CHAIN TRANSFER IN POLYMERIZATIONS—MOLECULAR

WEIGHT CONTROL AND MORE

Presented by:
Vijay R. Srinivas, Ph.D.
Principal Research Scientist
Arkema, Inc.
Research & Development
900 First Avenue, King of Prussia PA 19406
Phone: 610-878-6656 • Fax: 610-878-6730 • Email: vijay.srinivas@arkemagroup.com

Vijay R. Srinivas is a Principal Research Scientist in the Thiochemical Division of Arkema Inc.,
based at its R&D Center in King of Prussia, PA. He joined the then Pennwalt Corporation’s
Organic Chemicals Division in 1984 after a Post Doctoral stint at the University of Chicago as a
Senior Research Chemist to work on Process Development in the thiochemicals area. He was
involved with the development of several products and was responsible for implementing their
commercial production. He currently is in charge of Technical Service and Technology
Marketing for all thiochemical products that go into the energy market – refineries and
petrochemicals and the mercaptan products that are used in the polymerization and other
industries for North America.

He does not understand why he loves to play golf, since he gets his money’s worth whenever he
goes out to play. He also likes to play volleyball, but has a slight height disadvantage.
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Chain Transfer in Polymerizations-Molecular Weight

Control and More

Vijay R. Srinivas
Arkema Inc.

ABSTRACT:

Control of molecular size and molecular weight distribution is necessary so that the resulting
polymers have good processability and have specific properties required for their intended
applications. Chain transfer is the process of regulating and controlling molecular weight.
Some experts consider this process of chain transfer as the fourth process in polymerizations,
along with initiation, propagation and termination. Chain transfer was first observed in radical
polymerizations but occurs in ionic polymerizations also.

Alkyl thiols (Mercaptans) have been recognized to be one of the most efficient chain transfer
agents in polymerizations that produce polystyrene, styrene-butadiene rubber, ABS terpolymers,
polymethacrylates (e.g. PMMA), polyacrylates and other vinyl-type of polymers. Chain transfer
can also be used to make low molecular weight polymers (telomers), introduce branching and
cross-linking. t-Dodecyl mercaptan (TDM) and n-dodecyl mercaptan (NDM) are examples of
the two most common chain transfer agents. In many polymerizations, TDM is the choice due
to the fact that its Chain Transfer Constant (CT) is an aggregate of different numbers – since it is
a mixture of several tertiary mercaptans of carbon number C10 to C13. NDM, on the other hand is
a pure C12 mercaptan with a higher CT, thus giving a narrower molecular weight distribution.
Mechanism of the various reactions involved in chain transfer will be discussed. Some
strategies involving the use of chain transfer agents – mercaptans in particular, for improving
thermal stability of the polymers, increasing branching, providing enhanced cross-linking, will
also be discussed.

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Introduction: Kinetics of most polymerization processes involves a fourth step called “Chain
Transfer”, in addition to initiation, propagation and termination. The chain transfer reaction can
take place with the monomer, solvent, initiator, and polymer or even with a modifier. In all
cases the fundamental result is the reduction in the molecular weight of the polymer. The
amount of reduction in molecular weight is dependent on the reactivity of the growing macro
radical with the small molecule species. In the chain transfer process; the total number of active
centers before and after the reaction does not change even though a growing chain is terminated.
A term ‘Chain Transfer Constant’ is used to assess the ability of a solvent or other substance
added to be a chain transfer agent in polymerizations. This can be defined as:

CT = ktr/kp

Where CT is the chain transfer constant, ktr and kp are the rate constants for the transfer and
propagation reactions, respectively.

Chemistry of Chain Transfer:

Polymerization involves mainly three steps, although the fourth one is implicit and very
important in controlling the molecular weight of the polymer being formed.

Initiation: I • 2R•

2R• + 2M • 2RM•

kp
•
Propagation: RMn + M • RM(n+1)•

kt
Termination: RMn• + RMm• • RM(m+n)

The chain transfer reaction can take place with any molecular species present during
polymerization. In general this takes place via the abstraction of an atom, typically hydrogen or
halogen atoms, from a substrate and forming a dead polymer and a new radical. One may
consider chain transfer as another mode of termination.
ktr
•
Pn + XY • PnX + Y• (Chain Transfer)

This is followed by the addition of the formed radical to a monomer to afford a radical species
(can be termed as a re-initiation) as below:
ki
•
Y + M • YM1• (Reinitiation)

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Substrates containing labile atoms or groups of atoms tend to be active in this reaction.

TABLE-1

CASE Rel. Rate Constants Type of Effect Effect on Rp Effect on

Mol. Weight
1 kp>>ktr; ki•kp Normal CT None Decrease
2 kp <<ktr; ki•kp Telomerization None Large Decrease
3 kp>>ktr; ki < kp Retardation Decrease Decrease
4 kp <<ktr; ki <kp Degradative CT Large Decrease Large Decrease

The effect of chain transfer on the polymerization rate depends on whether the reinitiation rate is
comparable to that of the original propagating radical. Table-1 shows the various possible
situations one may encounter. In Cases 1 & 2 reinitiation is rapid and one observes no change in
the polymerization rate. The same number of monomer molecules is consumed per unit time
and a larger number of smaller sized polymer molecules are formed. The relative decrease in
the molecular weight (Xn) depends on the transfer constant. When the transfer constant (ktr) is
much greater than that of propagation (kp), as in Case-2 above, a very small sized polymer often
referred to as a ‘Telomer’ is formed. When reinitiation is slow compared to propagation (Cases-
3 & 4) one observes a decrease in the rate of polymerization (Rp) as well as in the Xn. Again
the amount of decrease in the rate depends on the kp and ktr. Retardation in the rate is observed
because, with reinitiation being slow, termination of the primary radical occurs, decreasing the
rate of polymerization as shown below:

ktp
· ·
Pn + Y • “Dead Polymer Chain”

Where ktp is the rate coefficient for primary radical termination.

Chain transfer is important because it can alter the molecular weight of the polymer in an
undesirable fashion. Controlled chain transfer, on the other hand, can be employed to control
the molecular weight at a specified level. As mentioned earlier, chain transfer reactions can
involve the initiator, monomer, solvent, an added compound (modifier) and the polymer being
made.

Chain Transfer to Initiators

Initiators that react with macro radicals, many times form a new radical that is similar to the one
obtained by their thermal decomposition. Such initiators can function as chain transfer agents,
for e.g. cumyl and t-butyl hydroperoxides in methyl methacrylate polymerizations, wherein the
process is faster compared to when benzoyl peroxide or 2,2’-azobis isobutyronitrile (AIBN) is
used as an initiator. Most initiators, however, do not encourage chain transfer. Additionally, the
initiator concentration is very low and so is its interaction with the growing chain. Thus chain
transfer to the initiator is not of much significance; although specific initiators are chosen for
specific polymerizations, with their chain transfer properties also contributing to the desired
property of the polymer being made.
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Chain Transfer to Monomers

Chain transfer to the monomer, however, would be significant if the monomer contains a labile
H or other atom. Reaction occurs by the abstraction of a hydrogen atom from the monomer or
the donation of a hydrogen atom from the polymer radical to the monomer:

Pn• + CH2=CHX • P nH + CH2=CX• for e.g.

•
Pn + CH2=CH-OCOCH3 • P nH + CH2=CH-OCOCH2•

Pn• + CH2=CH-CH2X • P nH + CH2=CH-CH•X

Or
•
Pn-1 –CH2-CHX + CH2=CHX • Pn-1 –CH=CHX + CH3CH•X

Chain transfer to the monomer intrinsically limits the length of the macromolecular chain. For
vinyl chloride monomers chain transfer to the monomer is one of the important modes of
• •
molecular mass control. Rearrangement, elimination of Cl followed by the addition of Cl to
another monomer unit can take place as shown below:

-CH2 -CHCl-CHCl-CH2• • -CH2 -CHCl-CH• -CH2Cl • Cl• + -CH2 –CH=CH-CH2Cl

or other isomers
Cl• + CH2=CHCl • CH2Cl-CH•Cl

Transfer to vinyl acetate also occurs easily, with the hydrogen atoms on the acetate being the
most labile. Allylic monomers such as the chloride, acetate etc., show an even greater tendency
to give up a hydrogen atom, that results in the formation of a relatively low energy radical,
stabilized by delocalization on carbon atoms 1 and 3. Due to this reason, allyl radicals have
very little tendency to reinitiate the polymer chain. Therefore the consequence here is a low
polymerization rate and a low degree of polymerization. This phenomenon is often referred to as
degradative chain transfer. It is important to note that chain transfer to the monomer produces
an unsaturated radical, which in many instances, can function both as a co-monomer and as an
active center for polymerization, giving rise to a branched macromolecule. Thus, when this
happens we can say that chain branching is an indirect consequence of chain transfer to the
monomer.

For acrylic monomers and styrene, the probability for the chain transfer to occur to the monomer
in comparison to propagation is very low (~ 10-5).

Chain Transfer to the Polymer

Chain transfer to polymer results in the formation of a radical site on a polymer chain. The
polymerization of the monomer at this site leads to the formation of branched polymer.
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H
Y
. P nH + CH 2
Pn + CH 2 C C
.

Y
CH 2 C

Pm

Formation of branched structures as opposed to reduction in molecular mass is the dominant

feature of chain transfer to polymer. Transfer to the polymer can be ignored when one is
attempting to determine precisely the constants CI, CS, CM for chain transfer to initiator, solvent
and monomer respectively, since these are determined from data at low conversions. However,
transfer to polymer cannot be ignored or neglected for practical situations where
polymerizations are carried out to near completion or high conversions. The effect of chain
transfer to the polymer plays a very significant role in determining the physical properties and
ultimately the applications of the polymer. Branching, as we know, drastically reduces the
cystallinity of a polymer. Hydrogen abstraction results in the formation of active centers inside
a preexisting or a growing polymer chain. Subsequent reinitiation and propagation steps give
rise to long-chain or short-chain branches.

The following cases can be distinguished, as each, results in the formation of a differently
branched polymer:

(i) Intermolecular chain transfer and termination by disproportionation (negligible wrt.

transfer) produces branched polymers.
(ii) Intermolecular chain transfer and termination by coupling gives rise to branched and
cross-linked polymers.
(iii) Intramolecular chain transfer can afford polymers with short-chain branches
(commonly referred to as a “back-biting reaction involving a quasi-cyclic
intermediate) and
(iv) Intermolecular chain transfer to preformed polymer of a different structure permits
the formation of graft-copolymers.

As examples, the presence of (i) and (iii) above is said to be responsible for the particular
structure of low-density polyethylene and the unique behavior of polyvinyl acetate. Here chain
transfer occurs to both the main chain (major) and the acetyl groups, giving rise to two types of
branching, one of which can be easily removed by saponification.

As an alternate route, transfer to monomer followed by copolymerization yields almost

exclusively hydrolysable branching. As a consequence, polyvinyl alcohol has a more linear
structure than the polyvinyl acetate from which it is obtained. The relevance of chain transfer to
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polymer and consequently of branching is dependent on the concentration of the polymer and
thus increases with increasing polymerization yield.

Vinyl Acetate Polymerization

.
OCOCH 3 OCOCH 2
.
Pn + CH2 C CH2 PnH + CH2 CH CH2

H
H
P

-
[OH ] OCOCH 2P
CH2 CH CH2 CH2 C CH2
H
OH

Linear Polymer

OCOCH3 OCOCH3
Pn. + CH2 C CH2 PnH + CH2 C. CH2
H

OH
OCOCH3
CH2 C CH2 [OH-]
CH2 C CH2
P
P
Branched Polymer
Chain Transfer to Chain Transfer Agent and Solvent

In all of the above cases, one has very little control of the chain transfer process. The role of the
solvent or intentionally added chain transfer agent can be well defined, primarily from their
activity standpoint and from the concentration used. The chemical and kinetic behavior of
several solvents and chain transfer agents are quite similar, in that they possess a loosely bound
atom or group of atoms that can homolytically cleave or do so in the presence of a propagating
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radical, under polymerization conditions. The chain transfer constants for various solvents used
with different propagating radical species are known.

TABLE-2: Chain Transfer Constants for Different Solvent/Radical Systems*

5
SOLVENT Cs*10 at Cs*105 at Cs*105 at 1000C 5 0
Cs*10 at 80 C Cs*105 at
0 0 0
60 C for 80 C for for ~CH2- for ~CH2- 60 C for
• • • •
PhCH CH2~ PhCH CH2~ C (CH3)COOCH3 C (CH3)COOCH3 ~CH2-
•
CHCOOCH3
Benzene 0.18 0.61 1.84 0.75 29.6
Cyclohexane 0.24 0.66 1.6 1.0 65.9
Toluene 1.25 2.98 6.45 5.25 208.9
Ethylbenzene 6.7 10.7 16.2 13.5 551.5
Cumene 8.2 13.1 20.0 19.0 899
Triphenylmethane 35.0 -- 80
Butyl chloride 0.4 -- 3.7
Dichloromethane 1.5 -- 118
Carbon 920 1330 1850 23.9
Tetrachloride

* Data from ‘Polymer Handbook’ Eds. Brandrup J. and Immergut E.H.; John Wiley & Sons, New York, 1975

Compounds with a hydrogen atom attached to a carbon or more commonly to a sulfur atom, a
halogen attached to a carbon, a sulfur atom attached to a carbon and/or another sulfur, are
common examples of active compounds used for chain transfer. Temperature has an influence
on the chain transfer activity of a solvent or agent. As an example, styrene polymerized in the
presence of carbon tetrachloride (CCl4), almost always yield lower molecular weight polystyrene
than when done so in the absence of a solvent. Additionally, in many cases initiation and
termination reactions are negligible compared to the transfer reaction and both chain ends could
be derived form the solvent as shown below:
M CCl4
. . .
Pn + CCl4 PnCl + CCl3 CCl3Pn CCl3PnCl + CCl3.

It is important to note that not all solvents behave the same in all polymerizations. For example,
CCl4 is not effective in butadiene polymerizations. The efficiency of solvents and chain transfer
agents varies by as much as six orders of magnitude as we go from say benzene to carbon
tetrabromide to n-dodecyl, t-dodecyl or butyl mercaptan or ethyl thioglycolate etc. In general
solvents with high chain transfer ability are used to make low molecular weight liquid polymers.
Many a times a solvent with a chemical structure similar to that of the monomer is chosen so
that the terminal end groups from the solvent do not effect the polymer structure and properties
drastically. This is sometimes referred to as ‘Telomerization’ and the solvent in such a case is
known as a ‘Telogen’. For example, polymerization of bromotrifluoro ethylene is carried out by
this technique using bromotrifluoro methane as the telogen.

In many industrial processes, specific chain transfer agents are intentionally added to control the
molecular weight of the polymer. Such agents are specifically called ‘chain modifier’. The
modifier prevents the uncontrolled growth of a polymer chain. It terminates growing chains and

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promotes fresh new chains in such a way that the average molecular weight of the polymer
remains within a close range. Mercaptans in general and n-dodecyl mercaptan (NDM) and
t-dodecyl mercaptan (TDM) are the most commonly used polymer chain modifiers in the
industry. Their interaction with a growing chain can be represented as follows:

CH2 CH. + n-C12H25SH CH2 CH2 + RS.

X X
Use of mercaptans to modify the molecular weight dates back to before World War II,
especially in the SBR industry. The chain transfer constants for several mercaptans used in
various recipes are known. A few select values are represented below in Table-3.

TABLE-3: Chain Transfer Constants for Select Mercaptans

Mercaptan Monomer Temperature(0C) CT Constant

Value(s)
n-Octyl Mercaptan Butadiene 50 16, 18, 19
n-Decyl Mercaptan Butadiene 50 18.2
n-Tetradecyl Mercaptan Butadiene 50 19.4
n-Butyl Mercaptan Ethylene 130 5.8, 15
Ethyl Mercaptan Methyl Acrylate 50 1.57
n-Butyl Mercaptan Methyl Acrylate 60 1.69 ± 0.17
n-Octyl Mercaptan Styrene 50 19
n-Dodecyl Mercaptan Styrene 60 18.7±1
t-Dodecyl Mercaptan Styrene 50 2.9

Experimentally, one can determine the value of the CT, the chain transfer constant of an added
agent using the Mayo equation. Hence mathematically one is able to calculate the amount of
chain transfer agent needed to obtain a specifically desired molecular weight of the polymer.
Agents that have a CT of 1 or greater are very useful since they can be used effectively in very
low concentrations. NDM and TDM are the most common chain transfer agents used as
mofidiers. NDM is a pure compound (>98.5% isomer purity of straight chain C12H25SH) and
TDM is a statistical mixture of C10 to C13 mercaptans, predominant in highly branched C12H25SH.
If one evaluates the regulating index of the mercaptans, one finds that for normal mercaptans the
index drops off rather quickly with increasing carbon number, that for the tertiary mercaptans
does not change too much until one goes past 12 carbons. Figure-1 shows the Regulating Index
of mercaptans as a function of carbon number. Temperature affects this index also slightly for
the tertiary mercaptans, higher the index at higher temperature. These values are approximate
since variables such as agitation, emulsifier employed, transport of the active mercaptan
between phases etc. impact them. Another aspect of chain transfer studies is that it corroborates
the concept of functional group reactivity independent of molecular size. Therefore, one can
vary the degree of polymerization by either using different chain transfer agents or by using
different amounts of the same transfer agent. Under these conditions the propagation rate
constant (kp) is independent of Xn and the transfer constant for a particular agent is independent
of the size of the propagating radical. This allows for molecular weight control by a mercaptan
throughout the polymerization, and obtain a desired molecular weight distribution. Using
mercaptans for example NDM, are known to give totally not cross-linked polymers of desired
molecular weight. Observations such as improved stability, possibly due to the suppression of
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undesired termination pathways, show that mercaptans can be used for several purposes in
polymerizations.
Regulating Index FIGURE-1

Higher the regulating index of a mercaptan faster is its depletion along the conversion profile. If
one plans to conduct a polymerization#toof Carbons
high conversions, employing a mercaptan with a high
regulating index will give a polymer with a broad molecular weight distribution. While
theoretically one can calculate this, experimental observations are less drastic since other
ingredients in the recipe, such as solvent, monomer, polymer etc. get involved in reducing or
modifying the molecular weight. Polymers with a broad molecular weight distribution have
been shown to breakdown during milling, because preferential breakdown of higher molecular
weight fraction of the polymer takes place. It is important to note that a narrow, optimum
molecular weight distribution and free chain ends impart good vulcanizate properties to SBR’s.
Mercaptan modifiers with a wide range of regulating indexes are available commercially and
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with careful selection it is possible to produce polymers with different molecular weight
distributions within the confines of the emulsion systems used. Further modification can be
effected in SBR polymerizations by the incremental addition of the mercaptan modifier. This
technique has been verified experimentally and is used commercially. Here there is a possibility
to make a polymer with a specific molecular weight distribution at higher conversions than by
using a single aliquot of the modifier. In order to see a significant difference in the molecular
weight distribution by using the incremental addition procedure, one needs to use a mercaptan
modifier of a relatively high regulating index, which magnifies the differences in the
polydispersity. The use of two or more additions (or continuous addition) of mercaptan
modifiers does offer the advantage of having a uniform viscosity during the course of the
polymerization.

Functionalized mercaptans or di-, tri- mercaptans have been shown to possess unique chain
transfer activity and could potentially be used as modifiers not only to control molecular weight
but also to obtain controlled amounts of branching and cross-linking.

Conclusion:

Chain transfer is intrinsic to all polymerization processes and can take place to several species
present or added. Majority of the processes add an agent to modify or control the process to
afford desirable molecular weights that impart beneficial and varied properties to the polymer.
The method used to add the chain transfer agent can influence the molecular weight distribution
of the polymer being produced. Continuous addition or multiple additions do offer advantages
and result in the use of the modifier more efficiently to control molecular weight and polymer
viscosity. Additionally, a combination of the different modes of chain transfer can be
beneficially used to make uniquely functional polymers with controlled molecular weight
distribution, viscosity and properties.

Acknowledgements: The author wishes to thank Arkema in general and its Thiochemical
Division for providing the opportunity to present this article.

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