Anionic Ring-Opening Polymerization of N-(tolylsulfonyl)azetidines to Produce Linear Poly(trimethylenimine) and Closed-System Block Copolymers

Article abstract of DOI:10.1021/jacs.8b10326

The anionic ring-opening copolymerization of N-(p-tolylsulfonyl)azetidine (pTsAzet) and N-(o-tolylsulfonyl)azetidine (oTsAzet) produces poly(pTsAzet-co-oTsAzet) as a statistical copolymer. The pTsAzet/oTsAzet copolymerization is living and allows for the synthesis of poly(sulfonylazetidine) of target molecular weights with narrow dispersities. ¹H NMR spectroscopy was used to monitor the kinetics of the polymerization and estimate the monomer reactivity ratios. It was found that the reactivity ratios for oTsAzet and pTsAzet at 180 °C are 1.66 and 0.60, respectively. The tosyl groups of p(pTsAzet-co-oTsAzet) were reductively removed to produce linear poly(trimethylenimine) (LPTMI). This represents the first route to LPTMI of controlled molecular weight and low dispersity. Finally, the slow kinetics of the sulfonylazetidine polymerization facilitated the synthesis of a block copolymer without requiring the sequential addition of monomer. Specifically, pTsAzet, oTsAzet, and (N-p-toluenesulfonyl-2-methylaziridine) (pTsMAz) were combined in solution. pTsMAz selectively polymerizes to form the first block at moderate temperature. After consumption of pTsMAz, the temperature was increased to copolymerize pTsAzet and oTsAzet and produce the block copolymer p(pTsMAz)-b-p(pTsAzet-co-oTsAzet).

Full text of DOI:10.1021/jacs.8b10326

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The Anionic Ring-Opening Polymerization of N-(tolylsulfonyl)azetidines to
Produce Linear Poly(trimethylenimine) and Closed-System Block Copolymers
Louis Reisman, Elizabeth A Rowe, Enrique M. Jackson,
Christian Thomas, Tomekia Simeon, and Paul A Rupar
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b10326 • Publication Date (Web): 08 Nov 2018
Downloaded from http://pubs.acs.org on November 8, 2018
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Closed-System Block Copolymers
Louis Reisman, Elizabeth A. Rowe, Enrique M. Jackson, Christian Thomas, Tomekia Simone, and Paul A. Rupar *
1Department of Chemistry and Biochemistry, The University of Alabama, Tuscaloosa, Alabama 35487-0336, United States
2Materials Test Branch, NASA Marshall Space Flight Center, Martin Rd SW, Huntsville, Alabama, 35808, United States
3Dillard University, Department of Chemistry, 2601 Gentilly Blvd, New Orleans, LA, 70122, United States
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Supporting Information Placeholder
hyperbranched PTMI (BPTMI, Scheme 1, TOP).4, 7-8, 12-17 Initial
ABSTRACT: The anionic ring-opening copolymerization of N-(p-
1
8
work on linear PTMI (LPTMI) was reported by Kobayashi.
Recently, Jones utilized this oxazine based route to LPTMI and
showed that its CO capture ability is superior to linear
polyethylenimine (LPEI) [-CH
there are no known routes to LPTMI that have demonstrated
control over molecular weight and dispersity.
tolylsulfonyl)azetidine (pTsAzet) and N-(o-tolylsulfonyl)azetidine
oTsAzet) produces poly(pTsAzet-co-oTsAzet) as a statistical
copolymer. The pTsAzet/oTsAzet copolymerization is living and
(
2
1
9
allows for the synthesis of poly(sulfonylazetidine) of target
2
2
CH NH-]. However, to date,
1
molecular weights with narrow dispersities. H NMR spectroscopy
was used to monitor the kinetics of the polymerization and estimate
the monomer reactivity ratios. It was found that the reactivity ratios
for oTsAzet and pTsAzet are 1.66 and 0.60, respectively. The tosyl
groups of p(pTsAzet-co-oTsAzet) were reductively removed to
produce linear poly(trimethylenimine) (LPTMI). This represents
the first route to LPTMI of controlled molecular weight and low
dispersity. Finally, the slow kinetics of the sulfonylazetidine
polymerization facilitated the synthesis of a block copolymer
without requiring the sequential addition of monomer. Specifically,
pTsAzet, oTsAzet, and (N-p-toluenesulfonyl-2-methylaziridine)
Inspired by recent breakthroughs in the AROPs of N-sulfonyl
aziridines20-33 as a way to access linear polyimines,34-36 we recently
reported on the AROP of N-(methanesulfonyl)azetidine (MsAzet)
(Scheme 1, bottom).37 The polymerization kinetics of MsAzet were
notably slower than N-sulfonylaziridines, and, surprisingly, the
resulting p(MsAzet) had a branched structure. The branching,
which arose due to transfer to the methanesulfonyl groups during
polymerization, precluded MsAzet as a precursor to LPTMI.
However, the fact that AROP of MsAzet did occur, suggests that a
suitable N-sulfonylazetidine could be used to form a linear polymer
and provide a controlled route to LPTMI.
(pTsMAz) were combined in solution. pTsMAz selectively
polymerizes to form the first block at moderate temperature. After
consumption of pTsMAz, the temperature was increased to
copolymerize pTsAzet and oTsAzet and produce the block
copolymer p(pTsMAz)-b-p(pTsAzet-co-oTsAzet).
NH2
N
N
N
N
NH
Lewis Acid
H2N
H
N
Azetidine
NH
NH2
Despite the structural similarities between cyclic imines and
cyclic oxides, their polymerizations are very different. For
example, ethylene oxide can be polymerized by both cationic ring-
N
HN
BPTMI
1
opening polymerization (CROP) and anionic ring-opening
2
-3
polymerization (AROP) to produce a linear polymer with high
degrees of control. In contrast, aziridine can only be polymerized
by CROP to produce a hyperbranched polymer. This has led to
nBu
H
m
O
N
S
N
S
N
S
n
O
S
N
1. nBuN(K)Ms
DMSO, 180 C
2. MeOH
O
O
O
O
O
4-8
O
the development of indirect routes to linear polyimines, the most
prominent being the polymerization of oxazolines, despite the
MsAzet
O
5
N
x
difficulties in this approach. However, controlled routes to
S
H
O
polyimines continue to be highly sought after due to their use in
high value applications (i.e. antimicrobial and antifouling
7
Scheme 1. (TOP) CROP of azetidine to produce BPTMI.
(BOTTOM) AROP of MsAzet.
9
10
37
coatings, chelation and polymer-assisted deposition, CO
capture, and non-viral gene transfection ).
2
11
5
We turned our attention to the polymerization of N-
(tolylsulfonyl)azetidines as their protons are less likely to be
activated under the polymerization conditions. We initially
attempted to use AROP to convert N-(p-tolylsulfonyl)azetidine
Poly(trimethylenimine) (PTMI) [-CH CH
2
2
CH
2
NH-] is among
the least studied of the simple polyimines. This is due to the
complexity of azetidine polymerization which exclusively forms
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(
pTsAzet) and N-(o-tolylsulfonyl)azetidine (oTsAzet) to the
MALDI-TOF mass spectrometric (MS) analysis of the polymers
revealed signals consistent with each polymer chain containing the
Bu(N)Ts initiator (Figure S22). Additionally, upon complete
consumption of the monomers, additional equivalents of monomers
could be added to the reaction mixture, and chain extension was
observed (Figure S21). This data shows that, as with
sulfonylaziridines, the copolymerization of pTsAzet and oTsAzet
appears to be living and controlled.
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corresponding homopolymers, however, both monomers only
formed low molecular weight homooligomers. The poor solubility
of p(N-(tolylsulfonyl)azetidine) homopolymers is not completely
unexpected as related poly(N-sulfonylaziridine) homopolymers are
n
2
6, 34
often similarly insoluble.
CH3
H3C
nBu
O
H
n
O
N
S
N
S
O
N
O
N
. nBuN(K)pTs
1
S
S
O
O
WAXS data revealed that p(pTsAzet-co-oTsAzet) was
crystalline, but the crystalline peaks are distinct from those of the
p(pTsAzet) and p(oTsAzet) homooligomers (Figure S28). This
suggests that p(pTsAzet-co-oTsAzet) does not have blocky
DMSO or NMP
O
+
O
>120 C
2. MeOH
pTsAzet
oTsAzet
CH3
0
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2
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CH3
p(pTsAzet-co-oTsAzet)
domains. DSC presents a well-defined T
C and TGA reveals a T of 360 °C (Table S5, entry 6). The
difference between the T of the copolymer and the homooligomers
213 and 190 °C for pTsAzet and oTsAzet homooligomers,
respectively, Table S5) further suggests an absence of blocky
segments.
g m
of 68 °C and T of 140
°
d
Li, tBuOH
HMPA, THF
-15 °C, 5 h
m
(
nBu
H
n
N
N
H
H
LPTMI
Scheme 2. Polymerization of TsAzet monomers to soluble
p(pTsAzet-co-oTsAzet) and transformation to LPTMI.
We next attempted the copolymerization of the two N-
(tolylsulfonyl)azetidine monomers (Scheme 2). This was
motivated by prior work showing that the solubility of poly(N-
sulfonylaziridine) random copolymers are greatly improved
3
4
compared
to
the
corresponding
homopolymers.
Copolymerization of pTsAzet with oTsAzet in a 1:1 ratio produced
p(pTsAzet-co-oTsAzet), which is soluble in DMF, DMSO, NMP
and HMPA. The weakly basic nature of the propagating anion
allows this copolymerization to proceed in NMP without any
apparent reaction with NMP. For the polymerizations performed in
DMSO, small amounts of transfer to solvent is likely occurring,
24
determined by 1H NMR end-group analysis vs
total]:[I] (▲). Dispersity vs [Mtotal]:[I] (◼ ).
In order to convert p(pTsAzet-co-oTsAzet) into LPTMI, the
Figure 1. M
n
3
7-
[M
3
8
although we were unable to observe and quantify this. DMF was
also a suitable solvent for the AROP of sulfonyl azetidines.
34, 45
1
tosyl groups were removed using Li (Scheme 2).
H NMR
The polymerization kinetics of the AROP of N-
tolylsulfonyl)azetidines in DMSOd6 were studied by real-time H
spectra (Figure S17) of the resulting polymer was consistent with
1
(
1
9
the formation of LPTMI. MS was used to confirm that chain
scission had not occurred during the deprotection. MALDI-TOF
mass spectrum of LPTMI (Figure S24) derived from low molecular
2
7, 29, 37
NMR spectroscopy.
The plot of natural log of total monomer
concentration with respect to time is linear, suggesting it is first
order with respect to total monomer concentration and that the
number of active chain ends remains constant during the
weight p(pTsAzet-co-oTsAzet)15 revealed a D
p
= 14.8 with Ð =
1
.04. The observed MALDI-TOF MS data of LPTMI implies that
3
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polymerization (Figure S1 and Table S2). Compositional drift
was observed during the course of the copolymerization, with
oTsAzet being incorporated at a faster rate (Figure S3). The
monomer reactivity ratios were estimated using Lynd’s non-
no chain scission is occurring during the removal of the tosyl
groups.
Lastly, we set out to produce block copolymers utilizing N-
(tolylsulfonyl)azetidine monomers, as this would provide a route to
novel polyimine block copolymers. Since pTsAzet and oTsAzet do
not polymerize at temperatures < 100 ℃, we proposed that a third
monomer, which polymerizes at lower temperatures, could do so in
the presence of the sulfonyl azetidines, and allow for a closed-
system block copolymer synthesis in which all monomers are
present at initiation. After this first monomer is consumed, the
reaction mixture could then be heated to higher temperature to
facilitate the copolymerization of the azetidines.
40
terminal model. This model assumes that the identity of the active
chain end does not impact subsequent monomer additions, which
4
1-42
is usually a valid assumption in ionic polymerizations.
non-terminal model is attractive as it allows determination of
reactivity ratios through the observation of single
copolymerization. This model calculated the reactivity ratios to be
.66 and 0.60 for oTsAzet and pTsAzet, respectively, at 180 °C
Lynd’s
a
1
(
43
Table S2). We also determined the reactivity ratios for oTsAzet
and pTsAzet by the Kelen-Tüdös method and there were found to
be similar (Figure S4 and Table S3).44
We chose to create a block copolymer using N-(p-tolylsulfonyl)-
2-methylaziridine (pTsMAz) as pTsMAz readily polymerizes at
lower temperatures and its propagating chain end could likely
initiate the N-(tolylsulfonyl)azetidines. To accomplish the block
copolymer polymerization, pTsMAz, pTsAzet, oTsAzet and
In order to determine the possibility of controlling the AROP of
the N-(tolylsulfonyl)azetidines, a series of copolymerizations were
performed where the monomers to initiator ratio was varied (the
1
ratio of the monomers was kept 1:1). The D
NMR spectroscopic end-group analysis closely matched the
theoretical values (Table S4) and the plot of M vs monomer:
p
, as measured by H
n
BuN(K)pTs were dissolved in DMSOd6 (Scheme 3). The reaction
mixture was heated to 50 °C for 4 h, during which time pTsMAz
was consumed (Figure 2A). Next, the reaction mixture was heated
to 180 °C to polymerize the second block, resulting in the formation
n
initiator was linear (Figure 1). All SEC traces are monomodal with
narrow Ð (Figure S20 and Table S4) and a decrease in retention
time was observed with increasing monomer to initiator ratio.
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of the desired block copolymer p(pTsMAz)20-b-p(pTsAzet-co-
oTsAzet)40
[pTsMAz]:[oTsAzet]:[pTsAzet]:[I] of 20:40:40:1 in NMP at 70
°C for 12 h, then 205 °C for 16 h.
1
2
3
4
5
6
7
8
9
.
CH3
This ability to produce block copolymers in a closed-system
provides a solution to a common issue with the synthesis of block
copolymers, especially high-performance block copolymer
materials. Traditionally, upon addition of the second monomer,
there is often a small amount of chain termination which leads to
CH3
CH3
1
. nBuN(K)pTs,
50 C
2. 180 C
O
S
N
O
O
S
N
O
O
S
nBu
O
+
pTsAzet
+
oTsAzet
N
S
H
N
n
m
46
3. MeOH
O
O
the presence of homopolymer impurity. This homopolymer
impurity can affect the properties of the block copolymer material.
This problem can be mitigated by the use of strenuous purifications,
pTsMAz
4
7-50
as well as high vacuum and break-seal techniques.
Recently,
CH3
p(pTsMAz)-b-(pTsAzet-co-oTsAzet)
1
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1
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9
0
Sumerlin reported block copolymers by RAFT polymerization
synthesized in a closed system where individual monomers were
segregated in the reaction mixture by temporarily freezing one
Scheme 3. Block copolymerization of pTsMAz with oTsAzet and
pTsAzet to produce p(pTsMAz)-b-p(pTsAzet-co-oTsAzet).
5
1
monomer in a high melting point solvent. More recently, Wurm
has utilized a similar closed-system to synthesize p(pTsMAz)-PEO
block copolymers, although there is some gradient in the transition
1
Monitoring the polymerization by H NMR showed no evidence
of sulfonylazetidine consumption at lower temperature (Figure
5
2
between the blocks.
2
A). As such, the resulting block copolymer is believed to have a
sharp transition between the two domains, with no region of
sulfonylaziridine and sulfonylazetidines mixing. In addition, the
SEC trace of the resulting polymer showed no evidence of lower
molecular weight p(pTsMAz) homopolymer (Figure 2B).
Subsequent sulfonyl group removal of this block copolymer would
allow for the synthesis of a LPPI-b-LPTMI block copolymer.
In conclusion, we have shown that the copolymerization of
pTsAzet with oTsAzet produces a soluble, statistical copolymer,
p(pTsAzet-co-oTsAzet), and reported the kinetics of the
polymerization as well as the reactivity ratios of the two monomers
in the copolymerization. The polymerization is living and
controlled and can be converted to LPTMI. This allows, for the first
time, the synthesis of LPTMI by a controlled, living anionic ring-
opening polymerization, an important finding due to the potential
high value of this polymer in non-viral gene transfection; studies
have shown that the length of the carbon spacer between the
5
3
nitrogens (i.e. ethyl vs propyl) influences nucleotide binding.
Additionally, the high barrier to ring-opening of N-
sulfonylazetidines can be exploited to produce block copolymers in
a closed-system process.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS
Publications website. Experimental procedures, NMR spectra,
MALDI-TOF mass spectra, SEC, WAXS, kinetic and
compositional drift data, and thermal analysis plots. (PDF).
Unprocessed, experimental data can be found online via Open
Science Framework at DOI: osf.io/pfje6
AUTHOR INFORMATION
Corresponding Author
*
E-mail: parupar@ua.edu
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
Figure 2. (A) Plot of conversion vs. time for the copolymerization
of pTsMAz, pTsAzet and oTsAzet in DMSOd6 to produce
p(pTsMAz)20-b-p(pTsAzet-co-oTsAzet)40. The reaction is kept at
50 °C for 4 h, then 180 °C for 10.25 h. The NMR measured
conversion of pTsMAz appears to not reach 100% due to signal
We thank the ACS-Petroleum Research Fund (55075-DNI7), the
Department of Education-GAANN (P200A150329), NASA
(80MSFC18M0041), and the University of Alabama (UA) for
1
financial support. We thank NSF (CHE-1726812) from the Major
Research Instrumentation (MRI) program for purchase of the
MALDI/TOF-TOF mass spectrometer. We thank Prof. Vincent
Scalfani (UA) for his assistance with the Open Science Framework,
Prof. Jared Allred (UA) for helpful discussions in determining
experimental parameters for and interpreting WAXS data, and
Prof. Patrick Frantom (UA) for helpful discussions on kinetics.
overlap between the monomer and polymer resonances in H NMR
spectra of the reaction mixture as the polymer signal grows in
intensity. (B) SEC trace of p(pTsMAz)20 prior to block copolymer
chain extension (---). SEC trace of p(pTsMAz)20-b-p(pTsAzet-co-
oTsAzet)80
(
). Block copolymerization to produce p(pTsMAz)20
-
b-p(pTsAzet-co-oTsAzet)80
was performed with
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Pang, S. H.; Lively, R. P.; Jones, C. W. Oxidatively-
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