Nylon–MOF Composites through Postsynthetic Polymerization

Article abstract of DOI:10.1002/anie.201812655

Hybridization of metal–organic frameworks (MOFs) and polymers into composites yields materials that display the exceptional properties of MOFs with the robustness of polymers. However, the realization of MOF–polymer composites requires efficient dispersion and interactions of MOF particles with polymer matrices, which remains a significant challenge. Herein, we report a simple, scalable, bench-top approach to covalently tethered nylon–MOF polymer composite materials through an interfacial polymerization technique. The copolymerization of a modified UiO-66-NH₂ MOF with a growing polyamide fiber (PA-66) during an interfacial polymerization gave hybrid materials with up to around 29 weight percent MOF. The covalent hybrid material demonstrated nearly an order of magnitude higher catalytic activity for the breakdown of a chemical warfare simulant (dimethyl-4-nitrophenyl phosphate, DMNP) compared to MOFs that are non-covalently, physically entrapped in nylon, thus highlighting the importance of MOF–polymer hybridization.

Full text of DOI:10.1002/anie.201812655

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Accepted Article
Title: Nylon-MOF Composites via Postsynthetic Polymerization
Authors: Mark Kalaj, Michael Denny, Kyle Bentz, Joseph Palomba, and
Seth Mason Cohen
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201812655
Angew. Chem. 10.1002/ange.201812655
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10.1002/anie.201812655
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Nylon-MOF Composites via Postsynthetic Polymerization
Mark Kalaj, Michael S. Denny Jr., Kyle C. Bentz, Joseph M. Palomba, and Seth M. Cohen *
Abstract: Hybridization of metal-organic frameworks (MOFs) and
polymers into composites yields materials that display the exceptional
properties of MOFs with the robustness of polymers. However,
realization of MOF-polymer composites requires efficient dispersion
and interactions of MOF particles with polymer matrices, which
remains a significant challenge. Herein, we report a simple, scalable,
bench-top approach to covalently tethered nylon-MOF polymer
composite materials by an interfacial polymerization technique. The
copolymerization of a modified UiO-66-NH2 MOF with a growing
polyamide fiber (PA-66) during an interfacial polymerization gave
hybrid materials with up to ~29 weight percent MOF. The covalent
hybrid material demonstrated nearly an order of magnitude higher
catalytic activity for the breakdown of a chemical warfare simulant
(dimethyl-4-nitrophenyl phosphate, DMNP) compared to MOFs that
are non-covalently, physically entrapped in nylon, highlighting the
importance of MOF-polymer hybridization.
that makes their handling and implementation considerably
easier than in the native, powder form.[5] Previous work has
shown that a polymer composite can actually enhance the
characteristics of MOFs through framework stabilization[6] or
enhanced uptake of
a
desired analyte.[7]
Significant
advances have been made in the field of MOF composites
by achieving covalent integration of MOF and polymer
components.[8]
Despite these advances, the covalent
integration of MOFs and polymers remains challenging. Two
primary methodologies to produce these covalent composite
materials has been pursued. The first method uses the
solvothermal synthesis of MOFs from polymeric ligands
resulting in MOF-polymer hybrid materials, termed
polyMOFs.[9] An alternative approach termed postsynthetic
polymerization (PSP)[8, 10] uses a reactive handle on the MOF
that can combine with a monomer to form an interstitial
polymer matrix around the MOF particles. PSP has been
successfully used to prepare membranes and stable, highly
connected monoliths.[8, 11]
Metal-organic frameworks (MOFs) are constructed from
inorganic metal nodes, termed secondary building units
(SBUs) and multitopic organic linkers, forming a highly
porous three-dimensional lattice.[1] The large, open cavities
form an interconnected porous network, and consequently,
MOFs display exceptional sorption capacities across a broad
range of applications. Coupled with catalytic activity deriving
from functional units on the ligands and active metal sites at
the SBU, MOFs have attracted great interest as functional,
porous materials.[2] For example, Zr4+-based MOFs have
been investigated as sorbents that can also catalytically
degrade chemical warfare agents (CWAs);[3] however, few
examples have demonstrated this activity in a functional form
factor.[4]
Nylon 6,6 (PA-66), is a simple linear polyamide (PA)
prepared from hexamethylenediamine (HMDA) and adipic
acid. PA-66 remains one of the most widely used polymers
today, especially in high-durability textiles. Given their utility,
ubiquity, and facile preparation, polyamides are a natural
choice for preparation of covalent composites with MOFs via
PSP. However, no methods currently exist to create
covalently linked nylon-MOF hybrid materials under mild
conditions. Formation of amide bonds on ligands has been
well established by postsynthetic modification (PSM) studies
with MOFs.[8b, 10, 12] Indeed, many common MOFs can be
prepared with amine functionalized ligands where the amine
is amenable to chemical modification to amide groups.[1, 13]
In related work by Choe et al., acyl chloride ligands were
utilized to crosslink amine functionalized metal-organic
polyhedral (MOPs).[14]
Assembly of composite materials with MOFs has proven
to be an effective way to exploit the desired properties of
MOFs, such as porosity and catalytic activity, in a form factor
Herein, the first example of a mild, scalable, bench-stable
preparation of nylon-MOF covalent hybridization is reported.
Previously, only Yu and coworkers reported a method to
covalently attach MOFs to nylon surfaces, but this method
required the use of harsh γ-ray irradiation, and was limited
only to the polymer surface.[15] The synthesis described here
covalently attaches UiO-66-NH2 to a growing PA-66 fiber
(designated as PA-66-UiO-66-NH2) via PSP. The Zr4+-based
UiO-series was selected due to its chemical stability and
previously reported catalytic activity toward CWAs.[3a-c] The
activity of this polymer-MOF hybrid toward CWA simulant
degradation is reported, which are largely not available for
polymer-MOF hybrids, with the vast majority of the literature
reporting only on powdered samples.[3c] The PSP prepared
materials show good activity compared to non-covalent,
nylon-entrapped MOF particles.[3b]
[*]
M. Kalaj, M. S. Denny Jr., K. C. Bentz, J. M. Palomba, Prof. Dr. S. M.
Cohen
Department of Chemistry and Biochemistry,
University of California, San Diego
La Jolla, California, 92093, USA
E-mail: scohen@ucsd.edu
[**]
This work was supported by a grant from the Department of Energy,
Office of Basic Energy Sciences, Division of Materials Science and
Engineering under Award No. DE-FG02-08ER46519 (S.M.C.) for the
synthesis and characterization of the nylon-MOF hybrid materials. We
acknowledge additional support from the Army Research Office,
Department of Army Material command, under Award No. W911NF-16-
2-0106 for evaluation of the catalytic properties of these materials
against CWA simulants. This work was performed in part at the San
Diego Nanotechnology Infrastructure (SDNI) of U.C. San Diego, a
member of the National Nanotechnology Coordinated Infrastructure,
which is supported by the National Science Foundation (Grant ECCS-
1542148). M.K. is supported by the Department of Defense (DoD)
through the National Defense Science and Engineering Graduate
(NDSEG) Fellowship Program.
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/anie.201xxxxxx.
The amine functionalized MOF, UiO-66-NH2, was
covalently incorporated as part of the growing polymer
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chains of PA-66, by pre-treating the MOF with adipoyl
chloride (Scheme 1). PSM prefunctionalization of UiO-66-
NH2 with adipoyl chloride generated reactive acyl chloride
groups on the MOF, which was followed by a PSP reaction
via interfacial polymerization with an aqueous layer
(Figure S10, S16) for up to 36 inches. Some degree of MOF
aggregation is observed by SEM (Figure 1). TGA analysis
showed that the MOF content throughout the fiber was
relatively consistent at ~29 wt% (Figure S19, Table S3).
containing HMDA
.
Scheme 1. PSM and PSP scheme used to prepare PA-66-
UiO-66-NH2
To synthesize the nylon composite, UiO-66-NH2 was
dispersed in ethyl acetate and PSM was performed with ten
equivalents of adipoyl chloride. This forms the acid chloride
UiO-66-int (int = intermediate, Scheme 1). Samples of UiO-
1
66-int were isolated and analyzed by H NMR to determine
the extent of amine functionality. Exposure of UiO-66-NH2 to
adipoyl chloride for 10 min resulted in ~25% functionalization
(Table S1). The 1H NMR spectra suggested the formation of
two different amide linked products, as well as free adipic
acid (from hydrolyzed adipoyl chloride, a byproduct of the
workup, Figure S4). One amide product is the desired
condensation of amino-benzene dicarboxylic acid (NH2-bdc)
Figure 1. ,Top: Interfacial fabrication of PSP. Bottom: SEM
image of PA-66-UiO-66-NH2.
Control studies were performed with three different MOFs
to confirm that covalent linkages between UiO-66-NH2 and PA-
66 was achieved, as opposed to physical entrapment of the
MOF particles within or onto the polymer. The parent UiO-66
material and two UiO-66 derivatives (UiO-66-AM6, UiO-66-
AM6COOH) were investigated to compare with UiO-66-NH2
(Figure 2). Consistent with an inability to covalently integrate
with PA-66, interfacial polymerization with control MOFs
proved to be less robust. For example, with UiO-66 only a ~30
cm continuous fiber could be pulled from the interface under
identical conditions as used with UiO-66-int (generated from
UiO-66-NH2, which gave >100 cm as described above). This is
likely due to the UiO-66 interfering with the polymerization at
the interface (detailed synthesis and characterization of these
control materials can be found in the ESI). Distinct differences
can be seen between the PSP product and noncovalent
hybrids, for example, the noncovalent PA-66@UiO-66
material is extremely thin and brittle compared to the PA-66-
UiO-66-NH2 PSP product (Figure S17).
with adipoyl chloride, while the second product is
a
bis(amide) wherein the adipoyl chloride has linked two NH2-
bdc ligands (Figure S5). The 1H NMR data revealed that
after 10 min of PSM, 25% of the ligands in the MOF were
functionalized with a ~1:1 ratio of the two amide products
(Table S2). To interrogate the possibility of inter- (vs. intra-)
particle cross-linking, dynamic light scattering (DLS)
experiments were performed.
DLS shows essentially
identical particle hydrodynamic radii for UiO-66-NH2 and
UiO-66-int during the PSM reaction, indicating that
intraparticle crosslinking is the predominant source of the
aforementioned bis(amide) product (Figure S9).
After PSM with adipoyl chloride, a suspension of UiO-66-
int in EtOAc (containing ten equivalents of adipoyl chloride)
was carefully layered on top of an aqueous solution of
HMDA. Polymerization occurs at the interface of the two
layers, during which UiO-66-int is covalently incorporated
into the forming polyamide, resulting in the desired PA-66-
UiO-66-NH2 hybrid material (Figure 1). The resulting PSP
product retains the flexibility of the PA-66 fiber after
incorporation of MOF (Video S1). The presence of the MOF
throughout the length of the fiber was confirmed by powder
X-ray diffraction (PXRD) patterns and scanning electron
microscopy (SEM) images. Pieces of the composite material
were cut every ~12 inches and analyzed by PXRD and SEM,
which showed evidence of MOF particles throughout the fiber
Figure 2. Four different MOFs used for PSP in nylon
composites.
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Thermogravimetric and differential scanning calorimetry
(TGA/DSC) analysis of the PSP product (PA-66-UiO-66-
NH2), as well as all three control materials (PA-66@UiO-66,
PA-66@UiO-66-AM6COOH, and PA-66@UiO-66-AM6),
were conducted in an effort to determine the extent of MOF
incorporation into the polymer as well as the melting point of
the materials. TGA data indicates 29% by weight of MOF
incorporation for the PSP product (PA-66-UiO-66-NH2)
compared to 20% incorporation for PA-66@UiO-66, 27%
incorporation for PA-66@UiO-66-AM6COOH, and 23%
incorporation for PA-66@UiO-66-AM6 (Table S3).
Pore accessibility of the hybrid materials was determined
by measuring the BET surface area of the composites.
Surface area analysis by N2 gas sorption measurements
show that the porosity of the MOFs is better retained in the
covalent PSP hybrid material relative to the non-covalent
materials. BET surface area measurements were performed
on all free MOF powders (Figure S31). Based on the percent
MOF content in the composite materials, the expected BET
surface area of the composites was calculated. If the MOF
component is completely accessible the BET surface areas
are calculated to be ~290 m2/g and ~220 m2/g, for PA-66-
UiO-66-NH2 (29 wt%) and PA-66@UiO-66 (20 wt%),
respectively. However, the measured surface areas were
found to be 107±2 m2/g and 35±1 m2/g for the PA-66-UiO-
66-NH2 and PA-66@UiO-66, respectively (Figure S32).
Whereas pore accessibility is decreased for both samples
compared to the free MOF particles, the BET surface area
shows that pore accessibility is better retained in the PSP
product (37%) compared to the non-covalent product (16%,
Table S4).
Covalent crosslinking of the polyamides in PA-66-UiO-
66-NH2 is supported by DSC melting point data (Table 1).
Specifically, samples were heated to 280 °C at 10 °C/min,
then cooled to 100 °C at 10 °C/min, and finally heated to 600
°C at 10 °C/min to determine the thermal characteristics of
the composite materials.
The initial heating step is
performed to clear the thermal history of the material
whereas the second heating step is used to determine the
accurate melting point of the material. Melt curves were
integrated and assessed by the onset and peak of the curve
(ESI). Pure PA-66 has an experimental second melt point
onset of 237 °C and melt peak of 252 °C. The PA-66@UiO-
66 material shows a very similar second melt suggesting that
the PA-66 and UiO-66 are phase segregated after the first
melt leading to a nearly pure nylon-like second melt (Table
1). PA-66@UiO-66-AM6COOH shows a second melting
point depression of ~5 °C at the onset and ~5 °C at the peak,
relative to PA-66. PA-66@UiO-66-AM6 has a second
melting point depression of ~5 °C at the onset and ~4 °C at
the peak. In contrast, the same melt with PA-66-UiO-66-NH2
results in a depression of the melting point by ~20 °C at the
onset and ~12 °C at the peak, when compared to pure PA-
66. This large melting point depression suggests the
covalent attachment of MOF as part of the nylon fibers, which
significantly disrupts the ability for polymer crystallization.
These results are consistent with other findings where
covalent attachment of large inorganic particles disrupt
polymer crystallinity and results in reduced melt
temperature.[16]
Covalent attachment of MOFs into processable polymer
materials is critical for the utilization of MOFs in real-world
applications. To assess the applicability of the materials as
functional textiles, the PA-66-MOF hybrid materials were
screened for catalytic activity against the nerve agent
simulant, dimethyl 4-nitrophenyl phosphate (DMNP) (Figure
3). DMNP has been employed as a safer alternative to study
the hydrolysis of phosphoester linkages that are present in
nerve agents, although the authors note that this is still a
high-hazard species and should be handled with extreme
care. A high-throughput screening (HTS) approach using
UV-visible spectroscopy was used to detect degradation of
the DMNP simulant,[3b, 17] at pH = 8 using UiO-66, UiO-66-
NH2, UiO-66-AM6, and UiO-66-AM6COOH, as both nylon
composites and powders. As shown in Figure 3, UiO-66 and
UiO-66-AM6 powders are approximately three times more
active than the UiO-66-NH2 and UiO-66-AM6COOH MOFs,
which is consistent with literature reports.[17] Incorporation of
the various functionalized MOFs into PA-66 composites had
a dramatic effect on the catalytic degradation of DMNP. The
covalently attached hybrid material, PA-66-UiO-66-NH2, was
nearly an order of magnitude more active than any of the
non-covalent incorporated PA-66 composites. Composite
materials were recycled and reused, displaying no loss in
catalytic activity toward DMNP degradation after four
catalytic cycles (Figure S30). These results, along with the
gas sorption analysis, demonstrate that the MOF particles in
the PA-66-UiO-66-NH2 composite are more accessible and
active than in the nylon-entrapped materials (i.e., PA-
66@UiO-66, PA-66@UiO-66-AM6COOH, and PA-66@UiO-
66-AM6).
Table 1. Second melting point of PA-66 and PA-66-MOF
hybrid materials highlighting the melting point depression of
PA-66-UiO-66-NH2.
2nd MP Onset
2nd MP peak
Material
(°C)
(°C)
PA-66
236 ± 2
238 ± 3
231 ± 1
232 ± 1
216 ± 5
252 ± 1
252 ± 2
248 ± 1
247 ± 1
240 ± 2
PA-66@UiO-66
PA-66@UiO-66-AM6
PA-66@UiO-66-AM6COOH
PA-66-UiO-66-NH2
Several MOF materials in powder form have been
screened for CWA catalysis, there are only a few examples
in the literature of CWA screening via polymer-MOF hybrid
materials.[4] Recent studies by Parsons et al. have utilized
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atomic layer deposition (ALD) by coating polymer fibers with
an intermediate metal oxide layer that provides a nucleation
site for MOF synthesis.[4] DMNP hydrolysis (pH = 10) using
the ALD generated materials indicated decreased
performance compared to the pure MOF powders.[4a] When
comparing fibers with different ALD coatings, increased
activity was observed when using ALD films that promoted a
higher quality of MOF crystal growth.[4a] Expectedly, their
studies showed the MOF was required for catalytic activity
when compared to the polymer alone.[4b] The ALD composite
materials displayed a loss of activity after the materials were
recycled only two times, whereas PA-66-UiO-66-NH2
showed retention of activity through at least four catalytic
materials. This is a rare example of examining CWA
degradation in a polymer-MOF hybrid material that is closer
to a usable form factor. Current experiments are focusing on
engineering of this material for potential textile incorporation.
Keywords: metal-organic framework • MOF-polymer hybrid
material • chemical warfare agent
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Figure 3. Top: DMNP degradation reaction. Bottom: Rate
of catalytic degradation of DMNP by MOF powders of PA-66-
MOF composites measured by UV-visible adsorption at
407nm.
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components, after which PSP was used to generate PA-66-
MOF hybrid materials. 1H NMR studies on small molecule
models, melting point measurements through DSC, and
surface area determination, were all indicative of a covalent
link between the MOF particles and the nylon fibers. The
covalently linked hybrid material showed significantly higher
activity against CWA simulant degradation compared to
MOF particles that were simply physically entrapped in the
polymer. This result underscores the benefits of PSP over
physical adhesion or entrapment of MOFs to polymer
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COMMUNICATION
Mark Kalaj, Michael S. Denny Jr., Kyle
C. Bentz, Joseph M. Palomba, and Seth
M. Cohen*
Page xx. – Page xx.
Nylon-MOF
Composites
via
Postsynthetic Polymerization
We report hybridization of metal-organic frameworks (MOFs) and nylon polymers into composites via postsynthetic polymerization.
This simple, scalable, bench-top approach provides a new method to design hybrid materials containing MOFs and polymers while
maintaining the desired properties of both materials.
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