8
80
S. Hahn, H.-J. Holdt / Reactive & Functional Polymers 72 (2012) 878–888
ꢀ
night, the resin was filtered and washed with methanol, methanol/
water mixture (1/1) and water. The resin was dried in an exsicca-
tor. All resins exhibited a beige colour.
(mmol g 1): P 1.10. FT-IR (KBr, cmꢀ1): 3026 (
m
aromatic), 2907
(m
as CH
2
), 2849 (
CAC), 1453 (d CH
818 (
m
2
s
CH
), 1262 (
CH
2
2
), 1601 (
P@O), 1100 (
), 698 (d aromatic-H).
m
aromatic CAC), 1493 (
m
m
aromatic
PAOAC),
m
m
CH ), 1028 (
3
Dimethyl-(butane-1,4-diyl) phosphate polymer (1a): yield of
m
PAOAC), 757 (
m
ꢀ
1
9
1% (7.23 g). EA (%): C 74.69, H 7.18, O 9.70. UV–Vis (mmol g ):
Dibutyl-(3,6-dioxaoctane-1,8-diyl) phosphate polymer (4c):
ꢀ1
P 1.39. FT-IR (KBr, cm ): 3024 (
m
aromatic), 2921 (
aromatic CAC), 1493 ( aromatic CAC), 1452
P@O), 1046 ( PAOAC), 846 ( PAOAC), 756
), 697 (d aromatic-H).
Diethyl-(butane-1,4-diyl) phosphate polymer (1b): yield of 88%
m
as CH
2
), 2851
yield of 68% (6.58 g). EA (%): C 77.05, H 7.93, O 10.28. UV–Vis
ꢀ
1
ꢀ1
(
(
(
m
s
CH
d CH
CH
2
), 1601 (
m
m
(mmol g ): P 1.02. FT-IR (KBr, cm ): 3026 (m aromatic), 2921
2
), 1273 (
m
m
m
(m
as CH
2
), 2855 (
CAC), 1452 (d CH
817 (
m
2
s
CH
), 1279 (
CH
2
2
), 1601 (
P@O), 1100 (
), 698 (d aromatic-H).
m
aromatic CAC), 1493 (
m
m
aromatic
PAOAC),
m
2
m
m
CH ), 1028 (
3
m
PAOAC), 758 (
m
ꢀ1
(
7.28 g). EA (%): C 75.87, H 7.98, O 8.28. UV–Vis (mmol g ): P 1.26.
ꢀ1
FT-IR (KBr, cm ): 3025 (
601 ( aromatic CAC), 1493 (
P@O), 1028 ( PAOAC), 817 (
matic-H).
Dibutyl-(butane-1,4-diyl) phosphate polymer (1c): yield of 84%
m
aromatic), 2920 (
aromatic CAC), 1452 (d CH
PAOAC), 755 ( CH ), 697 (d aro-
m
as CH
2
), 2850 (
m
s
CH
2
),
2.3. Instrumentation and characterisation of the resins
1H, 13C and 31P NMR analysis was performed on a Bruker Avance
300 NMR spectrometer using CDCl -d as a solvent that was also
used as an internal reference for H and C NMR measurements.
1
m
m
2
), 1275
(m
m
m
m
2
3
1
1
13
ꢀ1
31
(
7.52 g). EA (%): C 76.52, H 7.79, O 7.16. UV–Vis (mmol g ): P 1.15.
3 4
For P NMR analysis, H PO (85%) was used as an external refer-
ꢀ
1
FT-IR (KBr, cm ): 3025 (
601 ( aromatic CAC), 1493 (
P@O), 1026 ( PAOAC), 817 (
matic-H).
Dimethyl-(hexane-1,6-diyl) phosphate polymer (2a): yield of
m
aromatic), 2922 (
aromatic CAC), 1452 (d CH
PAOAC), 757 ( CH ), 697 (d aro-
m
as CH
2
), 2850 (
m
s
CH
2
),
ence. Elemental analysis (C, H, O) were determined with an Ele-
mentar Vario EL elemental analyser. Phosphorous content was
determined by the ammonium molybdate method with a Perkin
Elmer Lambda 2 UV–Vis spectrometer (wave length of 882.5 nm;
cell with path length of 1 cm). EI MS spectra were recorded using
a Thermo Scientific DSQII spectrometer in the solvent CHCl .
3
FT-IR-Nexus (Thermo Nicolet) was used to confirm the chemical
composition of the different resins by FT-IR spectroscopy (KBr pel-
1
m
m
2
), 1278
(m
m
m
m
2
ꢀ1
9
9% (8.20 g). EA (%): C 71.16, H 6.69, O 12.10. UV–Vis (mmol g ):
ꢀ1
P 1.88. FT-IR (KBr, cm ): 3024 (
CH ), 1631 ( aromatic CAC), 1601 (
aromatic CAC), 1451 (d CH ), 1218 (
56 ( PAOAC), 748 ( CH ), 697 (d aromatic-H).
Diethyl-(hexane-1,6-diyl) phosphate polymer (2b): yield of 92%
m
aromatic), 2919 (
aromatic CAC), 1490 (
P@O), 1026 ( PAOAC),
m
as CH
2
), 2846
(m
s
2
m
m
m
ꢀ
1
2
m
m
lets, transmission mode with 32 scans and a resolution of 4 cm ).
8
m
m
2
2.4. Reagents and solutions for batch experiments
ꢀ1
(
7.92 g). EA (%): C 75.18, H 7.03, O 8.26. UV–Vis (mmol g ): P 0.93.
ꢀ1
ꢀ1
ꢀ1
FT-IR (KBr, cm ): 3024 (
631 ( aromatic CAC), 1600 (
CAC), 1450 (d CH ), 1212 (
PAOAC), 757 ( CH ), 697 (d aromatic-H).
Dibutyl-(hexane-1,6-diyl) phosphate polymer (2c): yield of 59%
m
aromatic), 2918 (
aromatic CAC), 1490 (
P@O), 1027 ( PAOAC), 860 (
m
as CH
2
), 2848 (
m
s
CH
2
),
Platinum standard solution (1 g L
2
H [PtCl
6
] in 2 mol L HCl,
ꢀ3
ꢀ1
ꢀ
ꢀ1
1
m
m
m
aromatic
equates to 5.13 ꢃ 10 mol L
H
2
[PtCl
6
] in 2 mol L HCl) and rho-
in 1 mol L HCl, equates to
1
ꢀ1
2
m
m
m
dium standard solution (1 g L RhCl
3
ꢀ1
ꢀ
3
ꢀ1
m
2
9.72 ꢃ 10 mol L RhCl
3
in 1 mol L HCl) were obtained from
Bernd Kraft GmbH. Palladium standard solution (997 ppm in
ꢀ1
ꢀ3
ꢀ1
(
5.48 g). EA (%): C 76.86, H 7.22, O 6.56. UV–Vis (mmol g ): P 0.54.
5 wt.% HCl, equates to 9.37 ꢃ 10 mol L in 5 wt.% HCl) was pur-
chased from Fluka. Hydrochlorid acid (30%, suprapur) was received
from Merck KGaA.
ꢀ1
FT-IR (KBr, cm ): 3023 (
630 ( aromatic CAC), 1600 (
CAC), 1450 (d CH ), 1212 (
PAOAC), 756 ( CH ), 697 (d aromatic-H).
m
aromatic), 2917 (
aromatic CAC), 1489 (
P@O), 1026 ( PAOAC), 859 (m
m
as CH
2
), 2849 (
s 2
m CH ),
1
m
m
m
aromatic
2
m
m
m
2
2.5. Instrumentation for batch experiments
Dimethyl-(3-oxapentane-1,5-diyl) phosphate polymer (3a):
yield of 76% (6.18 g). EA (%): C 72.68, H 6.87, O 10.29. UV–Vis
The solid and the aqueous phases were mixed in an overhead
rotation shaker (Reax 2 from Heidolph) and separated by centrifu-
gation (Centrifuge 5416 from Eppendorf). The initial and final
metal content of the aqueous phase was determined using an ICP
OES (Optima 7300 DV from Perkin Elmer with cyclonic spray
chamber and Mira Mist nebulizer) and an S10 autosampler (Perkin
Elmer). Extraction experiments with temperature variation were
done in an MKR 13 cooling-thermo mixer (HLC).
All pH measurements were done with a WTW 340 pH hand-
held metre equipped with a SenTix 21 pH combined electrode
(Ag/AgCl with gel filling). Calibration of the system prior to use
was performed with standard buffer solutions at pH 4 and 7 (Radi-
ometer Copenhagen).
ꢀ1
ꢀ1
(
mmol g ): P 1.44. FT-IR (KBr, cm ): 3024 (
), 2852 ( CH ), 1632 ( aromatic CAC), 1601 (
aromatic CAC), 1451 (d CH ), 1273 ( P@O), 1022 (
PAOAC), 848 ( PAOAC), 755 ( CH ), 696 (d aromatic-H).
m
aromatic), 2918
(m
as CH
2
m
s
2
m
m
aromatic
CAC), 1492 (
m
2
m
m
m
m
2
Diethyl-(3-oxapentane-1,5-diyl) phosphate polymer (3b): yield
of 67% (5.67 g). EA (%): C 76.82, H 7.57, O 10.03. UV–Vis (mmol
ꢀ
1
ꢀ1
g
2
1
8
): P 1.18. FT-IR (KBr, cm ): 3025 (
851 ( CH ), 1601 ( aromatic CAC), 1493 (
453 (d CH ), 1274 ( P@O), 1101 ( CH ), 1027 (
17 ( PAOAC), 755 ( CH ), 697 (d aromatic-H).
Dibutyl-(3-oxapentane-1,5-diyl) phosphate polymer (3c): yield
m
aromatic), 2918 (
aromatic CAC),
PAOAC), 969,
2
mas CH ),
m
s
2
m
m
2
m
m
3
m
m
m
2
ꢀ1
of 67% (6.13 g). EA (%): C 77.96, H 7.85, O 8.69. UV–Vis (mmol g ):
ꢀ1
P 0.95. FT-IR (KBr, cm ): 3025 (
m
aromatic), 2919 (
aromatic CAC), 1493 ( aromatic CAC), 1452
P@O), 1025 ( PAOAC), 816 ( PAOAC), 756
), 697 (d aromatic-H).
Dimethyl-(3,6-dioxaoctane-1,8-diyl) phosphate polymer (4a):
yield of 81% (7.02 g). EA (%): C 72.79, H 7.18, O 0.73. UV–Vis
2
mas CH ), 2851
(
(
(
m
s
CH
d CH
CH
2
), 1601 (
m
m
2.6. General procedure for batch experiments
2
), 1278 (
m
m
m
m
2
The batch extraction experiments were performed using
50 mg ± 0.5 mg of the dry resin mixed with 5 mL of the appropriate
aqueous acidic metal solution. The metal solution was obtained by
diluting of the platinum(IV), palladium(II) and rhodium(III) stan-
dards in deionised water (Purelab ultra from Elga) or hydrochloric
acid in the relevant concentration. The mixed phases were shaken
with an overhead rotation shaker for 180 min, if not otherwise
stated. In order to examine the temperature dependency a
cooling-thermo mixer (1000 rpm) was used for 180 min. For the
determination of the equilibrium, samples were mixed for 0, 1,
ꢀ1
ꢀ1
(
(
mmol g ): P 1.38. FT-IR (KBr, cm ): 3024 (
), 2849 ( CH ), 1648 ( aromatic CAC), 1601 (
aromatic CAC), 1452 (d CH ), 1283 ( P@O), 1095
), 1029 ( PAOAC), 973, 846 ( PAOAC), 818, 749 ( CH ),
97 (d aromatic-H).
Diethyl-(3,6-dioxaoctane-1,8-diyl) phosphate polymer (4b):
yield of 88% (7.92 g). EA (%): C 76.25, H 7.72, O 11.29. UV–Vis
m
aromatic), 2907
mas CH
2
m
s
2
m
m
aromatic
CAC), 1493 (
m
2
m
(
m
6
CH
3
m
m
m
2