Synthesis of reactive poly(norbornene): Ring-opening metathesis polymerization of norbornene monomer bearing cyclic dithiocarbonate moiety

Article abstract of DOI:10.1002/pola.24523

A norbornene monomer bearing cyclic dithiocarbonate moiety (NB-DTC) was successfully synthesized from the corresponding precursor having epoxy moiety by its reaction with carbon disulfide. NB-DTC underwent the ring-opening metathesis polymerization (ROMP) catalyzed by a ruthenium carbene complex to give the corresponding poly(norbornene). The dithiocarbonate moiety incorporated into the side chain of the obtained poly(norbornene) reacted with amine to afford the corresponding thiourethane moiety with thiol group, which underwent oxidative S-S coupling and/or addition reaction to the C-C double bond in the main chain, leading to formation of a cross-linked polymer.

Full text of DOI:10.1002/pola.24523

Synthesis of Reactive Poly(norbornene): Ring-Opening
Metathesis Polymerization of Norbornene Monomer Bearing
Cyclic Dithiocarbonate Moiety
ATSUSHI SUDO, HIDETADA MORISHITA, TAKESHI ENDO
Molecular Engineering Institute, Kinki University, 11-6 Kayanomori, Iizuka, Fukuoka 820-8555, Japan
Received 10 September 2010; accepted 25 November 2010
DOI: 10.1002/pola.24523
Published online 3 January 2011 in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: A norbornene monomer bearing cyclic dithiocar-
bonate moiety (NB-DTC) was successfully synthesized from the
corresponding precursor having epoxy moiety by its reaction
with carbon disulfide. NB-DTC underwent the ring-opening
metathesis polymerization (ROMP) catalyzed by a ruthenium
carbene complex to give the corresponding poly(norbornene).
The dithiocarbonate moiety incorporated into the side chain of
the obtained poly(norbornene) reacted with amine to afford
the corresponding thiourethane moiety with thiol group, which
underwent oxidative S-S coupling and/or addition reaction to
the C-C double bond in the main chain, leading to formation of
a cross-linked polymer. VC 2011 Wiley Periodicals, Inc. J Polym
Sci Part A: Polym Chem 49: 1097–1103, 2011
KEYWORDS: copolymerization; functionalization of polymers;
ROMP
6
INTRODUCTION One of the current growing interests in the
field of transition-metal catalyzed polymerization has been
focused on development of new norbornene-type monomers
bearing various functional groups and their ring-opening me-
catalyst. The norbornene moiety of NB-CC underwent ROMP
successfully to afford the corresponding poly(norbornene)
bearing cyclic carbonate moiety in the side chain, of which
intrinsic high reactivity with amine allowed highly efficient
chemical modification of this new poly(norbornene).
1
,2
tathesis polymerization (ROMP). Recently, highly efficient
catalysts for ROMP that are compatible with those functional
groups have been developed to permit successful synthesis
The successful utilization of NB-EP for development of a
new norbornene monomer made us to demonstrate another
chemical transformation of NB-EP based on the reaction of
3
of various functionalized poly(norbornene)s. By introducing
functional groups into the side chains of poly(norbornene)s,
their intrinsic high thermal stability, high transparency, low
birefringence, and low dielectric constant can be combined
with additional advantages such as high processing ability,
compatibility with other materials, and improved adhesion
strength. In particular, ROMP of norbornenes bearing reac-
7
epoxide with carbon disulfide, a sulfur-containing analogue
of carbon dioxide, to afford a new norbornene monomer
bearing cyclic dithiocarbonate moiety (NB-DTC) bearing five-
membered cyclic dithiocarbonate (DTC). So far, we have
clarified that DTC undergoes the ring-opening reaction by
amine that proceeds readily and highly chemoselectively,
and this intriguing reactive feature of DTC has enabled its
application to our polymer synthesis. Besides, DTC under-
goes the isomerization to afford another type of cyclic dithio-
carbonate and the cationic ring-opening polymerization to
afford the corresponding polydithiocarbonate. These back-
grounds motivated us to synthesize NB-DTC as a monomer
for synthesizing new poly(norbornene)s that would be
endowed with the unique reactivity of DTCs. In general, sul-
fur atom exhibits high affinity to various metals at the cen-
ters of catalysts to deactivate them. So far, there have been
only a few successful examples of ROMP of norbornenes
bearing sulfur-containing functional groups such as dithioa-
cetal and trithiocarbonate moieties.
encouraged us to investigate ROMP of NB-DTC. Herein we
report the details of the synthesis of NB-DTC and its ROMP
8
4
tive groups would give reactive poly(norbornene)s, which
are expected as polymeric scaffolds for immobilization of
functional molecules, for further functionalization by chemi-
cal transformation of the side chains, and for cross-linking
reactions to obtain cross-linked poly(norbornene)s with
improved thermal stability, mechanical properties, and chem-
ical resistance.
9
10
11
Previously, we reported a new straightforward synthesis of a
norbornene derivative bearing epoxy group (2-bicyclo[2.2.1]-
5
hept-5-en-2-yl oxirane; NB-EP) (Fig. 1). With using this
functionalized norbornene as a precursor, its epoxy moiety
was converted into the corresponding five-membered cyclic
carbonate moiety to give a new monomer NB-CC, based on
the cycloaddition reaction of epoxide with carbon dioxide
under atmospheric pressure with using lithium chloride as a
1
2
This background
Correspondence to: T. Endo (E-mail: tendo@mol-eng.fuk.kindai.ac.jp)
Journal of Polymer Science Part A: Polymer Chemistry, Vol. 49, 1097–1103 (2011) V
2011 Wiley Periodicals, Inc.
C
SYNTHESIS OF REACTIVE POLY(NORBORNENE), SUDO, MORISHITA, AND ENDO
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JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
dropwise for 20 min. The resulting solution was stirred at
ꢁ
4
0 C for 12 h. After cooling, the solution was concentrated
under reduced pressure, and the resulting residue was dis-
solved in chloroform (150 mL), washed with distilled water
(
200 mL) three times. The chloroform layer was dried over
sodium sulfate, filtered, and concentrated under reduced
pressure. The residue was fractionated with column chroma-
tography (silica gel, eluent ¼ dichloromethane) to obtain a
diasteromeric mixture of NB-DTC as a yellow liquid (4.53 g,
21.3 mmol, 71%): IR (neat) 3053, 2961, 2865, 1432, 1330,
FIGURE 1 Norbornenes bearing reactive groups.
ꢂ1
1
1
182, 1054, 707 cm ; H NMR (CDCl ) d 6.34–5.89 (m, 2H,
3
vinyl), 5.00–4.42 (m, 1H, cyclic-dithiocarbonate-CH), 3.75–
catalyzed by a ruthenium carbene complex. A polymer reac-
tion of the resulting poly(norbornene) based on the reactiv-
ity of DTC with amine was also demonstrated.
3
1
.37 (m, 2H, cyclic-dithiocarbonate-CH2), 3.25–2.67 (m, 2H,
1
3
,4-CH), 2.66–0.60 ppm (m, 5H, 2-CH, 3-CH2, 7-CH2);
) d (mixture of four diastereomers) 212.05,
12.24, 212.26, 212.28, 139.48, 138.31, 137.71, 136.88,
C
NMR (CDCl
3
2
1
4
4
3
EXPERIMENTAL
36.10, 135.41, 132.49, 130.30, 97.25, 96.35, 95.60, 95.22,
9.59, 49.08, 49.05, 45.57, 44.96, 44.63, 44.32, 44.26, 43.97,
3.11, 43.06, 43.02, 42.68, 42.31, 42.11, 41.83, 39.11, 38.80,
Materials
Benzylidene-bis(tricyclohexylphosphine)dichlororuthenium (Grubbs
1st generation catalyst) (Aldrich), was used as received. NB-
8.70, 38.62, 30.30, 30.19, 29.13, 28.51 ppm; EI-MS m/z 212
EP was synthesized according to the procedure reported by
þ
(
M ).
5
us. 5-Butyl-2-norbornene (BNB) was provided by JSR Co.
Ring-Opening Metathesis Polymerization of NB-DTC
Homopolymerization)
and was purified prior to use by passing through alumina
column and distillation under vacuum. Carbon disulfide,
ethyl vinyl ether, dichloromethane, benzylamine, and chloro-
benzene were purchased from Wako Pure Chemical Indus-
tries and were distilled over calcium hydride prior to use.
Anhydrous lithium bromide and tetrahydrofuran (THF) were
purchased from Kanto Chemical Co. and used as received.
(
To a solution of NB-DTC (425 mg, 2.00 mmol) and 1,2,3,4-
tetrahydronaphthalene (added as an internal standard for GC
analysis; 107 mg, 0.809 mmol) in dichloromethane (2.6 mL),
a solution of Grubbs 1st generation catalyst in dichlorome-
thane (0.05 M; 0.4 mL, 0.02 mmol) was added at room tem-
perature. At 10 and 30 min, a small portion of the solution
was taken and analyzed by GC to determine the conversions
of NB-DTC. After 90 min, ethyl vinyl ether (0.25 mL) was
added to terminate the polymerization, and the mixture was
stirred at room temperature for 40 min. The mixture was
poured into methanol (50 mL), and the resulting precipitate
Measurements
Fourier-transfer IR measurement was carried out at room
temperature by casting a sample solution on a prism of an
ATR measurement unit on a Perkin-Elmer spectrum-one
1
13
spectrophotometer. H NMR (400 MHz) and C NMR (100.6
MHz) spectra were obtained with Varian NMR spectrometer,
a model Unit INOVA in CDCl3 with tetramethylsilane as an
internal standard. Number- and weight average molecular
ꢁ
was filtered with suction, and dried under vacuum at 50 C
to obtain the homopolymer 1a (178 mg, 42%): IR (neat)
ꢂ1
2930, 2852, 1436, 1334, 1180, 1045, 965 cm
.
n w
weights (M and M ) were estimated by size exclusion chro-
matography (SEC), performed on a Tosoh chromatograph
model HLC-8120GPC equipped with Tosoh TSK gel-Super
Ring-Opening Metathesis Polymerization of NB-DTC
Copolymerization with BNB)
(
NB-DTC (212 mg, 1.00 mmol), BNB (150 mg, 1.00 mmol),
and 1,2,3,4-tetrahydronaphthalene (added as an internal
standard for GC analysis; 107 mg, 0.809 mmol) were dis-
solved in dichloromethane (2.6 mL). To the obtained solu-
tion, a solution of Grubbs 1st generation catalyst in dichloro-
methane (0.05 M; 0.4 mL, 0.02 mmol) was added at room
temperature. At 5 min, 10 min, 20 min, 30 min, 45 min, 60
min, and 90 min, a small portion of the solution was taken
and analyzed by GC to determine the conversions of NB-DTC
and BNB. After 90 min, ethyl vinyl ether (0.25 mL) was
added to terminate the polymerization, and the solution was
stirred at room temperature for 40 min. The solution was
poured into methanol (50 mL), and the resulting precipitate
was filtered with suction, and dried under vacuum to obtain
the comopolymer 1b (283 mg): IR (neat) 2922, 2851, 1453,
HM-H styrogel columns (6.0 mm f ꢀ 15 cm), using CHCl as
3
an eluent at a flow rate of 1.0 mL/min after calibration with
polystyrene standards. Mass spectroscopy was performed on
a Shimadzu GCMS-QP5050A in electron impact (EI) mode.
Gas chromatography (GC) was performed on a Agilent Tech-
nologies 6850 Network GC system equipped with J and W
Scientific HP-1 (0.25 mm ꢀ 30 m) capillary column and a
Shimadzu GC-18A gas chromatograph equipped with J and
W Scientific DB-WAXETR (1 mm ꢀ 30 m) capillary column.
Thermo-gravimetric analysis (TGA) and differential scanning
calorimetric analysis (DSC) were performed with a SEIKO
EXSTAR6000 (Seiko Instruments).
Synthesis of 5-Bicyclo[2.2.1]hept-5-en-2-yl-
[1,3]oxathiolane-2-thione (NB-DTC)
ꢂ1
1
To a solution of NB-EP (4.09 g, 30.0 mmol) and lithium bro-
mide (0.25 g, 2.9 mmol) in THF (15 mL), a solution of car-
bon disulfide (2.9 g, 38 mmol) in THF (25 mL) was added
1189, 1048, 966 cm ; H-NMR (CDCl ) d 5.70–5.20 (broad
3
m, 2H; vinyl protons), 5.20–4.90 (broad m, 0.47H; methine
proton of DTC), 3.20–3.80 (broad m, 0.94H; methylene
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ARTICLE
RESULTS AND DISCUSSION
Synthesis of NB-DTC
Scheme 1 shows the synthetic route to NB-DTC. The precur-
sor NB-EP bearing epoxy moiety was synthesized from 5-
norbornene-2-carbaldehyde (a diastereomeric mixture of the
5
endo and exo isomers) according to our previous report.
The obtained NB-EP was mixed with carbon disulfide and
lithium bromide in THF, and the resulting solution was
ꢁ
heated at 40 C. As a result, the epoxide moiety of NB-EP
was converted successfully to the corresponding five-mem-
bered cyclic carbonate moiety to afford NB-DTC. The dithio-
carbonate structure was confirmed by its characteristic IR-
ꢂ1
absorptions at 1182 and 1054 cm [Fig. 2(a)]. Figure 3(a)
1
shows the H-NMR spectrum of the obtained NB-DTC. The
complexity of the spectrum suggested that NB-DTC was
obtained as a mixture of diastereomers due to the presence
of two chiral centers. It was difficult to resolve them by GC
because of the serious overlapping of the corresponding
peaks; however; during the GC-MS analysis, they were ion-
ized in EI mode to indicate the same m/z value of 212,
which was identical with the calculated molecular weight of
NB-DTC.
SCHEME 1 Synthesis of NB-DTC.
protons of DTC), 3.10–0.70 ppm (broad m, including a broad
singlet signal at 0.85 ppm for the methyl protons of the
BNB-derived unit). M
SEC, eluent ¼ chloroform, polystyrene standards).
n
¼ 14,000, M ¼ 26,000 (estimated by
w
Reaction of the DTC-Moiety of 2b with Benzylamine
To a solution of copolymer 2b (49.7 mg, amount of cyclic
carbonate moiety ¼ 0.28 mmol) in chlorobenzene (0.30 mL),
benzylamine (49 mg; 0.46 mmol) was added at ambient tem-
perature. The resulting solution was stirred at ambient tem-
perature for 16 h under air. The solution was poured into
methanol (25 mL), and the resulting precipitate was filtered
with suction and dried under vacuum to obtain the resulting
polymer 2 (40 mg) as a white powder: IR (neat) 3410,
Ring-Opening Metathesis Polymerization (ROMP)
of NB-DTC (Homopolymerization)
ROMP of NB-DTC was performed with employing benzyli-
dene-bis(tricyclohexyl phosphine)dichlororuthenium (Grubbs
1
st generation catalyst) (Scheme 2), which was efficiently
6
used for ROMP of NB-CC and those of monomers bearing
sulfur-containing functional groups. When the catalyst was
added to a dichloromethane solution of NB-DTC, its ROMP
1
2
2
928, 2855, 1662, 1511, 1455, 1392, 1343, 1170, 970, 733,
ꢂ1
698, 528 cm
.
FIGURE 2 IR spectra of (a) NB-DTC, (b) polymer 1a (¼ the
homopolymer of NB-DTC), and (c) polymer 1b (the copolymer
of NB-DTC and BNB; composition ratio ¼ 47.53).
1
FIGURE 3 H NMR spectra of (a) NB-DTC and (b) polymer 1b.
SYNTHESIS OF REACTIVE POLY(NORBORNENE), SUDO, MORISHITA, AND ENDO
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JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
the other hand, in the homopolymerization of NB-CC, NB-CC
was completely consumed within 120 min to afford the cor-
responding homopolymer almost quantitatively. This tend-
ency implied that the sulfur atoms of the cyclic dithiocarbon-
ate exhibited higher affinity to the ruthenium catalyst to
interfere approach of the C-C double bond of NB-DTC to the
central metal of the catalyst.
Ring-Opening Metathesis Polymerization (ROMP)
of NB-DTC (Copolymerization)
Copolymerization of NB-DTC and BNB in a feed ratio of
50:50 was performed (Scheme 2, Table 1, entry 2). The
resulting copolymer 1b was soluble in various organic sol-
vents such as dichloromethane, chloroform, acetone, and
THF, due to the incorporation of less polar n-butyl group in
the side chain. By virtue of this soluble nature, 1b was ana-
lyzed not only by IR but also by NMR and SEC. Figure 2(c)
SCHEME 2 ROMP of NB-DTC.
shows the IR spectrum, which clearly indicated two absorp-
ꢂ1
tions at 1189 and 1048 cm
attributable to the cyclic
1
proceeded slowly [Fig. 4(a)]. The resulting homopolymer 1a
was insoluble in dichloromethane and thus precipitated out
from the solution during the polymerization. After adding
ethyl vinyl ether to terminate ROMP, the mixture was poured
into methanol, and the precipitate was isolated by filtration
to obtain 1a in 42% (Table 1, entry 1). 1a was insoluble not
only in dichloromethane but also in other organic solvents
such as toluene, chloroform, THF, acetone, ethyl acetate, di-
methyl sulfoxide, and N,N-dimethylformamide. One of the
reasons for the insoluble nature may be the high polarity of
DTC moieties. Although this insoluble nature led to only a
limited structural analysis, IR was effectively employed to
confirm the structure of 1a. Figure 2(b) shows the IR spec-
dithiocarbonate moiety in the side chain. In the H NMR
spectrum [Fig. 3(b)], signals attributable to the methine pro-
ton of DTC and the vinyl protons of the main chain appeared
in the region from 5 to 6 ppm. Comparison of the integrated
signal intensity with that of the other signals allowed calcu-
lation of composition ratio [NB-DTC-derived unit]:[BNB-
derived unit], which was 47:53. SEC analysis of 1b permitted
estimation of its number average molecular weight (M ) and
n
weight average molecular weight (M ), which were 14,000
w
and 26,000, respectively.
Figure 4(b) shows the corresponding time-dependences of
conversions of NB-DTC and BNB, which revealed a significant
difference in polymerization ability between the two mono-
mers. Within 20 min, BNB was completely consumed, while
the conversion of NB-DTC at 20 min was 70%. From these
copolymerization behaviors, formation of segments rich in
BNB-derived unit in the early stages and that of segments
rich in NB-DTC-derived unit in the late stages to give a gra-
trum of 1a which indicated characteristic absorptions at
ꢂ1
1
180 and 1045 cm , which clarified that the side chain of
1a inherited the cyclic dithiocarbonate moiety from the
monomer NB-DTC.
The homopolymerization of NB-DTC was slower than that of
NB-CC, an analogous monomer having cyclic carbonate moi-
ety. In the homopolymerization of NB-DTC, as shown in Fig-
ure 3(a), the conversion of NB-DTC did not reach 50% even
when the polymerization time was prolonged to 90 min. On
1
3
dient copolymer can be assumed. In fact, after the com-
plete consumption of BNB, formation of insoluble polymer
by homopolymerization of NB-DTC was not observed, imply-
ing that NB-DTC molecules consumed after 20 min until 90
FIGURE 4 Time-conversion relation-
ships for (a) the homopolymerization
of NB-DTC and (b) the copolymeriza-
tion of NB-DTC and BNB (feed ratio ¼
5
0:50).
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ARTICLE
TABLE 1 ROMP of NB-DTC
Feed Ratio
Yield of
Composition
a
b
c
Entry
[NB-DTC]
0
:[BNB]
0
Polymer
Polymer/%
M
n
(M /M
w n
)
Ratio m:n
d
e
1
2
a
100:0
50:50
1a
1b
42
78
–
100:0
14,000 (1.86)
47:53
Methanol-insoluble parts.
b
c
Estimated by SEC (eluent ¼ CHCl
3
, polystyrene-standards).
1
Determined by H NMR.
d
3
SEC-analysis was not carried out because 1a was insoluble in CHCl .
e 1
3 6
H NMR was not measured because 1a was insoluble in CDCl and dimethylsulfoxide-d .
min were successfully converted into homo-sequences of
NB-DTC into the tails of the gradient copolymers.
throughout the reaction to let us expect the formation of a
linear poly(norbornene) 2 bearing thiourethane and thiol
moieties. The solution was poured into an excess amount of
methanol to attempt isolation of 2; however, the isolated
polymer was not soluble in chloroform, THF, DMSO, or DMF,
implying that 2 was crosslinked into the corresponding
cross-linked polymer 3. Figure 5 shows the IR spectrum of 3
along with that of polymer 1b, which confirmed the success-
ful conversion of DTC moiety by its reaction with benzyl-
amine into the corresponding thiourethane moiety. Although
the crosslinking process is not clear at present, the cross-
linked polymer 3 would bear two possible structures at the
crosslinking points: One possible structure is S-S linkage,
which can be formed by oxidative coupling of the thiol group
in the side chain of 2 during the isolation process. The other
one is S-C bond, which can be formed by addition reaction
of the thiol group to the C-C double bond in the poly(norbor-
nene) main chain.
Reaction of the Cyclic Dithiocarbonate Moiety
in the Side Chain with Amine
So far, we have reported the reaction of five-membered cyclic
dithiocarbonate (DTC) with amines, which affords the corre-
8
sponding thiourethanes having thiol group: The characteris-
tic feature of this reaction is its chemoselectivity, which per-
mits the nucleophilic addition of primary amine exclusively
in the presence of other nucleophiles such as water, alcohols,
carboxylic acids, and thiols. In addition, the reaction of DTC
with amine is much faster than the analogous reaction of
five-membered cyclic carbonate.
To investigate the reactivity of the cyclic moiety in the side
chain of poly(norbornene), the copolymer 1b was treated
with benzylamine ([DTC moiety] :[benzylamine] ¼ 1:1.6) in
0
0
chlorobenzene at ambient temperature (Scheme 3). Upon
adding benzylamine, the characteristic yellow color of DTC
disappeared to suggest its successful ring opening reaction.
In addition, there was no formation of insoluble fraction
In Figure 6, TGA profiles of the precursor polymer 1b and
the resulting cross-linked polymer 3 are shown. Upon
SCHEME 3 Reaction of 1a with benzyl-
amine and possible structures of cross-
linking points.
SYNTHESIS OF REACTIVE POLY(NORBORNENE), SUDO, MORISHITA, AND ENDO
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JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY DOI 10.1002/POLA
FIGURE 7 DSC thermograms of (a) copolymer 1b and (b)
cross-linked polymer 3.
reactive poly(norbornene), of which side chain was endowed
with the highly reactive nature of DTC with amine.
FIGURE 5 IR spectra of (a) copolymer 1b and (b) cross-linked
polymer 3.
ꢁ
heating 1b up to 310 C, it lost 20% of the initial weight,
REFERENCES AND NOTES
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mers are shown, in which glass transition temperatures (T )
were observed. T of 3 was 49 C. It was slightly higher than
that of 1b, 46 C, to suggest the more restricted motion of
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2
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14 We have encountered similar phenomena during vacuum
4065–4066.
distillation of various DTCs.
SYNTHESIS OF REACTIVE POLY(NORBORNENE), SUDO, MORISHITA, AND ENDO
1103