SEC-MALDI ToF/ToF MS - Waters Corporation Event... · SEC-MALDI ToF/ToF MS for the Advanced...

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