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Mastering Challenges in Polymer Characterization by Chromatography Mass Spectrometry Till Gründling International Symposium on GPC/SEC and Related Techniques - 01.10.2014
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
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
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
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
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
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
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
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
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)
Competence Center Analytics
time
m/z
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
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
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
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
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
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
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
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
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logarithmic plotting Compare weak and strong distributions across orders of magnitude
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
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)
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
Competence Center Analytics
Efficient polymer analysis by HPLC/MS … … is about processing complex 3D data the right way.
time
m/z
Competence Center Analytics
24
Taking the
Out of Critical Chromatography
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
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
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
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)
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
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
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
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
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
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
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
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
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
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
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
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
Competence Center Analytics
41
Thank You!