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SEC-MALDI ToF/ToF MS for the Advanced Characterization of Novel
Copolymers
Clemens Schwarzinger, October 2014
2
SEC/ESI-MS Hyphenation
DAD
HPLC
THF
CHCl3
Phenogel columns
5 µm, 4.6 mm
RT: 8.89 - 26.78
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26Time (min)
0
50000
100000
150000
200000
250000
300000
350000
400000
450000
500000
550000
600000
650000
700000
750000
800000
850000
900000
950000
1000000
1050000
1100000
uAU
NL:1.15E6Channel A UV MF_GPC_19
Pump
ESI-
Mass Spec
MeOH
MF_GPC_19 #393-544 RT: 16.69-21.15 AV: 76 SB: 1 6.44-6.46 NL: 2.13E7T: + p ESI Full ms [ 150.00-2000.00]
500 550 600 650 700 750 800 850 900 950 1000 1050m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rel
ativ
e A
bund
ance
687.13
717.13
673.13731.07
703.13657.13
643.13
747.07
761.07
613.13
629.07775.07
789.07599.20 925.33911.27 955.40581.20941.40 985.27881.33567.27
537.13 803.07 897.40835.20 999.27867.33521.20 559.07 1015.27819.13 1055.201095.13
3
Tetramethylmelamine resin
RN
N
N
N
N N
N
N
N
N
NH Nn
R = H, CH2OH, CH2OCH3
4
R2 = 0.9991
R2 = 0.9964
4.00
4.50
5.00
5.50
6.00
6.50
7.00
7.50
8.00
8.50
9.00
20 22 24 26 28 30 32 34 36
time / min
ln(M
M)
Tetramethylmelamine resin
Endgroups:
-NH
-NCH2OCH3 665 g.mol-1
257 g.mol-1
5
SEC-MALDI ToF MS
© pictures: ms-textbook.com, trendline.co.at
6
Poly-APMM
-1
0
1
2
3
4
5
6
4 5 6 7 8 9 10 11 12 13 14retention volume / ml
inte
nsity
F1F2F3F4F5F6F7F8F9F10F11F12F13F14APMM
N
NN
NN
N
7
Poly-APMM
0.0
0.5
1.0
1.5
2.0
2.5
4x10
Inte
ns.[
a.u.
]
2000 3000 4000 5000 6000 7000 8000 9000m/z
0
1
2
3
4x10
Inte
ns.[
a.u
.]
1000 2000 3000 4000 5000 6000m/z
0
2000
4000
6000Inte
ns.[
a.u
.]
2000 4000 6000 8000 10000 12000 14000m/z
0
1000
2000
3000
Inte
ns.
[a.u
.]
5000 7500 10000 12500 15000 17500 20000 22500 25000 27500 30000m/z
F14 F13
F12 F11
8
Poly-APMM
3.0
3.5
4.0
4.5
7.8 8.0 8.2 8.4 8.6 8.8 9.0 9.2 9.4
retention volume / ml
lnM
F14
F13
F12
F11
SECfraction molar mass
F11 12.500
F12 7.600
F13 4.480
F14 2.300
Calibration for SEC
9
SEC-online-MALDI ToF MS
split
10
SEC-online-MALDI ToF MS
11
SEC-online-MALDI ToF MS
12
PEG 600 and 1500
13
PEG 600 and 1500
1538.102
1626.172
1450.0331670.206
1406.000
1714.241
1361.967
1758.275
1802.3101317.936
1846.3451273.900
1890.3801229.866
1934.4161185.834
1802.310
1846.345
1818.284
Resolution: 25000
14
Polystyrene 2430
mass spectrometry chromatography
15
Polyester Possible structures:
HO-R-OH
HO-R-COOH
HOOC-R-COOH
cyclic
O O
O
O
OOH
H
Phthalic anhydride + diethylene glycol
16
Polyester
17
Polyester
18
Polyester
HO-R-OH HO-R-COOH
19
Styrene-Vinylmelamine-Copolymer
N
N
N
N
NNToluene
N N CNNC
NC
R
N
N N
N N
N
+
20
Styrene-Vinylmelamine-Copolymer
2000 3000 4000 5000 6000 7000 8000 9000 10000 1000
21
Styrene-Vinylmelamine-Copolymer 2050.617
2155.142
2222.804 2259.359 2272.668
2168.819
2118.6002064.389
2014.704
2235.825
2132.726
2027.927
2286.9842183.398
2078.738
2300.9132196.468
2091.329
* PSVPMM_20130524\0_E21\1\1Lin, Smoothed, "Baseline subt."
IBN-S18-H IBN-S18-M-H IBN-S16-M2-H IBN-S14-M3-H IBN-S17-IBN IBN-S17-M-IBN
22
* PSVPMM_20130524\0_K24\1\1Lin Raw
4500-7500
* PSVPMM_20130524\0_E21\1\1Lin, "Baseline subt."
1500-4500
Styrene-Vinylmelamine-Copolymer
* PSVPMM_20130524\0_I11\1\1Lin Raw
3000-6000
23
Styrene-Vinylmelamine-Copolymer
198.693
421.185
595.487
1545.008
814.730919.074697.531
1129.423
1961.598
5243.855
2481.8572586.308
2899.5233107.039 3419.924
* PSVPMM_20130524\0_I21\1\5552.5588.LIFT\1SRef
MS/MS of m/z=5552.6
24
Styrene-Vinylmelamine-Copolymer
197.360
279.266
419.480
487.554
117.140
3053.017
3171.129
3192.799
606.668
813.011
3156.223
708.834
1645.9591023.2221437.792
1335.555
3148.686
1854.837
PSVPMM_20130524\0_I1\1\3313.0459.LIFT\1SRef
MS/MS of m/z=3313.1
25
Summary and Outlook
SEC/MS allows “deeper insight” into polymer structure
especially suitable for lower molar mass polymers
limitation is ionization of polymers
Application to complex copolymers and mixtures
26
* PMMV-MMA\0_C4\1\1SRef Raw
* PMMV-MMA\0_C9\1\1SRef Raw
* PMMV-MMA\0_C19\1\1SRef Raw
* PMMV-MMA\0_C24\1\1SRef Raw
* PMMV-MMA\0_E21\1\1SRef Raw
* PMMV-MMA\0_F16\1\1SRef Raw
* PMMV-MMA\0_F11\1\1SRef Raw
* PMMV-MMA\0_F6\1\1SRef Raw
* PMMV-MMA\0_G1\1\1SRef Raw
* PMMV-MMA\0_J1\1\1SRef Raw
* PMMV-MMA\0_J6\1\1SRef Raw
* PMMV-MMA\0_J10\1\1SRef Raw
* PMMV-MMA\0_J11\1\1SRef Raw
* PMMV-MMA\0_J16\1\1SRef Raw
600 4000 m/z
MMA-Vinylmelamine-Copolymer
27
* PMMV-MMA\0_F11\1\1SRef Raw
1200 2500 m/z
MMA-Vinylmelamine-Copolymer
28
1726.000
1804.010
1757.029
1737.011
1748.042
1781.065
1793.032
1771.002 1815.061
* PMMV-MMA\0_F11\1\1SRef
1720 1820 m/z
MMA-Vinylmelamine-Copolymer
29
Acknowledgement
Dr Herbert Gabriel
DI Stefan Gabriel
DI Michael Heschik
Leila Maringer
Karl Schütz