LC/MS Polymer Additive Analysis by EI and APCI · • Demonstrate how EI and API can complement...

© 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


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


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


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


• 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


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


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


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


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


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)



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



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




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


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



• 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


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


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


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


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


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


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


Acknowledgement

• Mr. Roy Sparks from Huntsman PolymerCorporation

• Dr. Craig Dorschel from WatersCorporation

LC/MS Polymer Additive Analysis by EI and APCI · • Demonstrate how EI and API can complement...

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