Synthesis and characterization of new oligomeric/polymeric antistatic

additives for sheet molding composites

Katrin Schubert, Michaela Gedan-Smolka
Leibniz-Institut fu
€ r Polymerforschung Dresden e.V., Hohe Straße 6, Dresden D-01069, Germany
Correspondence to: K. Schubert (E-mail: schubert@ipfdd.de)

ABSTRACT: For various applications it is necessary to lower the specific surface resistivity of polymers in an electrostatically conduc-
tive area. To improve the antistatic properties of sheet molding composites (SMC) usually conductive inorganic additives, like carbon
black, inorganic salts, metal powder, or CNTs, are mixed physically into the matrix. A newly developed concept for antistatic treat-
ment is using oligomeric/polymeric additives, which are synthesized on the base of ingredients of the used polymeric matrix itself.
The received additives are compatible with the matrix. Furthermore, the migration of the additives to the surface is prevented and in
the case they exhibit double bonds they are able to be linked in the polymeric network permanently by covalent bonds. So unsaturat-
ed, polymer-based antistatic additives with ionic units were developed for unsaturated polyester resin based SMC. The synthesis was
realized by polymer analogous reactions and polycondensation reactions from monomer building blocks with ionic units. V C 2017 Wiley

Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44741.

KEYWORDS: duromeric composites; glass fiber; oligomeric/polymeric antistatic additives; sheet molding composites; unsaturated
polyester resins

Received 27 April 2016; accepted 7 November 2016

DOI: 10.1002/app.44741

INTRODUCTION observed. In a special area, percolation threshold, the conductivi-

The process technology of sheet molding composites (SMC) is one
of the most important techniques to produce duromeric fiber rein-
forced structures. SMC components are made of reactive resins
(mainly polyester or vinylester resins) and mostly glass fibers by a
pressing process of a flat semi-finished product.1–3 The major areas
of application of this material are the automotive industry, the elec-
trical industry, the mechanical engineering and the military aviation.
Its annual turnover in Europe in 2008 was around 280,000 t.4
In many applications, it is necessary to avoid an electrostatic
discharge of polymers, for example in electronic devices, or to
perform an electrostatic coating process of polymer components.
In such cases, the surface resistivity has to be lowered from
>1012 Ohm/square to a range between 109 and 106 Ohm/square
in dependence of their use. Often the integration of conductive
additives into polymers or the application of antistatic primers
allows lowering the specific surface resistivity of polymer materi-
als. To improve the antistatic properties of polymers conductive
additives are usually mixed physically into the matrix. For this,
mainly carbon black, but also inorganic pigments or inorganic
salts, metal powder or, recently, CNTs are used.5,6 The reduction
of the surface resistivity can be described on the base of the per-
colation theory (Scheme 1). Initially, with increasing additive
amounts only a slight decrease of the surface resistivity is
ty raises rapidly with a small addition of the conductive filler.7
In order to receive an efficient antistatic treatment and to prevent
the migration of the additives to the surface, a reactive coupling
of conductive substances with the polymer matrix is of advantage.
With this concept it was successful to receive an antistatic treat-
ment for MDF panels in the past.9–11 The scope of present work
was to transfer the general concept for the use in SMC-matrices
based on unsaturated polyester resins. Therefore, oligomeric/poly-
meric antistatic substances were synthesized by polymeric analo-
gous reactions of unsaturated polyesters or by polycondensation
reactions from monomers. The substances are characterized by
NMR, FTIR, and TGA measurements. Additionally their capability
to reduce the surface resistivity of the pure unsaturated polyester
resins into the required area was tested. Because of existing double
bonds in the resulting structures there is an opportunity that the
additives form covalent bonds with the matrix components during
the thermal molding process. Thus, the antistatic structures are
permanently integrated into the polymer matrix at the end.
EXPERIMENTAL
Commercial Materials
All commercials chemicals were utilized as received without fur-
ther manipulation. The unsaturated polyester resin Palapreg

C 2017 Wiley Periodicals, Inc.

V

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Scheme 1. Specific surface resistivity of a polymer material in the presence
of a conductive additive as function of the filler concentration (percola-
tion curve).8
P 18–03 (DSM) was used after separation of the containing sty-
rene in a rotary evaporator at 80 8C and subsequent drying in a
vacuum drying oven at the same temperature. The molar mass
of the styrene free polyester resin Palapreg P 18–03 was deter-
mined via viscometer and the [h]-M-relation with 960 g/mol.
Characterization Methods
1
H-NMR and 13C-NMR spectra were recorded on an Avance III
500 instrument at 500.13 MHz for 1H and 125.75 MHz for 13C.
The number of protons were determined by integration. The
proton signals of the deuterated solvents were used as reference.
The melting points were detected by a hot stage microscope
Leica Galen III. The received melting points are from a double
determination and uncorrected.
IR-spectra were recorded with a Fourier transform infrared
(FTIR) spectrometer of the Bruker-company, model Vertex 80V
including a Golden Gate unit, in a wave number range from
4000 to 600 cm21 with 32 scans per measurements and a reso-
lution of 4 cm21.
The thermogravimetric analysis (TGA) was performed with a
TGA Q5000 (TA Instruments) in a temperature range from room
temperature (r.t.) to 800 8C with a heating rate of 10 K/min in
air atmosphere. 8 to 20 mg were weighed in a platinum crucible.
The acid number of oligomeric/polymeric polyesters was deter-
mined potentiometrically according to standard DIN 53402, the
hydroxyl number referring to DIN 53240 and the iodine num-
ber according to the application instruction Nr. 141/312 of the
company Metrohm with a titrator Titrando 808 (Metrohm).
A characterization of the molecular weight by gel-permeation-
chromatography was not possible, because the synthesized poly-
esters were insoluble in all kinds of solvents, which are useable
for a determination. The inherent viscosity was received from
measurements with an automatic Ubelohde viscometer in
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dimethylformamide 1 10 wt %. water at 25 8C with a capillary
0a. The viscosity was calculated from the determinated runtimes
according to the eq. (1):
 
t 2t
ln 11 sampletsolventsolvent
h5 (1)
c
tsample runtime of the sample solution in s
tsolvent runtime of the solvent in s
c concentration in g/100 mL
The molar mass could be estimated using the following
equation:
½h5K  Mwa (2)
Because there is no realistic chemically and structurally compa-
rable [h]-M-relation for the synthesized oligomers/polymers
available, the obtained molar masses can only be compared
among themselves. So the molar mass was calculated by using
poly(acrylonitrile-co-vinyldene chloride) as polymer standard
with an aliphatic basic structure.13
The absolute specific surface resistivity was detected by a HM
307 D (Fetronic) with an annular electrode. Therefore, the syn-
thesized oligomeric/polymeric polyesters were solved in a mix-
ture of acetone/water, followed by an application onto card
boards with an area of about 15 3 15 cm. After drying in an
oven at 60 8C for 4 h the card boards were at least stored in a
conditioning cabinet KBF 240 (Binder) for 16 h (dry climate:
20 8C/35% humidity, normal climate: 23 8C/50% humidity).
Synthesis of the Quaternary Amines: Procedure for the
Synthesis of Triethylammoniumbromide Acetyl Chloride (1)
To a solution of 64.30 g (0.635 mol) triethylamine in 25 mL
acetonitrile in an inert-gas atmosphere at r.t. 5.00 g
(31.77 mmol) bromoacetyl chloride, which was solved in 5 mL
acetonitrile was added slowly over a time period of 1 h. The
reaction mixture was stirred at r.t. for 1 h followed by heating
at reflux for 1 h. After the solution was cooled to r.t., the vola-
tile compounds were removed by reduced pressure. The residue
was dried at 60 8C for at least 2 h in a vacuum drying oven and
this followed by suspending in 50 mL acetone, whereby the prod-
uct 1 is undissolved. The mixture was passed by a coarse frit and
washed with a small amount of acetone. Finally, the resulting
light brown, brilliant crystals were dried in a vacuum drying
oven once again at 60 8C over night.
The other quaternary amines (triethylammoniumbromide
ethyl alcohol (2), triethylammoniumbromide dimethyl malo-
nate (3), triethylammoniumbromide terephthalic acid (4), di-
triethylammoniumbromide succinic acid (5)) were synthesized
in an analogous manner. In the case of 3, the reaction mixture
was not heated at reflux for 1 h but at 60 8C. The necessary
amounts of initial substances are listed in Table I.
 1—Yield 5 7.50 g (29.00 mmol, 91%) of light brown, bright
crystals with Tm 5 253–254 8C; 1H-NMR (500.1 MHz,
DMSO-d6, d, ppm): 1.21 (t, J 5 7.4 Hz, 9 H), 3.08 (m, 6 H),
3.35 (s, 2 H); 13C-NMR (125.8 MHz, DMSO-d6, d, ppm):
8.44 (3 CH3), 45.46 (3 CH2), 72.35 (CH2), 165.12 (C); IR:
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Table I. Starting Quantities for the Synthesis of the Quaternary Amines 1,
2, 3, 4, and 5
Quaternary
amine Quantities for the reaction
1 64.30 g (0.635 mol) trimethylamine
in 25 mL acetonitrile, 5.00 g (31.77 mmol)
bromoacetyl chloride in 5 mL acetonitrile
2 323.81 g (3.200 mol) trimethylamine in 100 mL
acetonitrile, 20.00 g (0.160 mol) 2-bromoethanol
in 20 mL acetonitrile
3 76.90 g (0.760 mol) trimethylamine in 240 mL
nitromethane, 9.08 g (38.00 mmol) diethylbromo
malonate in 20 mL nitromethane
4 20.70 g (0.205 mol) trimethylamine in 60 mL
acetonitrile, 10.00 g (0.041mol)
2-bromoterephthalic acid in 50 mL ethanol
5 18.21 g (0.180 mol) trimethylamine in 25 mL
acetonitrile, 10.00 g (0.036 mol)
2,3-dibromosuccinic acid in 50 mL ethanol
m 5 3369, 3000, 2975, 2935, 2879, 2802, 2755, 2737, 2674,
2621, 2600, 2529, 2491, 1718, 1617, 1473, 1433, 1396, 1383,
1364, 1330, 1288, 1186, 1170, 1070, 1034, 849, 805, 760,
618 cm21.
 2—Yield 5 24.79 g (0.110 mol, 68%) of colorless, bright crys-
tals with Tm 5 278–280 8C; 1H-NMR (500.1 MHz, DMSO-d6,
d, ppm): 1.19 (t, J 5 7.1 Hz, 9 H), 3.30 (m, 8 H), 3.78 (t,
J 5 7.2 Hz, 2 H); 13C-NMR (125.8 MHz, DMSO-d6, d, ppm):
7.73 (3 CH3), 53.21 (3 CH2), 54.69 (CH2), 58.05 (CH2); IR:
m 5 3213, 2976, 2939, 2880, 2737, 2673, 2489, 1486, 1467,
1433, 1418, 1394, 1377, 1361, 1300, 1236, 1191, 1161, 1124,
1112, 1080, 1052, 1018, 998, 951, 923, 887, 844, 806, 781,
657 cm21.
 3—Yield 5 7.04 g (20.7 mmol, 54%) of colorless, bright crys-
tals with Tm 5 258–259 8C; 1H-NMR (500.1 MHz, DMSO-d6,
d, ppm): 1.25 (m, 15 H), 3.11 (dd, J 5 7.1 Hz, 6 H), 4.05 (s,
4H), 5.13 (s, 1H); 13C-NMR (125.8 MHz, DMSO-d6, d,
ppm): 8.46 (3 CH3), 13.78 (2 CH3), 45.67 (3 CH2), 60.48 (2
CH2), 82.45 (CH), 165.77 (2 C); IR: m 5 3294, 3058, 3001,
2974, 2934, 2877, 2801, 2736, 2672, 2599, 2570, 2527, 2489,
1468, 1432, 1396, 1384, 1363, 1331, 1287, 1186, 1169, 1068,
1033, 848, 803, 758, 631 cm21.
 4—Yield 5 5.95 g (17.2 mmol, 42%) of beige colored solid
with Tm 5 145–150 8C; 1H-NMR (500.1 MHz, DMSO-d6, d,
ppm): 1.20 (t, J 5 7.3 Hz, 9 H), 3.04 (q, J 5 7.3 Hz, 6 H),
7.50 (d, J 5 7.9 Hz, 1 H), 7.84 (dd, J 5 7.9 Hz, 1 H), 8.02
(m, 1 H); 13C-NMR (125.8 MHz, DMSO-d6, d, ppm): 8.43
(3 CH3), 44.97 (3 CH2), 118.34 (CH), 127.91 (CH), 128.66
(CH), 133.24 (2 C), 166.47 (C), 169.17 (2 C); IR: m 5 3412,
3102, 3078, 2985, 2947, 2881, 2779, 2637, 2498, 1701, 1598,
1549, 1475, 1449, 1393, 1362, 1317, 1285, 1175, 1135, 1118,
1065, 1029, 905, 868, 837, 770, 717, 659 cm21.
 5—Yield 5 6.57 g (13.7 mmol, 38%) of colorless, bright crys-
tals with Tm 5 259–261 8C; 1H-NMR (500.1 MHz, DMSO-d6,
d, ppm): 1.40 (t, J 5 7.6 Hz, 18 H), 3.15 (q, J 5 7.4 Hz,
12 H), 7.08 (s, 2 H); 13C-NMR (125.8 MHz, DMSO-d6, d,
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ppm): 9.11 (6 CH3), 46.63 (6 CH2), 136.42 (2 CH), 165.37
(2 C); IR: m 5 3443, 3058, 3001, 2974, 2934, 2877, 2801,
2736, 2671, 2599, 2570, 2527, 2489, 1468, 1432, 1396, 1383,
1363, 1331, 1287, 1186, 1168, 1068, 1033, 848, 803, 758,
631 cm21.
Synthesis of the Antistatic Unsaturated Polyesters by
Polymeric Analogous Reactions
 E1/E4—the necessary amounts of initial substances are listed
in Table II. A 250 mL three-necked round flask was charged
with the UP-resin, triethylammoniumbromide acetyl chloride
(1), p-toluene sulfonic acid, and a solvent mixture. Before the
heating started the equipment should be flushed for at least
15 min with argon. Afterwards the mixture was stirred at
reflux under inert-gas atmosphere for 3 days. The cool brown
solution was filtered and next the volatile compounds were
removed by reduced pressure. The residue was dried at 60 8C
in a vacuum drying oven overnight and this was followed by
suspending in acetone, whereby the excess amount of the
amine 1 is undissolved. From the mother liquor the solvent
was distillated and the obtained solid is dried again at 60 8C
in a vacuum drying oven over night.
 E1—Brown, clearly, solid resin; IR: m 5 3436, 3060, 2967,
2942, 2881, 2808, 2479, 1716, 1673, 1645, 1496, 1456, 1382,
1290, 1253, 1223, 1150, 1118, 1078, 1030, 1009, 977, 838,
818, 772, 682 cm21; specific surface resistivity: dry climate
3109 X/square, normal climate 9108 X/square; TGA:
TDTG,1 5 150 8C (Dm 5 10%), TDTG,2 5 272 8C (Dm 5 72%),
TDTG,3 5 495 8C (Dm 5 13%).
 E4—Brown, clearly, solid resin; IR: m 5 3442, 3065, 2977,
2950, 2890, 2822, 2499, 1718, 1685, 1641, 1499, 1476, 1389,
1292, 1260, 1161, 1101, 1078, 999, 972, 842, 777, 681 cm21;
specific surface resistivity: dry climate 2109 X/square, normal
climate 6108 X/square.
 E2—20.0 g (0.041 mol) of E1, 18.54 g (0.82 mol) triethylam-
moniumbromide ethyl alcohol (2) and 5 spatula tips of N,N-
dimethylpyridin-4-amine were weighed in a 250 mL three-
necked round flask, purged with argon for 15 min followed
by adding of 100 mL pyridine. The reaction mixture was
heated at reflux under inert-gas atmosphere for 3 days. After
Table II. Starting Quantities for the Synthesis of the Unsaturated Polyest-
ers E1 and E4
Polyester Quantities for the reaction
E1 UP-resin: 25 g Palapreg P 18-03 (hydroxyl
number 52 mg/g, 0.022 mol, 11.38 g
(0.044 mol) triethylammoniumbromide acetyl
chloride (1), p-toluene sulfonic acid 2.5 g
(0.015 mol), solvent: 25 mL
dimethylformamide and 75 mL ethylacetate
E4 UP-resin: 4.8 g EL5 (hydroxyl number
98 mg/g, 8.9 mmol), 20.18 g (0.078 mol)
triethylammoniumbromide acetyl chloride (1),
p-toluene sulfonic acid 1.0 g (5.81 mmol),
solvent: 20 mL dimethylformamide and 30 mL
ethylacetate
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Table III. Starting Quantities for the Synthesis of the Unsaturated Polyesters PL-1, PL-2, PL-3, and PL-4, PL-5, and PL-6

Temperature
Polyester Quantities for the reaction program
PL-1 5.00 g (0.051 mol) maleic anhydride, 3.80 g (0.061 mol) ethylene glycol, 1 h at 170 8C
0.44 g (1.7 mmol) sodium citrate, 0.025 g (0.23 mmol) hydroquinone
PL-2 5.00 g (0.051 mol) maleic anhydride, 8.64 g (6.85 mL, 0.061 mol) 30 min at 140 8C
diethanolamine hydrochloride, 0.025 g (0.23 mmol) hydroquinone
PL-3 12.75 g (0.130 mol) maleic anhydride, 27.50 g (0.130 mol) 1 h at 170 8C
diethylaminomalonate hydrochloride, 19.00 g (0.305 mol) ethylene glycol,
0.085 g (0.20 wt % of the ester) anhydrous calcium acetate, 0.175 g
(0.4 wt % of the ester) antimony trioxide, 0.125 g (1.14 mmol) hydroquinone
PL-4 2.55 g (0.026 mol) maleic anhydride, 8.12 g (0.026 mol) triethylammonium- 1 h at 170 8C
bromiddimethylmalonate, 3.80 g (0.061 mol) ethylene glycol, 0.017 g
(0.20 wt % of the ester) anhydrous calcium acetate, 0.035 g
(0.4 wt % of the ester) antimony trioxide, 0.100 g (0.91 mmol) hydroquinone
PL-5 4.03 g (0.041 mol) maleic anhydride, 5.00 g (0.011 mol) di- 1 h at 160 8C
triethylammoniumbromide succinic acid, 3.87 g (0.062 mol) ethylene glycol,
0.025 (0.23 mmol) hydroquinone
PL-6 5.00 g (0.051 mol) maleic anhydride, 4.52 g (0.013 mol) 1 h at 160 8C
triethylammoniumbromide terephthalic acid, 4.78 g (0.077 mol) ethylene
glycol, 0.050 (0.45 mmol) hydroquinone

the solution was cooled to r.t., the volatile compounds were
removed by reduced pressure. The residue was dried at 60 8C
in a vacuum drying oven overnight. Then the solid was sus-
pended in acetone, whereby the excess amount of the quater-
nary ammonium salt 2 got undissolved. The mixture was
passed by a coarse frit and washed with a small amount of
acetone. After further distillation of the solvent under
reduced pressure a brown solid was received. Finally, the
product is dried in a vacuum drying oven at 60 8C again over
night.
 Brown, clearly, solid resin; IR: m 5 3354, 3061, 2973, 2941,
2880, 2674, 2488, 1717, 1646, 1569, 1455, 1377, 1292, 1257,
1222, 1154, 1119, 1076, 1032, 1009, 980, 836, 818, 773, 709,
682 cm21; specific surface resistivity: dry climate 2107 X/
square, normal climate 4105 X/square; TGA: TDTG,1 5 222 8C
(Dm 5 32%), TDTG,2 5 278 8C (Dm 5 46%), TDTG,3 5 515 8C
(Dm 5 22%).
 E3—5.0 g commercial UP-resin Palapreg P 18–03 (hydroxyl
number 52 mg/g, 4.6 mmol; iodine number 0.77 g/100 g)
and 1.0 g MgSO4 were solved in a solvent mixture of 10 mL
water and 20 mL acetone. To the 0 8C cold solution 1.580 g
(10 mmol) KMnO4 solved in 20 mL ethylacetate, was added
slowly. The speed of addition complies with the actually reac-
tion temperature, which shouldn’t increase above 5 8C. After
complete addition of the solution the cold bath was removed
and the reaction mixture was stirred at r.t. for 2 h. The
resulting manganese dioxide was separated by a coarse frit
and washed with acetone. From the insulated mother liquor
the volatile compounds were removed by reduced pressure
and the solid residue was dried at 60 8C in a vacuum drying
oven over night.
 Colorless, clearly, solid resin; IR: m 5 3437, 3082, 2972, 2882,
1714, 1642, 1455, 1377, 1289, 1254, 1224, 1151, 1117, 1075,
977, 838, 773, 724, 672 cm21.
 E5—After purging a three-necked round flask with argon for
15 min, 10.0 g (hydroxyl number 52 mg/g, 9.2 mmol) com-
mercial UP-resin Palapreg P 18–03, 6.98 g (46.0 mmol) anhy-
drous glycidyl trimethyl ammonium chloride and 0.755 g
(0.73 mL, 9.2 mmol) 1-methylimidazole is solved in 40 mL
acetonitrile. The reaction mixture was stirred at r.t. for 1 h
followed by heating at 55 8C for 24 h. After the solution was
cooled to r.t., the volatile compounds were removed by
reduced pressure. The residue was dried at 60 8C for at least
2 h in a vacuum drying oven and this followed by suspend-
ing in acetone, whereby the excess amount of glycidyl tri-
methyl ammonium chloride is undissolved. The mixture was
passed by a coarse frit and washed with a small amount ace-
tone. After further distillation of the solvent under reduced
pressure the brown solid was received. Finally, the product is
dried again at 60 8C in a vacuum drying oven over night.
 Brown, clearly, solid resin; IR: m 5 3244, 3020, 2965, 2879,
1717, 1643, 1595, 1478, 1374, 1292, 1256, 1224, 1151,
1113, 1077, 1055, 973, 921, 841, 773, 666 cm21; specific
surface resistivity: dry climate 1108 X/square, normal climate
2107 X/square; TGA: TDTG,1 5 224 8C (Dm 5 53%), TDTG,2 5
344 8C (Dm 5 12%), TDTG,3 5 542 8C (Dm 5 16%).
Synthesis of the Antistatic Unsaturated Oligoesters from
Monomers (PL-1, PL-2, PL-3, PL-4, PL-5, and PL-6)
In a 100 mL three-necked round flask the exact amount of each
of the respective chemicals must be weighed in accordance with
Table III. The apparatus is completed by a water separator with
reflux condenser. Before the heating started the equipment
should be flushed for at least 15 minutes with argon. Afterwards
the reaction mixture is heated to 100 8C (exception: PL-2 only
to 90 8C, because the boiling point of the diethanolamine
hydrochloride is 100 8C) slowly, because of the highly exother-
mic reaction. This temperature is maintained constant for 1 h.

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The following heating steps are listed in Table III. The final oli-
goester was cooled to r.t. and the remaining water/ethanol was
removed by reduced pressure at 60 8C overnight.
 PL-1—Light yellow, slightly opaque resin with an acid num-
ber of 125 mg/g and a hydroxyl number of 161 mg/g; 1H-
NMR (500.1 MHz, DMSO-d6, d, ppm): 3.40 (s), 3.43–3.67
(m), 3.95–4.66 (m), 6.44–6.68 (m), 6.69–6.97 (m); 13C-NMR
(125.8 MHz, DMSO-d6, d, ppm): 58.70, 62.78, 66.68, 115.64,
129.92, 130.66, 133.26, 134.37, 135.86, 137.34, 164.41, 167.01,
167.76; IR: m 5 3422, 3081, 2955, 2885, 2663, 1712, 1643,
1582, 1450, 1374, 1293, 1258, 1220, 1156, 1075, 1030, 979,
881, 775, 672 cm cm21; specific surface resistivity: dry cli-
mate 1108 X/square, normal climate 7107 X/square; Mw:
390 g/mol; TGA: TDTG,1 5 232 8C (Dm 5 18%), TDTG,2 5 286 8C
(Dm 5 16%), TDTG,3 5 324 8C (Dm 5 35%), TDTG,4 5 553 8C
(Dm 5 17%).
 PL-2—Light yellow, clear resin with an acid number of
429 mg/g and a hydroxyl number of 635 mg/g; 1H-NMR
(500.1 MHz, DMSO-d6, d, ppm): 5 2.66–3.44 (m), 3.47–4.11
(m), 4.24–4.71 (m), 6.41–7.11 (m), 8.93–9.77 (m); 13C-NMR
(125.8 MHz, DMSO-d6, d, ppm): 45.16, 48.87, 56.29, 59.63,
128.43, 130.48, 131.78, 133.81, 134.93, 164.79, 165.71, 166.46;
IR: m 5 3320, 2957, 2887, 2801, 1712, 1643, 1446, 1376, 1295,
1257, 1155, 1063, 1029, 976, 887, 773, 634 cm21; specific sur-
face resistivity: dry climate 1106 X/square, normal climate
2106 X/square; Mw: 600 g/mol; TGA: TDTG,1 5 242 8C
(Dm 5 27%), TDTG,2 5 297 8C (Dm 5 31%), TDTG,3 5 552 8C
(Dm 5 20%).
 PL-3—Orange-yellow, clear resin with an acid number of
114 mg/g and a hydroxyl number of 451 mg/g; 1H-NMR
(500.1 MHz, DMSO-d6, d, ppm): 1.03–1.36 (m), 2.10 (s),
3.34–3.76 (m), 3.94–4.58 (m), 6.56–6.96 (m); 13C-NMR
(125.8 MHz, DMSO-d6, d, ppm): 13.81, 18.45, 55.91, 58.51,
61.48, 62.78, 66.86, 115.64, 132.51, 133.26, 134.56, 164.41,
165.71, 167.38; IR: m 5 3280, 3078, 2943, 2878, 1716, 1645,
1520, 1447, 1373, 1296, 1258, 1225, 1159, 1078, 1028, 978,
881, 859, 775, 670 cm21; specific surface resistivity: dry cli-
mate 3108 X/square, normal climate 8107 X/square; Mw:
340 g/mol; TGA: TDTG,1 5 198 8C (Dm 5 56%), TDTG,2 5 353 8C
(Dm 5 24%), TDTG,3 5 626 8C (Dm 5 18%).
 PL-4—Light yellow, slightly opaque resin with an acid num-
ber of 248 mg/g and a hydroxyl number of 363 mg/g; 1H-
NMR (500.1 MHz, DMSO-d6, d, ppm): 1.21 (t, J 5 7.3 Hz),
3.11 (q, J 5 7.4 Hz), 3.28–3.84 (m), 3.94–5.01 (m), 6.54–6.87
(m), 9.29–9.61 (br s); 13C-NMR (125.8 MHz, DMSO-d6, d,
ppm): 8.43, 10.85, 45.72, 58.70, 60.18, 62.78, 66.86, 72.24,
115.64, 132.51, 133.26, 134.56, 164.41, 165.71; IR: m 5 3338,
3079, 2973, 2938, 2878, 2802, 2736, 2672, 2489, 1717, 1644,
1513, 1466, 1432, 1396, 1382, 1296, 1259, 1159, 1074, 1033,
977, 885, 848, 803, 775, 671 cm21; specific surface resistivity:
dry climate 2107 X/square, normal climate 2107 X/square;
Mw: 390 g/mol; TGA: TDTG,1 5 262 8C (Dm 5 93%).
 PL-5—Colorless, slightly opaque resin with an acid number
of 232 mg/g and a hydroxyl number of 294 mg/g; 1H-NMR
(500.1 MHz, DMSO-d6, d, ppm): 1.21 (t, J 5 7.3 Hz), 3.10
(q, J 5 7.3 Hz), 3.54–3.71 (m), 3.99–4.13 (m), 4.14–4.23 (m),
4.26–4.57 (m), 6.30–6.98 (m), 9.44 (br s); 13C-NMR (125.8
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MHz, DMSO-d6, d, ppm): 8.43, 45.72, 58.70, 62.78, 66.68,
115.64, 132.51, 133.26, 134.56, 164.41, 165.71; IR: m 5 3434,
3349, 3077, 2957, 2882, 2735, 2672, 2488, 1707, 1644, 1513,
1452, 1398, 1371, 1294, 1257, 1154, 1072, 1033, 977, 884,
853, 774, 669, 650 cm21; specific surface resistivity: dry
climate 2108 X/square, normal climate 1107 X/square; Mw:
380 g/mol; TGA: TDTG,1 5 233 8C (Dm 5 66%), TDTG,2 5 343 8C
(Dm 5 22%), TDTG,3 5 520 8C (Dm 5 10%).
 PL-6—Light yellow, clear resin with an acid number of
256 mg/g and a hydroxyl number of 266 mg/g; 1H-NMR
(500.1 MHz, DMSO-d6, d, ppm): 1.19 (t, J 5 7.3 Hz), 3.07
(q, J 5 7.3 Hz), 3.43–3.49 (m), 3.52–3.66 (m), 3.70–3.74 (m),
4.00–4.21 (m), 4.22–4.67 (m), 6.44–6.63 (m), 6.70–6.90 (m),
7.54–7.63 (m), 7.85–8.00 (m), 8.01–8.11 (m); 13C-NMR
(125.8 MHz, DMSO-d6, d, ppm): 8.25, 45.35, 58.88, 62.78,
66.68, 115.64, 118.60, 128.06, 128.99, 130.48, 133.26, 135.86,
137.34, 142.34, 164.41, 166.65; IR: m 5 3359, 3075, 2952,
2882, 2702, 2499, 1716, 1644, 1584, 1477, 1451, 1373, 1254,
1154, 1076, 1034, 976, 884, 773, 754, 672 cm21; specific sur-
face resistivity: dry climate 2109 X/square, normal climate
3107 X/square; Mw: 450 g/mol; TGA: TDTG,1 5 182 8C
(Dm 5 28%), TDTG,2 5 362 8C (Dm 5 59%), TDTG,3 5 498 8C
(Dm 5 15%).
RESULTS AND DISCUSSION
Each SMC formulation consists of various ingredients: thermo-
setting resins, thermoplastic resins, fibers, fillers, and several
additives. Our intention was to get a permanent antistatic
behavior either by an integration of chemical compatible or a
chemical bonding of antistatic substances to one of the major
components. An initial pretesting has shown that an integration
of the antistatic effect via modified unsaturated oligo/polyesters
should be favored as the polymeric matrix is one of the largest
ingredients in the SMC formulation.14 Because of the existing
double bonds, which can form covalent bonds with the major
matrix component during the thermal molding process the
additive can be permanently integrated into the polymer matrix
at the end. There are two opportunities to develop appropriate
unsaturated oligo-/polyesters: on one hand by polymeric analo-
gous reactions on unsaturated polyesters and on the other hand
by polycondensation reaction from ionic monomer building
blocks.
Antistatic Additives by Polymeric Analogous Reactions
A closer look at the structure of the unsaturated polyester
(Scheme 2) illustrates, that there are two possibilities to perform
polymeric analogous reactions.14,15 First, the existing end groups
(acid and hydroxyl groups) or second, the unsaturated units of
the polyester could be transformed into ionic functionalities.
Scheme 2 demonstrates all of the realized polymeric analogous
reactions at the unsaturated polyester. Three different types of
reactions were carried out to create polymer-based antistatic
additives with ionic units.
First it is possible to transform the hydroxyl and acid end
groups of the polyester with an esterification to an ionic com-
pound (E1 and E2). In the case of E1 and E2 it is necessary to
synthesize the quaternary amines 1 and 2 in an additional step
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.44741
ARTICLE WILEYONLINELIBRARY.COM/APP

Scheme 2. Overview about the polymeric analogous reactions.

(Scheme 3), because they are not commercially available. It
should be noted that for an optimal thickening reaction during
SMC preparation the ratio of acid to hydroxyl group is impor-
tant, thus the SMC formulation itself has to be optimized later
on. Secondly the double bond of the polyester could be func-
tionalized in two steps by an addition reaction. Initially a dihy-
droxylation reaction with potassium permanganate generates
hydroxyl groups from the existing double bounds (E3), which
can be transformed via an esterification in a second step analo-
gous to E1 in ionic units (E4). It has to be taken note, that not
all of the existing double bounds of the unsaturated polyester
should be transformed, because they are necessary for the
covalent linking with the polymeric network. Thirdly the
hydroxyl group of the polyester can be transformed with a
direct addition from an epoxy compound (E5) in a compound
with antistatic potential.
After the application of all synthesized polyelectrolytes, the anti-
static properties are received by determination of the specific
surface resistivity (Table IV). It is assumed that a functionaliza-
tion of only one end group of the unsaturated polyester is not
sufficient in order to achieve a noticeable antistatic effect. The
biggest reduction of the specific surface resistivity was obtained
with the double esterification to E2, because in this case the
amount at ionic units has been increased a lot. However, also
E4 show a rise of functional groups, but do not achieve surface
resistivities from 105 Ohm/square. This phenomenon caused
very probably on the distribution of the ionic units within the
polyester, because this is important to realize the formation of a
percolation network through the material in the demanded way.
While E2 has ionic functionalities at both ends of the polyester,
which further differ in their structure, E4 has only one kind of
functionalities inside and, additionally, they are located in the
middle or also at one end of the polymer structure. Therefore
the generation of conductive pathways through the polymer

Table IV. Antistatic Property of End-Group Functionalized Polyesters

Specific surface Specific surface

resistivity dry resistivity normal
compound climate (Ohm/square)a climate (Ohm/square)b
Reference 11012 61011
9
E1 310 9108
7
E2 210 4105
E4 2109 6108
8
E5 110 2107
Scheme 3. Quaternization of tertiary amines to synthesize 1, 2, 3, 4, and a
Dry climate: 20 8C/35% humidity.
b
5 as necessary building blocks for the synthesis of antistatic additives. Normal climate: 23 8C/50% humidity.

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ARTICLE WILEYONLINELIBRARY.COM/APP
Scheme 4. Synthesis of several unsaturated polyesters as antistatic additives via polycondensation reaction.
material is complicated and to achieve the percolation threshold
is more difficult.
Antistatic Additives by Polycondensation Reaction
A comfortable way to get oligomeric antistatic structures on the
base of unsaturated polyesters is the direct synthesis by polycon-
densation reactions of monomer units.14,15 In this case, the
insertion of ionic units is possible with the use of specific diac-
ids/diesters/acid anhydrides or dialcohols. Based on the assump-
tion that the origin unsaturated polyester resin of the
considered SMC formulation consists of maleic anhydride and
ethylene glycol, one of these components will be replaced
completely or partly by specific monomer building blocks dur-
ing the polycondensation reaction, in order to introduce con-
ductive units. Also a monomer with acid as well as hydroxyl
functionality was used (PL-1). For an easier blending with the
unsaturated polyester resin of the SMC formulation the unsatu-
rated polyesters were synthesized with a low conversion rate,
thus they in consequence are only oligomers. Scheme 4 gives an
WWW.MATERIALSVIEWS.COM 44741 (7 of 9)
overview about the realized reactions to get six potential anti-
static additives for SMC. In three cases (PL-4, PL-5, PL-6) the
necessary ionic monomeric component has to be synthesized in
an additional step, because they aren’t available on the market
(Scheme 3).
In order to prove the suitability of the synthesis products as
antistatic additive for SMC, the obtained polycondensates are
tested as pure substances on card boards with regard to the spe-
cific surface resistivity. A comparison of the resistivity values in
Table V showed that the reduction of the specific surface resis-
tivity of the products is always in the same range. Contrary to
expectations the antistatic properties of the oligoesters are not
affected by various ionic units, the several chemical structures
and the amount of ionic units in the monomeric components.
Furthermore, only a slight dependence of the current humidity
was measured in most cases. The specific surface resistivity val-
ues are usually higher at dry climate than at normal climate.
However, PL-2 is an exception, because this polyester has at
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.44741
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Table V. Antistatic Property of Unsaturated Polyesters via Polycondensa- Initial Tests of the Antistatic Properties in an Unsaturated
tion Reactions Polyester Mixture
Because of the already mentioned independence of the climate
Specific surface Specific surface conditions in combination with good thermal resistance under
resistivity dry resistivity normal the manufacturing conditions PL-2 seems to be the best candi-
Compound climate (Ohm/square)a climate (Ohm/square)b date for an initial testing in mixtures with the unsaturated poly-
PL-1 1108 7107 ester resin Palapreg P 18–03.14 Nine samples with various
PL-2 110 6
2106 additive concentrations were prepared. The homogenization with
8 the UP-resin was performed without any problems by stirring.
PL-3 310 8107
PL-4 2107 2107 In contrast to the specific surface resistivity of the pure sub-
PL-5 310 8
510 7 stance a significant dependence of the humidity was observed
PL-6 2109 3107 (Figure 1). At dry climate the specific surface resistivity is
higher than at normal climate. Thus, for a successful antistatic
a
Dry climate: 20 8C/35% humidity. treatment higher amounts of additive are needed at dry climate,
b
Normal climate: 23 8C/50% humidity.
while 5 wt % at normal climate are sufficient.

both climatic conditions lower specific surface resistivities than
the others. This behavior is advantageous for an industrial use,
because the actual humidity needs not to be considered. Also
this oligoester has the lowest specific surface resistivity of all
synthesized oligoesters. One reason for this phenomenon could
be the presence of HCl moiety in the compound, but on the
other hand PL-3 have also this unit and isn’t in the same range.
The long time stability (release of antistatic property) under dry
and normal climate is unknown, but the thermal stability under
the processing conditions for SMC is given.
In terms of a later industrial application in commercial SMC-
formulations additives which can be synthesized from commer-
cial monomers are preferred (PL-1, PL-2, PL-3). The next step
toward the market is to test admixtures of selected additives
with the UP-resin of a real SMC formulation and with the com-
plete SMC formulation, so the ability to reduce the surface
resistivity in mixture, the influence of the manufacturing pro-
cess and the mechanical properties could be checked.
CONCLUSIONS
A series of novel oligomeric/polymeric antistatic additives based
on unsaturated polyesters was synthesized either via polymeric
analogous reactions or via polycondensation reactions from ion-
ic monomer building blocks. Additives which were obtained by
polycondensation reaction have to be preferred for a future
application, because they result in a stronger reduction of the
specific surface resistivity than additives which were prepared
via polymeric analogous reactions. Additionally, they can be
synthesized by a one pot procedure. Furthermore, preferred
oligomeric/polymeric antistatic additives are compatible with
the origin unsaturated polyester resin, most of them are ther-
mally stable under the SMC processing conditions and able to
form covalent bonds during the thermal molding process of the
SMC.
Initial application tests of the preferred PL-2 in an unsaturated
polyester resin were successful with regard to the antistatic
properties. For a commercial use as antistatic additives in SMC-
formulations the additive influence on the reactivity and the
mechanical properties has to be studied.

ACKNOWLEDGMENTS

We thank H. Komber for NMR measurements, L. H€aussler and K.

Arnhold for TGA measurements, M. Malanin for FT-IR measure-
ments. Furthermore, we thank B. Voit for helpful discussions and
support during my doctoral dissertation. Finally, we thank the POL-
YTEC COMPOSITES GERMANY GMBH for free samples of SMC basic
materials. This research was financially supported by the Federal
Ministry of Education and Research (BMBF 01 RI 0631 B).

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