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Ring-Opening Polymerization of Allyl-Functionalized Lactams

Article  in  Macromolecules · December 2018

DOI: 10.1021/acs.macromol.8b02148

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Cite This: Macromolecules XXXX, XXX, XXX−XXX
Ring-Opening Polymerization of Allyl-Functionalized Lactams
Ashlin Sathyan, Ryan C. Hayward,* and Todd Emrick*
Department of Polymer Science and Engineering, University of Massachusetts Amherst, 120 Governors Drive, Amherst,
Massachusetts 01003, United States
*
S Supporting Information
ABSTRACT: Aliphatic polyamides containing pendent allyl
groups were prepared by anionic ring-opening copolymerization
of ε-caprolactam with monomer 1, the substituted lactam 3-(3-
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propenyl)-2-azepanone. Copolymerization experiments revealed
that up to 11 mol % of 1 was integrated successfully into these
novel polyamides, which ranged in molecular weight from 27 to 72
kDa. Relative to the well-known commercial polyamide-6 (PA-6),
the degree of crystallinity of the copolymers decreased with
incorporation of functional monomer. Moreover, the pendent allyl
groups afforded rapid access to numerous functional aliphatic
polyamides, using photoinitiated thiol−ene chemistry, providing a
pathway to cross-linked polyamide films and gels.
■ INTRODUCTION
Aliphatic polyamides represent commercially important, high
volume engineering thermoplastics, the most common of
which, polyamide-6 (PA-6) or poly(ε-caprolactam), is
synthesized by anionic ring-opening polymerization of ε-
caprolactam.1,2 PA-6 exhibits excellent mechanical strength
and resistance to organic solvents, abrasion, and temperature.3
These remarkable properties are attributable to the high degree
of crystallinity of the polymer, which originates from hydrogen
bonding and dipole−dipole interactions between the amides of
adjacent polymer chains.4 These interactions are responsible
for backbone stiffness that contributes to the relatively high
glass transition temperature (Tg) of 47 °C and melting
temperature (Tm) of 220 °C.5 However, as expected, this
backbone stiffness also results in significant processing
challenges.6 Therefore, facile methods are needed to prepare
polyamides with pendent substituents that afford these
materials with tailored thermal properties, solubility, elasticity,
and adhesion, while enhancing polyamide compatibility with
other polymers as well as with particulate fillers.7
While numerous papers describe successful ring-opening
polymerizations of substituted lactones,8−12 few functional
lactams have been prepared, and there are very few published
accounts of their polymerizations.13−15 In principle, function-
alized aliphatic polyamides could be synthesized by ring-
opening polymerization of substituted lactams or by
postpolymerization reactions. However, producing PA-6 from
functional monomers is a synthetic challenge, since the
functional groups must be compatible with high polymer-
ization temperatures (typically about 140 °C) and the selected
initiators. The polymerization of substituted lactams is
additionally challenging because the substituents may interfere,
either sterically or electronically, with the ring-opening
mechanism.13,16 In one prior example of functional poly-
© XXXX American Chemical Society
Article
pubs.acs.org/Macromolecules
amides, Mathias et al.13 synthesized a ketone-containing
polyamide from γ-ethylene ketal ε-caprolactam, which proved
amenable to both thermal and photoinitiated cross-linking. In
another example, pendent functionalization of aliphatic
polyamides was achieved by polymerization of cyclic lysine
(α-amino-ε-caprolactam) substituents, which allowed for
polymer cross-linking via the pendent amines.15,17−19 Tunc
et al.15 synthesized aliphatic polyamides with pendent
fluoroalkyl groups by ring-opening polymerization of perfluor-
obutyryl-substituted α-amino-ε-caprolactam, producing mate-
rials that exhibited degradation temperatures up to 390 °C.
These examples are typical of known functional polyamides in
that they carry substituents at the γ-position and are
synthesized from cyclohexanedione and subsequent Beckmann
rearrangement. However, facile incorporation of reactive
functionality at the α-position of ε-caprolactam, followed by
ring-opening polymerization of the resultant substituted
lactam, to our knowledge has not been reported, despite the
apparent simplicity of this approach. Indeed, a recent review by
Becker and Wurm on ring-opening polymers also noted the
scarcity of examples of functional lactam polymerizations
relative to the abundance of lactones, N-carboxyanhydrides,
and other cyclic structures.20 Other approaches to functional
polyamides (not using lactams) are worth noting, using for
example multicomponent organic transformations,21 step-
growth methods,22 and thiolactone precursors.23
For the preparation of substituted lactams, we were attracted
to Kunishima’s description of α-allyl-substituted ε-caprolactam
(Figure 1) that was employed in studies of amide cleavage
reactions.24 Functional monomers of this type, and the
Received: October 6, 2018
Revised: November 27, 2018
A DOI: 10.1021/acs.macromol.8b02148
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Macromolecules
Figure 1. Schematic of the copolymerization of 3-(3-propenyl)-2-azepanone (monomer 1) with ε-caprolactam and subsequent modification via
thiol−ene reactions.
Figure 2. (a) Synthesis of 3-(3-propenyl)-2-azepanone (1). (b) Synthesis of allyl-substituted aliphatic polyamides by anionic ring-opening
copolymerization using 3 as initiator and 4 as activator.
resulting polymers and copolymers, hold potential to broaden
the base of polyamide properties and overcome limitations
associated with PA-6 processability. Moreover, incorporating
olefins as pendent groups into aliphatic polyamides would
allow tailoring of their physical/mechanical properties by
chemical modification, such as the thiol−ene reactions utilized
here.25 We specifically describe the successful synthesis of
functional aliphatic polyamides by anionic ring-opening
copolymerization of ε-caprolactam and monomer 1, in which
incorporation of allyl groups into the polymers was found to
alter their crystallinity and melting temperatures, while
providing a materials platform for subsequent transformations,
including the preparation of functional polyamide-based
networks and cross-linked gels.
■
RESULTS AND DISCUSSION
Monomer 1, synthesized as described by Kunishima,24 was
isolated as a white solid in ∼85% yield. As shown in Figure 2,
the two-step, one-pot synthesis involved the reaction of ε-
caprolactam with chlorotrimethylsilane in the presence of
lithium N,N-diisopropylamide (LDA) in anhydrous tetrahy-
drofuran (THF) at −78 °C. Then, addition of allyl bromide to
the caprolactam anion, followed by hydrolytic removal of the
B DOI: 10.1021/acs.macromol.8b02148
Article
TMS group, produced the desired monomer 1, which was
purified by column chromatography on silica gel.
This α-substituted lactam was characterized by nuclear
magnetic resonance (NMR) spectroscopy, noting the distinct
allyl proton signals at δ = 5.79 ppm (−CH−) and δ = 4.98
ppm (−CH2−) in the 1H NMR spectrum as well as the olefin
resonances at δ = 136.32 (−CH−) ppm and δ = 115.28 ppm
(−CH2−) in the 13C NMR spectrum. Monomer 1 was easily
prepared on a 10 g scale and proved stable for months when
stored under ambient conditions.
Attempts to homopolymerize monomer 1 by anionic ring-
opening polymerization were unsuccessful, despite testing a
variety of conditions and initiator systems (Table S1). In these
experiments, after addition of initiator, the reaction mixture
quickly became dark, and no polymer was produced. Analysis
of the reaction mixture by 1H NMR spectroscopy showed no
evidence of allyl protons, nor any indication of molecular
weight increase by gel permeation chromatography (GPC). In
contrast, copolymerization of monomer 1 with ε-caprolactam
proved successful when using 0.4 mmol of sodium
caprolactamate (3) as initiator and 0.06 mmol of hexam-
ethylene-1,6-dicarbamoylcaprolactam (4) as activator (Figure
2). Under the copolymerization conditions tested, up to 11
mol % incorporation of 1 into polyamide copolymers was
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Figure 3. 1H NMR spectrum of copolymer P4 (10% monomer 1) in TFE-d3. The inset shows signals for the methylene protons of c and the
methane proton of d.

Figure 4. 1H NMR spectra of polymer P2 in TFE-d3 at different time intervals of the ring-opening polymerization.

achieved. Polymerizations were conducted neat, in glass tubes,
at 140 °C under a nitrogen atmosphere. Monomers 1 and 2,
and initiator 3, were added to the tube as solids; subsequent
heating of the mixture to 140 °C melted the reagents and
addition of activator 4 caused the mixture to solidify. The
polymerization was quenched by immersing the reaction tube
into liquid nitrogen and then opening the tube to ambient
conditions. The solid polymer product conformed to the shape
of the tube and was collected after breaking the tube. For small
scale polymerizations (<1 g), polymer was recovered by
solubilizing the mixture in trifluoroethanol. Copolymerizations
were conducted on 1−5 g scales, and isolated yields were
C DOI: 10.1021/acs.macromol.8b02148
typically >85%. Reagent purity proved crucial to successful
polymerization, since water and other impurities interfere with
the initiating and propagating species (thus, it proved
important to use flame-dried glassware and to subject the
reagents to vacuum prior to use).1 The obtained polymers
were characterized by 1H and 13C NMR spectroscopy as
shown in Figure 3 and Figure S.1, respectively.
At a reaction time of 10 min, monomer conversion reached
85%, as determined by 1H NMR spectroscopy recorded on
aliquots withdrawn from the reaction mixture. In the 1H NMR
spectrum of P4 (Figure 3), the allyl protons resonated at δ =
5.79 ppm (−CH−) and δ = 4.98 ppm (−CH2−); in the 13C
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Macromolecules
NMR spectrum, allyl carbons appeared at δ = 137.2 ppm
(−CH−) and δ = 116.5 ppm (−CH2−). The characteristic
chemical shifts of monomer 2 were employed for evaluating
conversion, since the allyl resonances did not shift significantly
when converting from monomer to polymer; in 2, the 1H
NMR signals at δ = 2.30 ppm (−CH2−) were integrated
against the same methylenes at δ = 2.04 ppm (−CH2−) of the
polymer, as illustrated in Figure 4. ε-Caprolactam (como-
nomer) showed resonances for the δ-, β-, and γ-methylene
protons at 1.60 and 1.48 ppm at polymerization time <2 min;
these shifted to 1.45 (β-CH2) and 1.36 ppm (γ-CH2−) in the
polymer, with a new signal generated at 1.17 ppm (δ-CH2−) as
polymerization time increased.
The resultant aliphatic polyamides were purified by
precipitation in ethyl acetate to remove unreacted monomer,
affording a white fibrous material that was characterized by 1H
and 13C NMR spectroscopy. The pendent allyl groups proved
stable under these bulk polymerization conditions, and
polymers containing up to 11 mol % of monomer 1 were
obtained. Integration of monomer 1 into the polyamide
structure was confirmed by comparing the intensity of the
olefin signal at δ = 5.50 ppm (−CH−) against the resonance at
δ = 2.04 ppm (−CH2−) for the ε-caprolactam methylene units.
Interestingly, copolymerization attempts that employed over
20 mol % of monomer 1 in the initial feed ratio were
unsuccessful, yielding only ill-characterized dark brown liquids
and no polymer product. Thus, at least at this stage, polyamide
homopolymer from 1, and copolymers with large percentages
of pendent allyl groups, remain elusive.
Polymers P1−P5, listed in Table 1, were prepared using
identical initiator-to-activator ratios of 0.4:0.06 and polymer-
Table 1. Summary of Copolymerization Results of ε-
Caprolactam and Monomer 1
targeted conv of Mnb
entry mol % of 1 2a (%) (kDa) Đb mol % 1c
PA-6 0 99 19 1.81 0 P3
P1 1 98 72 2.09 1 P4
P2 5.5 97 45 2.03 4 P5
P3 8 96 69 1.93 9 a
P4 13 98 36 2.02 10
P5 15 97 27 3.35 11
a
Percent monomer conversion was determined by 1H NMR
spectroscopy prior to polymer purification. bMolecular weight and
PDI values were estimated by GPC, eluting in TFE. cMol % refers to
the percentage of monomer 1 incorporated into the copolymers as
determined by 1H NMR spectroscopy characterization on solutions of
the purified polymer.
ization times of 20 min. Table 1 indicates the extent to which
monomer 1 was incorporated into the copolymers, from 1 to
11 mol %, with molecular weights ranging from 27 to 72 kDa
as estimated by gel permeation chromatography (GPC)
(eluting in TFE). The copolymers were isolated in >85%
yield and exhibited polydispersity index (PDI) values in the
range 1.9−3.3. Use of sodium caprolactamate as initiator, a
strong base which can induce side reactions such as
transamidation and Claisen-type condensation (resulting in
branching and/or cross-linking), may be responsible for the
relatively high PDI values obtained.26,27
Noting that the reluctance of monomer 1 to homopoly-
merize contrasts the relatively easy polymerizability of allyl-
substituted lactones,12 the effect of inserting a methyl group α
D DOI: 10.1021/acs.macromol.8b02148
Article
to the lactam carbonyl group, as a small and unreactive group,
was tested. This monomer was prepared similarly to the route
shown in Figure 2, substituting methyl iodide for allyl bromide,
and the methyl-substituted lactam was isolated in ∼70% yield
(Figure S13). Interestingly, in our hands, even this simple
methyl group prevented homopolymerization, in contrast to
reports by Parker et al. on homopolymerization of α-methyl
caprolactam using sodium hydride as initiator and N-
acylcaprolactam as activator (notably, even these polymer-
ization conditions were unsuccessful in our hands with the
methyl-substituted monomer).28 However, when copolymer-
ized with ε-caprolactam, up to 16 mol % of the methyl-
substituted monomer was integrated successfully into the
copolymersa modest increase over the 11 mol % maximum
for the allyl-substituted version.
Thermal Properties of Allyl-Functionalized Polya-
mides. The bulk physical properties of the novel allyl-
containing polyamides, including solubility, crystallization
temperature (Tc), and melting temperature (Tm), were
evaluated to probe the impact of inserting small amounts of
functionality into these polymers. PA-6 is insoluble in most
organic solvents but is soluble in TFE at the level of 0.5 mg/
mL (PA-6 was synthesized under similar conditions as for the
copolymers). Allyl-substituted polymers P1−P5 exhibited
better solubility in TFE (0.75 mg/mL), which proved useful
for spectroscopic characterization and molecular weight
estimation. The crystallization and melting temperatures of
P1−P5 were determined by differential scanning calorimetry
(DSC), as reported in Table 2. The thermal stability of the
Table 2. Thermal Characteristics of the Polymers
Determined Using DSCa
entry mol % of 1 Tc (°C) Tm (°C) ΔHm (J/g) % crystallization
PA-6 0 170 220 67 36
P1 1 162 216 54 29
P2 4 150 201 40 21
9 148 190 21 11
10 118 188 16 9
11 117 188 16 9
Tc: crystallization temperature; Tm: melting temperature; percent
crystallization = (ΔHm/ΔH0m) × 100 where ΔH0m = 188 J/g is the heat
of fusion of polyamide-6.29
allyl-substituted polyamides was determined by thermogravi-
metric analysis (TGA), which was conducted at a heating rate
of 10 οC/min under a nitrogen atmosphere and revealed a 5%
weight loss temperature in the range 300−320 °C (Figure S.5).
DSC thermograms showed distinct melting and crystal-
lization temperatures, allowing for estimation of Tm and Tc,
which were recorded from the second heating and cooling
cycles; this data is given in Figure 5. The Tm and Tc values of
the functional polyamides were both lower than that of PA-6,
with Tc dropping from 162 to 118 °C in going from P1 to P5
and Tm declining from 216 to 188 °C over the same sample
set. The allyl substituents of these polyamides appear to
interrupt polymer crystallinity by weakening hydrogen bonding
interactions between the neighboring amides. PA-6, used in
our experiments as a reference, synthesized under similar
conditions as for the copolymers, had a molecular weight of 19
kDa and PDI of 1.81 (analyzed by GPC, eluting in TFE, with
PMMA standards). Although this particular PA-6 sample had a
lower molecular weight than the copolymers (27−72 kDa), the
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Macromolecules Article

Figure 5. DSC traces of polymers P1−P5. Left: cooling cycle; right: second heating cycle. PA-6 had a Mn of 19 kDa and PDI of 1.81.

Figure 6. Thiol−ene reactions for the modification of allyl-functionalized polyamides.

Figure 7. (a) 1H NMR spectrum of P4c in TFE-d3. (b) 31P NMR spectrum of P4c in TFE-d3.

molecular weight range of the samples utilized nonetheless
provided valuable comparisons.29,30
Reactivity of Allyl-Substituted Polyamides. The
pendent allyl groups of polyamides P1−P5 were converted
efficiently into other functional moieties by photoinitiated
thiol−ene reactions. This allows for the preparation of a range
of novel, functional polyamides with tailored physical and
chemical properties. Postpolymerization modifications were
performed using P4 (10 mol % of monomer 1) as the selected
example shown in Figures 6 and 8. Using this method, the
pendent allyl groups were converted easily to aliphatic alcohols
(P4a) and aromatic moieties (P4b) by 365 nm irradiation of a
TFE solution of polymer with the appropriate thiol (and 2,2-
dimethoxy-2-phenylacetophenone (DMPA) as the photo-
initiator), affording the desired substituted polymers in
∼95% yield. Polyamides P4a and P4b were purified by
repeated precipitation in ethyl acetate, dried under vacuum
E DOI: 10.1021/acs.macromol.8b02148
overnight to remove excess solvent, and then characterized by
1
H NMR spectroscopy.
While monitoring conversion of the thiol−ene reactions, an
absence of unreacted olefin resonances in the 1H NMR spectra
(δ = 5.79 ppm (−CH−) and δ = 4.98 ppm (−CH2−)) was
evident for polymers P4a and P4b. For P4a, signals from the S-
methylene group (−S−CH2−) appeared at δ = 2.48 and 2.25
ppm, and a new signal for the −CH2−OH− methylene was
found at δ = 3.52 ppm (Figure S.8). For P4b, aromatic signals
appeared from δ = 7.03−7.26 ppm (−CH−), while the
resonances representing −CH2−S− and −CH2− were found at
δ = 3.47 and 2.53 ppm, respectively (Figure S.9). Conjugation
of hydrophilic moieties to polyamides is especially interesting
for significantly altering their physical and solution proper-
ties.31,32 For example, thiol-substituted 2-methacryloyl-
oxyethylphosphorylcholine (MPC-SH) was synthesized33 and
successfully utilized in thiol−ene chemistry. In these reactions,
P4, MPC-SH, and DMPA were dissolved in TFE and
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Macromolecules
Figure 8. Schematic of polyamide network formation using multifunctional thiols and thiol−ene reactions.
Figure 9. (a) Polyamide organogels. (b) Rheological data of P4f: G′ (black: storage modulus), G′′ (red: loss modulus) against angular frequency.
(c) Clear, free-standing polyamide film.
irradiated at 365 nm for 2 h at room temperature (Figure 6).
The polymer was purified by precipitation in THF, and dialysis
aganist water, to remove excess PC-thiol (water-soluble), and
then lyophilized to obtain P4c as a white fluffy solid. In the 1H
NMR spectrum of P4c, the allyl signals at δ = 5.79 ppm
(−CH−) and δ = 4.98 ppm (−CH2−) were absent, and the
characteristic PC signals were observed, including −N+−
(CH3)3− at δ = 3.21 ppm, −CH2−N+− at δ = 3.21 ppm, −O−
CH2− at δ = 4.35 ppm, and −CH2−O− at δ = 4.18 ppm
(Figure 7a).
In the 31P NMR spectrum of P4c, a clean phosphorus signal
at δ = 0 ppm supported successful incorporation of PC groups
into the polyamide copolymers (Figure 7b). Interestingly, the
pendent PC groups did not produce perfectly homogeneous
polyamide solutions in DI water; instead, slightly cloudy, stably
suspended materials were obtained. 1H and 31P NMR spectra
of P4c in D2O showed resonances characteristic of the PC
moieties (Figure S.10), but no backbone polyamide signals,
suggesting that >10 mol % of pendent hydrophilic groups is
needed for complete aqueous solubilization of these polymers.
Though Weng et al.31 reported antibacterial zwitterionic
polyamide membranes by interfacial polymerization, to our
knowledge, this represents the first direct conjugation of
zwitterion moieties as pendent groups on a poly(ε-
caprolactam) backbone.
UV-absorbing and perfluoroalkyl-functionalized polyamides
were also accessed easily from polyamides P1−P5 as starting
materials. For example, 9-fluorenylmethylthiol was conjugated
successfully to allyl-substituted polyamide P4 to yield P4d,
using the same reaction conditions described before and given
F DOI: 10.1021/acs.macromol.8b02148
Article
in Figure 6. In this case, the reaction mixture was degassed
with nitrogen for 20 min and then irradiated at 365 nm for 2 h.
P4d was characterized by 1H NMR spectroscopy, noting the
absence of unreacted olefin resonances. Similarly,
1H,1H,2H,2H-perfluorodecanethiol was grafted to P4, and
the polymer product was characterized by 1H NMR spectros-
copy (Figure S.12). The versatility of thiol−ene chemistry, in
conjunction with these functional polyamides, will produce
new materials that enhance polyamide processability and allow
tracking of polyamide localization in blends.
Polyamide P4 was easily cross-linked with pentaerythritol
tetrakis(3-mercaptopropionate), the tetrathiol shown in Figure
8, in either solution or the solid-state and in the presence of
DMPA. In solution, a 3:1 thiol:alkene ratio in minimal TFE
(the minimal amount needed to solubilize the polymer) was
irradiated at 365 nm at room temperature for 10 min to afford
the clear, cross-linked gel, shown in Figure 9a as P4f. Rheology
experiments were performed on a stress-controlled rotational
rheometer (Malvern Kinexus Pro+) with a 20 mm parallel
plate geometry. Oscillatory frequency sweeps were performed
at 25 οC at a strain amplitude of 0.5% with frequencies ranging
from 1 to 100 rad/s. The rheological data, as shown in Figure
9a, displayed a storage modulus G′ that exceeded the loss
modulus G″ by 4 times, with little frequency dependence in
either. In an alternative experiment, the same polymer solution,
dropcast on a glass Petri dish and dried under a stream of
nitrogen for 5 min, was exposed at 365 nm for 1 min to afford
transparent polymer film P4g, as shown in Figure 9c. This film
peeled easily from the substrate to yield a free-standing
material; as expected, both the gel and film were insoluble in
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TFE, and the cross-linked polymers did not swell in water but
swelled rapidly in TFE.
In summary, a series of novel, allyl-substituted aliphatic
polyamides were prepared by anionic ring-opening copoly-
merization involving an allyl-functionalized ε-caprolactam
monomer. By adjusting mole percentages of allyl groups, the
crystallinity, melting temperature (Tm), and crystallization
temperature (Tc) of the polymers were modulated accordingly.
The alkene moieties were easily converted into the desired
chemical functionalities with high efficiency thiol−ene “click”
reactions, using a variety of mono- and multifunctional thiols
providing a modular method to a tremendous variety of
functional polyamide-6 derivatives. The ability to alter both
crystallinity and reactivity of these polymers will open new
opportunities in thermoplastics and other application areas.
Despite that incorporation of high mole percentages of
functional groups into these polymers was not achieved, the
levels that were realized are sufficient to significantly alter
physical and chemical properties. This work represents an
exceptionally simple and effective approach to functional
polyamide copolymers and will open new opportunities for
such structures in composite materials and blends.
■
EXPERIMENTAL SECTION
Materials. Aza-2-cycloheptanone (99%), chlorotrimethylsilane
(≥99%), n-butyllithium (2.5 M in cyclohexane), n-butyllithium (2
M in cyclohexane), diisopropylamine (99.95%), allyl bromide (99%),
mercaptoethanol (≥99%), 4-bromobenzyl mercaptan (97%), pentaer-
ythritol tetrakis(3-mercaptopropionate) (>95%), 2,2-dimethoxy-2-
phenylacetophenone (99%), 1,3-propanedithiol (99%),
1H,1H,2H,2H-perfluorodecanethiol (97%), and 9-fluorenylmethylth-
iol (97%) were purchased from Aldrich and used without further
purification. 2,2,2-Trifluoroethanol was purchased from Alfa Aesar
and used without further purification. 2-Methacryloyloxyethyl-
phosphorylcholine (MPC) was purchased from Aldrich and washed
with diethyl ether prior to use. Sodium caprolactamate (Brüggolen
C10) and hexamethylene-1,6-dicarbamoylcaprolactam (Brüggolen
C20) were obtained from Bruggemann and used without further
purification. Anhydrous THF was purified by distillation over
benzophenone and sodium metal. Deuterated solvents for NMR
spectroscopy were purchased from Cambridge Isotope Laboratories.
Chloroform, methanol, tetrahydrofuran, dichloromethane, sodium
sulfate, hexane, diethyl ether, and ethyl acetate were purchased from
Fisher Scientific.
Instrumentation. 1H NMR spectra were recorded on a Bruker
Avance-500 spectrometer operating at 500 MHz, and chemical shifts
reported in ppm were calibrated to residual solvent signals. 13C NMR
and 13P NMR spectra were recorded on a Bruker Avance-500
spectrometer operating at 126 and 202 MHz, respectively. Gel
permeation chromatography was performed at 40 οC using 0.02 M
sodium trifluoroacetate in TFE as eluent at a flow rate of 1 mL min−1
with three Agilent PL gel mixed columns (300 × 7.5 mm2), refractive
index (RI) detection, and calibration against PMMA standards.
Thermogravimetric analysis (TGA) was performed on a Q500 TA
Instruments with a heating rate of 20 °C/min under a nitrogen
atmosphere, heating from 0 to 600 °C with a gas flow rate of 200 mL/
min. Melting temperature (Tm) and crystallization temperature (Tc)
were determined by differential scanning calorimetry (DSC) on a
Q200 TA Instruments under a nitrogen atmosphere (method: heat
from −20 to 260 °C at 10 °C/min, hold at 260 °C for 2 min, cool
from 260 °C to −20 °C at 10 °C/min, and heat from −20 °C to 260
°C at 10 °C/min). Fourier-transform infrared (FT-IR) spectra were
recorded on a PerkinElmer Spectrum 100 spectrometer with
attenuated total reflectance (ATR).
Synthesis of 3-(3-Propenyl)-2-azepanone (Monomer 1).
Monomer 1 was synthesized per the previous literature with some
modifications.24 ε-Caprolactam (1 g, 8.86 mmol) was added to a
G DOI: 10.1021/acs.macromol.8b02148
Article
flame-dried round-bottom flask charged with a stir bar and THF (52
mL). To the clear reaction mixture, n-BuLi (3.54 mL, 9.38 mmol, 2.5
M in cyclohexanes) was added dropwise at −78 °C. After 15 min,
chlorotrimethylsilane (1.17 mL, 9.26 mmol) was added dropwise to
the reaction mixture at −78 °C, and the mixture was allowed to warm
to 0 °C for 15 min. The mixture was cooled again to −78 °C and
transferred carefully to a solution of freshly prepared LDA (20.3
mmol) at −78 °C. After 30 min, allyl bromide (1.87 mL, 22.1 mmol)
was added at −78 °C dropwise, followed by warming to room
temperature and stirring under a nitrogen atmosphere for 5 h. The
mixture was quenched by addition of saturated aqueous ammonium
chloride solution followed by addition of ethyl acetate. The organic
phase was separated and dried over anhydrous sodium sulfate, filtered,
and concentrated under reduced pressure. The crude product isolated
from that process was purified by column chromatography on silica
gel, eluting with a 3:2 mixture of hexanes and ethyl acetate and then a
1:1 mixture of the same solvents, affording the desired product, after
removal of solvents by evaporation, as a white powder in ∼85% yield.
1
H NMR (500 MHz, CDCl3, δ, ppm): δ 5.79 (m, 1H), 4.98 (m, 2H),
3.22 (m, 2H), 2.54 (m, 1H), 2.41−2.02 (m, 2H), 1.92−1.32 (m,
10H). 13C NMR (CDCl3, 126 MHz): δ 179.6, 137.2, 116.5, 43.4,
42.4, 35.9, 29.8, 29.6, 29.2.
General Procedure for Anionic Ring-Opening Copolymer-
ization. Prior to polymerization, the reagents were subjected to
vacuum for ∼8 h, and the glass reaction tube was flame-dried.
Synthesis of P4. Monomer 1 (370 mg, 2.40 mmol), ε-caprolactam
(1.70 g, 15.5 mmol), and initiator C10 (319 mg, 0.40 mmol) were
added to the flask, and the system was purged with nitrogen for 30
min (Figure 2b). The polymerization tube was heated by placement
into an oil bath that was preheated to 140 °C. After melting the
contents of the tube, activator C20 (138 mg, 0.06 mmol) was added
to the reaction mixture, and the polymerization was performed for 30
min under a nitrogen atmosphere. Multiple polymerizations were
carried out, side-by-side, in polymerization tubes, and aliquots were
withdrawn at different time intervals, with monomer conversion
monitored by 1H NMR spectroscopy and molecular weight evaluation
evaluated by GPC. To terminate the polymerization, the tube was
simply allowed to cool to room temperature.
For purification, the polymer was solubilized in hot TFE, followed
by precipitation in ethyl acetate. Precipitation was performed multiple
times to remove any excess monomer or other impurity, and the
precipitated polymer was dried under high vacuum to isolate the
polyamides as white, fibrous solids.
P4: 1H NMR (500 MHz, TFE-d3, δ, ppm): δ 5.50 (1.02H), 4.81
(2.00H), 2.97 (19.96H), 2.10−1.97 (20.81H), 1.41−1.21 (40.47H),
1.11 (20.89H). 13C NMR (CDCl3, 126 MHz, δ, ppm): δ 179.6, 137.2,
116.5, 43.4, 42.4, 35.9, 29.8, 29.6, 29.2.
Example Procedure for Thiol−Ene Reactions. Allyl-functionalized
polyamide P4 was dissolved in minimum amount of TFE in a 20 mL
glass scintillation vial charged with a stir bar. The respective thiols (3
equiv relative to alkene) and DMPA (0.3 equiv) were added to as
solids. The mixture was solubilized and degassed with nitrogen for
10−20 min. The stirring reaction mixture was exposed to 365 nm
(∼3.5 mW/cm2) light in a UV cross-linker chamber (model: CL-
1000L, UVP, Upland, CA) for 2 h at room temperature.
P4a, P4b, P4d, and P4e were purified by precipitation in ethyl
acetate to afford off-white solid products with a typical yield of ≤95%.
Phosphorylcholine-substituted polyamide P4c was purified by
precipitation in THF, followed by dialysis against water and
lyophilizing to obtain a white fluffy product with a yield of 85−90%.
P4f, the organogel, was obtained by solubilizing 50 mg of P4
(SH:alkene 3:1) in the presence of DMPA in TFE, degassing with
nitrogen for 10 min, and exposing to 365 nm UV light for 10 min.
P4g, the polymeric film, was obtained by dropcasting the polymeric
mixture (P4c) before UV exposure on a glass substrate and
evaporating the solvent under the stream of nitrogen and exposing
to 365 nm for 10 min.
Macromolecules XXXX, XXX, XXX−XXX
Macromolecules
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.macro-
mol.8b02148.
NMR, TGA, DSC characterization, and additional
synthetic procedures (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail rhayward@mail.pse.umass.edu (R.C.H.).
*E-mail tsemerick@mail.pse.umass.edu (T.E.).
ORCID
Ryan C. Hayward: 0000-0001-6483-2234
Todd Emrick: 0000-0003-0460-1797
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the BASF North American Center
for Research on Advanced Materials (NORA). The authors
thank Dr. Philippe Desbois, Dr. Sabine Hirth, and Dr.
Bernhard von Vacano at BASF for helpful discussions and
Vijesh Tanna for rheology experiments.
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I DOI: 10.1021/acs.macromol.8b02148
Macromolecules XXXX, XXX, XXX−XXX

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