Polymer 213 (2021) 123207

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Polymer
journal homepage: http://www.elsevier.com/locate/polymer

Chain flexibility and glass transition temperatures of poly(n-alkyl (meth)

acrylate)s: Implications of tacticity and chain dynamics☆
Tianyu Li a, Hui Li e, Huiqun Wang b, Wei Lu b, Masashi Osa d, Yangyang Wang e,
Jimmy Mays b, **, Kunlun Hong e, c, *
a
Department of Materials Science & Engineering, Knoxville, TN, 37996, USA
b
Department of Chemistry, Knoxville, TN, 37996, USA
c
Department of Chemical & Biomolecular Engineering, University of Tennessee, Knoxville, TN, 37996, USA
d
Department of Chemistry, Aichi University of Education, Kariya, 448-8542, Japan
e
Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA

A R T I C L E I N F O A B S T R A C T

Keywords: The relationship between chain microstructure and glass transition temperature (Tg) is complicated for poly
Poly(n-alkyl acrylate) (alkyl methacrylate)s and poly(alkyl acrylate)s. Despite intensive studies, relationships between the structures of
poly(n-alkyl methacrylate) these polymers and their properties, including solution characteristics and Tg, are still controversial. Solution
Tacticity
properties, chain conformations, including Flory’s characteristic ratio (C∞), persistence length (lp), and chain
Glass transition temperature
Characteristic ratio
diameters, and Tg are reported for series of poly(n-alkyl acrylate)s and poly(n-alkyl methacrylate)s having alkyl
Persistence length side chain lengths (n) ranging from 1 to 10 carbons in length, with uniform and well-characterized tacticities.
Chain flexibility Chain flexibilities of both series of polymers decrease as n increases, reflecting increased hindrances to rotation
Solution properties about backbone bonds as side chains become longer. Conversely, the Tgs for both series of polymers decrease
substantially as n increases, reflecting the greater side chain mobilities of long alkyl substituents. For shorter
alkyl chain lengths, Tgs for the poly(n-alkyl acrylate)s are much lower than for the corresponding poly(n-alkyl
methacrylate)s, a difference which has been attributed in the past to the presumed reduced chain flexibility of
polymethacrylates due to the presence of the α-methyl substituent. However, contrary to such expectations, C∞
and lp values for these two series of polymers are nearly identical at a given n value, except for the longest n-alkyl
substituents. Instead, the differences in Tg may be attributed to the differences in tacticity of the two series –
almost ideally atactic for the poly(n-alkyl acrylate)s but high in syndiotacticity for the poly(n-alkyl methacrylate)
s. The Tgs for the two series of polymers approach that of polyethylene at longer alkyl chain lengths. In addition,
the effects of tacticity and chain dynamics on C∞, lp, and Tg of poly(methyl methacrylate) is discussed.

1. Introduction
Poly(n-alkyl(meth)acrylate)s are industrially important polymers
used widely in adhesives, paints, and coatings [1]. They have also
attracted considerable fundamental interest from polymer physicists as
they offer the potential to explore the influence of alkyl side chain length
on basic materials parameters such as flexibility, as reflected in the glass
transition temperature (Tg), characteristic ratio (C∞), and persistence
length (lp). The effect of number of carbons in the side chain (n) on the
Tg of series of poly(n-alkyl methacrylate)s and poly(n-alkyl acrylate)s
has been studied since the 1950s and 1960s, respectively [2–6]. More
recently, several groups have focused on more detailed studies of the
dynamics and “fragility” of these families of complex and interesting
materials [5–12].
The effect of side chain length on the conformational characteristics
of poly(n-alkyl methacrylates)s, as reflected in C∞, has been studied

☆
This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US gov­
ernment retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable,
worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public
access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).
* Corresponding author. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA.
** Corresponding author.
E-mail addresses: jimmymays@utk.edu (J. Mays), hongkq@ornl.gov (K. Hong).

https://doi.org/10.1016/j.polymer.2020.123207
Received 4 September 2020; Received in revised form 15 October 2020; Accepted 3 November 2020
Available online 6 November 2020
0032-3861/© 2020 Published by Elsevier Ltd.
T. Li et al.
experimentally and theoretically by various workers and the results
have been summarized in review articles [13,14]. However, in many
cases the tacticities of the polymers studied were not reported [15,16].
Only for the case of poly(methyl methacrylate) (PMMA) has the effect of
tacticity on C∞ of samples having well-characterized tacticities been
studied [17].
In the case of poly(n-alkyl acrylate)s, there have been far fewer
experimental studies on their conformational characteristics, with only a
single report of unperturbed dimensions of poly(methyl acrylate) pre­
pared free radically without report on its tacticity [17]. A major
complication with characterization of the chain flexibility of poly­
acrylates prepared free radically, which is not a substantial issue with
polymethacrylates, is chain transfer to polymer involving the labile
α-hydrogen [19]. These chain transfer reactions lead to long chain
branching, which reduces the size of the polymer chain, affecting
measured solution properties and complicating the characterization of
conformational characteristics of linear polyacrylates.
In this work, we prepared series of poly(n-alkyl acrylate)s and poly
(n-alkyl methacrylate)s having n values ranging from 1 to 10 using
conventional free radical solution polymerization. The reaction condi­
tions produced polymers of weight-average molecular weights (Mw) of
the order of 105 g/mol, with broad dispersities (Mw/Mn > 1.5) and
consistent tacticities. By characterizing these materials using size
exclusion chromatography (SEC) with online light scattering and vis­
cosity detectors, Mark-Houwink equations in a SEC eluent (tetrahydro­
furan, THF) were derived, relating intrinsic viscosity ([η]) to molecular
weight (M) for each slice in the chromatograms. Branching was detected
at higher molecular weights in each of the poly(n-alkyl acrylate)s, as
expected, but not in the poly(n-alkyl methacrylate)s, as a downturn in
the linear Mark-Houwink plots at higher molecular weights [19]. By
restricting the data to the linear range of the Mark-Houwink plots, C∞
values were derived for each linear shaped polymer using Tanaka plots
[21] and persistence lengths and chain diameters were derived using the
touched bead helical wormlike chain model [22]. Tg values were
determined using differential scanning calorimetry (DSC). In addition, a
series of poly(methyl methacrylate)s (PMMAs) having widely varying
tacticities was synthesized and subjected to the same characterization
methods along with measurements of dynamic fragility (m), providing
insight into the effect of tacticity and chain dynamics on C∞, lp, and Tg.
Data are compared with theoretical predictions and with data from prior
studies where possible.
2. Experimental section
2.1. Materials
All reagents were used as received from the suppliers without further
purification unless otherwise noted. Methyl methacrylate (99%), ethyl
methacrylate (99%), n-propyl methacrylate (97%), n-butyl methacry­
late (99%), n-hexyl methacrylate (98%), methyl acrylate (99%), ethyl
acrylate (99%), n-butyl acrylate (99%), n-hexyl acrylate (98%), chro­
mium(III) acetylacetonate, aluminum oxide (activated, basic, Brock­
mann I) (Al2O3), 2,2′ -Azobis(2-methylpropionitrile) (AIBN), ytterbium
(III) oxide (99.99% trace metals basis) (Yb2O3) and anhydrous chloro­
benzene were purchased from Sigma-Aldrich. n-Amyl methacrylate, n-
propyl acrylate and n-pentyl acrylate were obtained from Pfaltz &
Bauer. n-Octyl methacrylate (99%) and n-decyl methacrylate (99%)
were purchased from Polyscience, Inc. n-Octyl acrylate (98%), n-decyl
acrylate, and 1,1,1,3,3,3-Hexafluoro-2-propanol (HFIP) were purchased
from TCI America, Scientific Polymer Products, Inc, and Oakwood
Chemical, respectively. Bis(trifluoromethanesulfonyl)imide (HNTf2)
and other solvents were obtained from VWR. AIBN was purified by
recrystallization from methanol. All acrylates and methacrylates were
purified by passing through the basic Al2O3 column to remove the
inhibitor.
2
Polymer 213 (2021) 123207
2.2. Synthesis of poly(n-alkyl acrylate)s and poly(n-alkyl methacrylate)s
Polyacrylates and polymethacrylates were polymerized by conven­
tional free radical polymerization using AIBN as the initiator. In a typical
procedure, monomer (1.0 eq), AIBN (0.5% eq) and anhydrous chloro­
benzene (0.58 M) were added into a round bottom flask. Then, the so­
lution was degassed by bubbling with nitrogen gas for at least 10 min.
After heating at 60 ◦ C with stirring under inert atmosphere for 24 h, the
reaction was quenched in a liquid nitrogen bath. These conditions
resulted in low to moderate conversions ranging from about 10 to about
50%. The solution was concentrated and precipitated into cold methanol
to yield the product from white solid to viscous liquid depending on the
length of the n-alkyl chains.
2.3. Synthesis of Lewis acid: Yb(NTf2)3
The Lewis acid was synthesized according to the literature [23,24].
Into a 250 mL round bottom flask, Yb2O3 (6.6 g, 16.80 mmol, 1.0 eq),
HNTf2 (25.0 g, 88.92 mmol, 5.3 eq) and 150 mL of DI water were added.
The solution was stirred at 90 ◦ C overnight under nitrogen atmosphere,
Then, the suspension was filtered, and the clear solution was dried by
blowing nitrogen gas at 120 ◦ C for 4 h. After drying completely under
high vacuum at 100 ◦ C overnight, the Lewis acid, which is a highly
hygroscopic white solid, was used and stored in an Ar-filled glovebox.
2.4. Synthesis of poly(methyl methacrylate) samples having different
tacticities
Poly(methyl methacrylate)s with controlled tacticity were synthe­
sized by conventional free radical polymerization by adding desired
amount of Yb(NTf2)3 [24]. Monomer (1.0 eq), AIBN (0.5% eq), HFIP
(0.58 M), and predetermined amounts of Yb(NTf2)3 were transferred
into a round bottom flask in a glovebox. Then, the solution was stirred at
room temperature and degassed by bubbling with nitrogen gas for at
least 20 min. After sealing the flask, the solution was heated and stirred
at 60 ◦ C for 24 h under inert atmosphere. The reaction was quenched in a
liquid nitrogen bath. Then, the solution was concentrated and precipi­
tated in cold methanol to yield the product as solids.
We attempted to prepare a series of poly(methyl acrylate)s by using
the same strategy but only low molecular weight samples were obtained
(the Lewis acid inhibited the polymerization).
2.5. Characterization
1
H and 13C NMR spectra were obtained on a Varian VNMRS 500
NMR spectrometer at 25 ◦ C in CDCl3 (7.27 ppm [1] H reference and
77.23 ppm 13C reference) unless otherwise noted. For the 13C NMR
sample preparation, chromium(III) acetylacetonate (3 mg/mL) was
added into CDCl3 to reduce the relaxation time. 13C NMR spectra were
obtained with a relaxation delay of 1.7 s, acquisition time of 1.232 s, and
a 90◦ pulse width.
Absolute molecular weights and intrinsic viscosities of the synthe­
sized polymers were determined with a Malvern OMNISEC system
equipped with OMNISEC RESOLVE and OMNISEC REVEAL, which
included a light scattering detector (RALS 90◦ angle and LALS 7◦ angle)
equipped with a 640 nm laser, a refractive index (RI) detector, and a
viscometer (4-capillary Wheatstone bridge with self-balancing mecha­
nism). Two PLgel mixed-C columns (5 μm particle size and 300 mm by
7.5 mm column dimensions, each) and one PLgel guard column (5 μm
particle size and 50 mm by 7.5 mm column dimensions) in series were
used. THF was the eluent with a flow rate of 1 mL/min at 30 ◦ C. Specific
refractive index increments (dn/dc) were measured for the various
samples by differential refractometry or from the chromatograms using
the sample concentrations.
Differential scanning calorimetry (DSC) measurements were per­
formed using TA Instruments calorimeters (Q2000 or Discovery 2500)
T. Li et al. Polymer 213 (2021) 123207

Table 1
Molecular Characteristic of Poly(n-alkyl methacrylate)s.
Polymer Mw (kg/mol) Mw/Mn Tacticity (mm/mr/rr)

Methyl 67.0 1.91 3/33/64

Ethyl 94.0 1.63 2/33/65
n-propyl 66.4 1.59 1/31/68
n-butyl 146 3.81 2/30/68
n-pentyl 130 2.08 2/32/66
n-hexyl 113 2.65 2/32/66
n-octyl 145 2.31 2/30/68
n-decyl 165 2.97 1/30/69

Table 2
Molecular Characteristics of Poly(n-alkyl acrylate)s.
Polymer Mw (kg/mol) Mw/Mn Tacticity (mm/mr/rr)

Methyl 111 2.26 30/38/32

Ethyl 128 1.67 24/44/32
n-propyl 86.7 1.85 25/40/35
n-butyl 99.1 2.18 25/41/34 Fig. 1. Tanaka’s plots of poly(n-alkyl methacrylate)s.
n-pentyl 109 2.37 25/41/34
n-hexyl 183 2.66 25/42/32
n-octyl 226 5.55 28/41/31
n-decyl 56.0 2.05 28/42/30

Table 3
Molecular Characteristics of PMMAs having Various Tacticities.
Yb(Ntf2)3 Mw (kg/ Mw/ Tacticity (mm/ Isotactic Diads (m
(mol/L) mol) Mn mr/rr) %)

0 67.0 1.91 3/33/64 19.5

0.005a 239 4.80 11/35/54 28.5
0.010a 62.1 1.35 16/37/47 34.5
0.005b 72.2 1.99 23/35/42 40.5
0.010b 80.2 2.08 30/36/34 48.0
0.020b 81.8 2.19 32/37/31 50.5
0.030b 95.3 2.30 38/36/26 56.0
0.040b 88.6 2.54 44/37/19 62.5
0.050b 93.4 2.44 47/37/16 65.5
0.070b 77.1 2.30 48/37/15 66.5
0.110b 75.8 2.21 50/37/13 68.5
a
Precipitated twice.
b
Precipitated once. Fig. 2. Tanaka’s plots of poly(n-alkyl acrylate)s.

under nitrogen flow. Approximately 4–6 mg of purified polymers were

loaded into Tzero aluminum pans. For the measurement of glass tran­
sition temperature, the samples were first heated to 120 ◦ C at 10 ◦ C/min
and equilibrated for 4 min to remove thermal history. A subsequent
cool/heat cycle was carried out at 10 ◦ C/min for ramp experiments. The
Tg data presented in the main text were taken from the second heating
curves. For poly(methyl methacrylate), the samples were heated to
160 ◦ C at 10 ◦ C/min because of this polymer’s higher Tg . In obtaining
dynamic fragility (m) for PMMAs with different tacticities, the samples
were first heated to 170 ◦ C at 20 ◦ C/min to remove thermal history.
After cooling at controlled cooling rates, designed as 30, 20, 10, 5, 1 and
0.5 ◦ C/min, each of which was then heating at a standard heating rate as
20 ◦ C/min. The temperature range of the measurement was set as − 50 to
170 ◦ C. The calculation of dynamic fragility can be found in Supporting
Information.

3. Results and discussion

3.1. Solution properties and chain flexibility

Molecular weights, dispersities (ratio of weight-average to number-
average molecular weights, Mw/Mn), and tacticities of the poly(n-alkyl
methacrylate)s, poly(n-alkyl acrylate)s, and PMMAs of various tactic­
ities are shown in Tables 1–3, respectively. Details of the NMR analysis
Fig. 3. Tanaka’s plots of PMMAs with varying tacticities.
and results are shown in the Supporting Information.
By using SEC to separate these polydisperse material into narrowly
dispersed slices, light scattering and viscosity detectors may then be

3
T. Li et al. Polymer 213 (2021) 123207

Table 4 Table 7
Mark-Houwink Coefficients (K and α) for Poly(n-alkyl methacrylate)s in THF at Structural information of poly(n-alkyl methacrylate)s.
30 ◦ C. Polymer Tacticity (% m) lp (nm) db (nm)
C∞ ML (nm− 1 )
Polymer K (dL/g x 104) α Corr. Coeff.
methyl 19.5 8.0 400 1.10 0.60
methyl 1.28 0.69 0.9980 ethyl 18.5 8.4 456 1.60 0.66
ethyl 1.37 0.70 0.9990 n-propyl 16.5 9.0 512 1.80 0.70
n-propyl 1.43 0.69 0.9982 n-butyl 17.0 10.3 568 1.90 0.77
n-butyl 1.58 0.68 0.9963 n-pentyl 18.0 10.4 624 2.05 0.87
n-pentyl 1.10 0.71 0.9995 n-hexyl 18.0 11.6 680 2.15 0.94
n-hexyl 1.34 0.68 0.9994 n-octyl 17.0 13.8 792 2.40 1.09
n-octyl 1.04 0.70 0.9997 n-decyl 16.0 14.9 904 2.60 1.28
n-decyl 0.81 0.71 0.9999

exception of our sample isotactic diads of 50.5% where α is higher and K

Table 5 is smaller. The MH exponents for poly(n-octyl acrylate) and poly(n-decyl
Mark-Houwink Coefficients for Linear Poly(n-alkyl acrylate)s in THF at 30 ◦ C. acrylate) are slightly smaller than those observed for the other polymers
and this may suggest some long chain branching at higher Mws, although
Polymer K (dL/g x 104) α Corr. Coeff.
the MH plots are strictly linear with very high correlation coefficients.
methyl 1.88 0.66 0.9999
Flory’s characteristic ratio (C∞ ) compares the mean square end-to-
ethyl 1.35 0.72 0.9999
n-propyl 1.33 0.71 0.9999
end distance of an unperturbed polymer chain (Flory theta conditions)
n-butyl 1.22 0.70 0.9999 to that of a freely jointed polymer chain, having no fixed bond angles
n-pentyl 0.79 0.74 0.9999 and no hindrances to rotation about backbone bonds. Thus, the freely
n-hexyl 1.11 0.71 0.9999 jointed chain would exhibit a C∞ of one, while larger values would
n-octyl 1.26 0.66 0.9999
reflect an increase in size brought about by both fixed bond angles and
n-decyl 1.38 0.65 0.9999
hindrance to rotation about backbone bonds. C∞ can be estimated from
intrinsic viscosity data obtained in thermodynamically good solvents.
The most common of these methods is the BSF plot, developed inde­
Table 6
pendently by Burchard [25] and by Stockmayer and Fixman [26]. In
Mark-Houwink coefficients for PMMA of varying tacticity.
general, the BSF plot gives a reliable estimate of unperturbed di­
Tacticity (% m) K (dL/g x 104) α Corr. Coeff. mensions (Kθ ) when the molecular weights are not too high and solvents
19.5 1.28 0.69 0.9980 are not too good in the thermodynamic sense (in other words, when
28.5 1.74 0.68 0.9843 excluded volume effects are not too large) [14]. However, based on our
34.5 1.59 0.67 0.9986 measured Mark-Houwink coefficients, THF is a good solvent for all of
40.5 1.49 0.68 0.9997
48.0 1.32 0.69 0.9996
the samples (α around 0.7). Thus, viscosity data were processed using
50.5 0.36 0.80 0.9846 Tanaka’s method [21], which gives a more linear fit to larger excluded
56.0 0.87 0.73 0.9995 volumes [26,27]. The Tanaka equation is given as [21]:
62.5 1.12 0.71 0.9995
65.5 1.20 0.70 0.9985 ⎛ ⎞53
5( )
66.5 1.21 0.71 0.9998 5
⎝[η]M ⎠ = Kθ3 + 0.667φ30 R2 0 M − 1 BM 12 (1)
− 1
2
68.5 1.64 0.68 0.9997

used to determine the molecular weight (Mw) dependence of intrinsic where φ0 is Flory hydrodynamic parameter for a flexible linear unper­
viscosity over a wide range of M from each peak slice. Figs. 1–3 and turbed coil with a value of 2.5 ×1021 mol− 1 [29], R2 0 is unperturbed
Tables 4–6 summarize the resulting Mark-Houwink (MH) plots for these mean square end to end distance, and B is excluded volume parameter.
materials. The MH parameters summarized in Table 4 for poly(n-alkyl Kθ is unperturbed parameter and can be expressed as [29]:
methacrylate)s and in Table 6 for PMMAs having various tacticities ( )3/2
are taken over the range of 40 kg/mol to the highest molecular weight Kθ = φ0 R2 0 M − 1 (2)
possible based on detector sensitivity and sample concentration. For the
⎛ ⎞53
poly(n-alkyl acrylate)s, where long chain branching due to chain
1
transfer to polymer is known to be present at higher molecular weight with Tanaka’s equation, Kθ can be calculated from a plot of ⎝[η]M− ⎠ 2

[19], the data were taken from 25 kg/mol up to the point where
branching was detected as a downturn in the MH plot [20]. The
1
vs. M2 and C∞ can be derived according to its definition [29]:
downturn reflects the smaller size of the branched polymer as compared [ ]
to a linear polymer having the same Mw. On the other hand, the 2
R2 0
m0 ( 2/3 )
R0 M Kθ mo
macromolecular architecture of lower molecular weight polymers is C∞ = lim 2 = = (3)
2 l2
essentially linear.
N→∞ Nl l φ0
The Mark-Houwink equations all show good linearity with high
where l is the bond length (0.154 nm) and ​ mo is the average mass per
correlation coefficients over the Mw ranges employed. The MH expo­ M
nents are in the range of 0.68–0.72 for all but a few of the poly­ main chain bond (mo = repeat
2
unit
), since there are two main bonds in each
methacrylates and polyacrylates, as expected for linear chains in repeating unit for poly(meth)acrylates.
1
thermodynamically good solvents. The exponent of 0.69 determined in Data from 200 g/mol1/2 ≤ M2 ≤ 400 g/mol1/2 were selected for
this work for free radically produced PMMA with isotactic diads of fitting in the Tanaka plots. When the molecular weight is too low, the
19.5% is in good agreement with values in the literature ranging from molecular weight measured from the light scattering detector is less
0.69 to 0.73 reported for “predominantly syndiotactic” PMMAs made by accurate, and when the molecular weight is too high linearity in the
both free radical and anionic polymerization [27–32]. The K and α Tanaka plot is lost due to the poor separation beyond the columns’
values we obtain for PMMA as a function of Mw are also in excellent exclusion volume. Tanaka plots for poly(n-alkyl methacrylate)s, poly(n-
accord with values reported by Jenkins and Porter [18], with the alkyl acylate)s, and PMMA of varied tacticity are shown, respectively, in

4
T. Li et al. Polymer 213 (2021) 123207

Table 8
Structural information of poly(n-alkyl acrylate)s.
Polymer Tacticity (% m) C∞ ML (nm− 1 ) lp (nm) db (nm)

methyl 49.0 8.1 344 1.05 0.55

ethyl 46.0 9.1 400 1.60 0.64
n-propyl 45.0 9.9 456 1.70 0.68
n-butyl 45.5 10.1 512 1.74 0.71
n-pentyl 45.5 9.4 568 1.88 0.76
n-hexyl 46.0 11.6 624 2.10 0.85
n-octyl 48.5 12.9 736 1.95 0.95
n-decyl 49.0 14.4 848 2.15 1.10

Table 9
Structural information of PMMAs with varying tacticities.
Tacticity (% m) C∞ ML (nm− 1 ) lp (nm) db (nm)

19.5 8.0 400 1.10 0.60

28.5 7.5 400 1.10 0.60
34.5 7.8 400 1.13 0.60 Fig. 5. Characteristic ratios (C∞) and persistence length (lp) vs the side chain
40.5 8.0 400 1.16 0.60
length (n) for both poly(n-alkyl methacrylate)s and poly(n-alkyl acrylate)s.
48.0 7.9 400 1.20 0.60
50.5 8.1 400 1.21 0.60
56.0 8.0 400 1.24 0.60 derived from published solution properties data on these materials [17,
62.5 8.7 400 1.26 0.60 30,31]. Differences in tacticity may in part account for these small dif­
65.5 8.8 400 1.28 0.60
ferences in C∞.
66.5 8.9 400 1.29 0.60
68.5 8.7 400 1.30 0.60 Our values of C∞ for PMMAs of varying tacticities are compared with
those reported by Jenkins and Porter [18] in Fig. 4. It is apparent that
there is good agreement between the two data sets, and C∞. increases in
a linear fashion with increasing isotactic content. Rotational isomeric
state (RIS) models have been applied to PMMA chains of varying tac­
ticity [33], [-34] and the results were compared with experimental data
available at the time. The earlier experimental data suggested that a
concave curve was needed to fit the data, whereas RIS models could not
be rendered concave with any reasonable adjustment of the model pa­
rameters. Vacatello and Flory [33] had noted the wide scatter in the
earlier data as well as the lack of precise information of the stereo­
chemical composition of the polymers studied. Our data, combined with
those of Jenkins and Porter [18], clearly show that such a plot is not
concave but is linear at least over the range of stereochemistries studied
and thus compatible with RIS models.

3.2. Analysis of detailed structural information using the touched-bead

wormlike chain model

The viscosity data were also analyzed using the touched-bead

Fig. 4. Characteristic ratios of PMMAs with varying tacticities.
Figs. 1–3. Table 7, Table 8 and Table 9 summarizes the unperturbed
dimensions and characteristic ratios of all polymers studied. While
precision of the measurements was very high (5 repeated measurements
of C∞ for highly syndiotactic PMMA gave a value of 8.03 ± 0.17), we
believe the C∞ values to be accurate to within 10% based upon the
methods employed (errors in Mw, [η], and extrapolation of Tanaka plot).
The values of the characteristic ratio for highly syndiotactic PMMA,
poly(ethyl methacrylate), poly(n-hexyl methacrylate), and poly(n-decyl
methacrylate) determined in this work, 8.0, 8.4, 11.6, and 14.9,
respectively, are in good accord (within 10%) with values of 7.3, 8.2,
11.1, and 13.4, respectively, as determined by viscometry under theta or
near-theta conditions for “highly syndiotactic materials” [14]. Likewise,
the values of C∞ determined in this work for poly(methyl acrylate)
(PMA), poly(ethyl acrylate, poly(n-butyl acrylate), and poly(n-hexyl
acrylate), of 8.1, 9.1, 10.1, and 11.6, respectively, are in good agree­
ment (within 10%) with values of 7.7, 9.7, 9.7, and 12.5, respectively,
wormlike chain model to extract detailed structural information on
poly(n-alkyl methacrylate)s and poly(n-alkyl acrylate)s. The persistence
lengths and the diameters of beads, or chain thickness, are summarized
in Tables 7–9. The tables also include the characteristic ratios C∞ esti­
mated from the intrinsic viscosity data in the previous section.
In Tables 7–9, ML is molecular weight per unit contour length and is
Mrepeat unit
calculated by ML = lrepeat unit , where the contour length lrepeat unit per
repeat unit is set to 0.25 nm estimated from their chemical structures. In
these tables, lp is persistence length, which correlates to chain stiffness,
and db is the diameter of beads, which indicates chain thickness. It can
be seen from Tables 7 and 8 that, for both poly(n-alkyl methacrylate)s
and poly(n-alkyl acrylate)s, lp increases as n increases, indicating that
the chain flexibility of the two polymers decreases as bulkiness of the
side chains becomes larger. As the chain get stiffer (increasing of lp), C∞
also increases with increasing n. Therefore, there are good correlations
between C∞ and lp and the side chain length n for both poly(n-alkyl
methacrylate)s and poly(n-alkyl acrylate)s. It is interesting to notice
that for some side chains, both C∞ and lp for poly(n-alkyl methacrylate)s
and poly(n-alkyl acrylate)s are comparable when compared at the same
side chain length (Fig. 5), indicating their similar chain characteristics in
solutions despite their differences in tacticities. As for db , it increases

5
T. Li et al. Polymer 213 (2021) 123207

Table 10
The unperturbed dimensions, characteristic ratios, glass transition temperatures and dynamic fragilities of poly(n-alkyl methacrylate)s.
Polymer Tacticity (% m) 3 C∞ Tg (◦ C) Dynamic fragility (m) from literaturea
(dLg 2 mol1/2 )
−

methyl 19.5 5.77 8.0 131 101[39], 103[40], 136[41]

ethyl 18.5 5.12 8.4 81 68[41], 78[39], 81[40]
n-propyl 16.5 4.80 9.0 75 63[40]
n-butyl 17.0 5.03 10.3 56 48[41], 56[40], 67[39]
n-pentyl 18.0 4.43 10.4 32 49[40]
n-hexyl 18.0 4.58 11.6 − 9 35[39], 45[40]
n-octyl 17.0 4.75 13.8 − 24 /
n-decyl 16.0 4.36 14.9 − 58 /
a
No information on the tacticities of samples.

Table 11
The unperturbed dimensions, characteristic ratios, glass transition temperatures and dynamic fragilities of poly(n-alkyl acrylate)s.
Polymer Tacticity (% m) 3 C∞ Tg (◦ C) Dynamic fragility (m) from literaturea
−
Kθ × 104 (dLg 2 mol1/2 )

methyl 49.0 7.41 8.1 20 102[42], 108[39]

ethyl 46.0 7.12 9.1 − 11 92[39]
n-propyl 45.0 6.60 9.9 − 34 /
n-butyl 45.5 5.72 10.1 − 45 75[39]
n-pentyl 45.5 4.39 9.4 − 60 /
n-hexyl 46.0 5.44 11.6 − 64 /
n-octyl 48.5 4.76 12.9 − 70 /
n-decyl 49.0 4.57 14.4 − 57 /
a
No information on the tacticities of samples.

Table 12
The unperturbed dimensions, characteristic ratios, glass transition temperatures
and dynamic fragilities of PMMAs with varying tacticities.
Tacticity (% m) 3 C∞ Tg (◦ C) m ma
Kθ × 104 (dLg 2 mol1/2 )
−

15.812 / / 12734 / 17312

19.5 5.77 8.0 131 / /
28.5 5.34 7.5 115 / /
34.5 5.57 7.8 109 / /
35.512 / / 10834 / 12112
40.5 5.87 8.0 108 / /
48.0 5.77 7.9 101 178 /
50.5 5.91 8.1 95 / /
56.0 5.84 8.0 92 171 /
62.5 6.61 8.7 86 / /
65.5 6.71 8.8 82 / /
66.5 6.79 8.9 82 159 /
68.5 6.57 8.7 77 / /
94.712 / / 5134 / 12012
a
Literature values.
Fig. 6. Correlation between Tg and solution characteristics for both poly(n-
alkyl methacrylate)s.
with increasing n for either poly(n-alkyl methacrylate) or poly(n-alkyl
acrylate), indicating that the chain thickness of the polymers increases
Besides solution characteristics (C∞ and lp), dynamic fragility (m), a
as bulkiness of their side chains becomes larger. On the other hand, it
parameter characterizing the deviation of the temperature dependence
can be seen from Table 9 that C∞ and lp for PMMA increase as the
of segmental relaxation time from Arrhenius behavior, has been used to
fraction of isotactic diads increases. Namely, the chain flexibility for
described glass transition phenomena in polymeric liquids [35–38].
PMMA becomes higher as their fraction of meso diad increases.
Recently, Shen and co-workers [12] reported the dynamic fragility m
From Tables 10 and 11, Tgs for both poly(n-alkyl methacrylate) and
values of two stereoregular PMMAs and three a-PMMAs with varying
poly(n-alkyl acrylate) are largely dependent on n: decreasing as n in­
molecular weights. Their results indicate that dynamic fragility (m)
creases. It can also be seen from Table 12 that Tg for PMMA greatly
decreases with increasing fraction of meso diads. Our fragility data from
depends on tacticity and it decreases as the fraction of meso diads of
PMMA with different meso diads ratios are shown in Fig. 8 and
PMMA increases. Taking into consideration the facts that C∞ and lp for
compared with Shen’s data. While a thorough study of the dynamic
poly(n-alkyl methacrylate) and poly(n-alkyl acrylate) are related to n
fragility of all the poly(alkyl methacrylate)s and poly(alkyl acrylate)s is
and that C∞ and lp for PMMA are related to the fraction of meso diad of
beyond the scope of our current work, our data do fit the trends reported
PMMA, it may be concluded that the solution characteristics represented
(Fig. 8 and Table 12). Detailed correlation of polymer chain dimension,
by C∞ and lp of both poly(n-alkyl methacrylate) and poly(n-alkyl acry­
as described by their characteristic ratios in solutions, with their flexi­
late) are reasonably correlated to their Tgs, which were shown in Figs. 6
bility in the solid state needs further investigation. We will report these
and 7.
results in future publications.

6
T. Li et al.
Fig. 7. Correlation between Tg and solution characteristics for both poly(n-
alkyl acrylate)s.
Fig. 8. Relationship between m, C∞ and isotactic diads of PMMA samples.
Dashed linear line is from the linear fitting of characteristic ratios vs. isotactic
contents in Fig. 4 and the direction of the right y-axis is inverted to emphasize
the negative correlation between characteristic ratio and m in this work.
In conclusion, we report the solution properties, chain conforma­
tions, including Flory’s characteristic ratio, persistence length, and
chain diameters, and glass transition temperatures (Tg) for series of poly
(n-alkyl acrylate)s and poly(n-alkyl methacrylate)s. Chain flexibilities of
both series of polymers decrease as n increases, reflecting increased
hindrances to rotation about backbone bonds as side chains become
larger. Conversely, the Tgs for both series of polymers decrease sub­
stantially as n increases, reflecting the greater side chain mobilities of
long alkyl substituents. For shorter alkyl chain lengths, Tgs for the poly
(n-alkyl acrylate)s are much lower than for the corresponding poly(n-
alkyl methacrylate)s, a difference which has been attributed in the
past to the presumed reduced chain flexibility of polymethacrylates due
to the presence of the α-methyl substituent, even though their C∞ and lp
values for these two series of polymers are very close. We believe tac­
ticities are playing roles in these discrepancies – almost ideally atactic
for the poly(n-alkyl acrylate)s but high in syndiotacticity for the poly(n-
alkyl methacrylate)s. The Tgs for the two series of polymers approach
that of polyethylene at longer alkyl chain lengths. Our results offer new
insight into the intriguing relationship between chain microstructure
and glass transition temperature (Tg) for poly(alkyl methacrylate)s and
7
Polymer 213 (2021) 123207
poly(alkyl acrylate)s.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
This research was conducted at the Center for Nanophase Materials
Sciences, which is a DOE Office of Science User Facility. We thank Prof.
A. Tonelli of NCSU for sharing his results of poly(methyl methacrylate)s
solution properties and ensued inspiring discussions.
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