HIGHLIGHT

“Charge Transfer” Polymerization—and the

Absence Thereof!

H. K. HALL, JR., ANNE BUYLE PADIAS

C. S. Marvel Laboratories, Department of Chemistry, The University of Arizona, P.O. Box
210041, Tucson, Arizona 85721-0041

Received 26 March 2001; accepted 27 March 2001

ABSTRACT: Mechanisms for
“charge-transfer” spontaneous po-
lymerizations and cycloadditions
between electron-rich olefins and
electron-poor olefins were re-
viewed. As for propagation, litera-
ture proposals involving charge-
transfer complexes were rejected.
Instead, alternating copolymeriza-
tion is ascribed to polar effects in
free-radical reactions. As for spon-
taneous initiation, literature pro-
posals involving charge-transfer
complexes, with or without proton
transfer, were rejected. Instead, the
initiating species is postulated to
be a tetramethylene zwitterion bi-
radical, which may initiate either
ionic homopolymerization or free-
radical copolymerization. A new
hypothesis proposes that any inter-
action that brings vinyl monomers
close together may facilitate tetra-
methylene formation and sponta-
neous polymerization. These inter-
actions include Coulombic, acid–
base, hydrophobic– hydrophilic
and templating–tethering interac-
tions. © 2001 John Wiley & Sons, Inc. J
Polym Sci Part A: Polym Chem 39: 2069 –
2077, 2001
Keywords: charge transfer poly-
merization; spontaneous polymer-
ization; tetramethylene; intermedi-
ate

H. K. Hall, Jr., received his undergraduate training at Brooklyn Polytech,

a Master’s degree at Pennsylvania State University, and a Ph.D. from the
University of Illinois in 1949. Postdoctoral work followed with Prof. P.
J. Flory at Cornell, and with Profs. W. Winstein and W. G. Young at
UCLA. After 17 years at DuPont, he moved to the University of Arizona
in 1969. He is the recipient of the 1996 ACS Polymer Chemistry Award
and of the 2000 Herman F. Mark Award from the Polymer Chemistry
Division of the American Chemical Society.

H. K. HALL, JR.

Correspondence to: H. K. Hall, Jr. (E-mail: hkh@

arizona.edu)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 39, 2069 –2077 (2001) 2069
© 2001 John Wiley & Sons, Inc.
2070 J. POLYM. SCI. PART A: POLYM. CHEM.: VOL. 39 (2001)

Anne B. Padias completed both her undergraduate degree and Ph.D.

(1975) at the University of Ghent in Belgium. She then joined Dr. H. K.
Hall’s research group at the University of Arizona, originally as a post-
doctoral associate, and later as a research scientist. She is currently the
organic laboratory instructional supervisor and a lecturer at the University
of Arizona.

ANNE B. PADIAS

INTRODUCTION Propagation in CT Polymerization

An often observed phenomenon in free-radical CT poly-
In the 1960s and 1970s, chemists became interested in a
merization is the alternating structure of the resulting
novel and widespread research area called “charge-trans-
copolymer. Early researchers were intrigued by this be-
fer” (CT) polymerization.1–5 The CT polymerizations
havior and suggested that this could be due to more than
occur between electron-rich (donor) and electron-poor
just “natural” selection of the monomers. The alternating
(acceptor) olefins and are often spontaneous, that is, no
copolymer structure was observed in both spontaneous
initiator is needed, although heating may sometimes be
or initiated free-radical polymerizations. A very popular
necessary. Donor monomers include unsaturated hydro-
theory proposed that the CT complex itself acts as a
carbons, vinyl ethers, p-methoxystyrene, and N-vinylcar-
monomer6 (Scheme 1). The color observed for the CT
bazole, whereas acceptor monomers usually have one or
complexes in solution, which faded as polymerization
more cyano, carbomethoxy, and/or nitro substituents.
and cycloaddition proceeded, made this a very attractive
The polymers are either strictly alternating 1/1 copoly-
theory. Kinetics studies also purported to show the par-
mers or the homopolymer of either or both monomers.
ticipation of the CT complex. However, a CT complex is
The bright colors associated with the charge-transfer
a very weak interaction between molecules of differing
complexes are often observed, and these fade as the
polarities. Although the CT complex has distinct spec-
reactions proceed. Cycloadducts between the donor and
troscopic signatures, it cannot be isolated and is not
acceptor olefins may accompany the polymerizations,
known to undergo chemical reactions. Another theory
and these cycloadducts can include cyclobutanes, Diels–
involved “matrix” polymerization in which the mono-
Alder adducts, and/or cyclohexanes. The polymeriza-
mers align themselves in an alternating fashion in the
tions can often be accelerated by Lewis acids or by light.
polymerizing mixture; this alignment was thought to be
A wide variety of explanations was offered by both
polarity-driven.
organic and polymer chemists around the world to ac-
count for these remarkable phenomena. The observed
polymerization behavior did not appear to be interpret-
able in terms of “classical” organic chemistry. Accord-
ingly, the researchers suggested explanations that might
be termed “baroque,” or even “rococo.” In fairness, the
correct organic chemistry rationale of these facts did not
become available until much later.
Polymerization mechanisms always have to take at
least two aspects into account, namely, initiation and
propagation. In the present treatise, we will discuss prop-
agation mechanisms first and then deal with the initiation Scheme 1. Literature explanations for alternating propaga-
subsequently. tion.
 HIGHLIGHT 2071

Structure 1

comes the concept of polar effects in free-radical chem-

Scheme 2. Alternating copolymerizations without CT com-
plex.
However, on closer examination neither of these ex-
planations leads to useful predictions about actual poly-
merization behavior. Let us take a very recent example of
a copolymerization described in the literature as a CT
copolymerization, namely, the copolymerization of nor-
bornene and maleic anhydride7 (Scheme 2). No CT com-
plex is visible, that is, no color can be seen when the
components are mixed. Although 1/1 alternation between
the comonomers occurs on the copolymerization of ma-
leic anhydride and norbornene, the terpolymer with t-
butyl methacrylate contains much more maleic anhy-
dride than norbornene.
Similarly, in the copolymerization of 2,3-dimethylbu-
tadiene with acrylonitrile, the reaction solution is clear
and transparent in UV light above 300 nm, indicating
that no CT complex was present.8 However, the poly-
merization rate was at a maximum for a 1/1 comonomer
ratio in the monomer feed, and the resulting copolymer
was close to alternating in structure. Thus, in this case
“CT” propagation behavior is observed, but a CT com-
plex is absent (Scheme 2).
On the other hand, CT propagation would be expected
to be prominent for very strong donor and very strong
acceptor monomers. When p-methoxystyrene is mixed
with dimethyl cyanofumarate, a bright yellow complex
immediately forms and fades as copolymerization pro-
ceeds9 (see Structure 1). We were able to solve the
following propagation kinetics equation for equal initial
concentrations:
istry, that is, electron-rich radicals prefer to react with
electron-poor substrates and vice versa. Pioneering work
in this field by Giese and colleague10,11 shows that the
electron-rich cyclohexyl radical reacted much faster with
electron-poor olefins than with electron-rich olefins. As
shown in Table I, the reaction of the cyclohexyl radical
with maleic anhydride was almost 200,000 times faster
than with 1-hexene. Similar behavior has recently been
demonstrated for the electron-rich methyl radical, which
reacts 100 times faster with acrylonitrile compared with
ethylene.12 In contrast, the same researchers demon-
strated that electron-poor trifluoroacetonyl radical adds
faster to electron-rich olefins such as ␣-methylstyrene
than to electron-poor olefins such as methyl acrylate,
although the effect is less pronounced in these cases, as
summarized in Table II.13
Taking inspiration from the organic chemistry results,
Jones et al.14 applied this knowledge to the reactions of
electron-rich alkyl radicals generated from the corre-
sponding mercury bromide with mixtures of polymeriz-
able olefins. n-Hexyl radical in the presence of a mixture
of styrene and acrylonitrile led to a mixture of n-octyl-
cyanide and 1-phenyloctane in a 25/1 ratio. No products
composed of the alkyl radical with both monomers were
Table I. Reactions of Cyclohexyl Radicals with Olefins

Rp⫽a[D]2⫹b[D]3

The expected rate of polymerization consists of two

terms: the first one involving free-monomer propagation,
and the second one was obtained assuming that a puta-
tive CT complex was involved in the propagation. How-
ever, the constant for the second term was 0, meaning
“no CT propagation could be detected.”
So far we have described what the explanation for
alternation is not. From organic chemistry in recent years
2072 J. POLYM. SCI. PART A: POLYM. CHEM.: VOL. 39 (2001)
Table II. Reactions of Trifluoroacetonyl Radical with
Olefins
detected, and the electron-rich radical clearly favored
reaction with the electron-poor acrylonitrile. Jones and
Tirrell15,16 found similar results in the reactions of n-
butyl radical with a mixture of N-phenylmaleimide
(NPM) as the acceptor olefin and 2-chloroethylvinyl
ether or styrene as the donor monomer. The simple
addition product of the butyl radical to the NPM double
bond was isolated in 87% yield, and the putative product
formed by the concerted addition of NPM and 2-chlor-
ethylvinyl ether was not detected by gas chromatogra-
phy/mass spectrometry. “Trapping experiments show
that consumption of NPM by the 1-butyl radical in
NPM-CEVE solutions occurs essentially only by simple
addition of the olefin. No evidence for concerted addition
of a comonomer CTC is provided.”35
With respect to the aforementioned maleic anhydride
and norbornene system, the reaction of a model cyclo-
hexyl radical with a mixture of these monomers was
recently investigated and gives exclusively cyclohexyl-
succinic anhydride, and the addition of the two mono-
mers was not observed; the researchers conclude7 that
“the participation of a CT complex in the copolymeriza-
tion of maleic anhydride and norbornene cannot be im-
portant.”
The hypothesis that free-radical copolymerization ki-
netics are consistent with the participation of CT com-
plexes as monomers in propagation reactions has been
refuted in a recent authoritative review that surmised that
no CT complexes are involved: “. . .the explicit penulti-
mate model should replace the terminal model as the
basis of copolymerization kinetics.”17 There is no men-
tion of CT complex involvement in the present review.
In conclusion, we can state that the CT complex plays
no role in the alternating propagation observed in the
polymerization of donor and acceptor monomers. Polar
effects establish alternation in the reactions of the grow-
ing free-radical polymer chain with monomers of differ-
ing polarities.
Initiation in Spontaneous CT Polymerizations
The mechanism of the spontaneous initiations observed
in these CT monomer mixtures puzzled the preceding
investigators. Depending on the nature of the donor and
acceptor monomers, either alternating free-radical copo-
lymerization or ionic homopolymerization of one or both
monomers was observed. Again, the literature is replete
with a variety of suggestions.
Many publications suggest that complete electron
transfer (ET) forms ion radicals. In ET, complete ET
leads to a cation-radical/anion-radical pair, whereas in a
CT complex a loose association of molecules resulting
from a partial ET can be observed in spectroscopic
methods. The essential difference between ET and CT is
the extent of ET taking place. In the case of ET, the
cation radical or anion radical might initiate either radi-
cal or ionic polymerizations, depending on which mono-
mers are present in the polymerizing mixture.
D 3 A 3 D•⫹ A•⫺
However, Eberson and Persson,18 using cyclovoltammet-
ric data and oxidation/reduction potentials, demonstrated
that for energetic reasons ET could only occur in the
reactions of extremely electron-rich olefins with ex-
tremely electron-poor olefins, as represented in Table III.
They explain that only the extremely electron-rich diene
1,4-bis(dimethylamino)-1,3-butadiene, as well as its bi-
cycloheptane analogue, can undergo ET even with the
extremely electrophilic tetracyanoethylene (TCNE). As
shown in Table III, such a reaction is completely ex-
cluded with conventional vinyl monomers.
A different approach based in organic chemistry taken
by Kim et al.19 led to the same deduction. The 3,3⬘-
dianisyl-diallylether 1 had been shown to form indepen-
dently a cation radical by one-electron oxidation. This
cation radical underwent cyclobutanation with the ex-
traordinarily high rate constant of 1.2 ⫻ 109 s⫺1, as
illustrated in Scheme 3. Nevertheless, cycloaddition of
very electrophilic TCNE proceeded to form the cyclobu-
tane derivative. “The results were decisive in excluding
an ET mechanism.”35
Another explanation for the spontaneous initiation
found often in the literature involves ET, leading to the
anion-radical/cation-radical pair followed by immediate

Table III. Outcome of Reactions of Donor and Acceptor Olefins
Donor Olefin
1,4-bis(Me2N)-1,3-Butadiene
PhSOCHACH2
N-Vinylcarbazole
1,4-bis(Me2N)-1,3-Butadiene
p-MeO-Styrene
Styrene
Styrene
proton transfer to form a vinyl radical and a hydro radical
(Scheme 4). In the case of styrene and maleic anhydride,
for example, this vinyl and “hydro” radical are proposed
to be the initiators of the free-radical polymerization. A
thorough study with spin trap nitroso reagents led to
electron spin resonance (ESR) evidence for this interpre-
tation. However, recent reinvestigations of the styrene/
maleic anhydride spontaneous copolymerizations by
Eberson and Persson18 exclude the vinyl radical as an
intermediate. Careful investigation of the ESR spectra
led to the deconvolution of these complex spectra into
four distinct signals. The first three signals were assigned
to “hydro” radicals and are subsequently described
(Scheme 5). The so-called vinyl radical spectrum (D-
spectrum) is actually due to the oxazinium cation radical
formed from two donor molecules and one nitroso mol-
ecule, proving that the spin trap methyl nitrosopropane
(MNP) was by no means an innocent bystander in the
reaction. The D-spectrum was shown to be generated
cleanly from the donor olefin and the nitroso compound
in the absence of acceptor olefin, but in the presence of
a little zinc chloride. Similar results were obtained by
Mash et al.20 who re-examined the spontaneous polymer-
ization of vinyl sulfide and diethyl fumarate.
Now that we have excluded various literature inter-
pretations, what is the correct explanation? Once again,
organic chemistry provides us with the clue. The seminal
work of Huisgen21,22 on the cycloaddition reactions of
electron-rich olefins and electron-poor olefins provides
Scheme 3. Reaction of 3,3⬘-dianisyl-diallylether with tetra-
cyanoethylene under irradiation.
HIGHLIGHT 2073
Acceptor Olefin Outcome
TCNE ET
TCNE No ET
TCNE No ET
Fumaronitrile No ET
Maleic anhydride No ET
Diethyl fumarate No ET
Acrylonitrile No ET
the tetramethylene intermediate as the key: “The tetram-
ethylene can be predominantly zwitterionic or predomi-
nantly diradical in its electron distribution. There is ac-
tually a continuous scale between biradical and zwitte-
rion depending on the terminal substituents.” In the
reaction of a vinyl ether with tetracyanoethylene forming
the cyclobutane adduct, the tetramethylene intermediate
has been shown to be zwitterionic using trapping agents.
In contrast, the dimerization of acrylonitrile to 1,2-dicya-
nocyclobutane proceeds via a diradical tetramethylene
intermediate. The zwitterions are predominantly in the
cis or syn conformation because of Coulombic attraction,
whereas the diradicals exist in the extended transconfor-
mation (Scheme 6).
It was reasonable to propose that the tetramethylene
may initiate spontaneous polymerizations in the case
where the electron-rich and electron-poor olefins are
polymerizable.23–26 Thus, a zwitterionic tetramethylene
would initiate ionic homopolymerizations, whereas a
diradical, even a polar diradical, would initiate free-
radical copolymerizations (Scheme 7). We have exam-
ined representative cases of each.
An example of a zwitterion-initiated polymerization
was found in the reaction of N-vinylcarbazole (NVCz)
with dimethyl 2,2-dicyanoethylene-1,1-dicarboxylate.27
The two olefins combine to form a zwitterionic tetram-
ethylene intermediate, which reversibly cyclizes to form
the cyclobutane adduct. In the tetramethylene, the two
charges are stabilized by the substituents. This tetram-
ethylene is the true initiator of the observed cationic
polymerization of NVCz. The kinetic study showed that
at high NVCz concentrations, the propagation rate is
Scheme 4. Literature mechanism of initiation by vinyl and
hydro radicals.
2074 J. POLYM. SCI. PART A: POLYM. CHEM.: VOL. 39 (2001)
Scheme 5. Trapping of diradicals in the styrene/maleic an-
hydride system.
first-order in cyclobutane concentration and second-or-
der in NVCz concentration, and this is completely con-
sistent with the reaction scheme depicted in Scheme 8.
We have already mentioned the spontaneous free-
radical copolymerization of p-methoxystyrene with di-
methyl cyanofumarate.9 In this case, the initiating inter-
mediate is a diradical tetramethylene formed by bond
formation between the two olefins (Scheme 9). To con-
firm this, the intermediate diradical was trapped with
2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO), and the
structure of the TEMPO adduct was determined by X-ray
crystallography. Moreover, with Eberson et al.,28 we
provided ESR evidence for this tetramethylene diradical
by trapping it with MNP.
Eberson and Persson18 also investigated the styrene/
maleic anhydride system in great detail. The so-called
D-spectrum was previously discussed in the context of
the propagation mechanism. The A, B, and C-spectra
correspond to trapped “hexamethylene” diradicals, that
is, diradicals composed of two of one monomer and one
of the other before being trapped by MNP. In this case,
the less stabilized and highly reactive tetramethylene is
able to add another monomer before being trapped.
Lewis acids can enhance the rates of spontaneous
copolymerizations, an unusual example of Lewis acid
catalysis of free-radical copolymerization.1–5 In view of
our foregoing discussion, the role of the Lewis acid is
Scheme 6. Mechanism of [2⫹2] cycloaddition.
Scheme 7. Tetramethylenes as initiators of spontaneous po-
lymerizations.
now clear: It enhances the electron-poor character of the
acceptor olefin. It does so by complexing to the lone
electron pairs of the electron-attracting substituent. As
shown in Scheme 10 to illustrate a few literature exam-
ples, addition of a Lewis acid to the polymerization of
styrene and acrylonitrile, styrene and methyl methacry-
late, and isobutene and acrylonitrile will result in strictly
alternating copolymers.29 –31 Implicit in this is that the
donor olefin must be a hydrocarbon such as butadiene or
styrene without heteroatoms, or else the Lewis acid
would of course complex to it with unfavorable electron
results. When used to cause alternation, alkylaluminum
chlorides have been noticed to initiate spontaneous po-
lymerizations. This may be because the weak aluminum-
to-carbon bond can form free radicals on spontaneous
combination with adventitious traces of oxygen; there-
fore, Lewis acidity is not only involved here.
As for spontaneous initiation in CT polymerization,
we deduce that the true initiating species is the tetram-
ethylene zwitterion diradical formed by the reaction of
two olefins with differing polarities. The nature of the
tetramethylene, be it zwitterionic or diradical, determines
the type of polymerization it will initiate, that is, ionic or
free-radical, respectively. Initiation of cationic homopo-
lymerization by a zwitterionic intermediate and initiation
of free-radical copolymerization by a diradical interme-
diate have been amply demonstrated; however, anionic
homopolymerization initiated by a zwitterionic interme-
diate is still under investigation. This leaves the occur-
rence of a CT complex in a polymerizing monomer
mixture as an indicator of polarity differences. These
Scheme 8. A zwitterion-initiated polymerization.

Scheme 9. A diradical-initiated polymerization.
polarity differences lead in turn to both the polar effect in
the free-radical alternating propagation and to the stabi-
lization of the initiating tetramethylene species.
New Directions
Any new theory should not only interpret existing data. It
should also point to new research directions. The CT
complex may play one other role, namely, it may serve to
bring the two monomers together so they can react to
form a tetramethylene intermediate.
We expand on this thought to present a generalized
hypothesis: Any force bringing donor and acceptor
monomers together will enhance the rate of tetramethyl-
ene formation as well as the rate of spontaneous poly-
merization. Beyond CT interaction, possible modes of
interaction would be protic acid/base, Coulombic attrac-
tion, hydrophobic and hydrophilic interactions, Lewis
acid/base, or the use of templates or tethering.
Coulombic attraction in spontaneous polymerization
has long been known from the classical work of Salam-
one and colleagues.32,33 On mixing styrenesulfonic acid
Scheme 10. Role of Lewis acids in copolymerization.
HIGHLIGHT 2075
Scheme 11. Coulombic attraction in spontaneous copolymer-
ization.
with 4-vinylpyridine, the vinylpyridinium styrenesulfon-
ate ion pair is formed, and spontaneous alternating co-
polymerization is observed at room temperature in aque-
ous solution (Scheme 11). Notice that proton transfer
would usually work against the strong donor and accep-
tor characters needed for a spontaneous tetramethylene
formation. However, the Coulombic interaction is deci-
sive.
Acid– base association can bring other comonomers
together and cause alternating 1/1 copolymerization, as
in a mixture of acrylic acid and 4-vinylpyridine.34 If the
monomers are mixed in bulk, exothermic copolymeriza-
tion ensues, which can be controlled by using solutions at
less than 2-M concentrations. Analogous phenomena are
observed on mixing methacrylic acid/4-vinylpyridine
and for acrylic acid/2-vinylpyridine.
Hydrophobic– hydrophilic interactions may also
present opportunities to induce spontaneous polymeriza-
tions. The enhancement of cycloaddition rates of water-
insoluble compounds when run in water has been re-
ported in the last decade.35 As an example, the Diels–
Alder reaction between cyclopentadiene and methyl
acrylate proceeds 730 times faster in water than in
isooctane.36 Similarly, the rate of cycloaddition of cy-
clopentadiene and benzoquinone is 6800 times faster in
water than in isooctane37 (Scheme 12). According to the
researchers, “even simple organic reactions in water
show hydrophobic effects if non-polar segments of the
molecules are brought together in the transition state.”35
“Besides the hydrophobic association, the acceleration
Scheme 12. Cycloadditions in water.
2076 J. POLYM. SCI. PART A: POLYM. CHEM.: VOL. 39 (2001)
contains a significant component arising from enhanced
polarization of the transition state and strong hydrogen
bonds.”35
Taking inspiration from these organic chemistry ex-
amples is not as farfetched as it might seem at first
glance. We look on cycloaddition as a polymerization
process with no propagation step, but with only initiation
and termination. An example of such a hydrophobic
acceleration already exists in the literature in the ho-
mopolymerization of vinylpyridinium salts.38 – 40
N-Methyl 4-vinylpyridinium sulfonate homopolymerizes
spontaneously in water if the concentration is higher than
1.2 M. In these high concentrations we can envision the
vinyl pyridinium salts forming micellar structures that
force the vinyl groups closer together, thereby enhancing
the chance of spontaneous polymerization (Scheme 13).
In this fashion attractive forces can contribute to the
initiation of spontaneous polymerizations.
Another mode of bringing potential monomers to-
gether is Lewis acid-based templating as seen in cycload-
dition reactions.41 Thus, trimethylaluminum was used to
template phenol and phenyl vinyl sulfoxide, which was
shown to favor cyclobutane formation, as shown in
Scheme 14.42 A similar tethering using trimethylalumi-
num occurred in the reaction of 2,4-hexadiene-1-ol and
3-phenylpropanol to bring these two reagents in contact
to favor the Diels–Alder cycloaddition.43
We are convinced that many new possibilities remain
in spontaneous polymerization examined along these
lines.
CONCLUSIONS
Mechanisms for “charge transfer” spontaneous polymer-
izations and cycloadditions between electron-rich olefins
and electron-poor olefins were reviewed. As for propa-
gation, literature proposals involving CT complexes
were rejected. Instead, alternating copolymerization is
ascribed to polar effects in free-radical reactions. As for
spontaneous initiation, literature proposals involving CT
complexes, with or without proton transfer, were re-
jected. Instead, the initiating species is postulated to be a
tetramethylene zwitterion biradical that may initiate ei-
Scheme 13. Homopolymerization of vinylpyridinium salts.
Scheme 14. Lewis acid/base templating in cycloaddition.
ther ionic homopolymerization or free-radical copoly-
merization. This interpretation in terms of polar factors
brings CT polymerizations into the accepted physical
organic chemistry interpretations. A new hypothesis pro-
poses that any interaction that brings vinyl monomers
close together may facilitate tetramethylene formation
and spontaneous polymerization. These interactions in-
clude Coulombic, acid– base, hydrophobic– hydrophilic
and templating–tethering interactions.
The authors thank their gifted coworkers and the Na-
tional Science Foundation, Division of Materials Re-
search, for making this work possible.
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