Acrylic Paints: An Atomistic View of Polymer

Structure and Effects of Environmental

Pollutants

Aysenur Iscen, Nancy C. Forero-Martinez, Omar Valsson, and Kurt Kremer∗

Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany

E-mail: kremer@mpip-mainz.mpd.de

S1
Supporting figures for atomistic model and force field

validation

In order to evaluate the accuracy of our model, we performed simulations with GAFF and
OPLS forcefields. The results obtained with GAFF are reported in the main text. In the
following figure, we show the Tg and SAXS using OPLS force field. Diffusion coefficients of
polymer chains with OPLS is given in Figure 2 of main text.

Figure S1: (A) Specific volume and glass transition temperatures and (B) small angle X-ray
scattering structure factor of PMMA, PEA, P(nBA) calculated using OPLS force field.

S2
Figure S2: The log of self-diffusion coefficients of PMMA, PEA, P(nBA) calculated using
GAFF (solid lines) and OPLS (dashed lines) as a function of temperature.

S3
Figure S3: The mean square displacement of center of mass of 15mer PMMA, PEA and
P(nBA) over last 10 ns of trajectory. A line with slope of 1 is plotted to guide the eye.

S4
Supporting figures for properties of acrylics found in

paints

10 1
Polymer
10 2 MMA-EA
D (1x10 5 cm2/s)

MMA-nBA
10 3

10 4

10 5

100 200 300 400 500 600

Temperature (K)
Figure S4: The log of self-diffusion coefficients of P(MMA-co-EA) and P(MMA-co-nBA) as
a function of temperature.

S5
Figure S5: The mean square displacement of center of mass of 15mer (A) P(MMA-co-EA)
and (B) P(MMA-co-nBA) over last 50 ns of trajectory. A line with slope of 1 is plotted to
guide the eye.

For each copolymer P(MMA-co-EA) and P(MMA-co-nBA), we show the contribution of

different monomers MMA, EA and nBA to the overall structure.

S6
Figure S6: Contributions of polymer backbone, side chain, methyl group and monomers to
the small angle x-ray scattering (SAXS) spectra for P(MMA-co-EA) and P(MMA-co-nBA)
at 300 K (A) and 500 K (B).

S7
Figure S7: Total Solvent accessible surface area (SASA) calculated for (A) P(MMA-co-EA)
and (B) P(MMA-co-nBA) at different temperatures. (C,D) SASA for MMA, (E) PEA
and (F) P(nBA) component of each copolymer. Only data from the last 10 ns of 100 ns
simulation is shown.

S8
Supporting figures for effects of VOCs and water on

acrylic structure

Diffusion mechanisms

Figure S8: The log of self-diffusion coefficients of acetic acid, formic acid, formaldehyde and
water in (A) P(MMA-co-EA) and (B) P(MMA-co-nBA) as a function of temperature.

Mean square displacement (MSD) of each pollutant molecule (acetic acid, formic acid,
formaldehyde, water) is used to calculate the diffusion coefficients, D, as a function of tem-
perature. The MSD shown below are for a single 10 ns trajectory. In our calculation of
average D, we divided a 40 ns trajectory into 4 blocks and took the mean of D calculated
from 0-10, 10-20, 20-30, 30-40 and 0-40 ns.

S9
Figure S9: The mean square displacement of center of mass of 1000 ppm acetic acid, formic
acid and formaldehyde in (A-C) P(MMA-co-EA) and (D-F) P(MMA-co-nBA) over 10 ns
of trajectory. A line with slope of 1 is plotted to guide the eye.

S10
Figure S10: The mean square displacement of center of mass of 1000 ppm water in (A)
P(MMA-co-EA) and (B) P(MMA-co-nBA) over 10 ns of trajectory. A line with slope of 1
is plotted to guide the eye.

S11
Figure S11: The mean square displacement of center of mass of (A-C) 3000 ppm and (D-
F) 6000 ppm acetic acid, formic acid and formaldehyde in P(MMA-co-EA) over 10 ns of
trajectory. A line with slope of 1 is plotted to guide the eye.

S12
Figure S12: The mean square displacement of center of mass of (A-C) 3000 ppm and (D-
F) 6000 ppm acetic acid, formic acid and formaldehyde in P(MMA-co-nBA) over 10 ns of
trajectory. A line with slope of 1 is plotted to guide the eye.

S13
Figure S13: The center of mass trajectories of acetic acid, formic acid and formaldehyde at
different temperatures in P(MMA-co-nBA). The equilibrated simulation box size is shown
with black lines. All distances (x,y,z) are in nm.

S14
 Acetic acid in MMA-EA Acetic acid in MMA-nBA
1.00 1.00
250 K
0.75 0.75 300 K
350 K
Fs(k,t)

0.50 0.50 400 K

0.25 0.25 450 K
500 K
0.00 0.00
101 102 103 104 101 102 103 104
Time (ps) Time (ps)
Formic acid in MMA-EA Formic acid in MMA-nBA
1.00 1.00
250 K
0.75 0.75 300 K
350 K
Fs(k,t)

0.50 0.50 400 K

0.25 0.25 450 K
500 K
0.00 0.00
101 102 103 104 101 102 103 104
Time (ps) Time (ps)
Formaldehyde in MMA-EA Formaldehyde in MMA-nBA
1.00 1.00
250 K
0.75 0.75 300 K
350 K
Fs(k,t)

0.50 0.50 400 K

0.25 0.25 450 K
0.00 500 K
0.00
101 102 103 104 101 102 103 104
Time (ps) Time (ps)

Figure S14: Self part of intermediate scattering functions for acetic acid, formic acid and
formaldehyde (1000 pppm concentrations) at different temperatures in P(MMA-co-EA) and
P(MMA-co-nBA). The Fs is evaluated at k=qmax (first peak) in the structure factors indi-
vidually for each temperature.

S15
Figure S15: The center of mass trajectories of water at different temperatures in P(MMA-
co-EA). The equilibrated simulation box size is shown with black lines. All distances (x,y,z)
are in nm.

S16
Figure S16: The center of mass trajectories of water at different temperatures in P(MMA-co-
nBA). The equilibrated simulation box size is shown with black lines. All distances (x,y,z)
are in nm.

S17
Intermolecular interactions

Radial distribution functions

Pair distribution functions for VOC - polymer interaction:

Acetic acid in MMA-EA Acetic acid in MMA-nBA

1.0 1.0 250 K
300 K
0.1 0.1 350 K
g(r)

0.5 0.5 400 K

450 K
0.0 0.0 500 K
0.0 0.15 0.20
0.0 0.15 0.20
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0
Formic acid in MMA-EA Formic acid in MMA-nBA
1.0 1.0 250 K
300 K
0.2 0.2 350 K
g(r)

0.5 0.1 0.5 0.1 400 K

450 K
0.0 0.0 500 K
0.0 0.15 0.20 0.0 0.15 0.20
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0
Formaldehyde in MMA-EA Formaldehyde in MMA-nBA
1.0 1.0 250 K
300 K
350 K
g(r)

0.5 0.5 400 K

450 K
500 K
0.0 0.0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0
r(nm) r(nm)
Figure S17: The pair distribution functions, g(r), between VOCs and copolymer chains
for acetic acid, formic acid and formaldehyde in P(MMA-co-EA) and P(MMA-co-nBA) at
different temperatures.

Pair distribution functions for VOC-VOC interactions:

S18
 Acetic acid-Acetic acid Acetic acid-Formic acid
250 K
20 300 K
20 350 K

g(r)
400 K
10 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Formic acid-Formic acid Formic acid-Formaldehyde
3 10 250 K
300 K
2 350 K
g(r) 5 400 K
1 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Formaldehyde-Formaldehyde Formaldehyde-Acetic acid
6 4 250 K
4 300 K
350 K
g(r)

2 400 K
2 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
r (nm) r (nm)

Figure S18: The pair distribution functions, g(r), between VOCs and other VOCs for 1000
ppm acetic acid, formic acid and formaldehyde in P(MMA-co-EA) at different temperatures.

Acetic acid-Acetic acid Acetic acid-Formic acid

15
10 250 K
300 K
10 350 K
g(r)

5 400 K
5 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Formic acid-Formic acid Formic acid-Formaldehyde
3 20 250 K
300 K
2 350 K
g(r)

10 400 K
1 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Formaldehyde-Formaldehyde Formaldehyde-Acetic acid
4
4 250 K
300 K
350 K
g(r)

2 2 400 K
450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
r (nm) r (nm)

Figure S19: The pair distribution functions, g(r), between VOCs and other VOCs for 1000
ppm acetic acid, formic acid and formaldehyde in P(MMA-co-nBA) at different tempera-
tures.

S19
 Acetic acid-Acetic acid 3000 ppm Acetic acid-Formic acid 3000 ppm
3
4 250 K
300 K
2 350 K

g(r)
2 400 K
1 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Formic acid-Formic acid 3000 ppm Formic acid-Formaldehyde 3000 ppm
15
10 250 K
10 300 K
g(r) 350 K
5 400 K
5 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Formaldehyde-Formaldehyde 3000 ppmFormaldehyde-Acetic acid 3000 ppm
4 6 250 K
300 K
4 350 K
g(r)

2 400 K
2 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
r(nm) r(nm)

Figure S20: The pair distribution functions, g(r), between VOCs and other VOCs for 3000
ppm acetic acid, formic acid and formaldehyde in P(MMA-co-EA) at different temperatures.

Acetic acid-Acetic acid 3000 ppm Acetic acid-Formic acid 3000 ppm
7.5 10 250 K
300 K
5.0 350 K
g(r)

5 400 K
2.5 450 K
500 K
0.0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Formic acid-Formic acid 3000 ppm Formic acid-Formaldehyde 3000 ppm
3 250 K
4 300 K
2 350 K
g(r)

400 K
1 2 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Formaldehyde-Formaldehyde 3000 ppmFormaldehyde-Acetic acid 3000 ppm
3
4 250 K
2 300 K
350 K
g(r)

2 400 K
1 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
r(nm) r(nm)

Figure S21: The pair distribution functions, g(r), between VOCs and other VOCs for 3000
ppm acetic acid, formic acid and formaldehyde in P(MMA-co-nBA) at different tempera-
tures.

S20
 Acetic acid-Acetic acid 6000 ppm Acetic acid-Formic acid 6000 ppm

4 3 250 K
300 K
2 350 K

g(r)
400 K
2 1 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Formic acid-Formic acid 6000 ppm Formic acid-Formaldehyde 6000 ppm
4 3 250 K
300 K
g(r) 2 350 K
2 400 K
1 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Formaldehyde-Formaldehyde 6000 ppmFormaldehyde-Acetic acid 6000 ppm
3 2 250 K
300 K
2 350 K
g(r)

1 400 K
1 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
r(nm) r(nm)

Figure S22: The pair distribution functions, g(r), between VOCs and other VOCs for 6000
ppm acetic acid, formic acid and formaldehyde in P(MMA-co-EA) at different temperatures.

Acetic acid-Acetic acid 6000 ppm Acetic acid-Formic acid 6000 ppm
3 4 250 K
300 K
2 350 K
g(r)

2 400 K
1 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
4Formic acid-Formic acid 6000 ppm Formic acid-Formaldehyde 6000 ppm
6 250 K
300 K
4 350 K
2
g(r)

400 K
2 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Formaldehyde-Formaldehyde 6000 ppmFormaldehyde-Acetic acid 6000 ppm
6 3 250 K
300 K
4 2 350 K
g(r)

400 K
2 1 450 K
500 K
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
r(nm) r(nm)

Figure S23: The pair distribution functions, g(r), between VOCs and other VOCs for 6000
ppm acetic acid, formic acid and formaldehyde in P(MMA-co-nBA) at different tempera-
tures.

S21
Hydrogen bonding

VOC - polymer hydrogen bonding interactions:

Figure S24: Probability distribution of number of hydrogen bonds between (A,C) acetic
acid and MMA, EA, nBA, (B,D) formic acid and MMA, EA, nBA and (E,F) water and
MMA, EA, nBA as a function of temperature.

VOC - VOC hydrogen bonding interactions:

S22
Figure S25: Probability distribution of number of hydrogen bonds between VOCs and copoly-
mer chains, comparing (A) acetic acid and formic acid and (B) P(MMA-co-EA) and P(MMA-
co-nBA) at 300 K and 500 K.

Figure S26: The probability distribution of the number of hydrogen bonds between high
concentrations of acetic acid and formic acid and (A,C) P(MMA-co-EA) or (B,D) P(MMA-
co-nBA) at different temperatures.

S23
Figure S27: Probability distribution of number of VOC-VOC hydrogen bonds for 1000 ppm
concentration.

Figure S28: Probability distribution of number of VOC-VOC hydrogen bonds for 3000 ppm
concentration.

S24
Figure S29: Probability distribution of number of VOC-VOC hydrogen bonds for 6000 ppm
concentration.

S25
Interactions of water

Figure S30: The pair distribution functions, g(r), between (A,B) water and copolymer chains
(C,D) water oxygen and copolymer chains, and (E,F) water and other water molecules at
different temperatures.

S26
 Figure S31: Probability distribution of number of water-water hydrogen bonds.

Structural changes induced by VOCs and water

Figure S32: The log of self-diffusion coefficients of copolymer chains with or without pollu-
tants at different temperatures for (A) P(MMA-co-EA) and (B) P(MMA-co-nBA).

S27
Figure S33: Effect of VOCs and water on (A,B) specific volume and Tg , (C,D) average end-
to-end distance, and (E,F) average radius of gyration for P(MMA-co-EA) (left panel) and
P(MMA-co-nBA) (right panel).

S28
Figure S34: Effect of (A)1000 ppm VOCs, (B) 3000 ppm VOCs, (C) 6000 ppm VOCs and
(D) 1000 ppm water on the solvent accessible surface area for P(MMA-co-EA) (left panel)
and P(MMA-co-nBA) (right panel).

S29