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NMP. Procedure I: 0.15 g of (1) or (2) and BlocBuilderTM
(ratio 100:1) were placed in a microwave vial. After the
addition of anisole (1 mol/L), the vial was sealed, degassed,
and placed in an oil bath (90 or 120 ꢀC). Procedure II:
0.15 g of (1) or (2), BlocBuilderTM (ratio 100:1), and SG-1
free radical (0.1% related to BlocBuilderTM) were placed in a
microwave vial. After the addition of anisole (1 mol/L), the
vial was sealed, degassed, and placed in an oil bath pre-
heated at 120 ꢀC. Procedure III: BlocBuilderTM (ratio 100:1)
was dissolved in anisole and placed in a sealed microwave
vial. In a second microwave vial, 0.15 g of (2) was dissolved
in anisole (1 mol/L). Subsequently, the degassed BlocBuil-
unit without endgroups: C, 69.29; H, 10.29; N, 6.22; found: C,
69.06; H, 10.47; N, 6.16. Tg ¼ 128 C.
ꢀ
P6ox: SEC (DMAc, PS-standard): Mn
¼
16,100 g/mol;
Mw ¼ 18,400 g/mol; PDI ¼ 1.15. Vapor pressure osmometry
(CHCl3): Mn ¼ 5960 g/mol. FTIR (ATR, cmꢁ1): 966 (w),
1145 (vs, vas(OCC¼¼O)), 1232 (m, vas(CC¼¼OO)), 1364 (m,
v(NAO)), 1463 (m, d(CH2)), 1724 (s, v(C¼¼O)), 2970 (m,
v(CH)). Anal. Calcd. for for repeating unit without endgroups:
C, 64.97; H, 9.23; N, 5.83; found: C, 64.03; H, 8.42; N, 5.49.
ESR: g ¼ 2.0064, Ns ¼ 1.61 ꢂ 1021 gꢁ1. Tg ¼ 160 C.
ꢀ
Instrumentation
derTM solution was placed in an oil bath preheated to 60 C.
Size exclusion chromatography (SEC) was used to determine
the molar masses and polydispersity indices of the polymer
samples with respect to polystyrene standards. Either an
Agilent 1200 series system (degasser: Polymer Standard
Service Mainz, pump: G1310A, auto sampler: G1329A, oven:
Techlab, diode array detector: G1315D, RI detector: G1362A)
using a pC/PSS GRAM 1000/30 Å column and dimethylaceta-
mide (þ0.21% lithium chloride) as eluent at a flow rate of 1
mL/min (40 ꢀC) or a Shimadzu system (controller: SCL-10A
VP, degasser: DGU-14A, pump: LC-10AD VP, auto sampler:
SIL-10AD VP, oven: Techlab, UV detector: SPD-10AD VP, RI
detector: RID-10A) using a PSS SDV pre/lin S column and
chloroform/iso-propanol/triethyl-amine [94:2:4] as eluent at
a flow rate of 1 mL/min (40 ꢀC). Absolute molar masses
were determined on a Shimadzu system (controller: SCL-10A
VP, degasser: DGU-14A, pump: LC-10AD VP, auto sampler:
SIL-10AD VP, oven: CTO-10A VP, detectors: UVD: SPD-10AD
VP, RID: RID-10A, Visco: PSS ETA-2010, MALS: PSS SLD 7000
(BIC) at k ¼ 635 nm) using a PSS SDV pre/104/102 Å col-
umn andꢀtetrahydrofurane as eluent at a flow rate of 1 mL/
min (40 C). Vapor pressure osmometry was measured on a
Knauer vapor pressure osmometer (K 7000) using chloro-
form solutions (temperature: 30 ꢀC). Conversion was deter-
mined by gas chromatography on a Shimadzu GC-2010 (car-
rier gas helium; flame ionization detector with hydrogen and
air as detector gases; Restek Rtx-5 column, 30 m length, 0.25
mm ID, 0.25 lm film thickness, 5% diphenyl polysiloxane
95% dimethyl polysiloxane). NMR spectra were obtained on
a Bruker AC 300 spectrometer. The MALDI-TOF MS spectra
were measured on an Ultraflex III TOF/TOF (Bruker Dalton-
ics GmbH) equipped with a Nd:YAG laser and a collision cell.
All spectra were measured in the positive reflector or linear
mode using 2,5-dihydroxy benzoic acid (DHB) or a-cyano-4-
hydroxycinnamic acid (CHCA) as matrix. Elementary analysis
was performed using a k EuroVector EuroEA3000 instru-
ment. The inkjet printing experiments were carried out on
an Autodrop system (Microdrop Technologies). The printer
was equipped with a piezo-based printhead (micropipette
system AD-K-501). The inner diameter of the used nozzle
was 70 lm. Voltages between 60 and 70 V and pulse lengths
between 40 and 50 ls were found as typical print settings
to create stable droplets for all tested polymers. Surface to-
pography as well as film thicknesses were measured using
an optical interferometric profiler Wyko NT9100 (Veeco,
Mannheim, Germany). Electrochemical measurements were
performed on an Autolab PGSTAT30 model potentiostat. For
ꢀ
After 40 minutes the temperature was raised to 120 ꢀC and
the degassed solution of (2) was transferred to the pre-
heated BlocBuilderTM solution.
Analytical Data of the Printed Polymers. P1: SEC (DMAc,
PS-standard): Mn > 300,000 g/mol (exclusion limit of the
SEC column). SEC (THF/NEt3, univ. calibration): Mn
¼
1
60,000 g/mol. H NMR (300 MHz, CDCl3, d, ppm): 0.65–1.55
(17H), 1.60–2.40 (4H), 5.06 (1H). FTIR (ATR, cmꢁ1): 970
(m), 1152 (vs, vas(OCC¼¼O)), 1236 (s, vas(CC¼¼OO)), 1377 (m,
ds(CH3)), 1456 (m, d(CH2)), 1718 (vs, v(C¼¼O)), 2960 (m,
v(CH)), 3332 (m), 3427 (m, v(NH)). Anal. calcd. for repeating
unit: C, 69.29; H, 10.29; N, 6.22; found: C, 68.17; H, 10.36; N,
ꢀ
6.33. Tg ¼ 143 C.
P1ox: SEC (DMAc, PS-standard): Mn > 300,000 g/mol (exclu-
sion limit of the SEC column; only soluble portion of poly-
mer tested). FTIR (ATR, cmꢁ1): ¼ 966 (w), 1141 (vs, vas(O-
CC¼¼O)), 1238 (m, vas(CC¼¼OO)), 1364 (m, v(NAO)), 1463
(m, d(CH2)), 1724 (s, v(C¼¼O)), 2974 (m, v(CH)). Anal. calcd.
for repeating unit: C, 64.97; H, 9.23; N, 5.83; found: C, 64.62;
H, 9.49; N, 5.51. ESR: g ¼ 2.0062, Ns ¼ 4.02 ꢂ 1021 gꢁ1
.
ꢀ
Tg ¼ 168 C.
P4: 1H NMR (300 MHz, CDCl3, d, ppm): 0.65-1.55 (17H),
1.60-2.40 (4H), 5.06 (1H). SEC (DMAc, PS-standard): Mn
¼
33,900 g/mol; Mw ¼ 38,800 g/mol; PDI ¼ 1.14. FR-IR (ATR,
cmꢁ1): 970 (m), 1148 (vs, vas(OCC¼¼O)), 1238 (s,
vas(CC¼¼OO)), 1377 (m, ds(CH3)), 1460 (m, d(CH2)), 1720
(vs, v(C¼¼O)), 2956 (m, v(CH)). Anal. calcd. for repeating unit
and bromine end-group: C, 67.93; H, 10.08; N, 6.09; Br, 1.56;
ꢀ
found: C, 67.74; H, 10.08; N, 6.06; Br, 1.51. Tg ¼ 113 C.
P4ox: SEC (DMAc, PS-standard): Mn ¼ 26,300 g/mol; Mw
¼
34,700 g/mol; PDI ¼ 1.31. FTIR (ATR, cmꢁ1): 964 (w), 1144
(vs, vas(OCC¼¼O)), 1232 (m, vas(CC¼¼OO)), 1364 (m, v(NAO)),
1464 (m, d(CH2)), 1724 (s, v(C¼¼O)), 2974 (m, v(CH)). Anal.
calcd. for repeating unit and bromine end-group: C, 57.75; H,
8.20; N, 5.18; found: C, 57.36; H, 8.51; N, 5.10. ESR: g ¼
2.0064, Ns ¼ 1.09 ꢂ 1021 gꢁ1. Tg ¼ 162 C.
ꢀ
P6: SEC (DMAc, PS-standard): Mn ¼ 24,500 g/mol; Mw
¼
29,100 g/mol; PDI ¼ 1.18. Vapor pressure osmometry
(CHCl3): Mn ¼ 5720 g/mol. 1H NMR (300 MHz, CDCl3, d,
ppm): 0.65-1.55 (17H), 1.60-2.30 (4H), 5.06 (1H). FTIR
(ATR, cmꢁ1): 970 (m), 1147 (vs, vas(OCC¼¼O)), 1238 (s,
vas(CC¼¼OO)), 1377 (m, ds(CH3)), 1460 (m, d(CH2)), 1720
(vs, v(C¼¼O)), 2956 (m, v(CH)). Anal. Calcd. for repeating
1406
JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY 2012, 50, 1394–1407