Functional-Polymer Library through Post-Polymerization Modification of Copolymers Having Oleate and Pentafluorophenyl Pendants

Article abstract of DOI:10.1002/chem.201703151

Poly[2-(methacryloyloxy)ethyl oleate-co-pentafluorophenyl methacrylate] [P(MAEO-co-PFPMA)] random copolymers with oleate and pentafluorophenyl side-chain pendants were synthesized. These copolymers were utilized as dual-reactive polymeric scaffolds in a range of post-polymerization modification strategies involving thiol-ene and para-fluoro-thiol substitution, amidation, trans-esterification, and epoxidation followed by amidation. The 2-(methacryloyloxy)ethyl oleate (MAEO) functional handle in the copolymer is open to functionalization at its internal double bond through thermally initiated thiol-ene reaction, whereas the pentafluorophenyl moiety of the pentafluorophenyl methacrylate (PFPMA) unit undergoes para-fluoro-thiol substitution under basic conditions at room temperature. By means of these modification approaches, the P(MAEO-co-PFPMA) copolymer was orthogonally ligated with thiol compounds having, for example, alkyl, hydroxyl, and protected amine functional groups. Furthermore, different functional groups such as benzyl, allyl, methacrylate, pyrene, and water-soluble poly(ethylene glycol) were easily introduced into the side chain of the P(MAEO-co-PFPMA) copolymer by amidation, trans-esterification, and epoxidation followed by amidation. Functionalization of both the reactive pendants with the various organic substituents was confirmed by ¹H and ¹⁹F NMR spectroscopy, gel permeation chromatography, and fluorescence spectroscopy.

Full text of DOI:10.1002/chem.201703151

A Journal of
Accepted Article
Title: Functional polymer library through post-polymerization
modification of copolymers having oleate and pentafluorophenyl
pendants
Authors: Binoy Maiti, Ujjal Haldar, Tota Rajasekhar, and Priyadarsi De
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To be cited as: Chem. Eur. J. 10.1002/chem.201703151
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Supported by

Chemistry - A European Journal
10.1002/chem.201703151
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Functional polymer library through post-polymerization
modification of copolymers having oleate and pentafluorophenyl
pendants
Binoy Maiti, Ujjal Haldar, Tota Rajasekhar and Priyadarsi De*[a]
polymeric networks,11 cross-linked materials, functionalized
surfaces,13 and many other materials. Nucleophilic aromatic
substitution of labile para-fluorine of pentafluorophenyl group
12
Abstract: Herein we have synthesized poly(2-(methacryloyloxy)ethyl
oleate-co-pentafluorophenyl methacrylate) (P(MAEO-co-PFPMA))
random copolymers with oleate and pentafluorophenyl side-chain
pendants. These copolymers were utilized as dual reactive
polymeric scaffolds in a range of post-polymerization modification
14
(
para-fluoro-thiol reaction: PFTR) by a panel of nucleophiles,
such as amines, thiols, and alcohols have been widely used in
organic chemistry to modify (pentafluorophenyl)porphyrins.
15
strategies involving thiol-ene, para-fluoro-thiol substitution, amidation, Very recently, this PFTR technique has been employed for post-
trans-esterification and epoxidation followed by amidation reaction.
The 2-(methacryloyloxy)ethyl oleate (MAEO) functional handle in the
copolymer is labile to functionalization via its internal double bond
polymerization with near-quantitative functionalization of
polymers.1
6,17
The pentafluorophenyl group is unreactive during
(
radical) polymerization, as well as radical post-modification
process, but it undergoes selective nucleophilic aromatic
through
pentafluorophenyl moiety from pentafluorophenyl methacrylate
PFPMA) unit undergoes para-fluoro-thiol substitution under basic
thermally
initiated
thiol-ene
reaction,
whereas
substitution reactions with thiols in the para- and in few cases
18
meta- positions under basic condition. Chen et al. synthesized
(
novel H-bond donor copolymers via grafting reaction of
condition at room temperature. Exploring these modification
approaches, the P(MAEO-co-PFPMA) copolymer was orthogonally
ligated with thiol compounds having alkyl, hydroxyl, protected amine
functionalities, etc. Furthermore, different functionalities such as
benzyl, allyl, methacrylate, pyrene and water soluble poly(ethylene
glycol) moiety were easily introduced to the side chain of the
P(MAEO-co-PFPMA) copolymer using amidation, trans-esterification
and epoxidation followed by amidation reactions. Functionalization of
both the reactive pendants with the various organic substituents
unprotected
mercaptoalcohols
onto
poly(2,3,4,5,6-
pentafluorostyrene) (PPFS). These functional polymers were
able to form inter-polymer complexes with poly(4-vinyl
pyridine).19 Schubert’s group reported the synthesis of
glycopolymers consisting of styrene (St) and pentafluorostyrene
(
PFS) via PFTR “click” reaction.20 Following that, Delaittre and
co-workers employed PFTR and amidation reaction for
modification of dual reactive block copolymer i.e., poly(methyl
methacrylate-stat-pentafluorophenyl
methacrylate)-b-
poly(styrene-stat-pentafluorostyrene).21
Modification
of
1
19
poly(ethylene
glycol)-b-poly(pentafluorostyrene)
with
were confirmed by H and F NMR, gel permeation chromatography
GPC) and fluorescence spectroscopy.
aminopropylisobutyl polyhedral oligomeric silsesquioxane
(
(
POSS), and the influence of POSS functionality on the solution
2
2
properties of the block copolymer was explored.
Modification of unsaturated fatty acids and their esters via the
addition of sulfur, phosphorus and also carbon radicals onto a
C=C bonds has been reported by Metzger et al. The efficient
Introduction
23
thiol addition onto oleic acid (a monounsaturated fatty acid),
leading to bio-based polyol, was demonstrated elsewhere.24
Meier et al. reported the synthesis of plasticizers from low-cost,
readily available oleic acid via addition of alkyl thiols, followed by
an inexpensive oxidation in the presence of hydrogen peroxide
In spite of tolerance to most of the functional monomers towards
controlled radical polymerization, it is difficult to polymerize
monomers with certain functionalities such as alkenes,
(
meth)acrylates, etc. in a controlled fashion due to the
and
polymerized side-chain oleic acid containing methacrylate
monomer, 2-(methacryloyloxy) ethyl oleate (MAEO), in
a
final esterification reaction.25 Recently, we have
incompatibility of these functional monomers towards commonly
used radical polymerization conditions.1 In this context, post-
polymerization modifications provide an alternative route for
tailoring functional materials, where chemical modification of
repeating units of pre-made (co)polymers produces new types of
a
controlled fashion via reversible addition-fragmentation chain
transfer (RAFT) process. The C=C double bond in oleate side-
chains of the homopolymer (PMAEO) was reacted with various
2
,3
functional macromolecules. Several click-type reactions such
4
5
6
7,8
26
as thiol-ene and -yne, thiol-maleimide, Michael addition,
organic thiol compounds via thermo initiated thiol-ene reaction.
activated ester-amine reaction, and metal/metal-free 1,3-dipolar
cycloaddition reactions between azide and alkyne,9 which all
practically ensure quantitative conversions during the post-
polymerization modification step. Among them thiol-ene reaction
is most versatile cost-effective synthetic tool.10 Thiols represent
an extremely useful synthetic reagent due to the high
commercial and synthetic availability of functional thiols. A range
of highly efficient thiol-ene reactions were employed to create
Post-polymerization functionalization of polymers bearing dual
functional reactive units in a sequential one-pot reaction could
be an important subject area for creating single reactive
polymers to generate a diverse library of functional polymers.
Very few reports are documented in the literature based on the
fsequential post-polymerization reaction. Recently, Kakuchi and
Theato reported
multifunctional polymers by sequential post-polymerization
modification of poly(pentafluorophenyl 4-
a new synthetic pathway to synthesize
2
7
vinylbenzensulfonate). Gibson et al. synthesized water-soluble
polymer library from poly(pentafluorophenyl methacrylate) via
one-pot/two-step sequential procedure.28 To combine the
advantages of thiol-ene reaction and PFTR process both
individually and in a sequential one-pot reaction for post-
[
a]
B. Maiti, U. Haldar, T. Rajasekhar, P. De*
Department of Chemical Sciences
Indian Institute of Science Education and Research Kolkata
Mohanpur - 741246, Nadia, West Bengal, India
E-mail: p_de@iiserkol.ac.in
polymerization
modification
of
polymers
with
high
functionalization, herein we have designed and synthesized
poly(2-(methacryloyloxy)ethyl oleate-co-pentafluorophenyl
Supporting information for this article is given via a link at the end of
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Chemistry - A European Journal
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Scheme 1. Synthesis of P(MAEO-co-PFPMA) random copolymer via RAFT polymerization and subsequent post-modification reactions with different thiols via
thiol-ene and PFTR reactions.
methacrylate) (P(MAEO-co-PFPMA)) random copolymers with
oleate and pentafluorophenyl side-chain pendants. Additionally,
this dual reactive copolymer’s segmental reactivity is examined
towards trans-esterification, epoxidation, amidation or their
combination to introduce different functionalities such as benzyl,
allyl, methacrylate, pyrene, poly(ethylene glycol) moiety, etc. into
side chain of both the segments in a quantitative fashion.
comparing the integration areas of stretching vibrations of the
-1
ester carbonyl C=O of PFPMA moiety (1784 cm ) and MAEO
-1
units (1738 cm ), the amount of incorporated PFPMA was
determined (Table 1). The GPC RI traces for all copolymers are
symmetric and unimodal (Fig. S3) with narrow Ð values (Table
1) for the copolymers indicating no chain transfer reactions and
bimolecular coupling reactions during the copolymerization. The
number average molecular weight (Mn,GPC) of copolymers
obtained from GPC are somewhat different from the theoretical
molecular weights calculated from stoichiometry and monomer
conversion; Mn,theo = (([M]/[CPDB] × average molecular weight
Results and Discussion
(
MW) of monomer × Conv.) + (MW of CPDB)). Such deviation
could be due to the PMMA standards while determining the
Mn,GPC values, which have different hydrodynamic volume than
the copolymers. Nevertheless, we used these copolymers for
various post-polymerization reactions, see below.
Copolymer synthesis. The 2-cyanopropan-2-yl benzodithioate
(
CPDB) as a chain transfer agent (CTA) produced polymers with
controlled molecular weights and narrow during RAFT
Ð
o
29
polymerizations of PFPMA in 1,4-dioxane at 65 C. Thus,
copolymerization reactions of PFPMA with MAEO were carried
out via RAFT method using CPDB as the RAFT agent at
Post-modification of MAEO units in P(MAEO-co-PFPMA).
Generally, internal double bond present in the side chain of
MAEO unit is less reactive towards thiol-ene reaction compared
to terminal double bond.31 Also, this double bond is inactive
towards photo initiated thiol-ene reaction but reactive towards
thermally initiated thiol-ene reaction in the presence of higher
concentration of thiol and AIBN.32 Thus, the MAEO units in the
copolymer were modified using thiol- functionalized compounds
via thiol-ene reactions (Scheme 1).33 The thiol-ene reaction is
[
monomer (M)]/[CPDB]/[AIBN]
Copolymers were characterized by H NMR spectroscopy (Fig.
A). The peak at 5.37 ppm and 4.0-4.3 ppm were attributed to
the internal double bond (–CH CH=CHCH –) and side chain
repeating units of ethylene oxide (EO) protons (-O-CH -CH -O-,
H) present in the side chain of MAEO units, respectively. The
=
100:1:0.2 (Scheme 1).
1
1
2
2
2
2
4
phenyl moiety of the CPDB unit was incorporated into the
polymer chain ends, which showed characteristic weak
resonance signals at 7.3-7.9 ppm. Comparison of the integration
areas of terminal phenyl protons (7.9-7.3 ppm, 5H) with the side
known to follow
a radical pathway via anti-Markovnikov
mechanism, where the addition of a thiyl radical to a double
bond is followed by chain transfer to thiol.34 Thermally initiated
thiol-ene modification was achieved herein with various thiols
(R-SH) such as 1-butanethiol, 1-thio-β-D-glucose tetraacetate,
2-mercaptoethanol, 2-(dansyl-amino)ethanethiol and 2-(Boc-
amino)ethanethiol. All corresponding peaks of the starting
copolymer P(MAEO-co-PFPMA) (Fig. 1A) and the products (Fig.
2 2
chain repeating unit protons (-O-CH -CH -O-, 4H) of MAEO units
allowed the calculation of number average degrees of
polymerization (DPn,MAEO) for MAEO unit. Since there was no
such distinguish peak in 1H NMR for PFPMA moiety, we were
unable to determine the number average degrees of
polymerization (DPn,PFPMA) for PFPMA. Nevertheless, presence
of terminal phenyl protons in the 1H NMR spectra indirectly
indicates RAFT CTA as chain ends in the polymer.
In order to determine the content of the PFPMA moiety,
the corresponding absorbance bands in the FT-IR spectra (Fig.
S2) were integrated. Due to baseline corrections and noise
reductions the FT-IR spectrum usually provides an
underestimated value in respect to the original one.30 By
1
1B for 1-butanethiol) are assigned in the H NMR spectra, which
shows complete disappearance of resonance signal at 5.37 ppm
corresponding to the side-chain double bonds in MAEO and
appearance of a new peak at 2.45 ppm due to the -H
2 2
C-CH -S-
protons for 1-butanethiol. Conversion of alkene group was
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Chemistry - A European Journal
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Figure 1. 1H NMR spectra in CDCl
of (A) P(MAEO-co-PFPMA) (CP3 in Table 1) and products from thiol-ene reactions of CP3 with (B) ethanethiol and (C) 2-
3
mercaptoethanol.
o
Table 1. Experimental results from the RAFT copolymerization of MAEO and PFPMA in 1,4-dioxane at 65 C for 8 h.
Polymera
PFPMA Content in
feed (mol%)
Conv.b
(%)
PFPMA Content in
copolymer (mol%) c
M
M
e
Ð e
f
n MAEO
DP ,
n,theo
(g/mol)d
n,GPC
(g/mol)
PPFPMA
100
65
100
16600
20600
1.32
0
7
CP1
CP2
90
70
72
71
91.0
71.2
19300
21100
15200
13600
1.40
1.37
22
41
71
94
CP3
CP4
50
20
65
65
45
50.9
25.6
0
20900
23900
18100
20000
17700
17800
1.37
1.34
1.38
PMAEO
0
a
CP means copolymer. Determined by gravimetric analysis on the basis of the amount of monomer feed. Determined from FT-IR. d
b
c
M
n
,theo = (([Monomer]/[CPDB]
average molecular weight (MW) of monomer × Conv.) + (MW of CPDB)). eMeasured by GPC in THF. Determined from H NMR.
f
1
×
obtained by comparing the intensity of –CH
2
CH=CHCH
2
– peak
spectra of P(MAEO-co-PFPMA) (Fig. 2A) and its 1-butanethiol
ligated product (Fig. 2B).
at 5.37 ppm with respect to -OCH -CH -O- protons at 4.03-4.39
2
2
ppm (Fig. 1B). For the 1-butanethiol ligated product, conversion
was quantitative.
To incorporate fluorescent moiety into the side chain,
dansyl protected aminoethanethiol (2-(dansyl-amino)ethanethiol)
has been used. Generally, 5-10% incorporation of dansyl group
in the polymer (as a florescent probe for tracking the protein
location and activation) is sufficient for potential biological
applications to avoid toxicity.36 In order to obtain lower content of
dansyl tagged fluorescent copolymer, lower equivalent of dansyl
thiol (MAEO/RSH = 1: 0.4) was used. Conversion (approx. 7-
10%) of alkene group was determined by comparing the
In the case of 2-mercaptoethanol (Fig. 1C) and 2-(Boc-
amino)ethanethiol (Fig. S4) around 56% and 43% conversions
were achieved after 24 h, respectively. The possible explanation
for the low reactivity of 2-mercaptoethanol is the presence of -
OH functionality resulting in radical quenching and the
3
5
subsequent non-generation of thioether. Similar kind of radical
quenching was observed for 2-(Boc-amino)ethanethiol. It is
noteworthy to mention that during the functionalization of MAEO
unit of the random copolymer, the PFPMA units in the copolymer
intensity of –CH
O-CH -CH -O- protons at 4.03-4.39 ppm (Fig. S5A). The
excitation and emission spectra of resulting dansyl tagged
copolymer was examined in chloroform (CHCl ) at room
2 2
CH=CHCH – peak at 5.37 ppm with respect to -
2
2
1
9
remains unaffected, as evident from comparison of the
F
3
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Chemistry - A European Journal
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were treated with the copolymer in presence DBU (Scheme 1).
First, 2-mercaptoethanol (10.0 equiv. with respect to the PFPMA
repeating unit) was reacted for 1 h with CP3 in presence of DBU
(
1.0 equiv.) in THF at room temperature. The 19F NMR of the
purified product is shown in Figure 2C, where a new set of
peaks between -112 to -134 ppm corresponding to the para- and
meta- substitution are observed. This result indicates that
PFPMA unit undergoes quantitative nucleophilic substitution at
para- and meta- position while ortho- position remains
unaffected. Although, only para-fluoro substitution occurs for
PFS, both para- and meta- substitution takes place in the case
of PFPMA, because the reactivity of PFPMA is quite different
than that of PFS.21 From H NMR spectroscopy it was revealed
that during PFTR the intensity of the signal at 5.37 ppm
1
2 2
corresponding to CH CH=CHCH – protons of MAEO unit
remains same as before the reaction proceeds (Fig. 2D), thus
indicates selective functionalization of PFPMA units. Similar
observations were made for reactions conducted with other
thiols such as ethanethiol, 1-butanethiol, and 2-(dansyl-
amino)ethanethiol. In case of 2-(dansyl-amino)ethanethiol the
purified product was fluorescent in nature due to the presence of
dansyl moiety, which is reflected in Figure S7.
Figure 2. 19F NMR spectra of P(MAEO-co-PFPMA) (CP3 in Table 1) (A)
before and (B) after undergoing thiol-ene reaction with 1-butanethiol, and (C)
after PFTR reaction with 2-mercaptoethanol and (D) 1H NMR spectrum after
reaction with 2-mercaptoethanol in the presence of DBU.
temperature (Fig. S5B). The absorption maxima (λabs) at 332 nm
and fluorescence emission maxima (λem) at 500 nm are
observed, which is characteristic of the green-yellow dansyl tag
as described elsewhere.37
There are several synthetic approaches to obtain glycolipid
based polymers,38,39 because this class of polymers offers
4
0
valuable biological characteristics, for example they show
antifungal, antibiotic, or even anticancer property.41 Herein,
sugar moiety was attached to the side chain of fatty acid based
polymer via thiol-ene click reaction. Attachment of glucose units
to the side chain of the copolymer is clearly seen in Fig. S6.
Conversion of the reaction (~67%) was determined by
Figure 3. 1H (A) and 19F (B) NMR spectrum of P(MAEO-co-PFPMA) (CP3 in
Table 1) after undergoing Type 2 dual functionalization with 1-butanethiol.
comparing the intensity of –CH
with respect to -OC(=O)CH -CH
2
CH=CHCH
2
– peak at 5.37 ppm
2
2
-O- (H , 2H) protons at 2.1 ppm.
c
One-pot dual functionalization of P(MAEO-co-PFPMA). For
one pot dual functionalization, we have adopted two strategies
Post-modification of PFPMA units of P(MAEO-co-PFPMA).
The PFTR was successfully used in the literature to functionalize
(
Scheme 2). The first strategy involves the following (Type1): in
a septum sealed vial, copolymer CP3 (1.0 equiv.), 1-butanethiol
15.0 equiv.), DBU (1.0 equiv.) and AIBN (0.5 equiv.) are
dissolved in dry THF and kept for stirring for 1 h at room
poly(pentafluorostyrene)
(PFS)
with
variety
of
thiol
4
2,43
compounds.
To evaluate the reactivity of the para-fluorine on
(
the pentafluorophenyl group of P(MAEO-co-PFPMA) towards
nucleophilic substitution by thiols, different thiol compounds
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Chemistry - A European Journal
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FULL PAPER
Scheme 2. One-pot dual functionalization of P(MAEO-co-PFPMA) with 1-butanethiol.
o
1
temperature, followed by heating at 60 C for 12 h. The H NMR
of the purified polymer indicates that all the MAEO units are not
quantitatively functionalized (only 36%) (Fig. S8). In contrast,
PFPMA unit which is susceptible towards PFTR, quantitatively
functionalizes by 1-butanethiol evident from 19F NMR spectrum
where the peaks -162.0 ppm and -156.0 ppm corresponding to
para- and meta- fluorine atom totally disappeared (Fig. S9).
Similar low functionalization of side-chain terminal double bonds
was reported in a similar dual functionalization,43 because of the
presence of DBU from the beginning of the reaction, which
abstract hydrogen from –SH group and thereby not available for
thiyl radical formation which is required for thiol-ene reaction.
In the second strategy, all necessary compounds are mixed
together in THF except DBU (Type 2 in Scheme 2). After
carrying out the reaction at 60 oC for 12 h (step (i)), DBU was
added into the reaction mixture and stirred the solution for
another 1 h. From Figure 3A it was observed that the peak at
emission spectra of resulting pyrene tagged copolymer are
3
examined in CHCl (Fig. S12), where absorption maxima (λabs)at
337 nm and fluorescence emission maxima (λem) at 372 and 384
nm are observed, which are characteristic signals of the pyrene
44
methanol.
It is difficult to make side chain methacrylate containing polymer
from dimethacrylate based monomer, because of formation of
cross-linked polymeric gel or hyperbranched polymer.4
5,46
Herein,
the benefit of trans-esterification reaction was proven by
incorporation of methacrylate moiety into the side chain of
P(MAEO-co-PFPMA) copolymer by reacting CP3 with HEMA.
1
The resultant polymer was characterized by
spectroscopy, where CH =C(CH
5.12 and 6.12 ppm (Fig. S11B). Comparison of the integration
areas of H (6.12 ppm) with the side chain repeating unit protons
(-O-CH -CH -O-, 4H) of MAEO units gave the amount of the
H
NMR
2
3
)- (2H) protons appeared at
b
2
2
methacrylate (11.1 mol%) incorporated into the polymer.
Following the same procedure, water soluble poly(ethylene
glycol) methyl ether (mPEG) was treated with P(MAEO-co-
PFPMA) and the product was characterized by 1H NMR (Fig.
S11C), where 15.6 mol% incorporation of PEGMA was
determined. Incorporation of mPEG moiety into the side chain of
the copolymer not only improve the overall aqueous solubility
but also important for several bio-relevant applications.47
5
.37 ppm corresponding to the side chain double bond in MAEO
unit fully disappeared. Similarly, from Figure 3B the peaks at -
62.0 and -156.0 ppm corresponding to para- and meta- fluorine
1
atom are fully vanished. Thus, this route allows quantitative
conversion of both the MAEO and PFPMA units in the
1
19
copolymer, as proven by H (Fig. 3A) and F NMR (Fig. 3B). In
Fig. S10 all GPC RI traces are superimposed on each other,
confirming that polymer architecture remained same after post-
polymerization modification reaction, without any detectable
crosslinking and degradation reactions. Herein different
polymers have been synthesized via one-pot/two-step procedure
using the same thiol, although polymers can also be modified
using different modifiers on sequentially after purification of each
step.
Amidation reaction. Pentafluorophenyl ester group is reactive
towards aminolysis reaction.4
8,49
Similarly, thiocarbonylthio
functional group at the chain end of P(MAEO-co-PFPMA)
copolymer in the form of dithiobenzoate species is also
particularly reactive towards primary and secondary amines.50
So, polymers with thiol chain end will be generated, which may
form disulfide bridges or participate in PFTR. Therefore, first
dithiobenzoate end group was removed by reacting CP3
copolymer with the calculated amount of AIBN in dioxane at 80
Trans-esterification. Trans-esterification reactions were carried
out to incorporate new functional groups into the side chain of
P(MAEO-co-PFPMA) copolymer by replacing pentafluorophenyl
ester moiety, which is an activated ester group. Several alcohols
were used to functionalize the P(MAEO-co-PFPMA) copolymer
by replacing only pentafluorophenyl ester unit using DMAP as a
catalyst in 1,4-dioxane (Scheme 3). First, we attempted to
incorporate pyrene fluorescent moiety and for this 2.0 equiv. of
o
C for 2.5 h (Scheme 3). To prove the complete removal of the
dithiobenzoate moiety, UV-Vis spectrum was taken of the
copolymer before and after AIBN treatment, which demonstrated
loss of the characteristic peak at 307 nm of the dithiobenzoate
group (Fig. S13).51 In order to incorporate different functionality
via amidation, chain end modified CP3 (after removal of
1-pyrenemethanol was treated with 1.0 equiv. of CP3 copolymer
in presence of DMAP. The resultant polymer was characterized
by H NMR spectroscopy where signals at 8.00 ppm for aromatic
dithiobenzoate moiety) was reacted with model amines such as
1
o
phenethylamine and allyl amine in presence of Et
3
N at 45 C in
protons and 5.7 ppm for methylene protons adjacent to pyrene
moiety were observed (Fig. S11A). The amount of pyrene
moiety (18.5 mol%) incorporated in the copolymer was
1,4-dioxane. Figure 4A shows the 1H NMR spectrum of the
polymer obtained after reaction of chain end modified CP3 with
phenethylamine. The peak centered at 7.2 ppm corresponds to
the phenyl protons from phenethylamine moiety. Peaks at 3.20
1
calculated from H NMR by following equation (1).
and 2.89 ppm are assigned to the CH
bond (PhCH CH NH(CO)-) and CH
phenyl ring (PhCH CH NH(CO)-),
2
protons next to the amide
group adjacent to the
I(8.0 ppm) / 9
2
2
2
Pyrene content (mol%) 
 100
(1)
2
2
respectively.
The
I(4.03-4.39 ppm) / 4 I(8.0 ppm) / 9
phenethylamine content (47.0 mol%) into modified copolymer
1
were calculated based on H NMR data, taking into account the
As pyrene moiety was attached to the side chain of the polymer,
it is expected to be fluorescent in nature. The excitation and
b 2 2
intensity of H (3.2 ppm) and -OCH -CH -O- protons (4H) at
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Chemistry - A European Journal
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Scheme 3. Post-polymerization modification of P(MAEO-co-PFPMA) via trans-esterification, amidation and epoxidation followed by amidation reactions with
different functional organic nucleophiles
reaction, PFPMA unit remain unaffected, confirmed from 19F
4
.03-4.39 ppm. The conversion was almost quantitative as
NMR (Figure S15A).
1
9
determined from F NMR, where very small signal from PFPMA
unit was observed (Fig. S14B).
In the next stage, phenethylamine was used as a model amine
compound to functionalize the epoxidized copolymer. In the
presence of amine, epoxide ring was opened as well as
The introduction of terminal (reactive) double bonds in the
side chain of the polymer could be more appealing for accessing
multifunctional polymers. To achieve this, allyl group was
introduced in the polymer side chain via amidation reaction
without cross-linking by reacting chain end modified CP3 with
1
allyl amine. The polymer was characterized by
spectroscopy (Figure 4B), where alkenyl protons (H
are detected between 5.0 and 6.0 ppm, and CH proton adjacent
H
NMR
b
, H
c
and H )
d
2
1
9
to the amide group appeared at 3.8 ppm. The F NMR
spectrum shows that the peaks originating from PFPMA
completely disappeared, thus confirms quantitative conversion
of PFPMA to the corresponding amide (Fig. S14C).
Methacrylamide content (49.0 mol%) of the modified copolymer
was determined by following equation 1, taking into account the
a 2 2
intensity of H (3.8 ppm) and -OCH -CH -O- protons (4H)
centered at 4.03-4.39 ppm. It is noteworthy to mention that
during amidation reaction with PFPMA unit, the MAEO unit
remained unaffected which was reflected in 1H NMR (Figure
S14B). Thus, we have successfully synthesized polymers having
reactive clickable groups.
Epoxidation reaction followed by amidation. To further
incorporate different functional groups into the polymer, in the
first stage epoxidation of chain end modified CP3 polymer was
carried out using meta-chloroperbenzoic acid (mCPBA, an
epoxidizing agent) at room temperature (Scheme 3). Figure 5A
confirmed that all the double bonds present in PMAEO (at 5.37
ppm) segment in the copolymer were converted to epoxide. A
new signal at 2.88 ppm is appeared due to the -CH protons
adjacent to epoxide group. Note that during the epoxidation
Figure 4. H NMR spectra of polymers obtained after the reaction of chain end
1
modified CP3 with (A) phenethylamine and (B) allyl amine in CDCl
3
1
PFP-ester moiety was cleaved. H NMR spectroscopy was used
to identify the structure of the amidation product (Fig. 5B), where
the signal at 7.2-7.1 ppm region is due to the phenyl protons
from phenethylamine moiety. Peaks at 3.20 and 2.89 ppm are
assigned to the CH
(PhCH CH NH(CO)-) and CH
ring (PhCH CH
NH(CO)-), respectively. 19F NMR suggests that
conversion was quantitative (Fig. S15B).
2
protons next to the amide bond
2
2
2
protons adjacent to the phenyl
2
2
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Chemistry - A European Journal
10.1002/chem.201703151
FULL PAPER
Cambridge Isotope Laboratories, Inc., USA for NMR spectroscopy.
Regular solvents such as dichloromethane (DCM), tetrahydrofuran (THF),
methanol (MeOH), ethyl acetate (EtOAc), 1,4-dioxane, hexanes (mixture
of isomers), acetone, etc. were purified by following general procedure.
Instrumentation. Molecular weights and molecular weight distributions
(
dispersity (Ð)) of polymers were determined by gel permeation
chromatography (GPC). The GPC instrument is equipped with Waters
15 HPLC pump, a Waters 2414 refractive index (RI) detector, HSPgel
5
HT 4.0 and HSPgel HT 2.5 columns connected in a series in THF at 30
o
C at 0.6 mL/min flow rate. Poly(methyl methacrylate) (PMMA) standards
were used to calibrate the instrument. The 1H and 19F NMR
spectroscopic measurements were conducted on Jeol 400 MHz
instrument. FT-IR spectroscopic measurements were carried out on KBr
pellets using a Perkin-Elmer Spectrum 100 FT-IR spectrometer. UV-Vis
measurements were done on
a Perkin-Elmer Lambda 35 UV-Vis
spectrophotometer. Fluorescence emission spectra were recorded on a
Horiba Jobin Yvon (Fluoromax-3, Xe-150 W, 250−900 nm) fluorescence
spectrometer.
1
Figure 5. H NMR spectra of the product after (A) epoxidation and (B) reaction
of phenethylamine with epoxidized product of chain end modified CP3.
Synthesis of PFPMA monomer. Methacrylic acid (2.80 g, 0.032 mol)
and DMAP (0.65 g, 5.40 mmol) were dissolved in 40 mL dry DCM in a
250 mL double neck round bottom (RB) flask equipped with a magnetic
Conclusions
2
stir bar. Then, the RB flask was kept on ice-water bath and dry N gas
was purged through it. In a separate vessel DCC (8.33 g, 0.041 mol) was
dissolved in minimum volume of DCM and was added to the reaction
mixture. Then pentafluorophenol (5.0 g, 0.027 mol) was added drop-wise
for 30 min. The ice-water bath was removed after 30 min and the
resulting mixture was stirred for 24 h at room temperature. Next, the
reaction mixture was filtered and 80 mL distilled water was added to the
In summary, we have successfully synthesized P(MAEO-co-
PFPMA) copolymer via RAFT polymerization, having two distinct
functionalities capable of undergoing post-modification reactions
via thiol-ene, para-fluoro-thiol substitution, amidation, trans-
esterification and epoxidation. By applying specific conditions for
thiol-ene addition, different thiols were orthogonally directed to
pendant double bonds in the MAEO moiety of the copolymer.
Quantitative nucleophilic substitutions at para- and meta-
positions were observed during PFTR process of the PFPMA
unit of the copolymer with various thiols, while ortho- position
remains unaffected. When performed separately or in a semi
batch system (Type 2), both the ligation reactions yielded to
near quantitative functionalization. Further, pentafluorophenyl-
ester demonstrated quantitative reactivity towards aminolysis
and near-quantitative functionalization for trans-esterification,
amidation, epoxidation followed by amidation reactions. Thus,
copolymers having oleate and pentafluorophenyl side-chain
pendants are an ideal platform to carry out facile post-
polymerization reactions to obtain various multifunctional
materials.
filtrate. The organic layer was further washed with saturated NaHCO
(120 mL × 4) followed by brine solution (100 mL × 2) and dried over
anhydrous Na SO . The solvent was removed by rotary evaporator and
3
2
4
purified by column chromatography using silica gel as stationary phase
and hexanes/EtOAc (95:5, v/v) as an eluent to obtain a colourless liquid
1
(yield: 85 %). H NMR (Fig. S1, 400 MHz, in CDCl
3
):  (ppm) = 6.44 and
2 2 3
5.9 (C=CH , 2H) and 2.07 (CH =CCH , 3H).
Copolymer synthesis. Typically, MAEO (609 mg, 0.29 mmol), PFPMA
390 mg, 0.29 mmol), AIBN (2.02 mg, 0.012 mmol, from stock solution),
CPDB (13.6 mg, 0.061 mmol) and 1, 4-dioxane (4.0 mL) were placed in a
0 mL reaction vial equipped with a magnetic stir bar. The vial was
(
2
purged with dry N
2
for 20 min and placed in a preheated reaction block at
o
65
C. The feed ratios of MAEO and PFPMA were varied to get
copolymers of various compositions. After 8 h, the polymerization
reaction was stopped by cooling the vial in an ice-water bath and
exposed to air. The copolymer was reprecipitated five times from
acetone/MeOH mixture and dried under vacuum at 30 oC for 24 h to
obtain a pink material.
Experimental Section
Materials. Oleic acid (OA, 99 %), pentafluorophenol (≥ 99%),
dicyclohexylcarbodiimide (DCC, 99%), 4-dimethylaminopyridine (DMAP,
9
1
9%), 2-hydroxyethyl methacrylate (HEMA, 97%), 1-butanethiol (≥ 98%),
-thio-β-D-glucose tetraacetate (97%), 2-(Boc-amino)ethanethiol (97%),
Post-modification of MAEO units of P(MAEO-co-PFPMA). The
copolymer (70.0 mg, 1.0 equiv.) was dissolved in 1.5 mL dry THF in a 20
mL vial, and then AIBN (14.6 mg, 0.5 equiv.) and 1-butanethiol (0.165 g,
10.0 equiv. with respect to the MAEO repeating unit) were added into the
meta-choloroperbenzoic acid (mCPBA), poly(ethylene glycol) methyl
ether (mPEG, average molecular weight 300 g/mol), 1,8-
=
diazabicyclo[5.4.0]undec-7-ene (DBU) and dansyl chloride were
purchased from Sigma and used without any further purification. The 2-
mercaptoethanol (99%) was purchased from Sisco Research
Laboratories Pvt. Ltd., India. Methacrylic acid, allyl amine,
phenethylamine and triethylamine (Et N) were purchased from Merck
3
Chemicals (India). MAEO monomer was synthesized as reported
earlier.26 The RAFT chain transfer agent (CTA), 2-cyanopropan-2-yl
2
vial. The vial was purged with dry N on an ice-water bath for 10 min, and
was stirred at 60 oC for 12 h. The resulting polymer was purified by
precipitation in MeOH (at least 5 times to ensure complete removal of
unreacted thiol), and finally the product was dried under high vacuum at
room temperature. Similarly, thiol-ene reactions were performed with
others thiols such as 2-mercaptoethanol, 2-(dansyl-amino)ethanethiol
and 2-(Boc-amino)ethanethiol.
benzodithioate (CPDB), was synthesized following the standard literature
procedure.53 The 2,2΄-azobisisobutyronitrile (AIBN, Sigma, 98%) was
Post-modification of PFPMA units of P(MAEO-co-PFPMA). In a 20
recrystallized from methanol (twice). CDCl
3
(99.8% D) was obtained from
mL vial, polymer solution was prepared in dry THF by dissolving 50 mg
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Chemistry - A European Journal
10.1002/chem.201703151
FULL PAPER
(
0.198 mol) of P(MAEO-co-PFPMA). Then DBU (22.0 mg, 1.0 equiv.,
Acknowledgements
with respect to PFPMA repeating unit) and 1-butanethiol (179.0 mg, 10.0
equiv.) were mixed into it. The reaction mixture was stirred at room
temperature for 1 h. The polymer was purified by precipitating in MeOH
to remove excess thiol. Finally, the polymer was dried under high
vacuum at room temperature.
BM acknowledges University Grant Commission, Government of
India, for the senior research fellowship. We thank Prof. Suhrit
Ghosh and Mr. Raju Bej from Indian Association for the
Cultivation of Science (IACS), Kolkata for allowing us to use
their GPC facility.
One-pot dual functionalization of P(MAEO-co-PFPMA). During one-
pot dual functionalization of copolymer we have followed two different
strategies. In first strategy (Type 1), the copolymer (40.0 mg, 1.0
equivalent) was dissolved in 1.5 mL dry THF in a 20 mL vial, and then
DBU (23.0 mg, 1.0 equiv. with respect to PFPMA repeating unit), 1-
butanethiol (180.0 mg, 20.0 equiv.) and AIBN (8.3 mg, 0.5 equiv. with
respect to MAEO) were added into the vial. The vial was purged with dry
N on an ice-water bath for 10 min, and stirred at room temperature
2
followed by heating at 60 oC for 12 h. Then, the resulting polymer was
purified by precipitation in MeOH and finally the product was dried under
high vacuum at room temperature. In second strategy (Type 2), the
copolymer (40.0 mg, 1.0 equiv.) was dissolved in 1.5 mL dry THF in a 20
mL vial, and then 1-butanethiol (180.0 mg, 20.0 equiv.) and AIBN (8.3 mg,
Keywords: Orthogonal functionalization • oleic acid • thiol-ene
reaction • trans-esterification • amidation
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Chemistry - A European Journal
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FULL PAPER
Entry for the Table of Contents
Layout 1:
Post-Polymerization
Modification
FULL PAPER
We describe a synthetic strategy to
prepare library of multifunctional
polymers from a random copolymer
Binoy Maiti, Ujjal Haldar, Tota
Rajasekhar and Priyadarsi De*
bearing
side-chain
oleate
and
Page No. – Page No.
pentafluorophenyl pendants through
Functional polymer library through
post-polymerization modification of
copolymers having oleate and
pentafluorophenyl pendants
post-polymerization
approaches.
modification
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