NMR Studies of polymeric materials ‐ an overview

Cheng, H. N.; Early, Thomas A.

doi:10.1002/masy.19940860103

Cited by 5 publications

(2 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A great variety of techniques has been developed to determine the structural properties of polymers since their invention. The conventional technique to obtain the molecular weight and dispersity of polymers is gel-permeation chromatography (GPC); Fourier-transform infrared (FTIR) spectroscopy and nuclear magnetic resonance spectroscopy (NMR) spectroscopy are used to give structural information, while differential scanning calorimetry (DSC) is used to determine the crystalline structure of polymers.…”

Section: Introductionmentioning

confidence: 99%

Investigation of Polymerization Mechanisms of Poly(n-Butyl Acrylate)s Generated in Different Solvents by LC−ESI−MS²

et al. 2010

View full text Add to dashboard Cite

Liquid chromatography-electrospray ionization-tandem mass spectrometry (LC−ESI−MS2) was employed for the characterization of three poly(n-butyl acrylate)s. These polymers were produced at high temperature using the same initiator, tert-butyl peroxy-3,5,5-trimethylhexanoate, but in different solvents, viz. pentyl propionate, xylene and butyl acetate. Exact mass experiments performed on these polymers in an Orbitrap instrument supplied valuable information on the end group structures. Study of the data allowed identification of many reactions during the polymerization such as beta-scission and chain transfer to solvent or radical transfer to solvent from the initiator. Different fragmentation pathways were observed from the same precursor mass on MS/MS experiments, indicating the presence of isomers. The comprehensive assignment of the peaks in the LC−MS data allowed us to describe the end group distribution in a semiquantitative way. The results clearly show that the relatively reactive solvents used for polymerization have strong influences on the polymer composition.

show abstract

Section: Introductionmentioning

confidence: 99%

Investigation of Polymerization Mechanisms of Poly(n-Butyl Acrylate)s Generated in Different Solvents by LC−ESI−MS²

et al. 2010

View full text Add to dashboard Cite

show abstract

“…Various analytical methods have been developed to obtain information about these properties. Conventional analytical techniques to study polymer systems include gel‐permeation chromatography (GPC),2a Fourier‐transform IR (FTIR),2b NMR spectroscopy,2c and differential scanning calorimetry (DSC) 2d…”

mentioning

confidence: 99%

High‐Resolution Ion Mobility Spectrometry–Mass Spectrometry on Poly(methyl methacrylate)

et al. 2010

View full text Add to dashboard Cite

Synthetic polymers are produced in industry to serve a global market across a wide range of areas. [1a-c] Increasingly complex polymeric structures have been developed to provide desirable properties and functions. [1d] The performance of these products depends on many factors such as endgroup composition, molecular weight distribution (MWD), and 3D conformation. [1e,f] Various analytical methods have been developed to obtain information about these properties. Conventional analytical techniques to study polymer systems include gel-permeation chromatography (GPC), [2a] Fourier-transform IR (FTIR), [2b] NMR spectroscopy, [2c] and differential scanning calorimetry (DSC). [2d] The development of "soft" ionization methods such as elecrospray ionization (ESI) [3a,b] and matrix-assisted laser desorption/ionization (MALDI) [3c,d] allowed mass spectrometry (MS) to become one of the most promising analytical methods for the analysis of polymeric systems. MS has the ability to characterize a dispersed polymer containing oligomers with different structures such as isomers or isobaric molecular weights. The combination of liquid chromatography (LC) and MS reduces the effects of ion suppression that may occur in an infusion MS analysis and provides an extra dimension of separation. [4] However, a relatively long separation time (> 30 min for HPLC, around 10 min for UPLC) is needed and a complex elution system using a variety of solvents has to be developed to suit a specific polymeric system.The combination of ion mobility spectrometry (IMS) and ESI-MS has been developed to analyze biomolecules and biopolymers. [5] Ion mobility describes how fast an ion in the gas phase moves through a drift cell that is filled with a carrier buffer gas under the influence of an electric field. More compact ions with a smaller collision cross-section will drift more quickly than expanded ions. The time-scale for separations in IMS is 100 ms to 10 ms, which is ideally suited for interfacing with an MS instrument. The extra dimension of separation based on drift time (t D ) provided by IMS is also highly complementary to the information obtained by MS. Although some studies on IMS-MS measurements of blends of disperse macromolecules, for example, poly(ethylene glycol) (PEG), have been reported, studies using IMS-MS on complex synthetic polymer systems are still limited. [6] Here, we demonstrate the power of using high resolution IMS-MS to study a poly(methyl methacrylate) (PMMA) synthesized by radical polymerization using peroxide initiator (tert-butyl peroxy-3,5,5-trimethylhexanoate) in solvent. Comprehensive studies on acrylic polymer produced by radical polymerization using MS have been done in the past decade. [7] It has been proven that high-resolution MS can discriminate between the effects of various polymerization mechanisms such as b-scission, chain transfer to solvent, radical transfer to solvent from the initiator, etc. [7] A system with complex endgroup combinations is expected since various initiation and termination ...

show abstract

High‐Resolution Ion Mobility Spectrometry–Mass Spectrometry on Poly(methyl methacrylate)

et al. 2010

View full text Add to dashboard Cite

Synthetic polymers are produced in industry to serve a global market across a wide range of areas.[1a-c] Increasingly complex polymeric structures have been developed to provide desirable properties and functions.[1d] The performance of these products depends on many factors such as endgroup composition, molecular weight distribution (MWD), and 3D conformation.[1e,f] Various analytical methods have been developed to obtain information about these properties. Conventional analytical techniques to study polymer systems include gel-permeation chromatography (GPC), [2a] Fourier-transform IR (FTIR), [2b] NMR spectroscopy, [2c] and differential scanning calorimetry (DSC).[2d]The development of "soft" ionization methods such as elecrospray ionization (ESI) [3a,b] and matrix-assisted laser desorption/ionization (MALDI) [3c,d] allowed mass spectrometry (MS) to become one of the most promising analytical methods for the analysis of polymeric systems. MS has the ability to characterize a dispersed polymer containing oligomers with different structures such as isomers or isobaric molecular weights. The combination of liquid chromatography (LC) and MS reduces the effects of ion suppression that may occur in an infusion MS analysis and provides an extra dimension of separation.[4] However, a relatively long separation time (> 30 min for HPLC, around 10 min for UPLC) is needed and a complex elution system using a variety of solvents has to be developed to suit a specific polymeric system.The combination of ion mobility spectrometry (IMS) and ESI-MS has been developed to analyze biomolecules and biopolymers.[5] Ion mobility describes how fast an ion in the gas phase moves through a drift cell that is filled with a carrier buffer gas under the influence of an electric field. More compact ions with a smaller collision cross-section will drift more quickly than expanded ions. The time-scale for separations in IMS is 100 ms to 10 ms, which is ideally suited for interfacing with an MS instrument. The extra dimension of separation based on drift time (t D ) provided by IMS is also highly complementary to the information obtained by MS. Although some studies on IMS-MS measurements of blends of disperse macromolecules, for example, poly(ethylene glycol) (PEG), have been reported, studies using IMS-MS on complex synthetic polymer systems are still limited. [6] Here, we demonstrate the power of using high resolution IMS-MS to study a poly(methyl methacrylate) (PMMA) synthesized by radical polymerization using peroxide initiator (tert-butyl peroxy-3,5,5-trimethylhexanoate) in solvent. Comprehensive studies on acrylic polymer produced by radical polymerization using MS have been done in the past decade. [7] It has been proven that high-resolution MS can discriminate between the effects of various polymerization mechanisms such as b-scission, chain transfer to solvent, radical transfer to solvent from the initiator, etc.[7] A system with complex endgroup combinations is expected since various initiation and termination reactions may ...

show abstract

NMR Studies of polymeric materials ‐ an overview

Cited by 5 publications

References 41 publications

Investigation of Polymerization Mechanisms of Poly(n-Butyl Acrylate)s Generated in Different Solvents by LC−ESI−MS²

Investigation of Polymerization Mechanisms of Poly(n-Butyl Acrylate)s Generated in Different Solvents by LC−ESI−MS²

High‐Resolution Ion Mobility Spectrometry–Mass Spectrometry on Poly(methyl methacrylate)

High‐Resolution Ion Mobility Spectrometry–Mass Spectrometry on Poly(methyl methacrylate)

Contact Info

Product

Resources

About

NMR Studies of polymeric materials ‐ an overview

Cited by 5 publications

References 41 publications

Investigation of Polymerization Mechanisms of Poly(n-Butyl Acrylate)s Generated in Different Solvents by LC−ESI−MS2

Investigation of Polymerization Mechanisms of Poly(n-Butyl Acrylate)s Generated in Different Solvents by LC−ESI−MS2

High‐Resolution Ion Mobility Spectrometry–Mass Spectrometry on Poly(methyl methacrylate)

High‐Resolution Ion Mobility Spectrometry–Mass Spectrometry on Poly(methyl methacrylate)

Contact Info

Product

Resources

About

Investigation of Polymerization Mechanisms of Poly(n-Butyl Acrylate)s Generated in Different Solvents by LC−ESI−MS²

Investigation of Polymerization Mechanisms of Poly(n-Butyl Acrylate)s Generated in Different Solvents by LC−ESI−MS²