A BN Aromatic Ring Strategy for Tunable Hydroxy Content in Polystyrene

Article abstract of DOI:10.1002/anie.201711650

BN 2-vinylnaphthalene, a BN aromatic vinyl monomer, is copolymerized with styrene under free radical conditions. Oxidation yields styrene–vinyl alcohol (SVA) statistical copolymers with tunable hydroxy group content. Comprehensive spectroscopic investigation provides proof of structure. Physical properties that vary systematically with hydroxy content include solubility and glass transition temperature. BN aromatic polymers represent a platform for the preparation of diverse functional polymeric architectures via the remarkable reaction chemistry of C?B bonds.

Full text of DOI:10.1002/anie.201711650

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Accepted Article
Title: A BN Aromatic Ring Strategy for Tunable Hydroxyl Content in
Polystyrene
Authors: Heidi Lee van de Wouw, Jae Young Lee, Elorm C. Awuyah,
and Rebekka S. Klausen
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201711650
Angew. Chem. 10.1002/ange.201711650
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A BN Aromatic Ring Strategy for Tunable Hydroxyl Content in
Polystyrene
Heidi L. van de Wouw,[a] Jae Young Lee,[a] Elorm C. Awuyah,[a] Rebekka S. Klausen*[a]
Dedication ((optional))
Abstract: BN 2-vinylnaphthalene, a BN aromatic vinyl monomer, is
copolymerized with styrene under free radical conditions. Oxidation
yields styrene-vinyl alcohol (SVA) statistical copolymers with tunable
hydroxyl content. Comprehensive spectroscopic investigation
provides proof of structure. Physical properties that vary
systematically with hydroxyl content include solubility and glass
transition temperature. BN aromatic polymers represent a platform
for the preparation of diverse functional polymeric architectures via
the remarkable reaction chemistry of C-B bonds.
described the synthesis and gram-scale free radical
polymerization of BN 2-vinylnaphthalene (BN2VN), as well as
the preparation of copolymers with 2-vinylnaphthalene (2VN).[26]
BN2VN polymers are attractive candidates for investigating
borapolyolefin oxidation due to the scalable monomer
synthesis.[26,32,33] We prepare BN2VN in high overall yield and in
two steps from commercially available starting materials. The
multistep syntheses of monocyclic azaborine vinyl monomers
limit polymerizations to milligram scale.[24,25] The successful
copolymerization of BN2VN and 2VN suggests the feasibility of
copolymerization of styrene and BN2VN (PBN2VN-co-PS).
The incorporation of polar functional groups into nonpolar
polymers is an essential strategy for modifying the strength,
toughness, and solvent resistance of a polymeric material.[1–4]
Industrial examples include acrylonitrile-butadiene-styrene
(ABS) and ethylene-vinyl acetate (EVA).[5,6] Challenges in the
copolymerization of nonpolar and polar monomers include
phase separation,[7] significant differences in reactivity (reactivity
ratios),[8,9] and the limited compatibility of polar functional groups
with polymerization catalysts.[4,10–12]
Here we describe a synthetic strategy that converts a
nonpolar BN aromatic group into a polar hydroxyl substituent.
This strategy ensures comonomer miscibility and compatible
reactivity, while caging the potent reactivity of organoboranes
within in a stable aromatic core, and accesses structures that
are a challenge for existing technology. Our solution is based on
the unique properties of 1,2-azaborines, aromatic rings in which
one CC bond is replaced with the BN bond.[13–15] Recognizing
the versatility of organoboranes in synthesis,[16,17] we
hypothesized that sodium hydroperoxide (NaOOH) oxidation[18]
of a vinylborane polymer would yield derivatives of water-soluble
poly(vinyl alcohol) (PVA) (Scheme 1). However, concerns about
the hydrolytic and oxidative stability of boron reagents, as well
as the propensity of vinyl boronic acids to undergo
protodeboronation,[19] have contributed to limited investigation of
vinyl boronate polymerization.[20]
Concept: Borapolyolefin Oxidation
NaOOH
n
n
OH
B
B
R
R
R
R
borapolyolefin
PVA
This Work: Styrene-BN2VN Polymerization-Oxidation
NaOOH
n
m
n
OH
m
+
Ph
S
B
H Ph
Ph
B
H
N
N
BN2VN
PBN2VN-co-PS
PVA-co-PS
Scheme 1. Preparation of PVA derivatives via organoborane oxidation. S =
styrene; BN2VN = BN 2-vinylnaphthalene; PVA = poly(vinyl alcohol).
Oxidative cleavage of the C-B bonds in PBN2VN-co-PS
yields PVA-co-PS, a copolymer of nonpolar styrene and polar
vinyl alcohol, in which the hydroxyl content is tuned by the
BN2VN content in the starting copolymer. The styrene-vinyl
alcohol (SVA) statistical copolymer is not directly accessible
from free radical copolymerization of styrene and vinyl acetate;
styrene-enriched polymer is obtained due to the reactivity of the
styrene radical relative to the vinyl acetate radical.[34]
The oxidation was probed with model compound 1 (Figure 1).
Upon treatment with NaOOH, complete conversion of 1 to two
products of was observed within 10 minutes at 0 °C. H NMR
spectroscopic analysis of the unpurified reaction mixture and
comparison to authentic samples supports the assignment of
these products as indole 2 and phenethyl alcohol 3 (Figure 1).
Indole arises from oxidation of both C-B bonds of 1 to an
intermediate enol that tautomerizes and cyclizes. Liu et al.
recently described oxidative functionalization of the exocyclic C-
B bond of azaborines in which the alkyl fragment dimerizes.[35]
Polymerization of azaborine vinyl monomers is promising
given their increased stability relative to other boranes.[21,22]
Building on Sneddon’s description of the polymerization of vinyl
borazine,[23] several groups have recently reported free radical
polymerization of azaborine vinyl monomers.[24–26] This
complements progress on inorganic main chain BN polymers
and azaborine-derived conjugated polymers.[15,27–31] We
1
[a]
Ms. H. L. van de Wouw, Mr. J. Y. Lee, Mr. E. Awuyah, Prof. R. S.
Klausen*
Department of Chemistry
Johns Hopkins University
3400 N. Charles St, Baltimore, MD 21218
E-mail: klausen@jhu.edu
Having established the viability of the organoborane
oxidation, we investigated the free radical copolymerization of
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201711650
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H
N
H
H
N
b
a
Ph
Ph
N
Ph
B
HO
B
1
3
1
2
3
3
2
2
1/NaOOH
1/NaOOH
NH
1
1
3.5
3.0
2.5
2.0
8.0
7.9
7.8
7.7
7.6
7.
1H (ppm)
1H (ppm)
Figure 1. 1H NMR analysis of NaOOH-mediated oxidation of compound 1 (CD2Cl2). Top to bottom: Phenethyl alcohol (3), indole (2), unpurified reaction mixture, 1.
a) Aromatic region. b) Aliphatic region.
BN2VN and styrene with a focus on quantifying the incorporation
of
BN2VN.
Polymerizations
were
conducted
with
a
b
azoisobutyrylnitrile (AIBN, 1 mol%) in toluene or in neat styrene
(Table 1). Copolymerizations were conducted with feed ratios of
60 wt. %, 33 wt. %, or 14 wt. % BN2VN.
58%
34%
57%
35%
Table 1. PBN2VN-co-PS and PS molecular weight characteristics.
15%
PS
13%
PS
Sample Name[a]
Before H2O2/NaOH[b]
Mn (kDa)
Polymerization conditions: AIBN (1 mol%), toluene ([monomers] = 10 M).
After H2O2/NaOH[b],[c]
Đ
Mn (kDa)
Đ
Retention time / min
Retention time / min
c
d
P(BN2VN48-co-S51
P(BN2VN32-co-S92
)
)
12.8
14.5
14.6
13.5
1.72
1.75
1.78
1.88
7.84
9.65
12.1
14.8
2.23
2.01
1.87
1.76
Before
NaOOH
Before
NaOOH
After
NaOOH
After
NaOOH
P(BN2VN14-co-S119
)
PS129
Polymerization conditions: AIBN (1 mol%), neat.
Retention time / min
Retention time / min
P(BN2VN127-co-S141
)
34.4
38.1
39.6
32.6
4.23
4.91
5.40
5.03
24.1
21.6
34.3
33.8
2.01
2.55
2.72
4.79
Figure 2. GPC curves of copolymers. a) Polymerization in toluene. Labels
refer to the wt. % of BN2VN. b) Polymerization in neat styrene. Arrow indicates
a high molecular weight shoulder. c) Response by absorbance at 310 nm.
GPC curves of PBN2VN32-co-PS92 before (solid) and after (dashed) NaOOH
treatment. d) Response by refractive index. GPC curves of PBN2VN32-co-PS92
before (solid) and after (dashed) NaOOH treatment.
P(BN2VN87-co-S236
P(BN2VN32-co-S332
PS313
)
)
[a] Subscript
= average degree of polymerization of comonomer. [b]
Determined by GPC analysis at 254 nm relative to a polystyrene standard. [c]
Oxidation conditions: 6 N NaOH, 30% H2O2, THF-EtOH, 65 °C, 15 hours.
Neat reaction conditions provided high molecular weight
polymers with high molecular weight distributions (32.6-39.6 kDa,
Đ = 4.23-5.40, Table 1). GPC curves show a shoulder at high
molecular weight that contributes to the high dispersity (Figure
2b, shoulder indicated with a black arrow). Homopolymerization
of each monomer is unlikely as the shoulder is also observed in
the PS control reaction. Additionally, the molecular weight
distribution is unchanged when the absorbance wavelength is
changed from 254 nm to 310 nm (Figure S1). Since PS is
transparent at 310 nm, if two homopolymers were present, only
one peak should be observed at 310 nm. Instead, we suggest
that the shoulder is a consequence of the gel effect in which at
All polymerizations proceeded to >75% conversion. The use
of toluene resulted in polymers of moderate molecular weight
and dispersity (12.8-14.6 kDa, Đ = 1.72-1.88 Table 1). Similar
results are obtained in a control reaction with styrene alone
(PS129). Gel permeation chromatography (GPC) curves of the
polymers are unimodal, consistent with formation of a single
copolymer instead of two homopolymers (Figure 2a).
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10.1002/anie.201711650
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high molecular weight, the slow diffusion of the viscous polymer
results in accelerated chain growth.[9]
borapolyolefins and PS samples would no longer be unimodal.
The intact macromolecular backbone is consistent with prior
work by Chung and others on functionalization of polyethylene
and polypropylene by hydroboration-oxidation of vinyl end
groups[3,36] or internal unsaturation arising from copolymerization
with dienes.[37–39] Table 1 summarizes the molecular weight
characteristics of all polymers in this study before and after
oxidation. Polymer fractionation during reisolation may be
occurring, as the polymers exhibiting a high molecular weight
shoulder (Figure 2c) show a narrower and more unimodal
dispersity after reisolation.
In our prior work on BN2VN-2VN copolymerization, we
described a UV-vis absorbance spectroscopy assay for BN2VN
incorporation based on the differential absorption of naphthalene
and BN-naphthalene at 320 nm.[26] A similar calibration curve
was constructed for BN2VN and styrene (Figure S2). A plot of
extinction coefficient at 320 nm (ε320) versus the wt. % PBN2VN
in binary mixtures of the homopolymers yields a straight line. A
linear regression analysis of the data yields eq. 1 in which X =
the weight percent of BN2VN incorporation. Using the
experimentally determined copolymer ε320 and eq. 1, the
PBN2VN-co-PS samples were analysed for wt. % BN2VN
incorporation. The experimentally determined incorporation
closely matched the feed ratio (Table 2). Elemental analysis is
consistent as well.
a Before NaOOH
b After NaOOH
ε!"# = 28.2ꢀ + 0.208 (ꢀꢁ 1)
ν(NH)
ν(OH)
Table 2. Copolymer optical properties and BN2VN incorporation.
free & H-bonded
Feed Ratio
wt. %
BN2VN
Experimental
wt. %
[a]
Sample Name
ε320
BN2VN[b]
P(BN2VN48-co-S51
P(BN2VN32-co-S92
)
)
60
33
14
60
33
14
16.8
9.74
4.50
16.4
10.2
3.79
58
34
15
57
35
13
Wavenumber / cm-1
Wavenumber / cm-1
c
P(BN2VN14-co-S119
P(BN2VN127-co-S141
)
)
After
P(BN2VN87-co-S236
P(BN2VN32-co-S332
)
)
Before
8.0
7.5
7.0
6.5
3.0
2.5
2.0
1.5
1.0
0.5
1H (ppm)
1H (ppm)
[a] In L g-1 cm-1. [b] Determined by ε320 according to eq. 1.
Figure 3. a) FTIR spectrum of P(BN2VN32-co-S92). b) FTIR spectrum of
oxidized P(BN2VN32-co-S92). c) 1H NMR spectra of P(BN2VN32-co-S92) before
(bottom) and after (top) NaOOH treatment. The gray box (left) highlights
changes in the aromatic region. The gray box (right) highlights the appearance
of new signals at higher field after oxidation.
NaOOH oxidation of PBN2VN-co-PS copolymers was
conducted. Data for P(BN2VN32-co-S92) are described here as a
representative example (see Figure S3 for other copolymers).
Reaction progress is monitored by GPC analysis at 310 nm. The
loss of absorption at 310 nm before and after oxidation (Figure
2c) is consistent with cleavage of the BN2VN chromophore from
the polymer. Extended reaction times and heating (15 h/65 °C)
are required to observe >90% loss of signal at 310 nm. The
need for forcing conditions is attributed to in situ cross-linking of
the polymer with boric acid formed from oxidation of the
azaborine (indole is also observed in crude reaction mixtures).
During isolation, a methanol azeotrope removes boric acid as
trimethyl borate.
Comparing GPC traces of oxidized P(BN2VN32-co-S92)
measured by optical response at 310 nm versus refractive index
(RI) provides compelling evidence that the polymer chains are
intact. While no absorbance at 310 nm is observed after
oxidation (Figure 2c), the RI data show a unimodal distribution
and a modest decrease in molecular weight consistent with loss
of the large BN naphthalene group (Figure 2d). Control reactions
with PS129 and PS313 do not show a decrease in molecular
weight. If unselective oxidation leading to backbone
fragmentation were occurring, the GPC traces of the
Infrared (IR) spectroscopy of the oxidized copolymers is
consistent with
a PVA-co-PS structure. PVA has several
characteristic features in its IR spectrum, including a strong,
broad OH stretching frequency at 3340 cm-1.[40] Hydrogen-
bonding is well known to broaden and shift the OH resonance to
lower frequencies[41] and the unusually low frequency hydroxyl
resonance in PVA is attributed to strong hydrogen-bonding
networks.[40] FTIR spectroscopic analysis of P(BN2VN32-co-S92)
before and after NaOOH treatment shows significant changes
(Figure 3a-b), including the loss of the NH stretching frequency,
but retention of aromatic CH stretching frequencies consistent
with polystyrene.[42] After oxidation, two features consistent with
an OH stretch are observed, a comparatively sharp resonance
at 3570 cm-1 and a broader resonance at 3430 cm-1 (Figure 3b).
These resonances are assigned to free OH and hydrogen-
bonded OH groups, respectively. As the BN2VN content of the
original copolymers increases, the resonance assigned to the
hydrogen-bonded OH group broadens, intensifies, and shifts to
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even lower frequency, consistent with increased hydrogen-
bonding (Figure S4). There is no evidence of hydroxyl groups in
NaOOH-treated PS control samples.
opens up a pathway for modulating the properties of two
industrially relevant polymers, PS and PVA. The concept of
oxidizing a protected borane is not limited to the statistical
copolymers described herein and BN2VN copolymers represent
a platform for the preparation of diverse polymeric architectures
via the remarkable chemistry of C-B bonds.
1H NMR spectra of P(BN2VN32-co-S92) before and after
NaOOH treatment show disappearance of the BN2VN peaks in
the aromatic region, but not the loss of styrenic signals in the
aromatic region (left box, Figure 3c). In the aliphatic region, after
NaOOH treatments new peaks are observed at 2.5-3.0 ppm that
are not observed in the borapolyolefin (right box, Figure 3c).
These peaks are assigned to protons adjacent to hydroxyl
functionality. This assignment is consistent with the greater than
2.0 ppm change in chemical shift of the protons adjacent to the
boron atom upon oxidation to phenethyl alcohol observed in
model system 1 (Figure 1).
Acknowledgements
Acknowledgment is made to the Donors of the American
Chemical Society Petroleum Research Fund for support of this
research. E. C. A. thanks the American Chemical Society for an
ACS Scholars Fellowship. R. S. K. thanks the Alfred P. Sloan
Foundation for a Sloan Research Fellowship and the American
Academy of Arts and Sciences for the Mason Award for Women
in the Chemical Sciences. We thank Johns Hopkins University
for the Catalyst Award. We thank Prof. H. E. Katz for DSC
access.
110 °C
Before NaOOH
After NaOOH
Keywords: copolymerization • boranes • heterocycles •
amphiphiles • oxidation
91.5 °C
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A versatile strategy for functional
polymer synthesis is described. An
aromatic cage around a vinyl boron
compound lends it styrene-like
reactivity, while postpolymerization
oxidation reveals a hydroxyl functional
group.
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