Sage Journals: Discover world-class research

Abstract

Electrospray ionization (ESI-MS) and matrix-assisted laser desorption/ionization (MALDI-MS) were used to determine the composition (monomer ratios) and structure (end group analysis) relative to ¹H nuclear magnetic resonance (NMR) spectroscopy and theoretical predictions for three different co-polymers: poly(butyl acrylate/vinyl acetate) (PBA/PVAc), poly(methyl methacrylate/vinyl acetate) (PMMA/PVAc) and poly (butyl acrylate/methyl methacrylate) (PBA/PMMA). We found that the ESI results were in excellent agreement with 1H NMR spectroscopy for PBA/PVAc and PBA/PMMA co-polymers, whereas there was more divergence in the case of PMMA/PVAc. In the case of PBA/PMMA co-polymers, a similar distribution of products was observed by ESI-MS and MALDI-MS with the two major product classes differing by their end-groups. One class has hydrogen and dodecylthio end groups while, in the other, the dodecylthio has been replaced by α-cyanoisopropyl from the initiator. The relative abundance of these distributions as a function of co-polymer conversion for a series of reaction conditions was investigated by both ESI and MALDI. MALDI results consistently underestimated (relative to ESI) the butylacrylate monomer ratio in PBA/PMMA and the abundance of co-polymer oligomers terminated by a dodecylthio group from the chain transfer agent.

Keywords

co-polymer electrospray ionization mass spectrometry (ESI-MS)end-group analysis matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS)monomer ratio NMR

Get full access to this article

View all access options for this article.

References

Rossignoli

P.J.

Duever

T.A.

, “The estimation of co-polymer reactivity ration: A review and case studies using the error-in-variables model and nonlinear least squares”, Polym. React. Eng. 3, 361 (1995).

Montaudo

M.S.

, “Mass Spectra of Copolymers”, Mass Spectrom. Rev. 21, 108 (2002). doi 10.1002/mas.10021

Hanton

S.D.

, “Mass spectrometry of polymers and polymer surfaces”, Chem. Rev. 101, 527 (2001). doi 10.1021/cr9901081

Karas

Bachmann

Bahr

Hillenkamp

, “Matrix -assisted ultraviolet leaser desorption of non-volatile compounds”, Int. J. Mass Spectrom. 78, 53 (1987). doi 10.1016/0168-1176(87)87041-6

Busch

K.L.

, “Desorption ionization mass spectrometry”, Int. J. Mass Spectrom. 30, 233 (1995). doi 10.1002/jms.1190300202

Stump

M.J.

Fleming

R.C.

Grong

W.-H.

Wilkins

C.L.

, “Matrix-assisted leaser desorption mass spectrometry”, Appl. Spectrosc. Rev. 37, 275 (2002). doi 10.1081/ASR-120014277

Fenn

J.B.

Mann

Meng

C.K.

Wong

S.F.

, “Electrospray ionization—principles and practice”, Mass Spectrom. Rev. 9, 37 (1990). doi 10.1002/mas.1280090103

Kebarle

Tang

, “From Ions in solution to ions in the gas phase/the mechanism of electrospray mass spectrometry”, Anal. Chem. 65, 972A (1993).

Gaskell

S.J.

, “Electrospray: Principles and Practice”, J. Mass Spectrom. 32, 677 (1997). doi 10.1002/(SICI)1096-9888(199707)32:7<677::AID-JMS536>3.0.CO;2-G

10.

Pramanik

B.N.

Ganguly

A.K.

Gross

M.L.

, Applied electrospray mass spectrometry. Marcel Dekker, Inc., New York, USA (2002).

11.

Barton

Kemp

T.J.

Buzy

Jennings

K.R.

, “Mass spectral characterization of thermal degradation of poly(propylene oxide) by electrospray and matrix-assisted laser desorption ionization”, Polymer. 36, 4927 (1995). doi 10.1016/0032-3861(96)81617-X

12.

Montaudo

Lattimer

R.P.

, Mass Spectrometry of Polymers. CRC Press, Boca Raton, Florida, USA (2002).

13.

Hunt

S.M.

Sheil

M.M.

Belov

Derrick

P.J.

, “Probing the effect of cone potential in the electrospray ion source: Consequences for the determination of molecular weight distributions of synthetic polymers”, Anal. Chem. 70, 1812 (1998). doi 10.1021/ac971288m

14.

Montaudo

M.S.

Puglisi

Samperi

, “Characterization of polymers by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry: Molecular weight estimates in samples of varying polydispersity”, Rapid Commun. Mass Spectrom. 9, 453 (1995). doi 10.1002/rcm.1290090514

15.

Murgasova

Hercules

D.M.

, “MALDI of synthetic polymers—an update”, Int. J. Mass Spectrom. 226, 151 (2003). doi 10.1016/S1387-3806(02)00971-5

16.

Huijser

Staal

B.B.P.

Huang

Duchateau

Koning

C.E.

, “Chemical composition and topology of Poly(lactide-co-glycolide) revealed by pushing MALDI-TOF MS to its limit”, Angew. Chem. Int. Ed. 45, 4104 (2006). doi 10.1002/anie.200600594

17.

Badeen

Dubé

M.A.

, “Modeling the co-polymerization of methyl methacrylate/alpha-methyl styrene at elevated temperatures using Java”, Polym. Chem. Eng. 11, 53 (2003).

18.

Dubé

M.A.

Penlidis

, “A systemic approch to the study of multicomponet polymerization kinetics—the butyl acrylate/methyl methacrylate/vinyl acetate example: 1. Bulk co-polymerization”, Polymer 36, 587 (1995). doi 10.1016/0032-3861(95)91568-R

19.

Jovanovic

Dubé

M.A.

, “Off-line montoring of butyl acrylate and vinyl acetate homo-polymerization and co-polymerization in toluene”, J. Appl. Polym. Sci. 82, 2958 (2001). doi 10.1002/app.2152

20.

Gao

Penlidis

, “A comprehensive simulator/database package for reviewing free-radical co-polymerization”, J.M.S. Rev. Macromol. Chem, Phys. C38, 651 (1998).

21.

Alicata

Montaudo

Puglisi

Samperi

, “Influence of chain end groups on the matrix-assisted laser desorption/ionization spectra of polymer blends”, Rapid Commun. Mass Spectrom. 16, 248 (2002). doi 10.1002/rcm.573

22.

Puglisi

Samperi

Alicata

Montaudo

, “End-groups dependent maldi spectra of polymer mixtures”, Macromolecules 35, 3000 (2002). doi 10.1021/ma011687q

23.

Cox

F.J.

Johnston

M.V.

Dasgupta

, “Charactrization and relative ionozation efficiencies of end group functionalized polystyrenes by matrix-assisted laser desorption/ionization mass spectrometry”, J. Am. Soc. Mass Spectrom. 14, 648 (2003). doi 10.1016/S1044-0305(03)00216-2

24.

Montaudo

Samperi

Montaudo

M.S.

, “Characterization of synthetic polymer by MALDI-MS”, Prog. Polym. Sci. 31, 277 (2006). doi 10.1016/j.progpolymsci.2005.12.001

25.

Billmeyer

F.W.

, Textbook of Polymer Science. John Wiley & Sons, New York, USA (1984).

26.

Barry

J.P.

Carton

W.J.

Pesci

K.M.

Evans

J.V.

, “Derivatization of Low Molecular Weight Polymers for Characterization by Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry”, Rapid Commun. Mass Spectrom. 11, 437 (1997). doi 10.1002/(SICI)1097-0231(199703)11:5<437::AID-RCM894>3.0.CO;2-1

27.

Nielen

M.W.F.

, “MALDI time-of-flight mass spectrometry of synthetic polymers”, Mass Spectrom. Rev. 18, 309 (1999). doi 10.1002/(SICI)1098-2787(1999)18:5<309::AID-MAS2>3.0.CO;2-L

28.

Scorah

M.J.

Hua

Dubé

M.A.

, “Bulk and solution co-polymerization of methyl methacrylate and vinyl acetate”, J. Appl. Polym. Sci. 82, 1238 (2001). doi 10.1002/app.1958

A Comparison of Electrospray Ionization and Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry with Nuclear Magnetic Resonance Spectroscopy for the Characterization of Synthetic Co-Polymers

Abstract

Keywords

Get full access to this article

References