Macro Chemistry Physics - 2015 - Blackburn - Synthesis of Cyclic Poly Methyl Methacrylate Directly From Dihalogenated

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Chemistry and Physics Full Paper
Synthesis of Cyclic Poly(methyl methacrylate)

Directly from Dihalogenated Linear Precursors
Scott C. Blackburn, Eric S. Tillman*
Cyclic poly(methyl methacrylate) (PMMA) is prepared by intramolecular radical trap-assisted

atom transfer radical coupling (RTA-ATRC) of dihalogenated PMMA precursors. The inclusion
of the radical trap nitrosobenzene (NBz) in the coupling sequence affords high yields of cyclic
polymers, as observed by gel permeation chromatography and confirmed by 1H NMR and
electrospray ionization mass spectra, which show the presence of the aromatic group from
the NBz incorporated into the cycle. Analogous coupling reactions in the absence of the rad-
ical trap do not lead to appreciable cyclization or even intermolecular elongation, consistent
with chain-end sterics preventing radical–radical coupling as the predominant termination
pathway. Thermolysis of the cyclic PMMA, possible because of the labile C O bond in the
alkoxyamine linkage contained in the macrocycle, causes a
reversion back to the linear form and is consistent with the
role of the radical trap in the coupling sequence. Differential
scanning calorimetry is also used to compare cyclic PMMA
with its linear analog, with a marked increase in glass transi-
tion temperatures found after cyclization.
1. Introduction modification, resulting in cycles in high yields.[15,16] The

inclusion of a radical trap in the cyclization reaction alters
Cyclic polymers have attracted renewed interest in the coupling reaction to a stepwise sequence,[17,18] essen-
the polymer community in recent years, at least par- tially allowing under less-extreme redox conditions by
tially due to controlled radical polymerization methods removing the bimolecular radical–radical reaction step in
allowing for easier synthetic routes. Atom transfer the ATRC method. The mechanistic steps and rate equa-
radical polymerization (ATRP) can be performed with tions of ATRC and the so-called radical trap assisted (RTA)
alkyne-containing initiators, and after displacement ATRC, as applied to macrocyclic synthesis, are summarized
of the chain-end bromide with an azide, an intramo- in Scheme 1.
lecular copper-catalyzed azide–alkyne cycloaddition PMMA radicals undergo disproportionation as their
(CuAAC) “click” reaction produces cycles in high yields.[1–8] primary termination pathway,[19–22] effectively prohib-
This method has been applied to the synthesis of mac- iting their use in ATRC despite their relatively high sta-
rocyclic polystyrene (PS)[9–11] and poly(methyl meth- bility and therefore the ability to be formed in concen-
acrylate) (PMMA).[12–14] In the case of preparing cyclic trations conducive to bimolecular reactions (Scheme 2).
PS, dibrominated precursors prepared by ATRP can Their chain-end sterics make them selective participants
be directly employed in intramolecular atom transfer even in radical trap-assisted atom transfer radical cou-
radical coupling (ATRC) reactions with no chain-end pling (RTA-ATRC) reactions, with the common radical trap
2-methyl-2-nitrosopropane (MNP) simply end-capping
S. C. Blackburn, Prof. E. S. Tillman the PMMA chains as opposed to coupling them in a step-
Department of Chemistry wise sequence.[23] Nitrosobenzene (NBz) as the radical
Bucknell University trap, however, leads to near quantitative dimerization of
Lewisburg, PA 17837, USA monobrominated PMMA chains in RTA-ATRC reactions,
E-mail: etillman@bucknell.edu which yields dimers with a mid-chain alkoxyamine,[23]
Macromol. Chem. Phys. 2015, 216, 1282−1290

1282 © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com DOI: 10.1002/macp.201500082
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Macromolecular
Synthesis of Cyclic Poly(methyl methacrylate) Directly from Dihalogenated Linear Precursors Chemistry and Physics
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Scheme 1. Mechanistic and kinetic comparison of intramolecular ATRC and RTA-ATRC, leading to macrocyclic polymers from dihalogenated
precursors.
implying that cyclic PMMA could be

prepared directly from dihalogenated
linear precursors.
2. Results and Discussion
As summarized in Scheme 3, reaction 1,

difunctionalized PMMA precursors were
prepared by ATRP, affording either dibro-
minated or dichlorinated PMMA chains
based on the reaction conditions.[24–26]
These linear precursors were then
Scheme 2. Fate of PMMA radicals in bimolecular termination reactions, with dispropor- employed in RTA-ATRC reactions with
tionation (top) heavily favored. NBz as the radical trap, carried out under

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Macromolecular
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Scheme 3. Preparation of dihalogenated linear PMMA precursors by 1) ATRP, 2) ring closure by pseudo-high dilute RTA-ATRC, and 3) ther-
molysis of alkoxyamine.
pseudo-high dilute conditions to favor intramolecular cou- precursor. In addition to higher molecular weight, step-
pling (Scheme 3, reaction 2). type product as a consequence of intermolecular cou-
To verify the necessity of the radical trap in the cycli- pling, a shift of the peak molecular weight (Mp) to longer
zation reaction, identical pseudo-high dilute coupling elution times indicated cyclic polymer was formed. This
reactions were performed both in the presence and in supports prior research showing that the linear PMMA
the absence of the radical trap NBz, with gel permeation chains could only be coupled in an RTA-ATRC sequence.[23]
chromatography (GPC) traces of the linear precursors and Further intramolecular RTA-ATRC reactions were car-
coupling products shown in Figure 1. In the absence of a ried out, with Table 1 listing the characteristics of the
radical trap, the product after the attempted intramolec- dihalogenated precursors as well as the results of the
ular ATRC reaction showed only minor molecular weight attempted cyclizations. Lower molecular weight pre-
adjustments, and no evidence of cyclization (Figure 1a). cursor chains (Mn = 5000 Da or less) were purposely tar-
When the coupling reaction was repeated but in the pres- geted to allow for ring closure, and polymerizations
ence of 5 eq. of NBz, substantial changes were observed were allowed to proceed to no more than 50% monomer
in the RTA-ATRC product compared with the linear conversion to ensure chain-end fidelity. The isolated
Figure 1. Role of the radical trap in intramolecular cyclization reactions. a) GPC trace of linear Cl-PMMA-Cl precursor (orange) and attempted
intramolecular ATRC (black; Scheme 1, top). Cl-PMMA-Cl: Mn = 4450; Mp = 5850, –D = 1.22. ATRC product: Mn = 5000, Mp = 5850, –D = 1.23.
b) GPC of linear Cl-PMMA-Cl precursor (orange) and product after pseudo-high dilute RTA-ATRC reaction with the inclusion of NBz radical
trap (black; Scheme 1, bottom). Cl-PMMA-Cl: Mn = 5000, Mp = 6500, –D = 1.17. RTA-ATRC product: Mn = 5250; Mp = 5450; –D = 1.68; <G> = 0.83.
Percent cyclic = 62% (Table 1, Trial 17).

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Table 1. Results of X-PMMA-X precursors RTA-ATRC under high dilution and pseudo-high dilution.
Br-PMMA-Br precursora) RTA-ATRC productsb)

Addition rate Percent
Trial Mnc) Mpc) Ðc) Mnc) Mpc) Ðc) [μmol h−1] cyclic [%] <G>d) Cyclic Ðe)
1 3400 3350 1.19 2900 2750 1.58 1.10 73 0.82 1.16
2 3750 3900 1.13 3400 3150 1.50 1.28 72 0.81 1.15
3 2850 2900 1.13 2700 2350 1.47 1.79 71 0.80 1.12
4 4250 4550 1.17 3800 3550 1.55 2.96 62 0.78 1.15
5 3800 4100 1.18 3500 3300 1.57 3.18 61 0.81 1.14
6 3000 3200 1.15 2900 2700 1.83 5.71 58 0.84 1.14
7 3100 3250 1.13 2600 2700 1.96 One pot / 21.88f) 57 0.84 1.17
Cl-PMMA-Cl precursorg) RTA-ATRC productsb)
8 4550 5900 1.18 4200 4900 1.66 0.41 73 0.83 1.13
9 4500 5850 1.17 4000 4700 1.70 0.79 72 0.80 1.13
10 1700 1850 1.18 1400 1550 1.58 1.19 72 0.85 1.07
11 4250 5150 1.14 3850 4150 1.79 1.72 72 0.81 1.09
12 1650 2250 1.19 1900 1900 1.59 1.92 70 0.83 1.10
13 4500 5650 1.18 4000 4550 1.82 1.98 69 0.81 1.15
14 5000 6550 1.18 5200 5600 1.71 2.39 66 0.85 1.10
15 2800 3300 1.15 2500 2750 1.55 2.57 66 0.83 1.15
16 4700 5500 1.15 4200 4300 1.95 2.87 63 0.78 1.11
17 5000 6550 1.17 5250 5450 1.68 3.01 62 0.83 1.11
18 4550 5850 1.18 4600 4900 1.66 4.58 61 0.84 1.13
f) 59 0.83 1.18
19 5000 6550 1.17 4100 5450 1.66 One pot / 13.08
a)Initial
equivalents 200:1:2:2 [MMA]:[Eb2biB]:[CuBr2]:[PMDETA] were used for ATRP reaction leading to Br-PMMA-Br; b)Initial equiva-
lents of 1:20:20:40:5 [X-PMMA-X]:[CuX]:[Cu0]:[PMDETA]:[Nbz] were used for all RTA-ATRC reactions, where CuX = CuBr for Br-PMMA-Br
precursors and CuX = CuCl for Cl-PMMA-Cl precursors; c)Mn, Mp, and dispersity (Ð) values were obtained from RI-GPC traces based on
linear PS standards; d)Calculated <G> from exact RI-GPC Mp values of linear to RTA-ATRC product; e)Dispersity index of isolated cyclic
product from RTA-ATRC reaction. Thermolysis was performed on all isolated cyclic products, and conversion back to Mn value of pre-
cursor was observed; f)One-pot reaction; no addition dropwise. Concentration in μmol corresponds to [X-PMMA-X]i gInitial equivalents
200:1:1:2:3 [MMA]:[Eb2biB]:[CuCl]:[CuCl2]:[PMDETA] were used for ATRP reactions leading to Cl-PMMA-Cl.
PMMA precursors were added dropwise as tetrahydro- comparison of typical results for the RTA-ATRC sequence
furan (THF) solutions via a gastight syringe into a redox- of both brominated and chlorinated PMMA precursors
active solution containing ligand-bound N,N,N′,N′,N″- can be seen in Figure 2a,b, which shows the RI-GPC traces
pentamethyldiethylene triamine (PMDETA), catalyst, of the precursors as well as the RTA-ATRC product.
the radical trap NBz, and a reducing agent (see the The shift of the Mp to longer elution volumes (as seen
Supporting Information for complete details). Both in Figure 1b and Figure 2) and lower apparent molecular
Br-PMMA-Br (trials 1–7) and Cl-PMMA-Cl (trials 8–19) weight values compared with a linear precursor is indica-
precursors were active in the RTA-ATRC reaction, showing tive of cyclization, while the presence of higher molecular
both intra- and intermolecular coupled product, indi- weight product is explained by intermolecular coupling.
cating that PMMA radicals could be formed in ample The <G> values, defined as the ratio of the Mp values of
amounts to participate in the RTA-ATRC sequence even the cyclic to linear species, are in line with the reported
in the case of the increased C Cl bond strength. This values of PMMA and other macrocyclic vinyl polymers
is not surprising, given the stability of the PMMA rad- prepared by the ring-closure methods.[27]
ical and the mechanistic sequence of RTA-ATRC only Yields of cyclic product were dependent on the rate
relying on the first-order reaction steps with respect of addition of the X-PMMA-X precursors into the redox-
to the concentration of the chain-end radical. A visual active RTA-ATRC reaction flask, with slower rates leading

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Figure 2. Effect of halogen chain ends on intramolecular RTA-ATRC reactions. a) GPC trace of linear Br-PMMA-Br precursor (orange), product
from RTA-ATRC coupling reaction (black), isolated cyclic product (blue), and thermolyzed product of purified cycle (red). Addition of pre-
cursor at 1.10 μmol h−1 addition rate into the RTA-ATRC reaction flask (Table 1, Trial 1). (Linear precursor Br-PMMA-Br: Mn = 3400, Mp = 3350,
–D = 1.19; RTA-ATRC cyclic product: Mn = 2900, Mp = 2750, –D = 1.58, <G> = 0.82, Percent cyclic = 73%; isolated cyclic product: Mn = 3000, Mp = 2800,
–D = 1.07; Thermolysis product: Mn = 3100, Mp = 3250, –D = 1.09. b) GPC trace of linear Cl-PMMA-Cl precursor (orange), product from RTA-ATRC
coupling reaction (black), isolated cyclic product (blue), and thermolyzed product of purified cycle (red). Addition of precursor at 1.72 μmol h−1
addition rate into the RTA-ATRC reaction flask (Table 1, Trial 11). Linear precursor Cl-PMMA-Cl: Mn = 4250, Mp = 5150, –D = 1.14; RTA-ATRC cyclic
product: Mn = 3850, Mp = 4150, –D = 1.79, <G> = 0.81, Percent cyclic = 72%; Cyclic only product: Mn = 3700, Mp = 4000, –D = 1.09; Thermolyzed
product: Mn = 4500, Mp = 5200, –D = 1.12.
to higher percentages of macrocycles (Table 1, Addition The electrospray ionization mass spectra (ESI-MS) of the
rate column). This trend was true for both the brominated isolated macrocyclic PMMA along with that of the linear
and chlorinated precursors, and is consistent with greater precursor are shown in Figure 3. The calculated weight
dilution favoring intra- versus intermolecular coupling values of the main series of both the linear and cyclic
reactions. Catalyst, copper reducing agent, ligand, and polymers match the calculated weight values within
radical trap (NBz) were held at 20:20:40:5 eq., respectively, 1 Da, when adjusted for the presence of an ammonium ion
in a ratio with functionalized polymer precursor. When complexed with the polymeric species.[3,4] For example,
the RTA-ATRC reaction was attempted by the addition of the experimentally found values were 1678.65 Da
all components (including X-PMMA-X precursors) into a (13 monomer units) and 1625.85 Da (13 monomer units)
single pot, cyclic yields were lowered than pseudo-high for the linear precursor and cyclic analog, respectively,
dilute trials even at the fastest addition rates (Table 1, compared with the calculated values of 1678.60 Da and
trials 7 and 19). This is not surprising, as intermolecular 1625.90 Da. The mass spectrum of the PMMA macrocycle
coupling becomes more competitive as the concentration verifies that the alkoxyamine is indeed incorporated
of the polymer chain ends increase. into the polymer, consistent with thermolysis results
The RTA-ATRC sequence is expected to lead to cyclic (Figure 2) and the mechanistic steps of RTA-ATRC.
polymer with a cleavable alkoxyamine linkage embedded In addition to cleavage, 1H NMR spectra of the cyclic
in the product (Scheme 3, reaction 2). Thermolysis of this product compared to linear precursor were obtained in
C O bond will transform the macrocycle back into a order to confirm the inclusion of the radical trap. The
linear form, which should be apparent as a shift in GPC cyclic product shows aromatic signals due to the inclusion
elution time of the cleaved product (Scheme 3, reaction of the NBz, while the linear analog lacked any signals in
3). As can be seen in Figure 2a, when the isolated macro- this region as expected (Figure 4).
cycle (blue trace) was heated to 130 °C, the thermolysis A well-known difference between cyclic polymers and
product (red trace) was seen to revert back to shorter linear polymers from which they are derived is their glass
elution times matching the linear precursor. Identical transition temperature (Tg) with the constrained architec-
results were found for the chlorinated PMMA system ture of cyclic polymers restricting long-range segmental
(Figure 2b, blue trace vs. red trace). The cyclic portion of motions and leading to an increased Tg value.[28] Figure 5
the RTA-ATRC products was easily separated from the shows differential scanning calorimetry (DSC) curves for a
higher molecular weight material by column fractiona- paired linear and cyclic PMMA. Care was taken to keep the
tion or fractional precipitation (Figure 2, blue trace shows cycling temperature below 124 °C; above which resulted
isolated cycle). in cleavage of the cycle due to the labile C O bond in the

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Figure 3. Electrospray ionization mass spectra of a) linear dibrominated PMMA precursor (–D = 1.13), and b) cyclic isolated PMMA polymer
prepared by intramolecular RTA-ATRC where in structure I = Eb2biB (Table 1, Trial 3). <G> 0.80, –D = 1.12; Mobile phase = THF:ACN 50:50. Cal-
culated values for inset peaks of spectrum a): 1578.48 Da, 1678.60 Da, 1778.72 Da. Calculated values for inset peaks of spectrum b): 1525.78
Da, 1625.90 Da, 1726.02 Da.
alkoxyamine. The cyclic PMMA (b) showed a Tg near 95 °C, containing the radical trap NBz. In the absence of the
with its linear analog (a) showing a Tg of approximately radical trap, no cyclization was observed. The incorpora-
41 °C. Note that the molecular weight of the linear PMMA tion of NBz into the cyclic architecture was confirmed by
was only 1700 Da, and therefore its Tg was significantly thermolysis of the alkoxyamine bond, while ESI-MS and
less than that of higher molecular PMMA.[29] 1
H NMR spectra also verified the incorporation of NBz into
the cyclic PMMA. DSC showed a dramatic increase in the
Tg value of the isolated cyclic product compared with the
3. Conclusion linear analog from which it was derived. Like other chain-
end closing methods, intramolecular RTA-ATRC is sensi-
In summary, cyclic PMMA was prepared directly from tive to the linear precursor chain length, the dilution of
linear dihalogenated precursors in an intramolecular the ring-closing reaction, and, like CuAAC click reactions,
RTA-ATRC cyclization reaction. Cyclic product up to 73% requires a metal–ligand catalyst. A benefit of producing
was obtained when either dibrominated or dichlorinated cyclic polymers by RTA-ATRC is the direct employment of
PMMA chains were added into a redox-active solution dihalogentated linear chains easily accessible by the ATRP
reactions. The use of the radical trap NBz in this work
expands the scope of polymeric chain-end structures, to
include methacrylates, that can undergo ring closure by
RTA-ATRC.
4. Experimental Section
4.1. Materials
Copper(I) bromide, (CuBr, 98%; Aldrich), copper(I) chloride (CuCl,
99.995+%; Aldrich), copper (II) bromide (CuBr2, 99%; Aldrich),
copper (II) chloride (CuCl2, 97%; Aldrich), and copper nanopo-
wder (Cu0, 99.8%; Acros) were stored in airtight desiccators until
Figure 4. 400 MHz 1H NMR spectra of the aromatic region of a)
use. Methyl methacrylate (MMA, 99%; Aldrich), ethylene bis(2-
isolated cyclic PMMA product and b) linear precursor (Table 1,
trial 15) obtained in acetone-d6. Peaks observed in spectrum (a) bromoisobutyrate) (Eb2biB, 97%; Aldrich), α,α-dibromotoluene
between 7.0 and 7.4 ppm are attributed to the aromatic group of (DBT, 97%; Aldrich, PMDETA, 99%; Aldrich), and tris(2-dimeth-
the nitrosobenzene radical trap. No signal (b) is observed for the ylaminoethyl)amine (Me6Tren, 99+%; Alfa Aesar,) were used as
linear precursor of PMMA in the aromatic region. received and stored at 5 °C. 2-Methyl-2-nitrosopropane dimer

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Figure 5. DSC diagrams of second heat cycle of heat/cool/heat sequence for: a) linear Cl-PMMA-Cl precursor, and b) isolated cyclic PMMA
product formed by intramolecular RTA-ATRC. Linear precursor Cl-PMMA-Cl: Mn = 1700, Mp = 1850, –D = 1.18. Cyclic isolated product: Mn = 1400,
Mp = 1550, RTA-ATRC –D = 1.58, Cyclic –D = 1.07, <G> = 0.85, percent cyclic = 72% (Table 1, Trial 10).
(MNP, 98%; Aldrich) and nitrosobenzene (NBz, ≥97%; Aldrich) and the solution was stirred for 0.22 h. The reaction was termi-
were used as received and stored at −20 °C. Dry THF was collected nated by submersing the flask in an ice bath and exposure to
from an Innovative Technology PureSolv solvent purification atmosphere. Copper was removed from the solution by column
system. chromatography and the resulting solution was concentrated
before precipitation. The resulting THF solution was precipitated
with hexanes in a centrifuge tube to form a white powder. The
resulting precipitant and solute were centrifuged and the precip-
4.2. Synthesis of Br-PMMA-Br Precursors by ATRP
itant was retained. The product was dried under vacuum for 2 h.
(CuBr2 System)
Mn = 4400, Mp = 5850, Ð = 1.31.
To a flame-dried 100 mL two-neck round-bottom Schlenk flask,
MMA (2.00 mL, 18.8 mmol), Eb-2biB (33.8 μL, 0.094 mmol), CuBr2
(41.9 mg, 0.187 mmol), 4.00 mL THF, and a dried magnetic stir bar 4.4. Synthesis of Cl-PMMA-Cl Precursors by ATRP (CuCl,
were added. The flask was then subjected to three freeze–pump–
CuCl2 System)
thaw cycles before placed in an oil bath at 71.0 °C. After 2 min
equilibration time, PMDETA (39.2 μL, 0.187 mmol) was added to To a flame-dried 100 mL two-neck round-bottom Schlenk flask,
the Schlenk flask via an argon-flushed gastight syringe to ini- MMA (6.00 mL, 56.3 mmol), Eb-2biB (101.4 μL, 0.282 mmol), CuCl
tiate the reaction and the solution was stirred for 1.5 h. The reac- (27.9 mg, 0.282 mmol), CuCl2 (75.7 mg, 0.563 mmol), 10.0 mL THF,
tion (CuBr2 catalyst only) underwent an AGET mechanistic-type and a dried magnetic stir bar were added. The flask was then sub-
addition reaction before ATRP could occur[1,2] and after was ter- jected to three freeze–pump–thaw cycles before placed in an oil
minated by submersing the flask in an ice bath and exposure to bath at 80.0 °C. After 2 min equilibration time, PMDETA (176 μL,
atmosphere. Copper was removed from the solution by column 0.845 mmol) was added to the Schlenk flask via an argon-flushed
chromatography and the resulting solution was concentrated gastight syringe to initiate the reaction and the solution was
before precipitation. The resulting THF solution was precipitated stirred for 0.42 h. The reaction was terminated by submersing
with hexanes in a centrifuge tube to form a white powder. The the flask in an ice bath and exposure to atmosphere. Copper was
resulting precipitant and solute were centrifuged and precipi- removed from the solution by column chromatography and the
tant was retained. The product was dried under vacuum for 2 h resulting solution was concentrated before precipitation. The
(Mn = 3400, Mp = 3350, Ð = 1.19). resulting THF solution was precipitated with hexanes in a centri-
fuge tube to form a white powder. The resulting precipitant and
solute were centrifuged and the precipitant was retained. The
4.3. Synthesis of Br-PMMA-Br Precursors by ATRP product was dried under vacuum for 2 h (Mn = 4250, Mp = 5150,
(CuBr, CuBr2 System) Ð = 1.14).
To a flame-dried 100 mL two-neck round-bottom Schlenk flask,
MMA (2.00 mL, 56.3 mmol), Eb-2biB (33.8 μL, 0.094 mmol), CuBr
(13.5 mg, 0.094 mmol), CuBr2 (41.9 mg, 0.188 mmol), 4.00 mL 4.5. Dropwise Syringe Addition Synthesis of Cyclic
THF and a dried magnetic stir bar were added. The flask was PMMA by Intramolecular RTA-ATRC from
then subjected to three freeze–pump–thaw cycles before being
ATRP-Brominated Precursors
placed in an oil bath at 80 °C. After 2 min equilibration time,
PMDETA (58.8 μL, 0.282 mmol) was added to the Schlenk flask To a flame-dried 100 mL two-neck round-bottom Schlenk
via an argon-flushed gastight syringe to initiate the reaction flask, the difunctional ATRP-synthesized polymer Br-PMMA-Br

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(Mn = 3400, Mp = 3350, Ð = 1.19, 71.3 mg, 0.021 mmol), NBz (11.1 flask and syringe, and the reaction flask was placed in a 60 °C
mg, 0.103 mmol), and 50.0 mL THF were added. The flask was fit oil bath to equilibrate. The syringe was equipped on the Cole
with a rubber septa and subjected to three freeze–pump–thaw Parmer single-syringe infusion pump at 6 mL h−1 (1.72 μmol h−1)
cycles via a Schlenk line. The polymer and Nbz solution-containing controlled addition rate and the syringe needle was pierced
flask were filled with argon and drawn into a Hamilton 60 mL through the septa of the reaction flask. The solution in reaction
argon-flushed gastight syringe. To a separate flame-dried 250 mL flask remained on heat with stirring until 2 h after syringe addi-
two-neck round-bottom Schlenk flask, CuBr (59.4 mg, 0.414 mmol), tion completion. The reaction was terminated by submersing the
Cu0 (26.3 mg, 0.263 mmol), PMDETA (172.8 μL, 0.828 mmol), flask in an ice bath and exposure to atmosphere. The raw reac-
50.0 mL THF, and a dried magnetic stir bar were added. The flask tion mixture was concentrated in a separate round-bottom flask
was filled with argon to equalize pressures between the reac- and a small aliquot of the solution was obtained for GPC analysis
tion flask and syringe, and the reaction flask was placed in a (Mn = 16 950, 3850, Mp = 19 850, 4150, Ð = 1.79). The GPC sample
60 °C oil bath to equilibrate. The syringe was equipped on the was prepared by diluting several drops of solution with THF and
Cole Parmer single-syringe infusion pump at 3 mL h−1 (1.10 μmol filtering through a 0.45 μm PTFE syringe filter. A second aliquot
h−1) controlled addition rate and the syringe needle was pierced was placed in a centrifuge tube for precipitation only to remove
through the septa of the reaction flask. The solution in reaction minimal degraded polymer with cold hexanes. After centrifu-
flask remained on heat with stirring until 2 h after syringe addi- gation the solid precipitate of product and copper was retained
tion completion. The reaction was terminated by submersing and solution was decanted. The precipitate was dissolved in
the flask in an ice bath and exposure to atmosphere. The raw 1 mL THF, filtered through a PTFE syringe filter, and analyzed via
reaction mixture was concentrated in a separate round-bottom GPC (Mn = 16 550, 4400, Mp = 20 150, 4550, Ð = 1.72). Fractional
flask and a small aliquot of the solution was obtained for GPC column chromatography was utilized as in the case from bro-
analysis (Mn = 2900, Mp = 2750, Ð = 1.58). The GPC sample was minated precursors. An aliquot of both fractions was removed
prepared by diluting several drops of solution with THF and fil- for GPC analysis, diluted with THF, and filtered through a PTFE
tering through a 0.45 μm PTFE (polytetrafluoroethylene) syringe syringe filter. The second fraction (Mn = 13 680, 3950, Mp = 8500,
filter. A second aliquot was placed in a centrifuge tube for pre- 4100, Ð = 1.29) mostly removed intermolecular coupled product
cipitation only to remove minimal degraded polymer with cold however some remained. The product was fractionally pre-
hexanes. After centrifugation the solid precipitate of productand cipitated with cold hexanes and centrifuged. The solution was
copper was retained and solution was decanted. The precipitate analyzed via GPC and either repeated for further separation or
was dissolved in 1 mL THF, filtered through a PTFE syringe filter, precipitated in whole to retrieve the cyclic product. The macrocy-
and analyzed via GPC (Mn = 11 750, 3050, Mp = 7400, 2800, Ð = clic white solid product was dried under vacuum for 2 h. A small
1.46). The remaining mixture was subjected to fractional column sample of product was dissolved in 1 mL THF and analyzed by
chromatography where a fraction of high molecular weight GPC (Mn = 4000, Mp = 4150, Ð = 1.09).
product was separated from the lower molecular weight, intra- The percent cyclic product compared to the total RTA-ATRC
molecular coupled product. An aliquot of both fractions was product (intra- and intermolecular coupled) was obtained by
removed for GPC analysis, diluted with THF, and filtered through Equation (1)
a PTFE syringe filter: Fraction 1: Mn = 11 150, 2900, Mp = 7000,
2600, Ð = 1.15. Fraction 2: Mn = 3000, Mp = 2850, Ð = 1.15. The
⎛ Cyclic peak area ⎞
remaining intramolecular coupled product was precipitated in %Cyclicexpt = ⎜ × 100 (1)
⎝ Total peak area RTA − ATRCproduct ⎟⎠
cold hexanes. The precipitant solution mixture was centrifuged
and the solvent solution was decanted. The white solid product
where cyclic peak area was the area of the shifted cyclic
was dried under vacuum for 2 h. A small sample of product was
product of symmetric peak area and total peak area contained
dissolved in THF and analyzed by GPC (Mn = 3000, Mp = 2900,
the total area under the peak.
Ð = 1.16).
4.7. Thermolysis of Cyclic PMMA Prepared by RTA-ATRC

4.6. Synthesis of Cyclic PMMA by Intramolecular
To an oven-dried round-bottom flask was added exclusively
RTA-ATRC from Chlorinated Precursors
cyclic PMMA product formed by RTA-ATRC (Mn = 3000, Mp =
To a flame-dried 100 mL two-neck round-bottom Schlenk 2900, Ð = 1.16) with a thermally cleavable nitrosobenzene (C O
flask, the difunctional ATRP-synthesized polymer Cl-PMMA-Cl cleavable bond) as part of the macrocyclic structure, which had
(Mn = 4250, Mp = 5150, Ð = 1.14, 71.2 mg, 0.014 mmol), NBz previously been passed through an alumina column and precipi-
(7.5 mg, 0.070 mmol), and 50 mL THF were added. The flask was fit tated. Dimethylformamide (2.0 mL) and a small dried magnetic
with a rubber septum and subjected to three freeze–pump–thaw stir bar were also added to the flask. The thermolysis was done
cycles via a Schlenk line. The polymer and Nbz solution-containing under atmospheric environment however was closed off with a
flask were filled with argon and drawn into a Hamilton 50 mL clean septum and a pressure-release syringe. The solution was
argon-flushed gastight syringe. To a separate flame-dried 250 mL submerged in an oil bath at 130 °C and allowed to reflux for
two-neck round-bottom schlenk flask, CuCl (27.6 mg, 0.278 7 h minimum. GPC analysis was performed on 0.8 mL of the
mmol), Cu0 (17.7 mg, 0.278 mmol), PMDETA (116 μL, 0.557 mmol), crude reaction mixture in 1 mL THF (Mn = 3150, Mp = 3250,
50 mL THF, and a dried magnetic stir bar were added. The flask Ð = 1.09) and was compared to the linear precursor (Mn = 3400,
was filled with argon to equalize pressures between the reaction Mp = 3350, Ð = 1.19).

Macromolecular
www.mcp-journal.de
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MWtheo = MWI + (n × MWMMA ) + MWn + MWNH + (2)
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4
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Macro Chemistry Physics - 2015 - Blackburn - Synthesis of Cyclic Poly Methyl Methacrylate Directly From Dihalogenated

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Macro Chemistry Physics - 2015 - Blackburn - Synthesis of Cyclic Poly Methyl Methacrylate Directly From Dihalogenated

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Macromolecular

Chemistry and Physics Full Paper

Synthesis of Cyclic Poly(methyl methacrylate)

Scott C. Blackburn, Eric S. Tillman*

Cyclic poly(methyl methacrylate) (PMMA) is prepared by intramolecular radical trap-assisted

1. Introduction modiﬁcation, resulting in cycles in high yields.[15,16] The

Macromol. Chem. Phys. 2015, 216, 1282−1290

implying that cyclic PMMA could be

2. Results and Discussion

As summarized in Scheme 3, reaction 1,

Macromol. Chem. Phys. 2015, 216, 1282−1290

Macromol. Chem. Phys. 2015, 216, 1282−1290

Br-PMMA-Br precursora) RTA-ATRC productsb)

Macromol. Chem. Phys. 2015, 216, 1282−1290

Macromol. Chem. Phys. 2015, 216, 1282−1290

Macromol. Chem. Phys. 2015, 216, 1282−1290

Macromol. Chem. Phys. 2015, 216, 1282−1290

4.7. Thermolysis of Cyclic PMMA Prepared by RTA-ATRC

Macromol. Chem. Phys. 2015, 216, 1282−1290

Macromol. Chem. Phys. 2015, 216, 1282−1290

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