Handles for controlled architecture and functionality in single-chain nanoparticles: Cross-linking by intra-chain ATRP EB.2.

12

Elizabeth R. Bright, Claudia Willis, Courtney Leo, Nathan Shipley, Christopher James LaSalle, Ashley Hanlon, and Erik B. Berda.
Department of Chemistry, University of New Hampshire.
EB.2.18

Introduction Tracking Intra-chain ATRP and Coupling Limiting Disproportionation

With the goal of creating functionalized single-chain Because of the wide variety of monomers compatible with copper-mediated A. CuBr/TPMA
Cu(0)
x\y

nanoparticles (SCNP) with tunable nanoenvironments, we polymerizations, the design imparts handles with which to control both architecture and
x\y
O OO O 55 °C O OO O
50:50 MeCN:THF

investigated the intra-chain ATRP of pendant functionality in SCNP. Figure 2 shows SEC-MALS traces for the parent chain P1 and O O O O

bromopriopionate-decorated poly(methyl methacrylates). corresponding SCNP, NP1. The molecular weight as determined by MALS increased after
Br

Parent polymer P1 was synthesized using RAFT. The polymerization, and the shift to a longer retention time is consistent with the successful
pendant bromopropionate groups were used to initiate intra- formation of SCNP through ATRC between the pendant alkyl bromide units. As a control, B. CuBr/PMDETA

chain polymerization under conditions favoring termination by the procedure was repeated using MMA as a monomer, removing the polymer’s ability to 5.9 5.8 5.7 5.6 5.5 5.4
O
5.3
OO
x\y
5.2
O
Cu(0)

5.1 80 °C
5.0 4.9 O 4.8
OO
x\y
O4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9
f1 (ppm)

coupling. MMA and initiator-functionalized monomers, M1, participate in ATRC. The expected increase in molecular weight was this time
disproportionation toluene

O O O O

were used to prepare brush (P2) and SCNP (NP1) examples. accompanied by a shift to a shorter retention time, which is consistent with the formation of Br

the anticipated brush polymer.

5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9
parent polymer ppm

MW = 37.0 kDa Figure 4: Careful catalyst selection limits the competition from
disproportionation, favoring bimolecular termination.

Because our design relies on bimolecular coupling

(ATRC) to form SCNP, it is important to limit competition
grafted oligomers single-chain nanoparticles from disproportionation. To do so, we relied on the rich
MW = 54.1 kDa MW = 50.3 kDa body of ATRP literature to select appropriate catalysts
and reaction conditions. Figure 4 compares the 1H NMR
x\y x\y
spectrum of the product obtained using a PMDETA/CuBr
Scheme 1: Strategic route to brush P2 and nanoparticle NP1. O OO O O OO O solution in toluene (4B) with that obtained using
O O
TPMA/CuBr in acetonitrile and THF (4A). Vinyl
O O

Formation of SCNP by ATRC P2 resonances from disproportionation products appear

O
exclusively in 4B. This result informed our choice of
O

O O
O
reaction conditions throughout this work.
O
A. ATRC
x\y x\y
O OO O
CuBr/TPMA
Cu(0)
O OO O
NP1
Summary and Conclusions
c b
d 55 °C Figure 2: SEC overlay of P1 (parent polymer), P2 (brush), and NP1.
O O 50:50 MeCN:THF
O O
We found that poly(methyl methacrylates) decorated
Br a a' with pendant bromopriopionate units can be converted to
e'
e
d 2
32 mol% M1 SCNP using a facile intra-chain polymerization process.
B. H NMR
1
x\y 100% bromides intact Our early findings suggest that the coupling of a small
O OO O
2
d 2
d
c
O
b
O
2 + 4 eq. proportion of the chains drives SCNP formation while the
2
Br
a
a b c majority of pendant ends remain active. This speaks to
P1
0.16 0.32 0.31 1
the possibility of building more complex systems through
x\y
further functionalization or chain extension. We are
SCNP
b c
e'
O OO O

1
currently working to exploring this potential with the hope
of creating a framework conductive to the modular
1
a' O O

1 M1

1
O
O
addition of application-specific functionalities to a
NP1
O
O controlled SCNP environment.
1 5.1 5.0 4.9 4.8
0.64
4.7 4.6 4.5
3.08
4.4 4.3
ppm
4.2 4.1
1
4.0 3.9 3.8 3.7 3.6 3.5 70% mol% M1
Parent Polymer e 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5
85% bromides intact
b c
a
Figure 3: H15.1
NMR overlay
5.0 4.9 4.8 of
4.7P14.6
and4.5NP1
4.4 showing
4.3 4.2
ppm

the
4.1 incorporation
4.0 3.9 3.8 of
3.7additional
functional monomer, highlighting the
3.6 3.5
Acknowledgements
ppm
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 region featuring methacrylolyl and alkyl bromide signals of interest.
ppm The author would like to thank the Army
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 Research Office for support through award
ppm The incorporation of functional monomer was tracked using 1H NMR experiments (Fig. 3). W911NF-14-1-0177 as well as Dr. Erik
C.
After intra-chain polymerization, the integration of the pendant ethylene signals increased Berda, Dr. John Tsavalas, and Dr. Gary
relative to those of the backbone methacryloyl moieties. An average conversion of 50% Weisman for sharing their time and
expertise.
was achieved over a 24 h reaction time. We determined that approximately 85% of the
bromide units remained unreacted by comparing the integration of signal a with those of b
and c. This finding indicates that a relatively small number number of cross-links were References
formed. As such, it may be possible to further react NP1 through these “live” pendants to
 1. Hanlon, A.M.; Chen, R.; Rodriguez, K.J.; Willis, C.; Dickinson, J.G.; Cashman, M.;
Figure 1: 1H NMR (1B) and GPC (1C) evidence of intramolecular atom transfer extend the chains, promote further collapse by intramolecular cross-linking, or introduce Berda, E.B., "Scalable Synthesis of Single-Chain Nanoparticles under Mild Conditions“.
radical coupling to form SCNP (1A).1
application-targeted functionalities. Macromolecules 2017.