Electronic Supporting Material
for
Prediction of Hildebrand solubility parameters of acrylate and
methacrylate monomers and their mixtures by molecular simulation
John L. Lewin,†,§ Katie A. Maerzke,† Nathan E. Schultz,‡ Richard B. Ross,‡ and
J. Ilja Siepmann†,*
†Departments
of Chemistry and of Chemical Engineering and Materials Science,
University of Minnesota, 207 Pleasant Street SE, Minneapolis, MN 55455
‡Corporate
§Department
Research Materials Laboratory, 201-2E-23, 3M Company, St. Paul, MN 55144
of Chemistry, Augsburg College, 2211 Riverside Avenue, Minneapolis, MN 55454
* Corresponding author:
siepmann@umn.edu
Tables listing literature values, correlation data, and simulation data for the solubility parameters
and molar volumes of various acrylates and methacrylates. Table with partial charges for methyl
and n-decyl acrylate.
1
Table S1. Hildebrand (total) solubility parameters of acrylate and methacrylate esters in units of
(cal/cm3)1/2 taken directly from the literature.
Polymer Hansen
CRCd
Literature
a
b
c
e
HB
HB
Hoy 57th ed. Askadskii Average Std. Dev.
Acrylate esters (linear alkyl unless noted)
methyl
8.9
9.37
9.38
8.9
8.9
9.09
0.3
ethyl
8.6
8.76
8.81
8.6
8.4
8.63
0.2
butyl
8.8
8.55
8.63
8.4
8.9
8.66
0.2
hexyl
8.69
8.69
2-ethylhexyl
7.8
7.77
7.87
7.81
0.1
2-hydroxyethyl
12.07
12.07
Methacrylate esters (linear alkyl unless noted)
methyl
8.8
8.76
9.23
8.8
8.7
ethyl
8.3
9.25
8.5
8.4
propyl
8.79
butyl
8.2
8.85
8.3
8.2
a ref. 6. b ref 13. c ref 9. d experimental values from ref. 37. e ref. 36.
2
8.86
8.61
8.79
8.39
0.2
0.4
0.3
Table S2. Hildebrand (total) solubility parameters of acrylate and methacrylate esters in units of
(cal/cm3)1/2 calculated from normal boiling points (eqns. 2, 5, and 6) and refractive indices (eqn.
8).
Rehberg &
Yaws’ Polymer CRC
refractive
Fishera Gardonb HBc
HBd 89th ed.e Askadskiif Eqn. 8g indexh
Acrylate esters
methyl
ethyl
propyl
butyl
pentyl
hexyl
heptyl
octyl
nonyl
decyl
2-ethylhexyl
6-methylheptyl
2-hydroxyethyl
9.01
8.60
8.44
8.33
8.21
8.14
8.06
7.98
7.91
7.86
8.9
8.4
8.9
9.30
8.93
8.74
8.37
9.0
8.6
8.8
8.6
8.3
8.5
8.2
8.0
7.86
7.9
10.1k
11.56
8.63
8.66
8.71
8.77
8.81
8.86
8.88
8.92
8.94
8.96
8.93
8.93
9.05
1.4040
1.4068
1.4130
1.4190
1.4240
1.4285
1.4311
1.4360
1.4380
1.4400
1.4365i
1.437j
1.450j
Methacrylate esters
methyl
8.59
8.7
9.10
8.7
8.7
8.6
8.72
1.4142
ethyl
8.38
8.4
8.48
8.4
8.4
8.5
8.73
1.4147
propyl
8.26
8.40
8.3
8.3
8.77
1.4190
butyl
8.15
8.2
8.04
8.1
8.1
8.4
8.81
1.4240
pentyl
8.06
8.85
1.4284
l
hexyl
8.00
7.4
8.89
1.4320m
heptyl
7.92
8.91
1.4351m
octyl
7.85
8.94
1.4374
nonyl
7.79
8.96
1.4401m
decyl
7.74
8.3
8.97
1.4418
2-ethylhexyl
7.6
8.95
1.4390
2-hydroxyethyl
9.07
1.453j
a calculated with eqns. 5 and 6; refs. 32 and 38. b reported as calculated with eqn. 6 in ref 8.
c correlation data from ref. 14. d calculated with eqn. 6 from experimental normal boiling points
in ref. 6. e calculated with eqn. 6 from experimental normal boiling points in ref. 33. f reported as
calculated from eqn. 6 in ref. 36. g calculated with eqn. 8 using refractive indices (20 °C) from
refs. 32, 38, 39 and 40. h refs. 32 and 38 unless noted otherwise. i ref. 39. j ref. 40, 25 °C. k molar
volume determined at 23 °C. l molar volume determined at 25 °C; anomalously low normal b.p.
of 162 °C. m calculated from data in reference 32.
3
Table S3. Experimental and correlation-based normal boiling points used to compute
Hildebrand solubility parameters in Table S2. References as in Table S2.
Rehberg & Polymer CRC
Fishera
HB 89th ed.
Acrylate esters
methyl
ethyl
propyl
butyl
pentyl
hexyl
heptyl
octyl
nonyl
decyl
2-ethylhexyl
2-hydroxyethyl
80.0b
98
122
145
167
188
207
227
245
263
80.7
99.4
122
145
190
229
217
191
Methacrylate esters
methyl
93
100
100.5
ethyl
117
118
117
propyl
140
140
141
butyl
162
161
160
pentyl
182
hexyl
203
162
heptyl
221
octyl
239
239.5
nonyl
257
decyl
274
327
2-ethylhexyl
218
2-hydroxyethyl
250
a calculated from eqn. 5 unless noted otherwise. b experimental value from ref. 38.
4
Table S4. Hildebrand (total) solubility parameters [in units (cal/cm3)1/2] of acrylate and
methacrylate alkyl and hydroxy alkyl esters computed with the TraPPE-UA force field and the
CED method [15].
Hildebrand (total) solubility parameter (cal/cm3)1/2
Lit. Rangea Lit. Avg. TraPPE std. err.b % err.c Dreiding
Acrylate esters
methyl
8.99.38
ethyl
8.48.81
propyl
butyl
8.4–8.9
pentyl
hexyl
8.69
heptyl
octyl
nonyl
decyl
2-ethylhexyl
7.77–7.87
6-methylheptyl
2-hydroxyethyl 12.07
MUPEd
9.09
8.63
8.66
8.69
7.81
12.07
9.075
8.649
8.478
8.427
8.364
8.354
8.324
8.303
8.314
8.259
8.057
8.195
12.047
0.009
0.017
0.006
0.011
0.014
0.014
0.014
0.019
0.018
0.017
0.009
0.016
0.034
–0.2
0.2
–2.6
–3.9
3.1
–0.2
1.7
10.51
10.67
10.19
9.40
9.32
9.25
8.96
8.79
8.70
8.54
8.56
8.94
12.92
% err.c
15.6
23.5
8.6
6.4
9.5
7.0
11.8
Methacrylate esters
methyl
8.79.23
8.86
8.836
0.008
–0.3
9.82
10.9
ethyl
8.39.25
8.61
8.499
0.020
–1.3
9.77
13.5
propyl
8.79
8.79
8.303
0.011
–5.6
9.34
6.2
butyl
8.28.85
8.39
8.255
0.017
–1.6
9.10
8.5
pentyl
8.207
0.018
8.88
hexyl
8.200
0.016
8.71
heptyl
8.180
0.019
8.41
octyl
8.174
0.015
8.47
nonyl
8.170
0.015
8.40
decyl
8.163
0.012
8.37
2-hydroxyethyl
11.399
0.026
11.92
d
MUPE
2.2
9.8
a where no range is listed, no data were available. b standard error of the mean for TraPPE-UA
simulations. c relative to the average of experimental values in the “Lit. Avg.” column. d mean
unsigned percent error.
5
Table S5. Molar volumes of acrylate and methacrylate esters in units of (cm3/mol), determined
from experimental 20 °C (293 K) densities unless noted otherwise. Original sources as in Table
S1.
Rehberg & Yaws
Polymer
Fisher
HBa
HB
Acrylate esters (linear alkyl unless noted)
methyl
90.3
90.714
90.1
ethyl
108.4
109.086 108.4
propyl
125.7
126.898 125.7
butyl
142.4
143.353 143.4
pentyl
159.7
159.4
hexyl
175.9
175.9
heptyl
192.5
192.5
octyl
209.2
209.2
nonyl
225.7
226.6
c
decyl
241.8
241.8
d
2-ethylhexyl
208.2
209.414 208.0
2-hydroxyethyl
115.214 114.9
6-methylheptyl
209.4
Hansen
HB
CRC
Barton &
Hoyb
90.3
108.8
90.3
108.4
90.6
109.4
143.8
144.0
143.2
177.9
176.9
209.2
208.2
114.9
209.4e
114.9f
209.2
105.0g
Avg.
Expt.
90.4
108.8
126.1
143.4
159.6
176.7
192.5
209.2
226.2
241.8
208.7
113.0
209.4
Methacrylate esters (linear alkyl unless noted)
methyl
106.1
106.828 107.0
106.1
106.8
107.7
106.7
ethyl
125.0
125.712 124.5
125.8
125.0
125.2
propyl
142.1
142.862 142.1
158.8
142.1
145.6
butyl
159.1
159.663 159.1
159.4
159.1
159.3
pentyl
175.7
175.7
h
e
hexyl
192.2
192.4
193.5
192.7
h
heptyl
208.7
208.7
octyl
225.2
225.2
h
i
nonyl
241.7
193.2
241.7
decyl
258.2
258.7
258.4
2-ethylhexyl
224.1
224.1
225.3
224.5
2-hydroxyethyl
120.6e
120.6
a group additive data for 25 °C from ref. 14. b ref. 5. c used average of two similar density
values. d ref. 39. e 25 °C. f 23 °C. g BASF MSDS. h determined from calculated density data in
ref. 32. i anomalously high density of 1.099 g/mL.
6
Table S6. Molar volume acrylate and methacrylate alkyl and hydroxy alkyl esters (in units of
cm3/mol) computed with the TraPPE-UA force field and the CED method [15].
Avg.
Acrylate esters
methyl
ethyl
propyl
butyl
pentyl
hexyl
heptyl
octyl
nonyl
decyl
2-ethylhexyl
6-methylheptyl
2-hydroxyethyl
MUPEc
Expt.a
90.4
108.8
126.1
143.4
159.6
176.7
192.5
209.2
226.2
241.8
208.7
209.4
113.0
Methacrylate esters
methyl
106.7
ethyl
125.2
propyl
145.6
butyl
159.3
pentyl
175.7
hexyl
192.7
heptyl
208.7
octyl
225.2
nonyl
241.7d
decyl
258.4
2-hydroxyethyl 120.6
MUPEc
molar volume (cm3/mol)
TraPPE
% err.b Dreiding
% err.b
92.39
110.72
127.89
144.41
160.77
177.08
193.39
209.82
225.75
242.59
209.06
210.01
108.50
2.2
1.8
1.4
0.7
0.8
0.2
0.5
0.3
–0.2
0.3
0.2
0.3
–4.0
1.0
91.6
105.4
125.4
144.0
163.4
179.6
200.3
219.4
236.1
252.8
219.4
230.6
112.7
1.3
–3.1
–0.5
0.4
2.4
1.6
4.1
4.9
4.4
4.5
5.1
10.1
–0.3
3.3
108.73
127.38
144.58
161.10
177.36
193.96
210.42
226.33
242.89
259.25
124.79
1.9
1.8
–0.7
1.1
0.9
0.7
0.8
0.5
0.5
0.3
3.5
1.2
107.7
125.4
145.6
161.6
183.8
200.3
222.0
236.1
255.8
269.5
131.5
0.9
0.2
0.1
1.5
4.6
4.0
6.4
4.8
5.8
4.3
9.0
3.8
a
values from Table S5. b relative to the average of experimental values in leftmost column.
c mean unsigned percent error. d ref. 32 value only.
7
Figure S1. Atom numbering scheme for methyl acrylate and decyl acrylate. See also Table S7.
Table S7. Comparison of united atom TraPPE and Dreiding ESP partial charges on methyl
acrylate and decyl acrylate in units of e. See Figure S1 for atom numbering.
atom
C1
C2
C3
O4
O5
C6
methyl acrylate
TraPPE
Dreiding
0.00
0.120
0.00
–0.263
0.40
0.994
–0.40
–0.619
–0.25
–0.480
0.25
0.247
atom
C1
C2
C3
O4
O5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
decyl acrylate
TraPPE
Dreiding
0.00
0.098
0.00
–0.231
0.40
1.042
–0.40
–0.650
–0.25
–0.623
0.25
0.346
0.00
0.041
0.00
–0.067
0.00
0.029
0.00
0.019
0.00
0.011
0.00
–0.046
0.00
0.009
0.00
0.124
0.00
–0.103
8