© Waters Corp. 20005
LC/MS PolymerAdditive Analysis by
EI and APCIKate Yu, Eric Block, and Michael Balogh
Waters Corporation,
34 Maple Street, Milford, MA 01757
© Waters Corp. 20005
Objective
• Demonstrate how EI and API cancomplement each other in chemical analysis
• Develop a novel analytical method foridentification and quantitation of polymeradditives using acetonitrile extract frompolypropylene powder as sample analyte
© Waters Corp. 20005
Experimental Conditions
• HPLC Conditions:– Waters AllianceTM 2690 System
– Waters Symmetry C8 Column: 3.9 x 150 mm
– Acetonitrile/Water as Mobile Phase
– 10 µL Injection with 0.4 ml/min Flow Rate
• MS Conditions:– Waters Integrity System for EI
– Micromass Platform LC System for API
© Waters Corp. 20005
LC/MS Polymer Additive Analysis
Quantitation of the Polymer Additives by API LC/MS
API: Confirm EI Leads with MW Information
Develop an MS Compatible LC Method
Additives Extracted from Polymer by :
Polymer Sample with Unknown Additive Package
Solvent Extration, Soxhlet Extraction, SFE
EI: To Generate Lead by Library Match andStructure Elucidation
Confirmation of Results by Obtaining Standards
© Waters Corp. 20005
• Comparison of three modes of detection:PDA, EI and APCI
• Matching EI spectra with library generateslead suspects
• Obtaining molecular weight informationfrom APCI helps to rule out wrong matches
• Generating limited fragmentation in APIwith Up-front Collision InducedDissociation (CID) helps to confirm EIresults
Compound Identification
© Waters Corp. 20005
Min12 14 16 18 20 22 24 26 28 30
PDA: 210 nm
1
2
43
5
7
EI: TIC
12
43
5
6
7
3
2
754
1
APCI-: TIC
© Waters Corp. 20005
1 Naugard Degradant MW 4362 NC-4 MW 4143 3-(3,5-di-tert-butyl-4-hydroxyphenyl)
propanoic acid MW 2784 7,9-Di-tert-butyl-1-oxaspiro(4,5)
deca-6,9-deene-2,8-dione MW2765 Naugard MW 6966 1-Octodecanol MW2707 Irgonox 1076 MW 530
© Waters Corp. 20005
m/z100 200 300 400 500
48
68
127
149159
219232
279 365436
200 300 400 500 600 700 800m/z
435
433
431
436
437
[M-H]--
APCI- : 12V
200 300 400 500 600 700 800m/z
277
231257
278 433279 431 436
APCI-: 40V
EI
HO
t-BuO
O
t-Bu
NHO
NHO
OH
Naugard Degradant MW 436
MS Spectra of Peak #1
© Waters Corp. 20005
100 200 300 400 500m/z
57
79105
119
133
177
206 279353 413232
O
O
O
O
HC OH
2H C OH
C2 H 55H 2C
NC-4: MW 414
200 300 400 500 600 700 800m/z
446
279
277
413
297298 827
830-
200 300 400 500 600 700 800m/z
279
277
249233
283
413284325 430
[M-H]-
[2M-H]-
APCI- : 40V
APCI- : 12V EI
MS Spectra of the Peak #2
© Waters Corp. 20005
100 200 300m/z
57
128147 219
247
263
278
200 300 400 500 600 700 800m/z
277
231
247 278
291
[M-H]-
200 300 400 500 600 700 800
231
m/z
205
277
247
APCI- : 12V
APCI- : 40V
EI
HO CH2CH2 COOH
MW 278 (51% Library Match)
MS Spectra of Peak #3
© Waters Corp. 20005
m/z100 200 300
57
7791
109
147161
175 189
205
217
232261
276
OO
O
MW 276 (98% Library Match)
200 300 400 500 600 700 800m/z
231
247
275
291
316
[M-H]-
200 300 400 500 600 700 800m/z
231
220
247
275
APCI- : 40V
APCI- : 12V EI
MS Spectra of Peak #4
© Waters Corp. 20005
219
100 200 300 400 500 600 700 800m/z
57
147
159
203
231245
278347 436
528 584640 696
HO CH CH
O
22
2
C O CH CH 2 2
NH C
O
Naugard: MW 696
200 300 400 500 600 700 800m/z
695
220 693231275247
415277409 692435
696
698
[M-H]-
m/z
200 300 400 500 600 700 800
277
220
231
247
417
415392
695
418693
477435 692
696
697
APCI- : 12V
APCI- : 40V
EI
MS Spectra of Peak #5
© Waters Corp. 20005
MS Spectra of Peak #656
6983
97
111
125139
153168
182196
210224
252
60.00 100.00 140.00 180.00 220.00
57
m/z
4369
83 97
111
125
139 153168
182196
210224 252
EI: Unknown Spectrum
EI: Library spectrum, 96% MatchH
3C (CH
2)15
CH CH OH2 2
© Waters Corp. 20005
200 300 400 500 600 700 800 100 200 300 400 500
m/z
529
527
233 489
531
543
[M-H]-
m/z
57
97 147
219
278
515
530
CH3CH2CH2 O (CH
2)17C
O
200 300 400 500 600 700 800
m/z
529
527
233 489
530
543
APCI-: 12V
APCI-: 40V
EI
Irgonox 1076: MW 530
(90% Library Match)
HO
MS Spectra of Peak #7
© Waters Corp. 20005
• Single Ion Recording (SIR) for data collection
• Four calibration curves were made with fourstandards available
• APCI+ was used for constructing the calibrationcurve
• Duplicate injection
• Linear range covers two orders of magnitude
• Amount in Original Polymer (w/w):NC-4 Naugard-XL 1-Octadecanol Irgonox1076
0.07% 0.04% 0.4% 0.06%
Quantitation
© Waters Corp. 20005
10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00Time0
100
%
0
100
%
0
100
%
0
100
%
14.30
11.81
SIR ChromatogramsIrgonox 1076
M/z 530.3
1-Octadecanol
M/z 294.3
Naugard-XL
M/z 473.2
NC-4
M/z 415.2
17.70
25.80
© Waters Corp. 20005
Correlation Coefficient: 0.996783
Calibration curve: 23.8168 * x + 11995Response: External Std, Area
0 500 1000 1500 2000 2500 3000 3500
ng/mL
Response
m/z 415
30.4 - 7600 ppb
NC-4
© Waters Corp. 20005
ng/mL
Correlation Coefficient: 0.997561Calibration curve: 16531 * x + 135.558Respons: External Std, Area
Response
0 500 1000 1500 2000 2500 3000 3500
m/z 473
14.4 - 3600 ppb
Naugard-XL
© Waters Corp. 20005
ng/mL
Correlation Coefficient: 0.998982Calibration curve: 0.538786 * x + 403.749Response: External Std, Area
0 1000 2000 3000 4000 5000 6000
Response
m/z 294
27.2 - 6800 ppb
1-Octadecanol
© Waters Corp. 20005
Correlation Coefficient: 0.979115Calibration curve: 4.90641 * x + 59456Response type: External Std, Area
0 1000 2000 3000 4000 5000 6000 7000
ng/mL
Response
m/z 530
12.8 - 3200 ppb
Irgonox 1076
© Waters Corp. 20005
Conclusion• Electron Ionization (EI) Offers Unknown
Identification– Fragementation Pattern
– Library Search
– Structure Elucidation
• Atomospheric Pressure Ionization (API)Confirms EI Results– Molecular Weight Information
– Limited Fragmentation by Up-front CID
• API Is Well Suited for Quantitation– Ion Monitoring Data Collection
© Waters Corp. 20005
Acknowledgement
• Mr. Roy Sparks from Huntsman PolymerCorporation
• Dr. Craig Dorschel from WatersCorporation