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1 Mastering Challenges in Polymer Characterization by Chromatography Mass Spectrometry Till Gründling International Symposium on GPC/SEC and Related Techniques - 01.10.2014

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Page 1: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

1

Mastering Challenges in Polymer Characterization by Chromatography Mass Spectrometry Till Gründling International Symposium on GPC/SEC and Related Techniques - 01.10.2014

Page 2: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Overview

Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite

Mastering Challenges in Polymer Characterization by Chromatography Mass Spectrometry

Software tools in polymer LC/MS

Method development in Critical Chromatography (LCCC)

2

Page 3: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

3

Verbund Site Ludwigshafen, Germany

Employees BASF SE 34,769 (as of Dec 31, 2012)

Site area 10 km² Sales products about 8.5 million metric tons p.a. Production facilities circa 160 production plants

Page 4: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Functional Leadership BASF Analytics 4

Quality control

Specialty Laboratories 4 Core Tech Platforms

Elemental analysis

Enzyme QC

Phys./Chem. analysis Spectroscopy

...

In General 58 senior scientists/scientists/engineers

347 technicians/research associates

> 300.000 samples/year > 6.000 methods

in 40 laboratories

Chromatography

Facts and Figures Competence Center Analytics

Page 5: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

5

Focused on 5 Buildings at Ludwigshafen Site

B009: NMR-Spectroscopy

D216: Gas- and Trace-Analysis

M320: Elemental Analysis Phys./Chem. Analysis

J550: Formulation Lab Phys./Chem. Analysis

E210: Chromatography Mass Spectrometry Optical Spectroscopy Enzyme Laboratory Polymer Hyphenation Lab

B 009

E 210

D 216

M 320

Where We Are in Ludwigshafen

J 550

Page 6: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Liquid Chromatography

Molar mass distribution and quantitative composition

GPC, HPLC, HPLC/IR

Polymer Hyphenation Lab

Mass Spectrometry

Structural characterization of large molecules and polymers

MALDI, LC/MS, GPC/MS Py-GC/MS, HT-GC

6

Bastiaan Staal Till Gründling

Page 7: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

HPLC, 2D-LC

Polymer Hyphenation Lab Key Analytical Techniques

LC/IR GPC / SEC

MALDI-MS HPLC/MS, GPC/MS Pyrolysis-GC/MS HT-GC

7

Page 8: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Chemical Analysis Across the Entire Molecular Mass Range

GPC / SEC

GPC/IR Pyrolysis-GC/MS

HPLC/MS

Molar Mass

Stru

ctur

al In

form

atio

n C

onte

nt

1 kDa 10 kDa 100 kDa 1 MDa

NMR, IR

FFF

MALDI-MS GPC/MS

HT-GC

Molar Mass Distribution Chemical Structure

Concentration

HPLC

8

Page 9: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Polymer Hyphenation Lab

Sample preparation facilities

Qualitative analysis in complex matrix

Use of analytical Method-Verbund

Multi-phase systems

Formulations, polymer blends, …

Evaporation

Extraction

Wet Chemistry Freeze Drying

Centrifugation

9

Page 10: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

HPLC, 2D-LC

Polymer Hyphenation Lab Key Analytical Techniques

LC/IR GPC / SEC

MALDI-MS HPLC/MS, GPC/MS Pyrolysis-GC/MS HT-GC

10 Internal – Dr. Till Gründling (GMC/C)

Page 11: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

time

m/z

Page 12: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Redundancy – Central Problem of Polymer Mass Spectrometry

12

Small molecules are fully described by one mass spectral peak

Qualitative: Molar mass (m)

Quantitative: Concentration (c) Theoretical Mass Spectrum

m/z

90amuSH

100amu

OMeO

Inte

nsity

Page 13: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Redundancy – Central Problem of Polymer Mass Spectrometry

13

Polymers exhibit chain-length distribution with n peaks in the spectrum

Qualitative: Molar mass of endgroup (mE) und monomer (mMMA)

Quantitative: Endgroup concentration (cE) and MWD (wn)

Theoretical Mass Spectrum

m/z

n

OMeO

HS

Inte

nsitä

t

100amu

m = mE + n∙mMMA

Page 14: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Redundancy – Central Problem of Polymer Mass Spectrometry

14

Co-Polymers exhibit n x o peaks in the spectrum

Qualitative: Molar mass of endgroup (mE) and monomers (mMMA, mSty)

Quantitative: Endgroup concentration (cE) and 2D-MMD (wn,o)

Theoretical Mass Spectrum

m/z

n o

PhOMe

H

O

S

Inte

nsity

100amu

104amu

m = mE + n∙mMMA + o∙mSty

Page 15: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Redundancy – Central Problem of Polymer Mass Spectrometry

Typical analytical problem:

Structure elucidation in formulations

Mixture of two polymers of differing functionality

15

Mass spectrum m/zE1,1, …, m/zE1,n m/zE2,1, …, m/zE2,o m/zE3,1, …, m/zE3,p

Relationship m = m/z ∙ z

Information of interest

mMMA, mEO mE2, mE3, mMAA

5 important values

Theoretical Mass Spectrum

m/z

Inte

nsity

Theoretical Mass Spectrum

m/z

Inte

nsity

E 1 nH

O

1 1

1 1

1

1 1

1 1

1

1 1

Theoretical Mass Spectrum

m/z

Inte

nsity

n

E 2

O HO

H

E 1 n

OH

1 1

1 1

1

1 1

1 1

1

1 1

2 2

2

2

2

2

Theoretical Mass Spectrum

m/z

Inte

nsity

o

E 2

O HO

H

E 1 n

OH

1 1

1 1

1

1 1

1 1

1

1 1

2 2

2

2

2

2 3 3

3

3 3

3

p

E 3

O HO

H

> 100 MS Peaks

Page 16: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Redundancy – Central Problem of Polymer Mass Spectrometry

Spectral information can be reduced to a small set of parameters

Endgroup mass

(Co)monomer mass

Chain-length distribution

Total concentration

Spectra are complex due to the chain-length and monomer distributions

Bottleneck: Manual spectrum interpretation

16

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Competence Center Analytics

Data Processing in SEC/MS and LC/MS

Handle third dimension added to the data by hyphenation

17 17

3D GPC/MS Spectrogram

Retention time

m/z

o

E 2

O HO

H

E 1 n

OH

p

E 3

O HO

H

Extracted Mass Spectrum

m/z

Inte

nsity

1

1 1

1

1

1 1

1 1

1

1 1

2

2

2

2 3

3 3

Integration range

Extracted Mass Spectrum

m/z

Inte

nsity

1

1 1

1

1

1 1

1 1

1

1 1

3D RP-LC/MS Spectrogram

Retention time

m/z

Copolymer LC/MS Spectrogram

Retention time

m/z

M2

M1

Page 18: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Data Processing in SEC/MS and LC/MS

Direct ESI-MS of a mixture of PEG and functional PMMA

Dominant distribution of multiply charged PEG

Weak PMMA distribution (low concentration and lower ion affinity)

18

400 600 800 1000 1200 1400 1600 1800 2000m/z

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

Inte

nsity

1200 1400 1600 1800m/z

100

200

300

400

Inte

nsity

Page 19: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Data Processing in SEC/MS and LC/MS

In-house developed software prototype

Extraction of polymer distributions from 3D LC/MS data

19

logarithmic plotting Compare weak and strong distributions across orders of magnitude

Page 20: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

PMMA (z=1)

PEG (z=1)

PEG (z=2)

PEG (z=3)

PEG (z=4)

PEG (z=5)

PEG (z=6)

time

m/z

Page 21: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Data Processing in SEC/MS and LC/MS

Classical (rectangular) integration of MS data

21

overlapping charge envelopes for PEG

PMMA barely discernable

PEG (z=2)

PEG (z=1)

PMMA (z=1)

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Competence Center Analytics

PEG (z=1)

Adapted 3D (Blob) integration of MS data

Data Processing in SEC/MS and LC/MS

22

PEG (z=2)

Clean doubly charged spectrum

PMMA (z=1)

Clean PMMA spectrum no PEG overlap

Before

Page 23: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Efficient polymer analysis by HPLC/MS … … is about processing complex 3D data the right way.

time

m/z

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Competence Center Analytics

24

Taking the

Out of Critical Chromatography

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Competence Center Analytics

Critical Chromatography (LCCC) by MS

Polyols are important co-reactants in polyurethane production

Impurities in polymeric diols hamper performance

Purity of the base material needs to be ascertained

25

n

O

O

NH

OR

O

O O

O

O

n

OR

O

O O HO

O

O

Termination MW reduction

n

O

O O O

O

O

n

O

O O O

O

O

no reaction

n

O HO

O

OOH

n

O

O

NH

NH

O

OO

O

O

OK

Page 26: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

Critical Chromatography (LCCC) by MS

External manufacturer‘s polyol with significant amounts of side products

Identify MALDI

Quantify Use Critical Chromatography

26

n

O

O O O

O

O

m/z

0

10

20

30

40

50

60

70

80

90

100 In

tens

ity

Mono OH

Di OH

Mono OH Mono OH

Di OH

Di OH

Cyclics Cyclics Cyclics

n

O HO

O

OOH

n

OR

O

O O HO

O

O

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Competence Center Analytics

Critical Chromatography (LCCC) by MS

3 modes of separation in polymer chromatography

LCCC allows endgroup separation regardless of molecular mass

Endgroup-quantification possible with classical detectors

27

A

B

Critical composition Critical chromatography (LCCC)

A B

Strong eluent Size exclusion mode (SEC)

Weak eluent Adsorption chromatography (LAC)

n=1 n=3 n=2 n=4

Log

M

Retention time

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Competence Center Analytics

Critical Chromatography (LCCC) by MS

Preconceptions about LCCC: Method development takes days/weeks

Need (to synthesize) molar mass standards of the polymer

Maintaining critical conditions is difficult

Challenges overcome! Online LC/MS1 for rapid method development

Use analyzed polymer itself as molar mass standard

Modern modified silica stationary phases provide robustness

28 1 Falkenhagen, Weidner, Anal. Chem. (2009) 81, 282.

(on bare silica)

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Competence Center Analytics

0 1 2 3 4 5 6 7 8 9Time (min)

0

50

100 1.86 NL: 4.08E8TIC MS 0848100223kep60_nhep-dcm_40-60_ymc_cn_0,5µl_(1-10verd_dcm)

0848100223kep60_nhep-dcm_40-60_ymc_cn_0,5µl_(1-10verd_dcm) RT: 0.01 - 9.99 Mass:

1 2 3 4 5 6 7 8 9Time (min)

200

400

600

800

1000

1200

1400

1600

1800

2000

m/z

Mono OH Di OH

Dicarbonate/Cyclics

Critical Chromatography (LCCC) by MS

60% DCM

40% n-Hep

GPC

CN

CN

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Competence Center Analytics

0 1 2 3 4 5 6 7 8Time (min)

0

50

100 2.16 NL: 1.19E8TIC MS 0848100223kep65_nhep-dcm_60-40_ymc_cn_0,5µl_(1-10verd_dcm)

0848100223kep65_nhep-dcm_60-40_ymc_cn_0,5µl_(1-10verd_dcm) RT: 0.01 - 8.64 Mass:

1 2 3 4 5 6 7 8Time (min)

200

400

600

800

1000

1200

1400

1600

1800

2000

m/z

Mono OH Di OH

Dicarbonate/Cyclics

Critical Chromatography (LCCC) by MS

40% DCM

60% n-Hep

GPC

CN

Page 31: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

0 1 2 3 4 5 6 7 8 9Time (min)

0

50

100 2.482.24 NL: 1.05E8TIC MS 0848100223kep67_nhep-dcm_70-30_ymc_cn_0,5µl_(1-10verd_dcm)

0848100223kep67_nhep-dcm_70-30_ymc_cn_0,5µl_(1-10verd_dcm) RT: 0.01 - 9.99 Mass:

1 2 3 4 5 6 7 8 9Time (min)

200

400

600

800

1000

1200

1400

1600

1800

2000

m/z

Mono OH Di OH

Dicarbonate/Cyclics

Critical Chromatography (LCCC) by MS

30% DCM

70% n-Hep

GPC

CN

Page 32: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

0 1 2 3 4 5 6 7 8 9Time (min)

0

50

100 3.26 3.542.78 NL: 4.22E7TIC MS 0848100223kep69_nhep-dcm_80-20_ymc_cn_0,5µl_(1-10verd_dcm)

0848100223kep69_nhep-dcm_80-20_ymc_cn_0,5µl_(1-10verd_dcm) RT: 0.00 - 9.98 Mass:

1 2 3 4 5 6 7 8 9Time (min)

200

400

600

800

1000

1200

1400

1600

1800

2000

m/z

Mono OH Di OH

Dicarbonate/Cyclics

Critical Chromatography (LCCC) by MS

20% DCM

80% n-Hep

GPC near critical

CN

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Competence Center Analytics

0 1 2 3 4 5 6 7 8 9Time (min)

0

50

100 1.96 2.011.335.90 6.243.12 5.61 6.703.39

NL: 1.39E7TIC MS 0848100223kep79_nhep-dcm_90-10_ymc_cn_0,5µl_(1-10verd_dcm)

0848100223kep79_nhep-dcm_90-10_ymc_cn_0,5µl_(1-10verd_dcm) RT: 0.00 - 9.98 Mass:

1 2 3 4 5 6 7 8 9Time (min)

200

400

600

800

1000

1200

1400

1600

1800

2000

m/z

Mono OH Di OH (breakthrough)

Dicarbonate/Cyclics

Critical Chromatography (LCCC) by MS

10% DCM

90% n-Hep

LAC

CN

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Competence Center Analytics

0 1 2 3 4 5 6 7 8 9Time (min)

0

50

100 9.60

2.59 4.95

NL: 2.02E7TIC MS 0848100223kep77_nhep-dcm_88-12_ymc_cn_0,5µl_(1-10verd_dcm)

0848100223kep77_nhep-dcm_88-12_ymc_cn_0,5µl_(1-10verd_dcm) RT: 0.01 - 9.98 Mass:

1 2 3 4 5 6 7 8 9Time (min)

200

400

600

800

1000

1200

1400

1600

1800

2000

m/z

Mono OH Di OH

Dicarbonate/Cyclics

Critical Chromatography (LCCC) by MS

12% DCM

88% n-Hep

LAC

CN

Page 35: Mastering Challenges in Polymer Characterization by ... Event/2014/Related... · Polymer Hyphenation Lab at the BASF SE Ludwigshafen Verbundsite Mastering Challenges in Polymer Characterization

Competence Center Analytics

0 1 2 3 4 5 6 7 8 9Time (min)

0

50

100 7.727.554.222.51

NL: 2.38E7TIC MS 0848100223kep75_nhep-dcm_86-14_ymc_cn_0,5µl_(1-10verd_dcm)

0848100223kep75_nhep-dcm_86-14_ymc_cn_0,5µl_(1-10verd_dcm) RT: 0.01 - 9.99 Mass:

1 2 3 4 5 6 7 8 9Time (min)

200

400

600

800

1000

1200

1400

1600

1800

2000

m/z

Mono OH Di OH

Dicarbonate/Cyclics

Critical Chromatography (LCCC) by MS

14% DCM

86% n-Hep

LAC

CN

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Competence Center Analytics

0 1 2 3 4 5 6 7 8 9Time (min)

0

50

100 6.08 6.503.79 6.96

NL: 2.41E7TIC MS 0848100223kep73_nhep-dcm_84-16_ymc_cn_0,5µl_(1-10verd_dcm)

0848100223kep73_nhep-dcm_84-16_ymc_cn_0,5µl_(1-10verd_dcm) RT: 0.01 - 9.98 Mass:

1 2 3 4 5 6 7 8 9Time (min)

200

400

600

800

1000

1200

1400

1600

1800

2000

m/z

Mono OH Di OH

Dicarbonate/Cyclics

Critical Chromatography (LCCC) by MS

16% DCM

84% n-Hep

LAC

CN

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Competence Center Analytics

0 1 2 3 4 5 6 7 8 9Time (min)

0

50

100 4.253.22 4.80

NL: 4.04E7TIC MS 0848100223kep71_nhep-dcm_82-18_ymc_cn_0,5µl_(1-10verd_dcm)

0848100223kep71_nhep-dcm_82-18_ymc_cn_0,5µl_(1-10verd_dcm) RT: 0.01 - 9.99 Mass:

1 2 3 4 5 6 7 8 9Time (min)

200

400

600

800

1000

1200

1400

1600

1800

2000

m/z

Mono OH Di OH

Dicarbonate/Cyclics

Critical Chromatography (LCCC) by MS

18% DCM

82% n-Hep

LCCC

CN

O H

O H

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Competence Center Analytics

0 1 2 3 4 5 6 7 8 9Time (min)

0

50

100 7.72 7.834.12 8.17

8.76

NL: 2.10E8TIC MS 0848100223kep85_nhep-dcm_70-30_ymc_diol_0,5µl_(1-10verd_dcm)

0848100223kep85_nhep-dcm_70-30_ymc_diol_0,5µl_(1-10verd_dcm) RT: 0.00 - 9.98 Mass:

1 2 3 4 5 6 7 8 9Time (min)

200

400

600

800

1000

1200

1400

1600

1800

2000

m/z

Mono OH Di OH

Dicarbonate/Cyclics

Critical Chromatography (LCCC) by MS

30% DCM

70% n-Hep

LCCC

O H

O H

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Competence Center Analytics

ELSD

Sig

nal

Time (min.)

Method directly after transfer from LC/MS to LC/ELSD

Di OH

Critical Chromatography (LCCC) by MS

39

Mono OH Cyclics/ Dicarbonate

Low molar mass oligomers not eluted in LCCC mode

Completion of binary scouting run after < 24h

Further „fine tuning“ of high molar mass on LC/ELSD system

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Competence Center Analytics

Conclusion

LC/MS is a powerful tool for both:

Method development in polymer chromatography

In-depth structural characterization of oligomers/polymers

Polymer mass spectra are complex and information-rich

Need dedicated software tools to assist efficient spectrum interpretation

Computational data processing algorithms can make MS amenable to a broader set of analytical challenges

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Competence Center Analytics

41

Thank You!