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Bibliographic Information
Polymer characterization methods.
Montaudo, G.; Montaudo, M. S. USA. Editor(s): Montaudo, Giorgio; Lattimer,
Robert P. Mass Spectrometry of Polymers (2002), 41-111. Publisher: CRC Press LLC, Boca Raton, Fla CODEN:
69DIB9 Conference; General Review written in English. CAN 138:107204 AN 2002:922969 CAPLUS (Copyright
(C) 2006 ACS on SciFinder (R))
Abstract
A review in 3 sections on the major applications of mass spectrometric anal. in the characterization of polymers and on
the most conventional techniques to det. polymer size and structure. In the first section, a brief account of the
conventional techniques to measure the av. molar masses and their distribution (osmometry, intrinsic viscosity, size
exclusion chromatog., and light scattering) is given. The detn. of the molar-mass distribution of a polymer sample from its
mass spectrum is discussed. In the second section, the focus is on various aspects of the detn. of polymer structure,
namely assessing the compn. of the macromol. chains, discrimination cyclic from linear and branched chains, end-group
detn., and detection of stereoregularity in polymers. In the last section, copolymers are considered: the detn. of
copolymer compn., sequence distribution, compn. heterogeneity, reactivity ratios, and bivariate distribution of chain
compns. and chain lengths is discussed.
Bibliographic Information
Matrix effects on matrix-assisted laser desorption/ionization mass spectrometry analysis of dendrimers with a
pyridine-based skeleton.
Chessa, Gavino; Scrivanti, Alberto; Seraglia, Roberta; Traldi, Pietro. Dipartimento di
Chimica, Universita di Venezia, Venice, Italy. Rapid Communications in Mass Spectrometry (1998), 12(20), 15331537. Publisher: John Wiley & Sons Ltd., CODEN: RCMSEF ISSN: 0951-4198. Journal written in English. CAN
130:25535 AN 1998:697779 CAPLUS (Copyright (C) 2006 ACS on SciFinder (R))
Abstract
Dendritic poly(pyridine)s based on diethyl-4-hydroxypyridine-2,6-dicarboxylate, with core of 1,3,5tris(bromomethyl)benzene were analyzed by laser desorption (LD) and matrix-assisted laser desorption/ionization
(MALDI) mass spectrometry. For all the compds. examd., readily detectable cationized mol. species were obtained under
LD conditions, while for MALDI a strong matrix effect was found, leading to fragments related to the original skeleton. To
study this aspect, three differently branched dendrimers were analyzed using three different matrixes, 3,5dihydroxybenzoic acid, -cyano-4-hydroxycinnamic acid, and 1,8,9-anthracenetriol, at different matrix/sample molar
ratios. The fragmentation yield was strongly dependent on the matrix used, on the matrix/sample molar ratios and on the
mol. structure of the dendrimer.
Bibliographic Information
Interpretation of the fragmentation patterns in static SIMS analysis of polymers. Part I. Simple aliphatic
hydrocarbons.
Van Ooij, W. J.; Brinkhuis, R. H. G. Dep. Chem., Colorado Sch. Min., Golden, CO, USA.
Surface and Interface Analysis (1988), 11(8), 430-40. CODEN: SIANDQ ISSN: 0142-2421. Journal written in English.
CAN 109:74309 AN 1988:474309 CAPLUS (Copyright (C) 2006 ACS on SciFinder (R))
Abstract
Fragmentation patterns from static SIMS anal. of several aliph. polymers resulted in fingerprint spectra which gave
information on the effect of branching, unsatn., and pendant groups on polymer fragmentation and ion stability,
rearrangements, and recombinations. For satd. polymers, branching led to an increase of the C8/C2 cluster ratio, while
for polymers with pendant Me groups, formation of Me-substituted cyclopropyllium ions was obsd. Beam damage effects
were noted for LDPE, in which an increase in unsatn. was obsd., and polypropylene, in which preferential loss of the Me
group occurred.
Bibliographic Information
Mass spectrometry of step-growth polymers.
Klee, Joachim E. Dentsply De Trey, Konstanz, Germany.
European Journal of Mass Spectrometry (2005), 11(6), 591-610. Publisher: IM Publications, CODEN: EJMSCL ISSN:
116102382
1469-0667. Journal; General Review written in English.
(C) 2006 ACS on SciFinder (R))
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CAN 145:293555
AN 2006:37346
CAPLUS (Copyright
Abstract
A review. For at least two decades, different mass spectrometric techniques have been applied for polymer anal.,
including the qual. detn. of chem. compns., end group identification, functionality type distribution and the detn. of the
extent of cyclisation at each degree of polymn. Mol. wts. exceeding 100 KDa are provable by matrix-assisted laser
desorption/ionisation mass spectrometry (MALDI-ToF-MS). However, there are some hints that there is a discrimination
against higher mol. wt. species in samples with polydispersity of more than 1.2. Pathways for dendritic and hyperbranched polymers, supramol. polymers and nano condensates are analyzed with the help of mass spectrometry.
Bibliographic Information
MALDI-TOF MS Study of Poly(p-phenylene Terephthalamide) Fibers.
Gies, Anthony P.; Hercules, David M.;
Ellison, Sparkle T.; Nonidez, William K. Department of Chemistry, Vanderbilt University, Nashville, TN, USA.
Macromolecules (2006), 39(3), 941-947. Publisher: American Chemical Society, CODEN: MAMOBX ISSN: 00249297. Journal written in English. CAN 144:254674 AN 2006:15888 CAPLUS (Copyright (C) 2006 ACS on
SciFinder (R))
Abstract
MALDI-TOF MS was used to study the end group distribution of a series of poly(p-phenylene terephthalamide) and Kevlar
fibers. Poly(p-phenylene terephthalamide) fibers were synthesized using various percent mole ratios of diamine-to-diacid
chloride (70:30, 51:49, 50:50, 49:51, and 30:70), and their resulting MALDI-TOF mass spectra were compared with the
mass spectra of Kevlar fibers. Oligomers synthesized with excess diamine or excess diacid chloride were found to
contain abundances of amine or carboxylate end groups, resp., along with side products that were specific to their
synthesis. Oligomers synthesized with near equimolar ratios of reactants produced dominant species with amine-carboxyl
end groups along with small quantities of cyclic and imine branched species, which were also found in the oligomeric
portion of com. produced Kevlar. Exptl. results from this study indicate that mass spectra derived from the oligomeric
portion of high mol. wt. polymers can yield useful information about their synthesis.
Bibliographic Information
Determination of chemical composition distributions in synthetic polymers.
Philipsen, Harry J. A. Oce
Technologies, Research and Development Department (AM, Location 3N12), Venlo, Neth. Journal of Chromatography,
A (2004), 1037(1-2), 329-350. Publisher: Elsevier Science B.V., CODEN: JCRAEY ISSN: 0021-9673. Journal;
General Review written in English. CAN 141:89583 AN 2004:383613 CAPLUS (Copyright (C) 2006 ACS on
SciFinder (R))
Abstract
A review. A characteristic feature of synthetic polymers is their dispersity in molar mass and, in many cases, chem.
compn. Since dispersity is highly relevant in relation to polymer properties, ongoing efforts are being put in the
development of appropriate anal. methods. In this respect, size-exclusion chromatog. (SEC) is well known for the detn. of
molar mass distributions. Methods for chem. compn. distributions are less mature than SEC and mainly include liq.
chromatog. and mass spectrometry and the combination of these techniques. The term chem. compn. distribution is
considered broad in this paper, i.e. for the chem. compn. distribution of a (co)polymer backbone, for the functionality type
distribution of a polymers' functional end groups, for the block length distribution of a block copolymer, for the branching
distribution and for the tacticity distribution. In this paper, anal. methods for all types of chem. compn. distributions are
reviewed. Special attention is paid to practical requirements and common misconceptions that sometimes arise.
Applications within the last 5 yr are summarized.
Bibliographic Information
HPLC and MALDI-TOF MS Analysis of Highly Branched Polystyrene: Resolution Enhancement by Branching.
Im, Kyuhyun; Park, Soojin; Cho, Donghyun; Chang, Taihyun; Lee, Kwanyoung; Choi, Namsun. Department of
Chemistry and Center for Integrated Molecular Systems, Pohang University of Science and Technology, Pohang, S.
Korea. Analytical Chemistry (2004), 76(9), 2638-2642. Publisher: American Chemical Society, CODEN: ANCHAM
116102382
ISSN: 0003-2700. Journal written in English.
ACS on SciFinder (R))
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CAN 140:407317
AN 2004:252905
CAPLUS (Copyright (C) 2006
Abstract
Temp. gradient interaction chromatog. (TGIC) and matrix-assisted laser desorption/ionization time-of-flight mass
spectrometry (MALDI-TOF MS) were applied for the characterization of highly branched polystyrenes (PS) prepd. by
linking living polystyryl anions using 4-chlorodimethylsilylstyrene. Reversed-phase (RP)-TGIC showed an unexpectedly
high resoln. according to the no. of branches despite significant overlap of the mol. wt. as confirmed by MALDI-TOF MS.
The enhancement of the resoln. is ascribed to the contribution of the nonpolar groups in the branched PS: the
dimethylsilyl groups in the branching unit as well as the sec-Bu initiator groups. As the no. of branches increases, the no.
of nonpolar groups increases, which in turn increases the RP-TGIC retention synergistically with increasing mol. wt. In
contrast, a poorer resoln. was found in normal-phase-TGIC, in which the nonpolar groups reduce the retention. The
resoln. in RP-TGIC appears superior to that of liq. chromatog. at the chromatog. crit. condition (LCCC) of PS. It is
seemingly due to the synergistic contribution of the incremental PS mol. wt. to the functionality in the branched PS in RPTGIC while only the functionality contributes to the sepn. in LCCC. This type of resoln. enhancement could be utilized
efficiently for the anal. of highly branched polymers such as dendrimers or hyperbranched polymers.
Bibliographic Information
Analysis of polyethyleneimine by ESI-MS and MALDI-TOF-MS.
Girard, James E.; Konaklieva, Monika; Gu,
Jianghong; Guttman, Charles M.; Wetzel, Stephanie J. Department of Chemistry, American University, Washington,
DC, USA. PMSE Preprints (2003), 88 79. Publisher: American Chemical Society, CODEN: PPMRA9 ISSN: 15506703. Journal; Miscellaneous; Computer Optical Disk written in English. AN 2003:222554 CAPLUS (Copyright (C)
2006 ACS on SciFinder (R))
Abstract
The mol. mass distributions (MMD) obtained from com. polyethylenimine by electrospray ionization and matrix-assisted
laser desorption/ionization time-of-flight mass spectrometry were compared. The results of these two techniques give
distributions that are quite different and the differnce may be caused by preferential desorption/ ionization, preferential ion
attachment, or degrdn. and fragmentation due to the desorption process. In this study we focus on the effect of matrix
and laser energy in MALDI on the MMD of four PEI's of low polydispersity and varying degrees of polymer branching. The
matrix in which the polymer is analyzed may also influence the laser energy effect of MALDI and was also considered.
Three common matrixes were considered, sinnapinic acid, caffeic acid and 2,5-dihydroxybenzoic acid. Analyses of the
mol. mass distributions, obtained by varying laser energy and matrixes, reveal trends in the data. These trends can be
used to describe the influences of matrix and laser energy on MALDI-TOF-MS data measurement of polyethyleneimine
polymers. A statistical anal. revealed that matrix has a greater effect on the polymer MMD than was expected.
Polyethyleneimine analyzed by electrospray shows preferential ion attachment to most mols. A study with monovalent
cations suggests the branched polyethylenimine contains cyclic mols. that surround the cation. A study with six
monovalent cations of varying radii suggests an est. of the size of the cycles produced by polyethylenimine.
Bibliographic Information
Polymer characterization methods.
Montaudo, G.; Montaudo, M. S. USA. Editor(s): Montaudo, Giorgio; Lattimer,
Robert P. Mass Spectrometry of Polymers (2002), 41-111. Publisher: CRC Press LLC, Boca Raton, Fla CODEN:
69DIB9 Conference; General Review written in English. CAN 138:107204 AN 2002:922969 CAPLUS (Copyright
(C) 2006 ACS on SciFinder (R))
Abstract
A review in 3 sections on the major applications of mass spectrometric anal. in the characterization of polymers and on
the most conventional techniques to det. polymer size and structure. In the first section, a brief account of the
conventional techniques to measure the av. molar masses and their distribution (osmometry, intrinsic viscosity, size
exclusion chromatog., and light scattering) is given. The detn. of the molar-mass distribution of a polymer sample from its
mass spectrum is discussed. In the second section, the focus is on various aspects of the detn. of polymer structure,
namely assessing the compn. of the macromol. chains, discrimination cyclic from linear and branched chains, end-group
detn., and detection of stereoregularity in polymers. In the last section, copolymers are considered: the detn. of
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copolymer compn., sequence distribution, compn. heterogeneity, reactivity ratios, and bivariate distribution of chain
compns. and chain lengths is discussed.
Bibliographic Information
Analytical techniques for polymers with complex architectures.
Pasch, Harald. Deutsches Kunststoff-Institut,
Darmstadt, Germany. Macromolecular Symposia (2002), 178(Polymer Characterization and Materials Science), 2537. Publisher: Wiley-VCH Verlag GmbH, CODEN: MSYMEC ISSN: 1022-1360. Journal; General Review written in
English. CAN 136:370178 AN 2002:199499 CAPLUS (Copyright (C) 2006 ACS on SciFinder (R))
Abstract
A review, on anal. techniques used in detn. of chem. compn., functionality, mol. wt. distribution, and mol. architecture of
complex polymer structures. Liq. chromatog. techniques, including size exclusion chromatog. (SEC) where sepn. is
based on hydrodynamic vol. and liq. adsorption chromatog. (LAC) where sepn. is according to chem. compn., are
described. Liq. chromatog. at the crit. point of adsorption (LC-CC) is a versatile method for detn. of functionality
distribution of macromonomers, mol. architecture of homopolymers, and chem. heterogeneity of block and graft
copolymers. Branched block and graft copolymers can efficiently be analyzed with respect to chem. compn. and molar
mass by LC-CC and two-dimensional chromatog. The chem. heterogeneity as a function of molar mass can be detd. by
combining interaction chromatog. and FTIR spectroscopy. For the anal. of star-like polymers LC-CC is a powerful
technique when the molar mass of different segments (blocks, grafts) must be detd.
Bibliographic Information
Fragmentation studies of poly(propylene imine) dendrimers in the gas-phase by using electrospray ionization
mass spectrometry (ESI-MS).
Weener, J. W.; Van Dongen, J. L. J.; Hummelen, J. C.; Meijer, E. W. Laboratory of
Organic Chemistry, Eindhoven University of Technology, Eindhoven, Neth. Polymeric Materials Science and
Engineering (1997), 77 147-148. Publisher: American Chemical Society, CODEN: PMSEDG ISSN: 0743-0515.
Journal written in English. CAN 127:234834 AN 1997:582193 CAPLUS (Copyright (C) 2006 ACS on SciFinder
(R))
Abstract
Electrospray ionization mass spectrometry (ESI-MS) in combination with a simple statistical simulation program were
used to fully characterize the com. available poly(propylene imine) dendrimers, taking into account statistical errors.
Fragmentation reactions of the poly(propylene imine) dendrimers were studied in detail in the gas-phase using ESI-MS.
Collision activated dissocn. (CAD) of the [M + H]+ ions from DAB-dendr-(NH2)n (n = 4, 8, 16) all followed the same
mechanistic pathway involving a chain mechanism of nucleophilic displacement reactions. The chain starts at the
diaminobuthane (DAB) core, leading to a split dendrimer and proceeds outwards through the successive dendritic layers.
Bibliographic Information
Matrix-assisted laser desorption ionization mass spectrometric analysis of aromatic polyether dendritic systems.
Hayes, Wayne; Freeman, Adam W.; Frechet, Jean M. J. Department of Chemistry, University of California-Berkeley,
Berkeley, CA, USA. Polymeric Materials Science and Engineering (1997), 77 136-137. Publisher: American
Chemical Society, CODEN: PMSEDG ISSN: 0743-0515. Journal written in English. CAN 127:221205 AN
1997:582188 CAPLUS (Copyright (C) 2006 ACS on SciFinder (R))
Abstract
Matrix-assisted laser desorption ionization mass spectroscopy (MALDI-TOF MS) methods were developed and used to
study the structural characteristics of a wide range of arom. polyether dendritic systems. Most of the dendritic systems
that were studied carried a large no. of functional groups either at their peripheral surface or at their focal point. The
technique was also evaluated for the anal. of hybrid dendritic-linear polymers. MALDI-TOF MS is useful to ascertain the
purity of dendrimers and allows monitoring of the progress of reactions on dendritic components. These mass spectral
analyses provide valuable structural information on the dendritic systems and reaction intermediates that was not evident
from either 1H NMR spectroscopic anal. or size exclusion chromatog.
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Bibliographic Information
Hyphenated polymer separation techniques. Present and future role.
Barth, Howard G. Exp. Stn., DuPont,
Wilmington, DE, USA. Advances in Chemistry Series (1995), 247(Chromatographic Characterization of Polymers), 311. Publisher: American Chemical Society, CODEN: ADCSAJ ISSN: 0065-2393. Journal; General Review written in
English. CAN 123:170715 AN 1995:788093 CAPLUS (Copyright (C) 2006 ACS on SciFinder (R))
Abstract
A review, with 20 refs., is given on recent developments in the use of hyphenated multidimensional sepn. and detection
techniques for the characterization of polymeric materials. Online mol.-wt.-sensitive detectors for size-exclusion
chromatog. (SEC) based on measuring Rayleigh light-scattering or intrinsic viscosity of the eluting polymer for detn. of
abs. mol. wts. and branching, mol. size, and polymer conformation as a function of mol. wt., without the use of column
calibration, are discussed. The detn. of compositional heterogeneity using SEC with online selective detectors, such as
UV, Fourier transform IR, mass spectrometry, NMR, and even Raman spectrometry is described. Multidimensional
hyphenated techniques, such as orthogonal chromatog., temp.-rising elution fractionation-SEC, and SEC-highperformance liq. chromatog., are briefly discussed.
Bibliographic Information
Structural Characterization of Polyesters by Transesterification and Time-of-Flight Secondary Ion Mass
Spectrometry.
Kim, Yeonhee L.; Hercules, David M. Department of Chemistry, University of Pittsburgh, Pittsburgh,
PA, USA. Macromolecules (1994), 27(26), 7855-71. Publisher: American Chemical Society, CODEN: MAMOBX
ISSN: 0024-9297. Journal written in English. CAN 122:161864 AN 1995:212955 CAPLUS (Copyright (C) 2006
ACS on SciFinder (R))
Abstract
The structural characterization of a series of polyesters has been done by time-of-flight secondary ion mass spectrometry
(TOF-SIMS) combined with transesterification. Polymer fragments and intact oligomers composed of large nos. of repeat
units were obsd. Transesterification of polyesters by trifluoroacetic acid (TFA) and chlorodifluoroacrtic acid (CFA) was
carried out to produce TOF-SIMS spectra. The shapes and intensities of clusters in transesterification spectra showed
good agreement with theor. isotope patterns. TOF-SIMS spectra were used to monitor the progress of the
transesterification reaction. Transesterification products of branched poly(1,3-butylene adipate) were identified in the
TOF-SIMS spectra, providing information about polymer branching.
Bibliographic Information
Interpretation of the fragmentation patterns in static SIMS analysis of polymers. Part I. Simple aliphatic
hydrocarbons.
Van Ooij, W. J.; Brinkhuis, R. H. G. Dep. Chem., Colorado Sch. Min., Golden, CO, USA.
Surface and Interface Analysis (1988), 11(8), 430-40. CODEN: SIANDQ ISSN: 0142-2421. Journal written in English.
CAN 109:74309 AN 1988:474309 CAPLUS (Copyright (C) 2006 ACS on SciFinder (R))
Abstract
Fragmentation patterns from static SIMS anal. of several aliph. polymers resulted in fingerprint spectra which gave
information on the effect of branching, unsatn., and pendant groups on polymer fragmentation and ion stability,
rearrangements, and recombinations. For satd. polymers, branching led to an increase of the C8/C2 cluster ratio, while
for polymers with pendant Me groups, formation of Me-substituted cyclopropyllium ions was obsd. Beam damage effects
were noted for LDPE, in which an increase in unsatn. was obsd., and polypropylene, in which preferential loss of the Me
group occurred.
Bibliographic Information
Investigation of short-chain branches in polyethylene by pyrolysis - GCMS.
Haney, M. A.; Johnston, D. W.;
Clampitt, B. H. Polym. Res. Cent., Gulf Oil Chem. Co., Houston, TX, USA. Macromolecules (1983), 16(11), 177583. CODEN: MAMOBX ISSN: 0024-9297. Journal written in English. CAN 99:176513 AN 1983:576513 CAPLUS
(Copyright (C) 2006 ACS on SciFinder (R))
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Abstract
Pyrolysis-hydrogenation-gas chromatog.-mass spectrometry was used to detn. short-chain branching in high- and lowpressure polyethylene [9002-88-4]. Pyrolysis was effected at low temps. (360) and conversions (.apprx.2% volatilized).
This gave a high content of pyrolysis products related to branch points. Model ethylene--olefin polymers showed that
such products can be predicted solely by considering C-C scissions  and  to branch points. The variety of products
from high-pressure polyethylene, however, is greater than that predicted by the branching mechanism of M.J. Roedel
(1952) and A.H. Willbourn (1959). An expanded mechanism was derived including intramol. 1,3-H transfer and intramol.
1,5-H transfer in short-chain branching.
Bibliographic Information
Polymethylene and the structure of polyethylene: Study of short-chain branching.
Willbourn, A. H. Imp. Chem.
Inds. Ltd., Herts, UK. Journal of Polymer Science (1959), 34 569-97. CODEN: JPSCAU ISSN: 0022-3832. Journal
language unavailable. CAN 53:48419 AN 1959:48419 CAPLUS (Copyright (C) 2006 ACS on SciFinder (R))
Abstract
Model compds. in the form of polymethylenes, linear and branched, were prepd. by the action of BF3 on diazomethane in
ethereal soln. and trimethyl borate on mixts. of diazomethane with the appropriate diazoalkane, resp. The
polymethylenes used for calibration work contain deuterated butyl branches, the no. of which were established by direct
assay for deuterium and by mass spectrometric analysis of the irradiated products. By using this series a new infrared
technique was calibrated absolutely to measure the total no. of methyl groups and butyl branches. By using the same
technique and reference samples of ethylbranched polymers, a method of estg. ethyl branch concn. was developed. All
branches in low-d. polythene are ethyls and butyls in ratio of 2:1. High-density polythenes contain a few ethyl branches.