfer to monomer
Different types of CTR (dependonchaintransferringagent)
2. Transfer to initiator
3. Transfer to solvent
36
Meankinetic chainlength: inthepresenceof CTR
Assumef =1
Terminations include
Coupling
Disproportionation
CTR
tr
= R
p
= R
p
R
t
R
t
+R
tr, M
+R
tr, I
+R
tr, S
k
tr
tr
37
Mayo-Walling Equation
1. Coupling+CRT
2. Disproportionation+CRT
X
n
=2
tr
X
n
=
tr
Evaluationof X
n
inthepresenceof CRT
Reverse
tr
tr
where ()
o
= without chain transfer
tr
= with chain transfer
C
M
, C
I
, C
S
= Rate constants for chain transfer to monomer, initiator,
and solvent, respectively
1 = 1 + C
tr
x [CT agent]
tr

o
[M]
38
Evaluationof chaintransfer constants
1 = 1 + C
S
x [S]
tr

o
[M]
Assume:CRT to MandI areignored
1
X10
5
[S]
[M]
Effect of CTRto solvent for PS at 100
o
C.
DatafromR. A. GreggandF. R. Mayo, Discuss. FaradaySoc., 2, 328(1947).
1
0
Slope= C
s
39
Easyto process
Desirable for particular applications suchas lubricants or plasticizers
ControllingX
n
of polymer by CTR
CTRreduces MW
solvent or CT agent is chosen
andits concentrationselectedto
producethedesiredvalueof
1 = 1 + C
S
x [S]
tr

o
[M]
1 = 1 + C
tr
x [TRagent]
tr

o
[M]
Mercaptans(R-SH)have particularly largeC
tr
for many common monomers
and are especially useful for molecular weight regulation.
Ex.At 60C, styrene has C
tr
for C
4
H
9
-SH=21 (107 times >C
tr
for C
6
H
6
at 60
o
C)
40
Chaintransfer to polymer
1) Inter-molecular chaintransfer
Polymer side chain branching
(Graft copolymer)
Monomer
M
-
M
-
M
-
M
-
M
41
graft copolymershavepolymeric sidechainswhichdiffer inthenatureof
therepeat unit fromthebackbone.
Graft copolymerization
polybutadiene PS radical
Ex.Butadiene-styrene
copolymer (SBS) =
Highimpact PS (HIPS)
42
2) Intra-molecular chaintransfer
Back-biting
Longchainbranchingcanoccur at highpressureto produceLDPE.
Short chain branching
(normally ethyl or butyl group)
0.941g/cm
3
, lowdegreeof branching
0.9100.940g/cm
3
, highdegreeof chainbranching
0.9150.925g/cm
3
, significant numbers of short branches
(higher tensile strengthandhigher impact thanLDPE).
Commontypes of PE
43
Suppressingpolymerization
1. Inhibition:
2. Retardation:
Commercialmonomersarerequiredtopreventtheirprematurepolymerization
duringstorageby addingeitherretardersorinhibitors
depending on degree of protection
blocks polymerizationcompletelyuntil it is removed
slows downpolymerizationprocessby competingfor radicals
Less protection efficiency
Hydroquinone
Nitrobenzene

2 Chain-Growth Polymerization

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Chai n- growth Pol ymeri zati on

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