Received: 10 April 2020 Revised: 27 April 2020 Accepted: 27 April 2020

DOI: 10.1002/pol.20200250

ORIGINAL ARTICLE

A systematic study of stereochemical effects in homologous

poly(alkenamer)s: Dewar benzene versus norbornene

Stanfield Y. Lee1 | Jinwon Seo1 | Christopher W. Bielawski1,2,3

1
Center for Multidimensional Carbon
Materials (CMCM), Institute for Basic
Abstract
Science (IBS), Ulsan, Republic of Korea Two diastereomeric derivatives of norbornene, dimethyl (1R,2R,3S,4S)-bicyclo
2
Department of Chemistry, Ulsan [2.2.1]hept-5-ene-2,3-dicarboxylate and dimethyl (1R,2S,3S,4S)-bicyclo[2.2.1]
National Institute of Science and
hept-5-ene-2,3-dicarboxylate, were synthesized and polymerized using ring-
Technology (UNIST), Ulsan, Republic of
Korea opening metathesis polymerization (ROMP). For comparative purposes, diaste-
3
Department of Energy Engineering, reomeric derivatives of Dewar benzene, dimethyl (1R,2S,3R,4S)-bicyclo[2.2.0]
Ulsan National Institute of Science and hex-5-ene-2,3-dicarboxylate and dimethyl (1R,2S,3S,4S)-bicyclo[2.2.0]hex-
Technology (UNIST), Ulsan, Republic of
Korea 5-ene-2,3-dicarboxylate, were also synthesized and polymerized using ROMP.
The polymerization reactions proceeded in a controlled manner as evidenced
Correspondence
in part by linear relationships between the monomer-to-catalyst feed ratios
Christopher W. Bielawski, IBS & UNIST,
Ulsan 44919, Republic of Korea. and the molecular weights of the polymer products. Chain extension experi-
Email: [email protected] ments were also conducted which facilitated the formation of block copoly-
mers. Although the poly(norbornene) derivatives exhibited glass transition
Funding information
Institute for Basic Science, Grant/Award temperatures that were dependent on their monomer stereochemistry (cis:
Number: IBS-R019-D1 115 C vs. trans: 125 C), more pronounced differences were observed upon
analysis of the polymers derived from Dewar benzene (cis: 70 C vs. trans:
95 C). Likewise, microphase separation was observed in block copolymers that
were prepared using the diastereomeric monomers derived from Dewar ben-
zene but not in block copolymers of the norbornene-based diastereomers. The
differential thermal properties were attributed to the relative monomer sizes as
reducing the distances between the polymer backbones and the pendant
stereocenters appeared to enhance the thermal effects.

KEYWORDS
Dewar benzene, glass transition temperature, polymer stereochemistry, poly(norbornene), ring-
opening metathesis polymerization

1 | INTRODUCTION practical perspectives. Since the Tg can be considered to

be the transitioning point from where freely moving poly-
As the glass transition temperature (Tg) plays an influen- mer chains become increasingly immobile, factors that
tial role in determining many of the physical properties favor stacking into well-ordered structures and/or chain
displayed by polymeric materials, methods to manipulate immobilization tend to increase the transition tempera-
Tg values are of high interest from fundamental to ture.1,2 For example, poly(acrylate)s3 and poly(carbonate)s4,5
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2020 The Authors. Journal of Polymer Science published by Wiley Periodicals, Inc.

J Polym Sci. 2020;58:1687–1698. wileyonlinelibrary.com/journal/pol 1687

1688 LEE ET AL.

exhibit relatively high Tg values when the corresponding

monomers contain bulky side chains that effectively hin-
der polymer chain rotation and mobility. Configuration
has also been shown to affect the glass transition
temperature.6–9 The trans isomers of poly(1,3-butadiene)
and poly(isoprene)10 exhibit higher glass transition tem-
peratures than their cis analogues because the former
geometry tends to facilitate the stacking of polymer
chains. Likewise, the Tg of syndiotactic poly(propylene) is
higher than its isotactic analogue.11–13
A lesson learned from the aforementioned and other
studies is that the movement of polymer chains can be
decreased by rigidifying the polymer backbone or by incor-
porating functional groups that restrict bond rotation. The
ring-opening metathesis polymerization (ROMP) of bicy-
clic monomers is an effective technique for imparting and
manipulating such effects because it yields polymers that
feature alkenyl and cyclic repeat units. Each of these fea-
tures effectively constrain bond rotation along the polymer
backbone in a manner that can significantly affect the
thermal properties displayed by the corresponding poly-
mers. For example, cis-poly(norbornene) exhibits a Tg at a
temperature that is approximately 30 C higher than its
trans analogue.14–18 Likewise, the Tgs of various endo-poly
(norbornene-dicarboximide) derivatives are approximately
30–40 C higher than their exo analogues. The origins of
these effects can be attributed to reduced chain mobil-
ity19,20 concomitant with enhanced intermolecular pack-
ing of the polymer chains.21
Despite these advances, the role of substituent stereo-
chemistry in influencing the thermal properties of poly-
mers that are synthesized through the ROMP of
substituted bicyclic monomers remains relatively unclear.
For example, as summarized in Figure 1,
poly(norbornene) derivatives containing endo-ester and
endo-cyano substituents exhibit glass transition tempera-
tures that are approximately 40 C higher than their exo- F I G U R E 1 Structures of selected polymers and their
analogues,22 although the origin of the differences could respective glass transition temperatures (Tg)
not be exclusively attributed to electronic or steric effects.
In contrast, polymers synthesized from mono-substituted polymer backbone to influence segmental packing, bond
endo- or exo-phenyl norbornene exhibit no significant dif- rotation, packing effects, and other factors that govern
ferences in their respective glass transition temperature the thermal properties displayed by the corresponding
values.17,23 The paucity of studies may be due in part to polymeric material.
catalyst limitations as diminished polymerization rates To test our hypothesis, two diastereomeric derivatives of
have been observed with monomers that feature endo- norbornene, dimethyl (1R,2R,3S,4S)-bicyclo[2.2.1]hept-
substituents.22,24–33 Regardless, the ROMP of substituted 5-ene-2,3-dicarboxylate and dimethyl (1R,2S,3S,4S)-bicyclo
norbornene derivatives with ester groups in the 5- and [2.2.1]hept-5-ene-2,3-dicarboxylate, were synthesized and
6-positions were still found to proceed to high conver- polymerized using ROMP.34 Methyl ester groups were
sions and in a controlled manner, even when one or both selected in lieu of longer alkyl chains to minimize internal
of the substituents were in an endo-position.34 Thus, we plasticization17 and other potential effects that could alter
hypothesized that if the stereochemistry of the pendant the intrinsic thermal properties displayed by the
substituents can influence the rates of polymerization, corresponding polymers. Furthermore, if the stereochemis-
such substituents should be sufficiently close to the try of the pendant ester groups (e.g., endo- vs. exo-) was found
LEE ET AL. 1689

to have a measurable thermal effect, enhancement may be sodium amalgam (3 wt%) afforded 8, which was purified by
realized by decreasing the distance between the pendant recrystallization from aqueous sulfuric acid and isolated in
groups and the polymer backbone. As a contracted variant of 70% yield. Subsequent dehydration of the resulting
norbornene, Dewar benzene (bicyclo[2.2.0]hexa-2,5-diene) 1,3-cyclohexadiene derivative using acetic anhydride
was envisioned to serve in such capacity. Therefore, two afforded the corresponding anhydride 9, which was purified
substituted diastereomeric derivatives of Dewar benzene, by sublimation and collected in 75% yield as a white crystal-
dimethyl (1R,2S,3R,4S)-bicyclo[2.2.0]hex-5-ene- line solid. Photochemical isomerization of 9 was conducted
2,3-dicarboxylate and dimethyl (1R,2S,3S,4S)-bicyclo[2.2.0] in diethyl ether at room temperature and monitored over
hex-5-ene-2,3-dicarboxylate, were also synthesized and poly- time by 1H NMR spectroscopy. Although sublimation has
merized using ROMP.35–37 As will be described below, com- been used to isolate the photoisomerized product 10,38 the
prehensive thermal analyses revealed that both the glass technique was found to be inefficient in our hands as were
transition and the decomposition temperature of the other common purification techniques (e.g., column chro-
corresponding polymers were affected by the stereochemis- matography and extraction). Therefore, following removal
try of the pendant substituents, although the differences of the residual solvent under reduced pressure, the crude
were found to be more pronounced in the polymers that product mixture obtained after 34 hr was treated with
were derived from Dewar benzene as opposed to their methyl alcohol in the presence of a catalytic amount of sul-
norbornene analogues. furic acid. Subsequent purification via column chromatog-
raphy afforded 5 as colorless liquid in 24% yield over the
two steps. Epimerization of 5 under basic conditions
2 | R ES U L T S A N D D I S C U S S I O N followed by acidification using an aqueous solution of
hydrochloric acid (1 N) afforded 11 in 98% yield after extrac-
As summarized in Scheme 1, the norbornene derivatives tion.40 The dicarboxylic acid was subsequently esterified
1 and 2 were synthesized following previously reported with methyl alcohol in the presence of a catalytic amount of
procedures.34 Briefly, cis-5-norbornene-exo-2,3-dicarboxylic sulfuric acid. Subsequent removal of the residual methanol
anhydride (3) was treated with methyl alcohol and a cata- afforded 6 as a clear liquid in 97% yield after extraction with
lytic amount of sulfuric acid. After 12 hr at 75 C, the crude dichloromethane. Monomers 5 and 6 were further purified
product was extracted, concentrated to a colorless oil, and via distillation (90 C, 0.05 Torr) prior to being subjected to
then precipitated in excess cold hexane to afford 1 as a the polymerization conditions described below.
white crystalline solid in 91% yield. Although a lower reac- Our initial efforts involved the ROMP of monomers
tion temperature was used (50 C), monomer 2 was pre- 1 and 2 using the Grubbs third generation (G3) catalyst
pared in a similar manner from 5-norbornene- by following previously reported procedures.34 Briefly,
2-endo,3-exo-dicarboxylic acid (4) and isolated as a white various quantities of G3 were added to anhydrous dic-
crystalline solid in 85% yield. hloromethane solutions of 1 or 2 ([monomer]0 = 0.2 M)
Monomers 5 and 6 were synthesized as shown in and then stirred under an atmosphere of nitrogen at
Scheme 2 and using modifications to previously reported ambient temperature. The progress of the reaction was
procedures.35,38,39 Reduction of phthalic acid (7) with a periodically monitored by thin layer chromatography and
the monomer appeared to be quantitatively consumed
after approximately 30 min. An excess of ethyl vinyl ether
relative to the catalyst was added to quench the polymeri-
zation reaction and the resulting product mixtures were
poured into cold hexane. The precipitates that formed
were then filtered and dried to afford poly(1) or poly(2)
depending on the monomer employed. Subsequent analy-
sis by size exclusion chromatography (SEC) revealed that
the experimental molecular weights determined for the
series of polymers prepared agreed with their theoretical
values and exhibited low polydispersity index (Đ) values
(see Table 1). In addition, the 1H NMR spectra recorded
for the isolated polymers displayed signals that were con-
sistent with reported values (see Figures S35 and S36).34
S C H E M E 1 Synthesis of dimethyl (1R,2R,3S,4S)-bicyclo[2.2.1] Similar methodology was used to polymerize 5 and 6,
hept-5-ene-2,3-dicarboxylate (1) and dimethyl (1R,2S,3S,4S)-bicyclo and the corresponding polymers were also characterized
[2.2.1]hept-5-ene-2,3-dicarboxylate (2) using NMR spectroscopy as well as SEC. In accordance
1690 LEE ET AL.

S C H E M E 2 Synthesis of dimethyl (1R,2S,3R,4S)-bicyclo[2.2.0]hex-5-ene-2,3-dicarboxylate (5) and dimethyl (1R,2S,3S,4S)-bicyclo[2.2.0]

hex-5-ene-2,3-dicarboxylate (6)

TABLE 1 Summary of data recorded for poly(1), poly(2), poly(5), and poly(6)

Polymer [M]0/[C]0a Mn,theory (kDa)b Mn (kDa)c Mw (kDa)c Đ Yield (%)d Tg ( C)e Td ( C)f
Poly(1) 72 15.0 18.8 20.3 1.1 89 73.4 436.1
Poly(1) 95 20.0 24.9 28.8 1.1 89 75.7 430.7
Poly(1) 357 75.0 79.6 92.8 1.2 92 71.4 441.5
Poly(2) 72 15.0 14.3 15.6 1.1 85 85.6 431.8
Poly(2) 95 20.0 19.8 21.6 1.1 93 85.6 425.2
Poly(2) 357 75.0 93.3 108.9 1.2 94 89.4 432.2
Poly(5) 76 15.0 14.6 17.1 1.2 95 68.3 217.8
Poly(5) 102 20.0 19.7 23.6 1.2 87 67.5 217.9
Poly(5) 382 75.0 66.4 82.8 1.2 87 72.6 224.0
Poly(6) 76 15.0 16.6 18.6 1.1 89 92.0 243.1
Poly(6) 102 20.0 20.3 22.2 1.1 87 94.1 245.9
Poly(6) 382 75.0 62.8 69.8 1.1 87 99.5 241.9

Abbreviations: DSC, differential scanning calorimetry; SEC, size exclusion chromatography.

a
Initial monomer-to-catalyst feed ratio.
b
Theoretical Mn values were based on the monomer-to-catalyst feed ratios and assumed quantitative conversion of monomer to polymer.
c
Values were determined by SEC and are reported relative to poly(styrene) standards in tetrahydrofuran.
d
Isolated yields.
e
Determined by DSC. Samples were first subjected to two full heating and cooling cycles at a rate of 20 C min−1 under an atmosphere of
nitrogen before being analyzed.
f
The Td value was determined from the onset of mass loss as monitored by TGA. Measurements were taken under an atmosphere of nitrogen
at a heating rate of 10 C min−1.

with data reported for other polymers prepared using 5 ([5]0/[G3]0 = 38, Mn = 9.4 kDa, Ð = 1.2), an increase in
ROMP,41,42 the 1H NMR spectra recorded for poly(5) and molecular weight was observed upon the addition of
poly(6) exhibited broad signals that were diagnostic of 6 (([5]0 + [6]0)/[G3]0 = 76, Mn = 15.7 kDa, Ð = 1.2).
alkenes (δ 5.2–5.8 ppm; CDCl3) (see Figures S37 and S39) Slightly larger Ð values (1.3 vs. 1.2) were observed when
and relatively upfield when compared to analogous sig- the order of monomer addition was reversed (see Fig-
nals recorded for the corresponding monomers ures 2b and 3b), which may be due to the substituents in
(6.2–6.4 ppm) (see Figures S30 and S33).43 SEC revealed the endo- position hindering catalytic activity (vide
that the relationship between the number average molec- infra).44 Collectively, these results suggested to us that
ular weight (Mn) of the polymer produced and the the polymerization of the monomers proceeded in a con-
monomer-to-catalyst feed ratio was linear and that the trolled fashion.
polymers exhibited relatively low Ð values (see Figures 2a Previous reports have shown that the thermal properties
and 3a). A series of chain extension experiments were of synthetic polymers can be altered by increasing the
also conducted. After the complete consumption of degree of polymerization until an asymptotic value is
LEE ET AL. 1691

F I G U R E 2 (a) Plots of Mn (red) and Đ (blue) values versus the initial 5-to-G3 feed ratio. Conditions: [5]0 = 0.20 M, CH2Cl2, 30 min.
Isolated yields were >85%. (b) Representative size exclusion chromatograms recorded for poly(5) (black) and chain extension upon the
addition of 6 (blue). Conditions and data: [5]0/[G3]0 = 38, CH2Cl2, Mn = 9.4 kDa, Đ = 1.2 (black); 6 was added after 30 min: ([5]0 + [6]0)/
[G3]0 = 76, CH2Cl2, Mn = 15.7 kDa, Đ = 1.2 (blue) [Color figure can be viewed at wileyonlinelibrary.com]

F I G U R E 3 (a) Plots of Mn (red) and Đ (blue) values versus the initial 6-to-G3 feed ratio. Conditions: [6]0 = 0.20 M, CH2Cl2, 30 min.
Isolated yields were >85%. (b) Representative size exclusion chromatograms recorded for poly(6) (black) and chain extension upon addition
of 5 (blue). Conditions and data: [6]0/[G3]0 = 38, CH2Cl2, Mn = 7.0 kDa, Đ = 1.2 (black); 5 was added after 30 min: ([6]0 + [5]0)/[G3]0 = 76,
CH2Cl2, Mn = 16.2 kDa, Đ = 1.3 (blue) [Color figure can be viewed at wileyonlinelibrary.com]

reached.2,45–48 At low degrees of polymerization, polymeric To ensure that the thermal properties exhibited by
materials can be soft due to limited entanglement; however, the polymers presented in this study were uninfluenced
as the chain lengths increase, the individual polymer chains by the degree of polymerization, homopolymers of 1, 2, 5,
begin to entangle and physically crosslink with each other. and 6 of various molecular weights were independently
As a result, movement of the polymer chains becomes hin- synthesized and characterized using SEC, ther-
dered, which leads to enhanced thermomechanical proper- mogravimetric analysis (TGA), and differential scanning
ties. Once the molecular weight of the polymers reaches a calorimetry (DSC). Key data are summarized in Table 1.
threshold, the rate of disentanglement of the polymer While the glass transition temperatures measured for all
chains becomes equal to the rate of entanglement and thus of the polymers studied occurred within the range of
significant changes are no longer observed.49 67–100 C, the decomposition temperatures exhibited by
1692 LEE ET AL.

poly(5) and poly(6) were approximately 200 C lower than were dissolved in CH2Cl2 and then poured into cold hex-
those measured for poly(1) and poly(2), presumably due ane. The precipitated solids were then collected, dried, and
to the strained four membered rings in the former. No analyzed by DSC. A similar procedure was applied to cre-
significant deviations (ca. 4 C) in the glass transition ate a mixture of poly(5) (Mn = 19.7 kDa) and poly(6)
temperatures were measured for poly(1) or poly(2) (Mn = 20.3 kDa). Single Tg values were measured for each
regardless of molecular weight and poly(2) consistently mixture (79.0 C for poly(1) and poly(2), 74.7 C for poly(5)
exhibited a Tg value that was approximately 10 C higher and poly(6); see Figure S22). Since theory developed by
than that of poly(1). Likewise, the decomposition temper- Flory states that high degrees of polymerization are
atures (Td) measured for poly(1) and poly(2) were rela- required to facilitate microphase separation for monomers
tively constant (ca. 433 C) over a wide range of of similar structure,1,50 efforts were redirected toward poly-
molecular weights. Poly(5) and poly(6) also exhibited dis- mers of relatively high molecular weight. Although DSC
cernable differences in their thermal characteristics. For measurements of a mixture consisting of equal masses of
example, the Tg measured for poly(6) was approximately poly(1) (Mn = 79.6 kDa) and poly(2) (Mn = 93.3 kDa) still
25 C higher than that measured for poly(5) (cf. 95 vs. displayed a single Tg value (83.0 C), two glass transition
70 C, respectively) irrespective of molecular weight. Poly temperatures (77.1 and 97.3 C) consistent with the values
(6) also consistently exhibited a higher decomposition for the constituent homopolymers were observed upon
temperature than poly(5) (cf. 244 vs. 220 C, respectively). analysis of a mixture of poly(5) (Mn = 66.4 kDa) and poly
Since the aforementioned sets of polymer stereoiso- (6) (Mn = 62.8 kDa) (see Figure S22).
mers exhibited different Tg values, efforts were directed To verify the aforementioned results, subsequent
toward assessing if the materials would undergo efforts were directed toward the synthesis of block and
microphase separation. To facilitate mixing, equal masses random copolymers consisting of 5 and 6. As outlined in
of poly(1) (Mn = 24.9 kDa) and poly(2) (Mn = 19.8 kDa) Scheme 3, a solution of monomer 5 was charged with a

SCHEME 3 Synthesis of diblock and random copolymers of monomers 5 and 6

LEE ET AL. 1693

solution of G3 ([5]0/[G3]0 = 38) dissolved in anhydrous molecular weight of the diblock polymer (Mn = 15.7 kDa,
dichloromethane ([5]0 = 0.2 M) and the resulting mixture Đ = 1.2) was in good agreement with the theoretical
was stirred for 30 min at 0 C. After the monomer was molecular weight (Mn = 14.3 kDa), which was based on
consumed, as determined by analyzing aliquots removed the overall yield of the reaction (95%) and assumed quan-
from the reaction mixture using thin layer chromatogra- titative initiation. As summarized in Table 2, the afore-
phy, the mixture was portioned into two fractions. One mentioned procedure was utilized to synthesize a series
fraction was poured into a mixture of excess hexane and of diblock copolymers with low Đ values and different
ethyl vinyl ether to terminate the polymerization reac- molecular weights. Over the course of these copolymeri-
tion. The precipitate that formed was collected and ana- zation reactions, it was observed that adding 6 before
lyzed by SEC (Mn = 9.4 kDa, Đ = 1.2). The second 5 consistently led to copolymers with relatively large Đ
fraction was charged with a solution of 6 dissolved in values which may be because contemporary ROMP cata-
anhydrous dichloromethane ([5]0 + [6]0)/[G3]0 = 76). lysts exhibit the following order of activity toward disub-
After running the polymerization for 30 min at 0 C, the stituted norbornenes: exo, exo > exo, endo > endo,
reaction was quenched with ethyl vinyl ether. Subse- endo.22,27,51–54 The trend can be attributed to sterics in
quent precipitation from cold hexane afforded diblock conjunction with functional group chelation to the metal
copolymer poly(5-block-6). Diblock copolymer poly(6- catalyst, effects that may be exacerbated by proximal sub-
block-5) was synthesized in a similar manner except that stituents in endo configurations.22,27,51–55 Block copoly-
the order of monomer addition was reversed. The 1H mers of 1 and 2 were also synthesized following similar
NMR spectra recorded for the copolymers revealed an procedures (see Scheme S1).
upfield shift of the alkenyl signals (δ 5.1–5.9 ppm; CDCl3) Random copolymers were envisioned to serve as con-
when compared to the analogous signals recorded for the trols and thus were also synthesized. A solution of G3 dis-
corresponding monomers (δ 6.2–6.5 ppm; CDCl3; see Fig- solved in anhydrous dichloromethane was injected into
ures S30, S33, S41, and S43). In addition, the 13C NMR an equimolar solution of 5 and 6 (([5]0 + [6]0)/
spectra recorded for the block copolymers revealed diag- [G3]0 = 102; [5]0 = [6]0 = 0.2 M). The polymerization
nostic signals (171–174 ppm, CDCl3) that were in accord was monitored via thin layer chromatography and
with those recorded for poly(5) (173 ppm, CDCl3) and quenched with ethyl vinyl ether after 30 min. Precipita-
poly(6) (171 and 173 ppm, CDCl3), and indicated that tion from cold hexane afforded poly(5-random-6), which
both monomers were incorporated (see Figure S49). The was isolated in 84% yield and found to exhibit a number

TABLE 2 A summary of data recorded for diblock and random copolymers of 5 and 6

Mn,first block
Copolymer [5 + 6]0/[C]0a (kDa)b Mn (kDa)b Mn,theory (kDa)c Đ Yield (%)d Tg ( C)e Td ( C)f
Poly(5-block-6) 76 9.4 15.7 15.0 1.2 95 78 227
Poly(5-block-6) 254 25.9 44.9 50.0 1.2 93 82 235
Poly(5-block-6) 510 53.9 92.8 100.0 1.2 89 87 235
Poly(5-block-6) 612 58.4 111.3 120.0 1.2 98 75 and 91 235
Poly(5-block-6) 764 68.0 118.7 150.0 1.1 95 76 and 93 233
Poly(6-block-5) 76 7.0 16.2 15.0 1.3 80 79 231
Poly(5-random-6)g 102 N/A 23.5 20.0 1.1 84 79 232
g
Poly(5-random-6) 382 N/A 62.8 75.0 1.1 82 87 235

Abbreviations: DSC, differential scanning calorimetry; SEC, size exclusion chromatography.

a
Total monomer-to-catalyst feed ratio. Equimolar mixtures of the two monomers were used.
b
Values were determined by SEC and are reported relative to poly(styrene) standards in tetrahydrofuran. The Mn,first block value refers the
molecular weight of the homopolymer formed prior to the addition of the second monomer.
c
Theoretical Mn values were based on the monomer to catalyst feed ratios and assumed quantitative conversion of monomer to polymer and
quantitative initiation.
d
Isolated yields.
e
Determined by DSC. Samples were first subjected to two full heating and cooling cycles at a rate of 20 C min−1 under an atmosphere of
nitrogen before being analyzed.
f
The Td value was determined from the onset of mass loss as monitored by TGA. Measurements were taken under an atmosphere of nitrogen
at a heating rate of 10 C min−1.
g
A random copolymer of 5 and 6 was prepared using an equimolar mixture of the two monomers.
1694 LEE ET AL.

TABLE 3 A summary of data recorded for diblock and random copolymers of 1 and 2

Mn,first block
Copolymer [1 + 2]0/[C]0a (kDa)b Mn (kDa)b Mn,theory (kDa)c Đ Yield (%)d Tg ( C)e Td ( C)f
Poly(1-block-2) 72 9.2 18.5 15.0 1.1 84 82 431
Poly(1-block-2) 238 29.3 51.3 50.0 1.1 96 77 435
Poly(1-block-2) 476 54.5 95.9 100.0 1.1 93 82 437
Poly(1-block-2) 570 80.6 122.9 120.0 1.1 97 81 434
Poly(1-block-2) 714 78.3 139.0 150.0 1.1 93 83 430
Poly(2-block-1) 72 8.1 18.6 15.0 1.2 81 78 433
g
Poly(1-random-2) 96 N/A 24.1 20.0 1.1 80 83 433
g
Poly(1-random-2) 356 N/A 76.9 75.0 1.2 83 85 436

Abbreviations: DSC, differential scanning calorimetry; SEC, size exclusion chromatography.

a
Total monomer-to-catalyst feed ratio. Equimolar mixtures of the two monomers were used.
b
Values were determined by SEC and are reported relative to poly(styrene) standards in tetrahydrofuran. The Mn,first block value refers the
molecular weight of the homopolymer formed prior to the addition of the second monomer.
c
Theoretical Mn values were based on the monomer to catalyst feed ratios and assumed quantitative conversion of monomer to polymer and
quantitative initiation.
d
Isolated yields.
e
Determined by DSC. Samples were first subjected to two full heating and cooling cycles at a rate of 20 C min−1 under an atmosphere of
nitrogen before being analyzed.
f
The Td value was determined from the onset of mass loss as monitored by TGA. Measurements were taken under an atmosphere of nitrogen
at a heating rate of 10 C min−1.
g
A random copolymer of 1 and 2 was prepared using an equimolar mixture of the two monomers.

FIGURE 4 DSC data recorded for (a) poly(5-block-6) (black-to-orange) and poly(6-block-5) (magenta) as well as (b) poly(1-block-2)
(black-to-orange) and poly(2-block-1) (magenta). Samples were first subjected to two heating and cooling cycles prior and then data shown
were recorded at a temperature ramp rate of 20 C min−1. DSC, differential scanning calorimetry [Color figure can be viewed at
wileyonlinelibrary.com]

average molecular weight (Mn = 23.5 kDa, Đ = 1.1) that initial monomer-to-catalyst ratio was used (([5]0 + [6]0)/
was in good agreement with the theoretical value [G3]0 = 382). Random copolymers of 1 and 2 were also
(Mn,theory = 20.0 kDa). Random copolymers with rela- synthesized (see Scheme S1).
tively high molecular weights (Mn = 62.8 kDa, Đ = 1.1) As summarized in Tables 2 and 3, the copolymers pre-
were polymerized in a similar manner, although a greater pared from either the substituted norbornenes or the
LEE ET AL. 1695

Dewar benzene derivatives exhibited Td values that were Schlenk techniques. Phthalic acid, sodium acetate, mer-
similar to their constituent homopolymers. Single Tgs were cury, 5-norbornene-2-endo,3-exo-dicarboxylic acid,
identified upon analysis of diblock copolymers poly(5- Grubbs second generation catalyst (G2), and anhydrous
block-6) and poly(6-block-5) with Mn values of less than dichloromethane were purchased from Sigma-Aldrich.
100 kDa, which indicated that the homopolymer constitu- The Grubbs third generation catalyst (G3) was gener-
ents did not undergo microphase separation.56,57 Similar ated from G2 following previously reported proce-
to observations made with the physical mixtures of poly(5) dures.58 Sulfuric acid, hydrochloric acid, and acetic
and poly(6), only the relatively high molecular weight anhydride were purchased from the Samchun Chemical
diblock copolymers exhibited two distinct Tgs that agreed Company. 3-Bromopyridine was purchased from Tokyo
with the values measured for poly(5) and poly(6) (see Chemical. cis-5-norbornene-exo-2,3-dicarboxylic anhy-
Figure 4a). For comparison, random copolymers poly(5- dride was purchased from Alfa Aesar. Sodium metal
random-6) exhibited single Tg values that were intermedi- and all solvents were purchased from Daejung Chemical
ate of their respective homopolymers. Consistent with the unless otherwise noted. The photoirradiation experi-
data recorded for the physical mixture of poly(1) and poly ments were performed using a 450-W medium pressure
(2), single Tg values were measured upon analysis of poly mercury lamp connected to a photo reactor (Ace Glass).
(1-block-2), poly(2-block-1), and poly(1-random-2) even at All photoreactions were conducted in quartz vessels.
high molecular weights which indicated that microphase Nuclear magnetic resonance (NMR) spectra were
separation was not observed (see Figure 4b). recorded at ambient temperature (22.0 ± 1.0 C, unless
stated otherwise) on a Bruker Avance III HD spectrome-
ter (operating at 400 MHz for 1H). Chemical shifts are
3 | C ON C L U S I ON S given in ppm and relative to tetramethylsilane (TMS)
using the residual, nondeuterated solvent as an internal
Diastereomeric methyl ester derivatives of norbornene and standard. For 1H NMR: (CD3)2CO: 2.05 ppm, CDCl3:
Dewar benzene were synthesized and polymerized in a 7.26 ppm.59 For 13C NMR: CDCl3, 77.16 ppm.59 Abbrevi-
controlled manner using ROMP. The stereochemistry of ations used for the description of the spectra are: s, sin-
the pendant ester groups (endo-, endo- vs. endo-, exo-) was glet; d, doublet; t, triplet; m, multiplet; and br, broad.
found to affect the glass transition temperatures displayed Coupling constants (J) are expressed in hertz (Hz). SEC
by the corresponding homopolymers with pronounced dif- was performed on a Malvern GPCmax system. Two fluo-
ferences being observed in the polymers derived from rinated poly(styrene) columns (IMBHW-3078 and I-
Dewar benzene. Similarly, block copolymers comprised of MBHMW-3078) were used in series and maintained at
the diastereomeric derivatives of Dewar benzene exhibited 35 C. THF was used as the mobile phase at a flow rate
two distinct glass transitions whereas their norbornene of 0.8 mL min−1. Detection was performed using a Vis-
analogues exhibited only one. The smaller size of the cotek VE3580 refractive index detector. Molecular
corresponding monomer can be expected to reduce the weight and polydispersity data are reported relative to
distance between the pendant functional groups and the poly(styrene) standards in THF. DSC data were recorded
polymer backbone, particularly when compared to using a TA Q2000 Differential Scanning Calorimeter
substituted poly(norbornene) analogues. Thus, while the (TA Instruments, New Castle, DE). Measurements were
thermal properties of poly(alkenamer)s can be altered recorded under nitrogen (flow rate = 50 mL min−1) and
through stereochemical modifications, differences become over a temperature range of −20 to 250 C. The samples
amplified as the pendant stereocenters reduce their prox- were subjected to two heating and cooling cycles at rates
imity to the polymer backbone. The results reported of up to 20 C min−1 prior to recording of the data. TGA
herein provide a systematic and quantitative evaluation of data were recorded under nitrogen (flow
−1
such relationships and can be expected to guide the devel- rate = 60 mL min ) on a TA Instruments TGA Q500 at
opment of new classes of poly(alkenamer)s, particularly a heating rate of 10 C min−1. Attenuated total reflec-
for high performance applications. tance infrared spectroscopy (ATR-IR) measurements
were taken using a diamond crystal on a Cary 630 FT-IR
Spectrometer (Agilent). High-resolution mass spectra
4 | EXPERIMENTAL SECTION (HR-MS) were obtained from a Waters, Inc. JMS-
T100LP AccuTOF LC-plus 4G atmospheric pressure ion-
4.1 | General methodology ization high-resolution time-of-flight mass spectrometer.
Melting points were determined with a MPA
Unless otherwise noted, all reactions were conducted 100 Optimelt automated melting point system at a
under an atmosphere of nitrogen using standard heating rate of 2 C min−1 and are uncorrected.
1696 LEE ET AL.

4.2 | General homopolymerization 30 min, with monomer consumption being monitored by

procedure thin layer chromatography. Upon complete monomer
consumption, the reaction was quenched with ethyl vinyl
All glassware were flame dried before being used. Mono- ether and the polymer mixture was poured into excess
mer (100 mg) was dissolved in anhydrous dic- cold hexane. The precipitate that formed was collected
hloromethane ([monomer]0 = 0.2 M) and injected under via filtration, washed with hexane, and then dried at
a positive flow of nitrogen into a 25 mL Schlenk tube. 55 C under reduced pressure. See Tables 2 and 3 for addi-
Various quantities of G3 were dissolved in a minimal tional details.
amount of anhydrous dichloromethane and then imme- Poly(5-block-6) 1H NMR (400 MHz, CDCl3): δ
diately injected into the reaction vessel containing the 5.90–5.22 (br, 2H), 3.91–3.50 (br, 6H), 3.49–2.81 (br, 4H).
monomer under a positive flow of nitrogen. Monomer Poly(6-block-5) 1H NMR (400 MHz, CDCl3): δ
consumption was monitored over time using thin layer 5.91–5.24 (br, 2H), 3.86–3.53 (br, 6H), 3.51–2.85 (br, 4H).
chromatography. Once the monomer was consumed (typ- Poly(1-block-2) 1H NMR (400 MHz, CDCl3): δ
ically 30 min at 25 C), the reaction was quenched with 5.64–5.06 (br, 2H), 3.91–3.52 (br, 6H), 3.50–2.51 (br, 4H),
excess ethyl vinyl ether and the product mixture was 2.28–1.78 (br, 1H), 1.57–1.04 (br, 1H).
poured into excess hexane. The precipitate that formed Poly(2-block-1) 1H NMR (400 MHz, CDCl3): δ
was subsequently collected via filtration, washed with 5.67–5.02 (br, 2H), 3.96–3.48 (br, 6H), 3.47–2.57 (br, 4H),
hexane, and then dried at 55 C under reduced pressure. 2.35–1.75 (br, 1H), 1.52–1.04 (br, 1H).
See Table 1 for more details.
Poly(1) 1H NMR (400 MHz, CDCl3): δ 5.52–5.13 (br,
2H), 3.77–3.51 (br, 6H), 3.48–3.19 (br, 1H), 3.12–2.71 (br, 4.4 | General random copolymerization
3H), 2.27–1.89 (br, 1H), 1.34–0.97 (br, 1H). procedure
Poly(2) 1H NMR (400 MHz, CDCl3): δ 5.68–4.97 (br,
2H), 3.99–3.45 (br, 6H), 3.40–2.48 (br, 4H), 2.18–1.79 (br, All glassware were flame dried before being used. The
1H), 1.52–1.35 (br, 1H). monomers (50 mg each) were dissolved in anhydrous
Poly(5) 1H NMR (400 MHz, CDCl3): δ 5.69–5.33 (br, dichloromethane (0.2 M) and injected under a positive
2H), 3.79–3.53 (br, 6H), 3.51–2.85 (br, 4H). flow of nitrogen into a 25 mL Schlenk tube. G3 was then
Poly(6) 1H NMR (400 MHz, CDCl3): δ 5.84–5.23 (br, dissolved in a minimal quantity of anhydrous dic-
2H), 3.83–3.50 (br, 6H), 3.52–2.85 (br, 4H). hloromethane and immediately injected under positive
nitrogen flow. The reaction mixture was stirred at 25 C
under an atmosphere of N2 for 30 min, with monomer
4.3 | General block copolymerization consumption being monitored by thin layer chromatog-
procedure raphy. Upon complete monomer consumption, the reac-
tion was quenched with ethyl vinyl ether and the
All glassware were flame dried before being used. The product mixture was poured in excess cold hexane. The
corresponding monomer for the first block (50 mg) was precipitate that formed was collected via filtration,
dissolved in anhydrous dichloromethane (0.2 M) and washed with hexane, and then dried at 55 C under
injected under a positive flow of nitrogen into a 25 mL reduced pressure. See Tables 2 and 3 for additional
Schlenk tube. G3 was then dissolved in a minimal details.
amount of anhydrous dichloromethane and immediately Poly(5-random-6) 1H NMR (400 MHz, CDCl3): δ
injected under positive nitrogen flow. The reaction mix- 5.87–5.24 (br, 2H), 3.93–3.53 (br, 6H), 3.50–2.78 (br, 4H).
ture was stirred at 0 C under a N2 atmosphere for Poly(1-random-2) 1H NMR (400 MHz, CDCl3): δ
30 min, with monomer consumption being monitored by 5.64–5.05 (br, 2H), 3.96–3.53 (br, 6H), 3.49–2.57 (br, 4H),
thin layer chromatography. Upon complete monomer 2.29–1.83 (br, 1H), 1.56–1.06 (br, 1H).
consumption, a small aliquot was removed and poured
into a mixture of hexane and ethyl vinyl ether to induce
precipitation and to facilitate isolation of the 4.5 | Physical mixing of homopolymers
corresponding homopolymer. The monomer
corresponding to the second block (50 mg) was then dis- A mixture of two homopolymers in a 1:1 weight ratio
solved in a minimal amount of anhydrous dic- was dissolved in dichloromethane and then poured into
hloromethane and injected into the reaction mixture cold hexane. The precipitate that formed was collected
under positive nitrogen flow. The reaction mixture was via filtration, washed with hexane, and then dried at
stirred at 0 C under a N2 atmosphere for an additional 55 C under reduced pressure.
LEE ET AL. 1697

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[59] G. R. Fulmer, A. J. M. Miller, N. H. Sherden, H. E. Gottlieb,

A. Nudelman, B. M. Stoltz, J. E. Bercaw, K. I. Goldberg, How to cite this article: Lee SY, Seo J,
Organometallics 2010, 29, 2176.
Bielawski CW. A systematic study of
stereochemical effects in homologous poly
S UP PO RT ING IN FOR MAT ION (alkenamer)s: Dewar benzene versus norbornene.
Additional supporting information may be found online J Polym Sci. 2020;58:1687–1698. https://doi.org/10.
in the Supporting Information section at the end of this 1002/pol.20200250
article.