Investigation of the thermal degradation of poly(acrylic acid) and poly(methacrylic acid) by high-resolution carbon-13 CP/MAS NMR spectroscopy

Fyfe, C. A.; McKinnon, Michael S.

doi:10.1021/ma00161a021

Cited by 97 publications

(48 citation statements)

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“…This reaction could proceed in a charge-induced mechanism, as described in Scheme 1. Elimination of a carbon dioxide molecule was systematically found to be a major thermal degradation route for PAA [33,34,[43][44][45] and PMAA [43]. All thermal degradation studies also indicate that decarboxylation was slower than dehydration and required higher temperatures to proceed.…”

Section: Tandem Mass Spectrometry Of Singly Charged Oligomersmentioning

confidence: 96%

“…Water was shown to be one major product in thermal degradation study of PAA [33,34,[43][44][45] or PMAA [43]. This dehydration process would occur with the formation of a six-membered ring anhydride from two pendant acid groups (Scheme 1), as previously demonstrated studying thermally degraded PAA and PMAA resins by nuclear magnetic resonance (NMR) [43] or mass spectrometry [33]. The six-membered ring mechanism proposed in Scheme 1 to account for the water loss requires two consecutive neutral monomers in the precursor ion.…”

Section: Tandem Mass Spectrometry Of Singly Charged Oligomersmentioning

confidence: 99%

“…The fragment ion detected at m/z 215 (C 11 H 19 O 4 Ϫ ; DBE: 2.5; error: ϩ8.9 ppm) would indicate the loss of a carbon dioxide molecule from the precursor ion m/z 259, as described in Scheme 2. This direct decarboxylation, poorly detected at a 20 eV collision energy, does not appear to proceed at a high rate and would not compete efficiently with the dehydration process, as concluded from thermal degradation studies of neutral PAA and PMAA [33,34,[43][44][45] ; DBE 3.5; error: ϩ16.2 ppm) was to consider a different structure for m/z 197, as depicted in Scheme 4. This structure implies deprotonation has occurred on the MAA monomer linked to the initiating group; then, after a first dehydration step has occurred, a decarboxylation reaction would have proceeded in a direct mechanism.…”

Section: Tandem Mass Spectrometry Of Singly Charged Oligomersmentioning

confidence: 99%

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Tandem mass spectrometry of poly(methacrylic acid) oligomers produced by negative mode electrospray ionization

Giordanengo

Viel

Allard-Breton

et al. 2009

J. Am. Soc. Mass Spectrom.

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Dissociation of small poly(methyl acrylic acid) (PMAA) anions produced by electrospray was characterized by tandem mass spectrometry. Upon collisional activation, singly, and doubly deprotonated PMAA oligomers were shown to fragment via two major reactions, dehydration and decarboxylation. The elimination of a water molecule would occur between two consecutive acid groups in a charged-remote mechanism, giving rise to cyclic anhydrides, and was shown to proceed as many times as pairs of neutral pendant groups were available. As a result, the number of dehydration steps, together with the abundance of the fragment ions produced after the release of all water molecules, revealed the polymerization degree of the molecule in the particular case of doubly charged oligomers. For singly deprotonated molecules, the exact number of MAA units could be reached from the number of carbon dioxide molecules successively eliminated from the fully dehydrated precursor ions. In contrast to dehydration, decarboxylation reactions would proceed via a charge-induced mechanism. The proposed dissociation mechanisms are consistent with results commonly reported in thermal degradation studies of poly(acrylic acid) resins and were supported by accurate mass measurements. These fragmentation rules were successfully applied to characterize a polymeric impurity detected in the tested PMAA sample. (J Am Soc Mass

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Section: Tandem Mass Spectrometry Of Singly Charged Oligomersmentioning

confidence: 96%

Section: Tandem Mass Spectrometry Of Singly Charged Oligomersmentioning

confidence: 99%

Section: Tandem Mass Spectrometry Of Singly Charged Oligomersmentioning

confidence: 99%

See 1 more Smart Citation

Tandem mass spectrometry of poly(methacrylic acid) oligomers produced by negative mode electrospray ionization

Giordanengo

Viel

Allard-Breton

et al. 2009

J. Am. Soc. Mass Spectrom.

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“…No detectable domain can be observed on a scale of [20][21][22][23][24][25][26][27][28][29][30] A for PV A/PMAA complexes. For PVA/PAA= 1/1 blend, the same conclusion can be reached as that for PV AjPMAA complexes.…”

Section: Resultsmentioning

confidence: 99%

“…In this paper, we provide some information about intermolecular hydrogen bonding between two different polymers in the solid state by 13C CP/MAS NMR techniques. The domain structure and miscibility of PV A/PMAA and PV A/PAA systems on a scales of [20][21][22][23][24][25][26][27][28][29][30] A to 200---300 A were also investigated by measuring the 1 H spin-lattice relaxation times both in rotating (TiP) and laboratory frames (Tl)'…”

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confidence: 99%

Miscibility of Poly(vinyl alcohol)/Poly(methacrylic acid) and Poly(vinyl alcohol/Poly(acrylic acid) Systems II. High-Resolution Solid-State CP/MAS 13C NMR Studies

Zhang

Takegoshi

Hikichi

1991

Polym J

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ABSTRACT:Miscibility of poly(vinyl alcohol)/poly(methacrylic acid) complexes and poly-(vinyl alcohol)/poly(acrylic acid) blends is investigated by high-resolution 13C solid-state NMR method. Observed 13C spectra are discussed in terms of hydrogen-bonding effects on chemical shift. The results indicate that poly(vinyl alcohol) and poly(methacrylic acid) are intimately mixed on a scale of 20--30 A due to intermolecular hydrogen bonding to form equimolar-ratio complexes, For the poly(vinyl alcohol)/poly(acrylic acid) = l/l blend, the two polymers are also miscible, the crystalline phase of PVA is destroyed completely and no detectable domain can be observed for For two dissimilar polymers to be miscible, some exothermic intermolecular interactions should occur. Among many possible interactions, the hydrogen-bonding interaction has been studied extensively in recent years. [1][2][3][4][5][6] High-resolution 13e solid-state NMR is particularly useful for investigating hydrogenbonding interaction. Helpful information about the hydrogen bonding can be obtained through characteristic downfield shifts of 13e nuclei participating in hydrogen bonding. 7 ,8 Although such downfield shift induced by hydrogen bonding in solution reflects an average of bonded and non-bonded states, a rigid structure of hydrogen bonding in the solid state would cause further downfield shift. 9 ,IO Furthermore, the high-resolution 13e solidstate NMR method enables us to measure the relaxation time of I H spins of individual components of polymers through well-resolved 13e signals and to examine the domain structure and miscibility of polymer blends in the solid state. Ifpolymer chains are intimately mixed, fast spin diffusion among I H spins equalizes spin-lattice relaxation times of all protons. On the other hand, if the domain size of multi-phase structure of polymer blends is larger than the characteristic spin diffusion path length, the relaxation time can be observed separately for each component of polymers. In this work, we examine the hydrogenbonding interaction and miscibility of poly-(vinyl a1cohol)jpoly(methacrylic acid) (PV Aj PMAA) and poly(vinyl a1cohol)jpoly(acrylic acid) (PV AjPAA) systems. Since PV A, PMAA, and PAA all have strong hydrogen-bonding donors and acceptors, there would be inter-

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Solid-state13C NMR study on thermal dehydration process of poly(methacrylic acid)(PMAA)

Asano

Eguchi

Kurotu

1999

J. Polym. Sci. B Polym. Phys.

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Investigation of the thermal degradation of poly(acrylic acid) and poly(methacrylic acid) by high-resolution carbon-13 CP/MAS NMR spectroscopy

Cited by 97 publications

References 2 publications

Tandem mass spectrometry of poly(methacrylic acid) oligomers produced by negative mode electrospray ionization

Tandem mass spectrometry of poly(methacrylic acid) oligomers produced by negative mode electrospray ionization

Miscibility of Poly(vinyl alcohol)/Poly(methacrylic acid) and Poly(vinyl alcohol/Poly(acrylic acid) Systems II. High-Resolution Solid-State CP/MAS 13C NMR Studies

Solid-state13C NMR study on thermal dehydration process of poly(methacrylic acid)(PMAA)

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