Letter

pubs.acs.org/macroletters

Tetrakis(dialkylamino)phosphonium Polyelectrolytes Prepared by

Reversible Addition−Fragmentation Chain Transfer Polymerization
C. Tyler Womble,† Geoffrey W. Coates,‡ Krzysztof Matyjaszewski,† and Kevin J. T. Noonan*,†
†
Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213-2617, United States
‡
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, United States
*
S Supporting Information

ABSTRACT: A tetrakis(dialkylamino)phosphonium cation ([P-

(NR2)4]+) was appended to a styrenic monomer and explored in
reversible addition−fragmentation chain transfer polymerization
(RAFT) to conduct random copolymerizations of the cationic
monomer with styrene. Well-defined polyelectrolytes with molec-
ular weights up to ∼30 100 and dispersities between ∼1.2 and 1.4
were obtained. Up to 18.9 mol % of the ionic monomer could be
incorporated into the polymer with hexafluorophosphate or bis(trifluoromethane)sulfonimide acting as the counterion during
polymerization. Differential scanning calorimetry of the hexafluorophosphate polymers revealed glass transition temperatures
higher than polystyrene likely due to interactions between the anion and the polymer. Thermogravimetric analysis indicated
these materials have high thermal stability with decomposition temperatures approaching 400 °C.

P olyelectrolytes are an important class of materials that have

unique chemical and physical properties derived from the
electrostatic interactions of ions along a polymer chain.1 They
have a wide range of potential uses in water purification,
catalysis, antimicrobial coatings, gas separation, and electro-
chemical cells.2 Cationic polyelectrolytes, in particular, have
attracted attention as anion-exchange membranes (AEMs) for
alkaline fuel cells (AFCs).3 AFCs are promising alternatives to
proton exchange membrane fuel cells (PEMFCs) since non-
noble metal electrocatalysts can be used in alkaline media.3a−c
However, the long-term stability of AEMs under fuel cell
operating conditions remains challenging.3a−c,4
Tetraalkylammoniums are the most common cations
employed in polyelectrolytes for hydroxide conduction, but
[NR4]OH lifetime is an issue.3b,5 Resonance-stabilized organic
cations such as the guanidinium6 and imidazolium7 are also
being explored in AEMs with concurrent investigations of their
durability under alkaline conditions.8 Beyond the second row
elements, transition metals9 and phosphorus-based cations10
are also attracting attention. Tetraalkylphosphonium polymers
and ionic liquids exhibit lower viscosities, higher thermal
stabilities, and greater ionic conductivities as compared to their
nitrogen counterparts (Figure 1).11 However, since [PR4]+
cations are susceptible to deprotonation under basic conditions,
these ions may not be ideal candidates for AEMs. Alternatively,
employing dialkylamino substituents ([P(NR2)4]+) rather than
alkyl groups can provide resonance-stabilized phosphorus-based
cations (Figure 1).
Tetrakis(dialkylamino)phosphoniums are derived from a
well-known class of phosphazene superbases.12 These robust
cations have already been evaluated as phase transfer catalysts
under alkaline conditions,13 making them particularly attractive
as pendant ions for polymer materials in harsh chemical
Figure 1. Styrene-based phosphonium monomers for reversible
deactivation radical polymerization (RDRP).
environments. Incorporation of these cations into polymers has
been explored in two reports by manipulation of polyphospha-
zenes.14 One of these systems was investigated in the presence
of hydroxide,14a but the polymer had stability issues due to the
cationic moiety directly in the polymer main chain.
Surprisingly few reports have described polymers with
tethered [P(NR2)4]+ ions. We recently reported a cyclo-
octene-based monomer with an appended [P(NR 2 ) 4 ] +
substituent that can be copolymerized with cyclooctene using
ring-opening metathesis polymerization (ROMP).15 Upon
hydrogenation, the resulting polyethylene materials exhibited
good conductivity and exceptional alkaline stability. However,
the challenging monomer synthesis and limited control over
molecular weight prompted us to develop alternative strategies
to these phosphonium materials.
Received: December 12, 2015
Accepted: January 19, 2016
Published: February 1, 2016

© 2016 American Chemical Society 253 DOI: 10.1021/acsmacrolett.5b00910

ACS Macro Lett. 2016, 5, 253−257
ACS Macro Letters
Herein, we present a simplified synthetic approach to a
styrenic tetrakis(dialkylamino)phosphonium monomer and the
preparation of well-defined polymers with tunable ionic content
by reversible addition−fragmentation chain transfer (RAFT)
polymerization. RAFT is a reversible deactivation radical
polymerization (RDRP) protocol that produces polymers
with predictable molecular weights and narrow dispersities
and offers access to more complex architectures.16 RDRP tools
are quite versatile for synthesizing polyelectrolyte materials, as
they have wide monomer scope and exceptional functional
group tolerance. Monomers with tethered [PR4]+ cations have
been explored previously using free radical,17 RAFT,18
nitroxide-mediated,19 and atom-transfer radical polymerization
(ATRP).20 Consequently, RAFT was explored for the polymer-
ization of the tetrakis(dialkylamino)phosphonium monomer.
Cyclohexylazide was prepared according to a published
procedure.21 The azide was combined with PCl3 in a Staudinger
reaction to produce the desired trichlorophosphazene in
moderate yield (51%). Subsequently, treatment with N-
methylcyclohexylamine afforded a phosphonium with one
pendant N−H group. This precursor can be transformed into
a polymerizable group by deprotonation and simple sub-
stitution. Styrene was chosen since it is suitable for RDRP, and
polymerization affords a relatively inert hydrocarbon backbone.
Monomer 1 was synthesized by reaction of the phosphonium
precursor with 4-(iodomethyl)styrene in a biphasic reaction at
room temperature (Scheme 1). 4-(Iodomethyl)styrene was
Scheme 1. Phosphonium Monomer Synthesis
employed to ensure alkylation could be conducted at room
temperature, preventing any autoinitiation of the styrene
moiety. A final workup using lithium bis(trifluoromethane)-
sulfonimide (Li[NTf2]) or potassium hexafluorophosphate
(K[PF6]) produced the desired 1[PF6] or 1[NTf2]. 19F NMR
and 31P NMR spectroscopy were used to confirm anion
metathesis from −[PF6] to the −[NTf2] salt. In comparison to
the previous monomer synthesis, this route requires only four
synthetic steps and does not necessitate toxic alkylating agents
such as dimethylsulfate.15
A random copolymerization of styrene with monomer 1 was
conducted with 2-cyano-2-propyl dodecyl trithiocarbonate as
the chain transfer agent or CTA (Scheme 2). Preparation of the
polyelectrolyte materials could be conducted in a controlled
manner using anisole as the solvent. GPC traces of the
synthesized materials were obtained using THF doped with 10
mM Li[NTf2], and molecular weights were determined relative
to polystyrene standards.22 These standards may not be ideal
candidates for direct comparison to ionic polymers, but they
provide a good basis for comparison of all synthesized
materials.
254
Letter
Scheme 2. Copolymerization of Phosphonium Monomer
with Styrene using RAFT
Molecular weights up to 30 100 were observed for the
random copolymers along with low dispersities (Đ = 1.16−
1.37) (Table 1). 1H NMR spectroscopy was used to determine
monomer conversion and compare differences between the
initial phosphonium monomer feed and the final phosphonium
composition in the resultant polymer (Table 1 and Supporting
Information). Successful incorporation up to 20 mol % of
1[NTf2] was achieved with final incorporation of the cation up
to 18.9 mol %; however, an induction period was observed at
this higher concentration of 1. Attempts to increase the ionic
content further by conducting a homopolymerization of
1[NTf2] and a 1:1 random copolymerization of styre-
ne:1[NTf2] both failed to produce high-molecular weight
polymer. The large steric bulk of the phosphonium core likely
contributes to the difficulty of these reactions. Considering
some bulky ethyl ferrocene phosphonium salts have been
polymerized free radically,23 we also attempted a free radical
polymerization of 1[NTf2] using AIBN at 75 °C in anisole (5
M). Unfortunately, the polymerization of these tetrakis-
(dialkylamino)phosphoniums still did not proceed and
provided further evidence that steric congestion is an issue.
More studies are necessary to probe this behavior in detail.
A slight increase in the apparent rate constant, kapp, was
observed with increasing ionic content (from 5 to 15%,
Supporting Information). The observed rate increases are likely
due to a change in dielectric constant of the reaction medium.
The rate did not increase further from 15 to 20 mol % which
could be due to the increase in viscosity with more cationic
monomer in the solution. Changes in the apparent rate
constant have been observed previously in free radical and
RAFT polymerization in the presence of ionic liquids, while
added salts have been shown to dramatically affect ATRP with
styrene.24 All polymerization reactions were terminated at
moderate conversions (32.4−58.4%, Table 1), and the RAFT
process was well controlled as indicated by the first-order
kinetic behavior and linear Mn versus conversion plot (Figure
2).
The degree of polymerization in a RAFT process can be
estimated from the monomer consumed and RAFT agent (Mn,
16
theo, Table 1). While two of the Mn, theo values were quite close
to the experimentally determined Mn (entries 1 and 8, Table 1),
significant deviation from the expected value was observed. It
could be partially attributed to differences in cationic monomer
incorporation along the chain as well as inaccurate estimation
of the Mn using neutral polystyrene standards.
The thermal stability of the synthesized polyelectrolytes was
investigated using TGA. The polymers demonstrated high
thermal stabilities (between 350 and 400 °C) with slightly
higher decomposition temperatures for the −[NTf2] polyelec-
DOI: 10.1021/acsmacrolett.5b00910
ACS Macro Lett. 2016, 5, 253−257
ACS Macro Letters Letter

Table 1. Random Copolymerization of Styrene and Phosphonium Monomer 1 Using RAFT

[styrene]/[1] feed mol % CTA/mol % time total monomer conv. % 1 in Tg
−
entry ratioa X AIBN (h) (%) polymerb Mn, theoc Mn, GPCd Đ (°C)
−
1 95/5 [NTf2] 0.5/0.25 10 46.9 3.6 13 300 14 800 1.18 100
−
2 90/10 [NTf2] 0.5/0.25 10 57.0 7.5 20 500 16 700 1.22 104
−
3 85/15 [NTf2] 0.5/0.25 10 57.5 11.6 25 100 19 000 1.22 105
−
4 80/20 [NTf2] 0.5/0.25 10 58.4 18.9 29 900 15 600 1.16 102
−
5 90/10 [NTf2] 0.2/0.1 10 32.4 8.2 29 100 18 300 1.20 102
−
6 90/10 [NTf2] 0.1/0.05 10 32.6 7.8 58 700 30 100 1.37 107
−
7 90/10 [PF6] 0.5/0.25 8 48.9 8.8 16 300 15 500 1.20 126
−
8 85/15 [PF6] 0.5/0.25 8 56.4 12.8 22 300 18 400 1.23 137
a
All polymerization reactions were conducted at 5 M in anisole at 75 °C. bPolymer composition was determined using 1H NMR spectroscopy.
Theoretical molecular weights were estimated using a weighted average of the initial monomer feeds according to the equation: p × [( fstyrene·
c

MWstyrene + fcation·MWcation) ÷ % CTA], where p is the percent monomer conversion determined from 1H NMR spectroscopy; f is the initial
monomer feed; and MW is the monomer molecular weight. dGPC profiles were recorded at 40 °C versus polystyrene standards using THF with 10
mM Li[NTf2] as the eluent.

Figure 2. Left: plot of ln([M]o/[M]) vs time. Middle: GPC traces illustrating molecular weight evolution with time. Right: plot of Mn and dispersity
vs conversion. Polymerization conditions: 5 M in anisole at 75 °C with 15% 1[NTf2] (Entry 3, Table 1).

trolytes (Figure 3). The primary decomposition pathway is
likely polymer backbone degradation.25
An appropriate glass transition temperature (Tg) is necessary
for optimizing ion transport in polyelectrolyte membranes.
Operating at or above the Tg the material has been shown to
increase ion conductivity by orders of magnitude.26 DSC curves
show one broadened glass transition, which is indicative of a
random copolymer (Figure 3). A second transition was not
observed, which would have suggested partial formation of an
ion-rich microphase. The polymer samples with −[NTf2] as the
counterion exhibit Tg values similar to polystyrene (104 °C),
and these values do not change significantly with increasing ion
content. Interestingly, the Tg increased to 126 °C with 10%
1[PF6] (Figure 3) and up to 137 °C with 15% 1[PF6]. This
behavior could be due to a stronger interaction between the
cation−anion pair for a −[PF6] counterion and is consistent
with previous reports on cationic polyelectrolytes.27 We
attempted to cast thin-film membranes of these materials by
slow evaporation from acetone and chloroform. The resulting
films were optically transparent; however, they were brittle, and
Figure 3. TGA (left) and DSC (right) curves of phosphonium
polyelectrolytes.
255
free-standing membranes did not have sufficient integrity for
ion-exchange measurements. We suspect that chain-entangle-
ment molecular weights have not yet been reached, and further
efforts will focus on higher molecular weights with these
systems.
Several recent reports have illustrated that block copolymers
can be used as AEM materials to enhance performance.28 To
further highlight the degree of control over phosphonium
polymerization, we synthesized a polyisoprene macro-RAFT
agent (Mn = 10 100, Đ = 1.23)29 and used this macroinitiator to
copolymerize 1[PF6] with styrene (Mn = 26 000, Đ = 1.27).
GPC data confirmed formation of the desired copolymer
(Supporting Information). Block copolymers of this type will
be explored as a method to improve the mechanical integrity of
these phosphonium materials.
In conclusion, we have developed a new synthetic route to a
styrene-based tetrakis(dialkylamino)phosphonium monomer.
Well-defined random copolymers were prepared with styrene
using 2-cyano-2-propyl dodecyl trithiocarbonate as the RAFT
agent. Kinetic data and GPC traces indicate controlled behavior
of the polymerization reaction. Ion content in the polymers
could be tuned by adjusting the monomer feed prior to
polymerization, and up to 18.9 mol % phosphonium
incorporation was achieved. TGA curves demonstrate the
high thermal stability of these materials, and DSC analysis
illustrates the glass transition temperature can be tuned by
varying the counterion. The reported synthesis expands the
scope of polymerizable cations by RDRP methods and has
potential for making durable and stable anion exchange
membranes. Further efforts will focus on higher molecular
weights, block copolymers, and investigation of the stability of
this class of materials. The benzylic position will be explored in
DOI: 10.1021/acsmacrolett.5b00910
ACS Macro Lett. 2016, 5, 253−257
ACS Macro Letters
depth to investigate how this tether influences stability of the
tetrakis(dialkylamino)phosphonium cation.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsmacro-
lett.5b00910.
Complete descriptions of experimental procedures
including monomer and polymer synthesis, NMR
spectra, GPC traces, and TGA and DSC curves (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: noonan@andrew.cmu.edu.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
KJTN is grateful to the NSF for support through a Career
Award (CHE-1455136). This technical effort was also
performed in support of the U.S. Department of Energy’s
National Energy Technology Laboratory’s ongoing research on
CO2 capture under the contract DE-FE0004000. NMR
Instrumentation at Carnegie Mellon was partially supported
by the NSF (CHE-0130903 and CHE-1039870).
■
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■ NOTE ADDED AFTER ASAP PUBLICATION

This paper was published on February 1, 2016, with text errors
in the abstract and references. The corrected version was
republished on February 2, 2016.

257 DOI: 10.1021/acsmacrolett.5b00910

ACS Macro Lett. 2016, 5, 253−257