Chapter 5 Anionic Polymerization

Cationic Chain Polymerization
Introduction
Initiation
Propagation
Chain Transfer and Termination
Number Average Degree of Polymerization
Rate Constants
Effect of Solvent and Counterion
Industrial Cationic Polymerization
Comparison between radical, cationic, and
anionic polymerization
1
Introduction
Initiation
Propagation
Rate Constants
2
Introduction:
The propagation center is a cation and the counterion is an anion.
Anions encountered in cationic polymerization are usually larger ions
(sulfate, perchlorate).
CH3 O
CH2 C O Cl O
CH3 O
Being large, the charge density of these anions yields smaller

electrostatic interactions between the propagating cation and the

k
counterion. The ion pairs are loose for cationic polymerization. p is
usually larger than for anionic polymerization.
3
Introduction
Initiation
Propagation
Rate Constants
4
Initiation using protonic acids (Brnsted):
Background: A Brnsted acid is a substance that can donate a proton to
a base.
Protonation of the olefin
CH3 CH3
A H + CH2 C CH3 C A
CH3 CH3
The anion should not be too nucleophilic to avoid recombination with
the carbocation.
CH3 CH3
reactive CH3 C A CH3 C A not reactive
CH3 CH3
5
loose ion pair covalent species
Initiation using protonic acids (Brnsted):
Hydrogen halides (HF, HCl, HBr) do not initiate polymerization. They
merely undergo addition onto the double bond.
In order to initiate polymerization, the acid should be strong and the
resulting anion should not be too nucleophilic.
Examples:
Perchloric acid Fluorosulfonic Methane Trifluoromethane

acid sulfonic acid sulfonic acid
O O O O
H O Cl O H O S O H O S O H O S O
O F CH3 CF3
6
Initiation using Lewis acids:
Background: A Lewis acid is any molecule or ion that has an affinity for
an extra pair of electron.
Lewis acids are the most important means to initiate cationic
polymerization.
Metal halides: AlCl3, (BF3), SnCl4, SbCl5, ZnCl2, TiCl4, (PCl5)
Organometallic derivatives: Al(C2H5)Cl2, Al(C2H5)2Cl, Al(C2H5)3
Oxyhalides: POCl3, CrO2Cl2 (phosphorus oxychloride,

chromyl chloride)
7
Due to highly electronegative Cl
8
A Lewis acid works in combination with either a proton donor (H2O,
ROH, HCl) or a carbocation donor (tert-butyl chloride, trityl chloride).
CH3
CH3 C Cl C Cl
CH3
tert-butyl chloride
trityl chloride
9
The proton donor or carbocation donor is called the initiator and the
Lewis acid is referred to as the co-initiator. One speaks of the initiator-
co-initiator complex.
Initiation with boron trifluoride and water
F H F H
K formation of the initiator-
F B + O F B O
co-initiator complex
F H F H
F H CH3 k CH3 F
i
F B O + CH2 C CH3 C F B OH
F H CH3 CH3 F
10
Initiation with aluminum chloride and tert-butyl chloride
CH3 CH3
K
CH3 C Cl + AlCl3 CH3 C AlCl4
CH3 CH3
CH3 CH3 CH3 CH3

ki
H3C C AlCl4 + CH2 C H3C C CH2 C AlCl4
CH3 CH3 CH3 CH3
11
Generalization
K
I + ZY Y (IZ)
ki
Y (IZ) + M Y-M (IZ)
I : Lewis acid: co-initiator

ZY : proton donor or carbocation donor: initiator
M : monomer
12
Comparison: Initiation with a protonic acid (Brnsted) yields an anion
with the potential of being too nucleophilic. Initiation with a Lewis acid
has the advantage of resulting in the formation of a less nucleophilic
anion. H H
Brnsted protonic acid H F + CH2 C CH3 C F
F F
K
Lewis acid F B + H F F B F H
F F
F H H F
ki
F B F H + CH2 C CH3 C F B F
F F
13
In general, the factors that enhance initiation are those that enhance the
association between initiator and co-initiator (K) and the rate of addition
to the monomer (ki).
The activity of the Lewis acid follows the acidity of the lewis acids
AlCl3 > Al(C2H5)Cl2 > Al(C2H5)2Cl > Al(C2H5)3
The activity of the initiator-co-initiator complex increases with the

acidity of the initiator
HCl > CH3COOH > C6H5-OH > H2O > CH3-OH
14
Stability of the
Initiation The carbocation:
carbocation
CH3 k1 CH3
H3C C Cl H3C C Cl
CH3 CH3
H k2 H
H3C C Cl H3C C Cl
CH3 CH3
k 1 > k2 > k3 > k4
H k3 H
H3C C Cl H3C C Cl
H H
H H
k4
H C Cl H C Cl
H H 15
Initiation with a carbocation must meet a few criteria. The carbocation
must be stable enough so that it can be formed in sufficient quantities.
However the carbocation should not be too stable so that it can still react
with the vinyl monomer.
Primary and secondary carbocations are formed too slowly and in too
small quantities.
Tertiary carbocations are more stable and are obtained in higher

yields. They are also less stable than the carbocations obtained after
their addition onto a vinyl monomer (isobutylene, styrene, or N-
vinylcarbazole).
16
Initiation with a carbocation must meet a few criteria. The carbocation
must be stable enough so that it can be formed in sufficient quantities.
However the carbocation should not be too stable so that it can still react
with the vinyl monomer.
In summary!
CH3 CH3
K
CH3 C Cl + AlCl3 CH3 C AlCl4 (high yield)
CH3 CH3
CH3 CH3 ki CH3 CH3

CH3 CH3 CH3 CH3
(less stable) (more stable) 17

The tert-butyl and cumyl carbocations can initiate the polymerization of
isobutylene and styrene.
CH3 H
H3C C (tert-butyl) CH2 C (styrene)
CH3
CH3 CH3
C (cumyl) (isobutylene)
CH2 C
CH3 CH3
18
CH3 CH3 CH3 CH3
CH3 CH3 CH3 CH3
CH3 CH3 CH3 CH2

C AlCl4 + CH2 C C CH2 C AlCl4
CH3 CH3 CH3 CH3
CH3 CH3
C AlCl4 + CH2 C C CH2 C AlCl4
CH3 CH3
CH3 CH3
AlCl4 + CH2 C CH2 C AlCl4
CH3 CH3 19
The trityl and cycloheptatriene carbocations are more stable and they can
not initiate the polymerization of isobutylene and styrene. However,
they can initiate the polymerization of more reactive monomers such as
vinyl ethers and paramethoxystyrene.
Trityl Cycloheptatriene Vinyl methyl para-

ether methoxystyrene
H
CH2 C
H
H CH2 C
C
O
CH3
O
20
CH3
Initiation initiator/co-initiator ratio:
When using an initiator-co-initiator complex to initiate a polymerization,
the rate of polymerization Rp can be affected by the ratio of the initiator-
to-co-initiator. At high initiator/co-initiator ratios, Rp decreases to a
plateau. The initiator molecules inactivate the co-initiator.
SnCl4OH2 SnCl3OH + HCl

Rp
(not reactive)
H2O
SnCl4OH2 H3O SnCl4OH
(not reactive)
initiator/co-initiator
21
Initiation Other initiator:
Cl2, Br2, and I2 can initiate polymerization in the presence of a Lewis
acid (Al(C2H5)3 or Al(C2H5)2X where X = Cl, Br, I). Only I2 can initiate
polymerization of the more reactive monomers without co-initiator.
(addition) (elimination)
H H I H
I2 + CH2 C ICH2 C I HI + CH C
O O O
CH3 CH3 CH3
H H I2 + CH2 CH OCH3 H H
HI + CH2 C CH3 C I CH3 C CH2 C I
O O O O
CH3 CH3 CH3 CH3
H
CH3 C I The presence of I2
O polarizes the C-I 22
bond
(without I2) CH3 and allows propagation.
Initiation Electroinitiation:
Oxidation of a polynuclear aromatic compound yields a radical-cation
that can initiate polymerization via electron transfer.
(radical-cation)
H
e H

+ CH2 C + CH2 C
O O
CH3 CH3
H H
Propagation continues from both ends. C H2C CH2 C
O O
H3C CH3
Perchlorate salts are used as the supporting electrolyte. 23

They can also act as counterions for the propagating chain.
Introduction
Initiation
Propagation
Rate Constants
24
Propagation:
After initiation of isobutylene with water and BF3:
CH3 CH3 CH3

H CH2 C CH2 C BF3OH + CH2 C
CH3 n CH3 CH3
kp
CH3 CH3
H CH2 C CH2 C BF3OH
CH3 n+1 CH3
25
Propagation Rearrangements:
Rearrangements frequently occur in cationic polymerization. Their
probability of occurring depends on the stability of the resulting
carbocation.
Example #1: Cationic polymerization of 3-methyl-1-butene
H
CH2 C
CH2=CHCH(CH3)2
CH3 C H
CH3
26
H H
kp
R + CH2 C R CH2 C
CH3 C H CH3 C H
CH3 CH3
27
Stability of the
carbocation
CH3 k1 CH3
H3C C Cl H3C C Cl
CH3 CH3
H k2 H
H3C C Cl H3C C Cl
CH3 CH3
k 1 > k2 > k3 > k4
H k3 H
H3C C Cl H3C C Cl
H H
H H
k4
H C Cl H C Cl
H H 28
H H H
kp krearr
R + CH2 C R CH2 C R CH2 C H
CH3 C H CH3 C H CH3 C
CH3 CH3 CH3
(1,2 hydride ion shift)
CH3
R CH2 CH2 C
CH3
This species represents 70 100% of the final polymer composition!

29
H H H
kp krearr
R + CH2 C R CH2 C R CH2 C H
CH3 C H CH3 C H CH3 C
CH3 CH3 CH3
Comparison of the rates at which rearrangement and propagation occur

determines whether rearrangement is possible.
If kp >> krearr, no rearrangement occurs.
If kp << krearr, rearrangements occur. This is the case for the cationic
polymerization of 3-methyl-1-butene for which mostly the rearranged
structure is obtained.
30
Example #2: Cationic polymerization of 4-methyl-1-pentene
H H H H
R + CH2 C R CH C R CH C H
H C H H C H H C H
CH3 C H CH3 C H CH3 C H
CH3 CH3 CH3
1,2 hydride shift H H H H

R CH C H R CH C H
H C H C CH3
CH3 C H CH3 C H
CH3
H H
R CH C H
H C H
CH3 C
31
CH3
H H H H
H C H H C H H C H
CH3 CH3 CH3

R CH C H R CH C H
H C H C CH3
CH3 C H CH3 C H
CH3
H H
R CH C H
H C H
CH3 C
32
CH3
H H H H
H C H H C H H C H
CH3 CH3 CH3
1,2 methide shift H H H H

R CH C H R CH C H
H C H C CH3
CH3 C H CH3 C H
CH3
H H
R CH C H
H C H
CH3 C
33
CH3
H H H H
H C H H C H H C H
CH3 CH3 CH3

R CH C H R CH C H
H C H C CH3
CH3 C H CH3 C H
CH3
Most stable carbocation H H

R CH C H
that represents 40-50%
H C H
of the repeating units in CH3 C
34
the polymer. CH3
Example #3: Cationic polymerization of b-pinene
CH2
35
Example #3: Cationic polymerization of b-pinene
H + CH2 CH3
CH3
CH3 CH3 C
CH3
36
Rearrangements result in polymer backbones that are more complex than
when no rearrangement is taking place. Monomers that yield
carbocations that can be stabilized (for example by resonance like for
styrene or electronic inductive effects like for vinyl ethers) will not
undergo rearrangement. Those that can not be stabilized will undergo
rearrangements (propylene, 1-butene). The cationic polymerization of
propylene and 1-butene results in the formation of short oligomers (Xn <
20) with an irregular structure.
37
Introduction
Initiation
Propagation
Rate Constants
38
Chain Transfer and Termination:
As for radical chain polymerization, chain transfer reactions occur
frequently in cationic polymerization.
1. Chain transfer to monomer:
A b-proton is transferred from the polymer to the monomer.
H CH3 CH3 k CH3 CH3
tr,M
CH C BF3OH + CH2 C CH2 C + CH3 C BF3OH
H C H CH3 CH2 CH3
H
CH3 CH3
ktr,M
CH C + CH3 C BF3OH
CH3 CH3
39
A b-proton is transferred from the polymer to the monomer.
Polymerization of styrene and ethyl vinyl ether yields the second
species only.
H H H H H
ktr,M
CH C BF3OH + CH2 C CH C + CH3 C BF3OH
40
A hydride ion is transferred from the monomer to the growing
carbocation.
CH3 H CH2 CH3 CH2 BF3OH

ktr,M
CH2 C BF3OH + C CH2 CH2 CH + CH2 C
CH3 CH3 CH3 CH3
The process of chain transfer to the monomer (either proton or hydride

ion transfer) depends on the stability of the resulting carbocation. In the
case of isobutylene, proton transfer is more frequent.
41
Usually: Ea(chain transfer) > Ea(propagation)
The activation energy of chain transfer to monomer is usually larger than
that of propagation. Thus, chain transfer to monomer can be reduced by
working at lower/higher temperatures.
42
The plain result of chain transfer to the monomer is the termination of a
growing chain and the formation of a new reactive center. Chain transfer
limits the molecular weight but not the rate of polymerization.
To calculate the molecular weight, an equation similar to the Mayo

equation is used. In the case of chain transfer to the monomer, CM is the
chain transfer constant for the monomer.
ktr , M
CM
kp
43
Chain Transfer and Termination 2. Spontaneous Termination:
The initiator-co-initiator complex is regenerated during spontaneous
termination.
CH3 CH3
kts
CH2 C BF3OH CH2 C + BF3OH2
H2C H CH2
Polymerization can start again with BF3OH2. Spontaneous termination

occurs much less frequently than chain transfer to the monomer.
44
Chain Transfer and Termination 3. Combination with the counterion:
CH3 CH3
kt
CH2 C BF3OH CH2 C OH + BF3
CH3 CH3
CH3 CH3
kt
CH2 C BCl3OH CH2 C Cl + BCl2OH
CH3 CH3
Bond strength: B-F > B-O > B-Cl
F Cl
F B OH Cl B OH
45
F Cl
Chain Transfer and Termination 3. Combination with the counterion:
CH3 CH3
kt
CH2 C Al(CH3)3Cl CH2 C CH3 + Al(CH3)2Cl
CH3 CH3
(alkylation : transfer of CH3-)
CH3 CH3
kt
CH2 C Al(C2H5)3Cl CH2 C H + H2C CH2 + Al(C2H5)2Cl
CH3 CH3
(hydridation : transfer of H-)
All these processes result in the termination of the growing chain and
of the reactive center.
46
Chain Transfer and Termination Chain Transfer to Polymer:
Intramolecular electrophilic aromatic substitution:
H
CH2 C CH2 C A CH2 CH CH2 + A H
H H CH
Intermolecular hydride transfer to polymer:

propagation
H H H A
CH2 C A + CH2 C CH2 CH + CH2 CH
CH3 CH3 CH3 CH3
The second mechanism leads to the formation of 47
short branches for 1-alkenes.
4. Chain Transfer to Chain Transfer Agents:
(S = XB)
ktr,S
P A + X-B P-B + X-A
Chain transfer agents can be solvent, impurity, or any chemical

deliberately added to the reaction system to limit molecular weight.
48
Introduction
Initiation
Propagation
Rate Constants
49
Number-Average Degree of Polymerization:
H CH3 CH3 ktr,M CH3 CH3
1. Chain transfer CH C BF3OH + CH2 C CH2 C + CH3 C BF3OH
to Monomer
H C H CH3 CH2 CH3
H
2. Spontaneous
CH3 kts CH3
CH2 C BF3OH CH2 C + BF3OH2
termination
H2C H CH2
CH3 CH3
3. Termination by kt
combination CH2 C BF3OH CH2 C OH + BF3
CH3 CH3
4. Chain transfer ktr,S

to X-B P A + X-B P-B + X-A
50
Since cationic polymerization is more subject to termination than anionic
polymerization, Xn can be estimated from the kinetic chain length (n).
Rp Rp
Xn
Rt Rt Rts Rtr , M Rtr , S
51
Rp Rp
Xn
Rt Rt Rts RTr , M Rtr , S
1. Chain transfer to
P A+MP+M A Rtr,M=ktr,M[P+(A-)][M]
monomer:
2. Spontaneous
P AP+A Rts = kts[P+(A-)]
termination:
3. Termination /
P AP+A Rt = kt[P+(A-)]
recombination:
4. Chain transfer to
P A + S P + S-A Rtr,S=ktr,S[P+(A-)][S]
solvent:
P A+MP A
Propagation: Rp=kp [P+(A-)][M]
52
Rp Rp
Xn
Rt Rt Rts Rtr , M Rtr , S
1 kt 1 kts 1 ktr ,M ktr ,S [ S ]

X n k p [M ] k p [M ] k p k p [M ]
1 kt 1 kts 1 [S ]
CM C S
X n k p [M ] k p [M ] [M ]
This equation is similar to the Mayo equation obtained for radical chain
polymerization. 53
Introduction
Initiation
Propagation
Rate Constants
54
Rate Constants:
One approach consists of determining Rp through a thorough kinetic
analysis of the polymerization.
Ki
Initiation: RA R A Ri = ki[R+A-][M] = kiKi[RA][M]
ki
R A + M RM A ( P A )
Propagation: kp
P A + M P A Rp = kp[P+A-][M]
Termination:
kt
P A P-A Rt = kt[P+A-]
55
Rate Constants:
The steady-state assumption can be applied to estimate [P+A-]:
Ri = ki[R+A-][M] = kiKi[RA][M]
Rp = kp[P+A-][M]
Rt = kt[P+A-]
-ki K i ki K i
Ri = Rt [P A ] [ RA][ M ] Rp k p [ RA][ M ]2
kt kt
Rp scales as [RA]1 and [M]2. This result is different from radical chain
polymerization where Rp increases as [I]1/2 and [M]1.
56
Rate Constants:
Unfortunately, the steady-state assumption is not valid in many, if not
most, cationic polymerizations! Cationic polymerizations proceed so
quickly that steady-state conditions are never achieved. Some of these
polymerizations are essentially complete in a matter of seconds or
minutes.
An estimate of kp for cationic polymerization requires that [P+A-] be
measured. As in anionic polymerization, this is complicated by the
presence of two propagating species: the ion pairs and the free ions.
It is often assumed that: Rp = kp [M][P+A-] where [P+A-] represents the

concentration of ion pairs. This is wrong!
57
Rate Constants:

Rp k papp[M ] [ P A- ] [ P ] k p [M ][ P A- ] k p [M ][ P ]
with
k p [ P A- ] k p [ P ] [ P ][ A- ]
k papp and K
-
[P A ] [P ]
[ P A- ]
Since only free ions conduct, conductivity measurements yield [P+].

Since ion pairs are relatively loose, their absorption is similar to that of
free ions and absorption measurements yield the total concentration of
ions [P+A-] + [P+]. Combining the conductivity and absorption
measurements yields [P+A-] and [P+]. Since all ion concentrations can
app
be measured, k p , K can be determined. 58
Rate Constants:

Rp k papp[M ] [ P A- ] [ P ] k p [M ][ P A- ] k p [M ][ P ]
with
k p [ P A- ] k p [ P ] [ P ][ A- ]
k papp and K
-
[P A ] [P ]
[ P A- ]
As for anionic polymerization, addition of a salt to the polymerization
mixture shifts the equilibrium towards the ion pairs, which slows down
the reaction and yields a smaller kp value. Conducting several
polymerization reaction with different salt concentrations would yield
k p , k p . In practice, this procedure which is commonly used for anionic
polymerization has not been much applied to cationic polymerization.
59
Rate Constants Comparison of Rate Constants:

Monomer k (10-4 L.mol-1.s-1) k (10-4 L.mol-1.s-1)
p p
CH2
CH 120 10
(styrene)
CH2
10
H3CO CH 36 4
(p-methoxystyrene)
CH2 CH
N
60 5
60
(N-vinylcarbazole)
Rate Constants Comparison of Rate Constants:
In general, k p is one order of magnitude larger than k p . The difference
between k p and k p ( 10) is less than between k p- and k p ( 1,000)
observed for anionic polymerization. This effect is due to the larger size
of the counterion in cationic polymerization.
As for anionic polymerization, cationic polymerization proceeds faster
than radical polymerization due to a lower rate of termination and a
higher concentration of propagating species.
61
Introduction
Initiation
Propagation
Rate Constants
62
Effect of Solvent:

Since k p is one order of magnitude larger than k p , any effect
app
increasing the concentration of the free ions will increase k p . Polar
solvents increase dissociation which results in increased Rp (or k papp).
The solvent must be able to solvate the different reactants. If this is

not the case, the monomer might solvate preferentially the ionic
propagating centers which results in a higher dependency of Rp on
the monomer concentration (Rp ~ [M]3 for the polymerization of
styrene in carbon tetrachloride).
63
Effect of the Counterion:
Since the counterions are large, there are less electrostatic interactions
between the propagating carbocation and the counterion (loose ion
pairs). There is little effect of the counterion on the reactivity of the ion
pairs. Of course, there is no effect of the counterion on the reactivity of
the free ions.
64
Introduction
Initiation
Propagation
Rate Constants
65
Cationic Chain Polymerization CH3
Industrial Cationic Polymerization: CH2 C
Isobutylene-based polymers are very important commercially. CH3
Very low molecular weight: (Mn < 3000, 80% isobutylene and 20% 1-
butene) These polymers are used as adhesives, sealants, lubricants,
plasticizers, and motor oil additives. They are called polybutenes.
Low molecular weight: (Mv < 5104) Polyisobutylenes are either
viscous liquids or tacky solids which are used for sealant applications.
High molecular weight: (Mv > 105) These polyisobutylenes are rubbery
solids that are produced by conducting the polymerization at low
temperature with a chain transfer agent to control the molecular weight.
Butyl Rubber: It is a copolymer of isobutylene and small amounts of
isoprene (0.5 2.5%). Incorporation of isoprene enables crosslinking.
Butyl rubber remains flexible down to 50 oC (no crystallization like
polyisoprene). The material does not contain many unsaturated double66
bonds and exhibits good resistance against aging, moisture, chemicals.
Cationic Chain Polymerization CH3
Industrial Cationic Polymerization: CH2 C
Isobutylene-based polymers are very important commercially. CH3
Chewing Gum: It is made by copolymerizing isobutylene and small
amounts of isoprene. It is clear and odorless, chewable even at low
temperatures, absorb large amount of fillers and additives, resistant to
oxidation, and available in a wide variety of grades that conform with the
U.S. Food and Drug Administration's (FDA) requirements for food uses.
67
Introduction
Initiation
Propagation
Rate Constants
68
Differences between Radical, Anionic, and Cationic Polymerizations:
Temperature: Ionic polymerizations are conducted at temperatures lower
than 0 oC. Radical polymerizations are carried out at temperatures
larger than 0 oC.
Solvent polarity: It affects ionic polymerizations much more than radical
polymerizations.
Protic solvents: protic solvents (water, alcohol) terminate ionic
polymerization, but not affect radical polymerization.
69
Radical scavenger: A radical scavenger will stop a radical
polymerization but not an ionic polymerization.
Example of radical scavenger 2,2-diphenyl-1-picrylhydrazyl
(DPPH)
(2,2,6,6-Tetramethylpiperidin-1-yl)oxyl or (2,2,6,6-
tetramethylpiperidin-1-yl)oxidanyl, (TEMPO)
70

Chapter 5 Anionic Polymerization

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Chapter 5 Anionic Polymerization

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Cationic Chain Polymerization

Being large, the charge density of these anions yields smaller

Perchloric acid Fluorosulfonic Methane Trifluoromethane

Metal halides: AlCl3, (BF3), SnCl4, SbCl5, ZnCl2, TiCl4, (PCl5)

Organometallic derivatives: Al(C2H5)Cl2, Al(C2H5)2Cl, Al(C2H5)3

Oxyhalides: POCl3, CrO2Cl2 (phosphorus oxychloride,

CH3 CH3 CH3 CH3

I : Lewis acid: co-initiator

The activity of the initiator-co-initiator complex increases with the

Tertiary carbocations are more stable and are obtained in higher

CH3 CH3 ki CH3 CH3

(less stable) (more stable) 17

CH3 CH3 CH3 CH2

Trityl Cycloheptatriene Vinyl methyl para-

SnCl4OH2 SnCl3OH + HCl

Perchlorate salts are used as the supporting electrolyte. 23

CH3 CH3 CH3

Example #1: Cationic polymerization of 3-methyl-1-butene

This species represents 70 100% of the final polymer composition!

Comparison of the rates at which rearrangement and propagation occur

1,2 hydride shift H H H H

1,2 hydride shift H H H H

1,2 methide shift H H H H

1,2 hydride shift H H H H

Most stable carbocation H H

CH3 H CH2 CH3 CH2 BF3OH

The process of chain transfer to the monomer (either proton or hydride

To calculate the molecular weight, an equation similar to the Mayo

Polymerization can start again with BF3OH2. Spontaneous termination

Bond strength: B-F > B-O > B-Cl

(alkylation : transfer of CH3-)

(hydridation : transfer of H-)

Intermolecular hydride transfer to polymer:

Chain transfer agents can be solvent, impurity, or any chemical

4. Chain transfer ktr,S

1 kt 1 kts 1 ktr ,M ktr ,S [ S ]

It is often assumed that: Rp = kp [M][P+A-] where [P+A-] represents the

Since only free ions conduct, conductivity measurements yield [P+].

The solvent must be able to solvate the different reactants. If this is

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