SpiralTOF™-plus Polymer Analysis System

JMS-S3000 SpiralTOF™-plus 3.0
MALDI Imaging SpiralTOF™-plus Time-of-Flight (TOF) mass spectrometer

A MALDI-TOFMS ideal for polymer analysis

The JMS-S3000 SpiralTOF™-plus 3.0 is a matrix-assisted laser desorption/ionization time-of-flight mass spectrometer (MALDI-TOFMS) with ultra-high mass resolution and high sensitivity that employs JEOL's proprietary SpiralTOF ion optical system. Its high mass resolution, high mass accuracy, and wide dynamic range make it ideal for the analysis of synthetic polymers.

Synthetic polymers are polydisperse which means that they have a molar mass distribution. As a result, homopolymers with a variety of end groups and copolymers are highly complex mixtures. Therefore, it is important to maintain ultra-high mass resolution over a wide mass range for the analysis of synthetic polymers. It is also important to resolve trace components from major components and other unwanted interferences. The SpiralTOF™-plus 3.0 ion optics, which consists of energy-filtering electric sectors, eliminates chemical noise derived from post source decay (PSD) and resolves trace components from other sample components. Synthetic polymer analysis requires high mass-resolving power over a wide mass range and wide dynamic range with low chemical noise. The SpiralTOF™-plus 3.0 satisfies both requirements. Polymer mass spectra obtained with SpiralTOF™-plus 3.0 are extremely complex and contain a large amount of information, making it impractical to analyze them manually. The solution is msRepeatFinder, a state-of-the-art polymer analysis software.

Polymer Analysis

JMS-S3000 SpiralTOF™-plus 3.0 is ideal for Polymer Analysis

Industrial polymeric materials based on mixtures of polymers with different end groups or copolymers contain a wide variety of compounds. It is necessary to detect all the components in order to grasp the whole picture, which requires ultra-high mass resolution in a wide mass range. In addition, it is important to detect not only the base material but also trace components because multiple types of polymers and trace additives are blended for higher functionality.
With its wide dynamic range and ultra-high mass resolution over a wide mass range, SpiralTOF™-plus 3.0 is the solution that meets these requirements.
Elimination of post source decay (PSD) derived ions, which is a major feature of SpiralTOF ion optics, also contributes significantly to clear mass spectrum analysis.
We provide the most effective and unique solution for polymer analysis, which has become more and more complicated in recent years due to its high functionality and recycling.
Mass spectrum of polymethylmethacrylate (PMMA) (m/z 2,000 – 9,000)

End-group analysis of polymers

By applying msRepeatFinder software to the mass spectrum measured by JMS-S3000 SpiralTOF™-plus 3.0, mixtures of homopolymers with different end groups can be separated and grouped. It is also possible to search and group the points on the KMD plot by specifying the composition of the end groups. Relative ionic intensities and polymer index values are calculated for the grouped series as shown in the table. In the example below, the KMD plot shows that there are at least four series with different end groups. By using the KMR (Kendrick Mass Remainder) plot, it is possible to confirm that there are actually five series.
MALDI mass spectrum, KMD plot and KMR plot of a polyethylene oxide mixture with different end groups
Sum of Intensities Sum of Intensities (%) No. average of molecular weight Weight average of molecular weight Dispersity Monomer End group α End group ω Adduct ion Charge No. average degree of polymerization Weight average degree of polymerization Dispersity (degree of polymerization)
1 826378 61.26 1092.769 1109.324 1.015 C2H4O H OH Na 1 23.89 24.28 1.016
2 239802 17.78 1434.544 1453.005 1.013 C2H4O C12H25 OH Na 1 27.832 28.323 1.018
3 174958 12.97 1347.449 1365.068 1.013 C2H4O C16H33 OH Na 1 24.581 25.079 1.02
4 90119 6.68 1371.922 1387.459 1.011 C2H4O C18H37 OH Na 1 24.5 24.949 1.018
5 17689 1.31 1280.546 1291.183 1.008 C2H4O C18H35 OH Na 1 22.47 22.783 1.014

Elucidation of end-group structures from accurate mass measurement and MS/MS measurement (product ion mass spectrum)

msRepeatFinder can determine the elemental composition of the ions from the measured accurate mass. The result obtained for the elemental composition of the end group for group ④ is shown. The 4 candidates have the same elemental composition, but different degrees of polymerization. The information obtained from the product ion mass spectrum is utilized to narrow down the candidates. When a peak at m/z 23 is observed in the product ion mass spectrum, the precursor ion is recognized as being an Na adduct ion. The characteristic neutral loss indicates that the size of one end group is about 254 u while that of the other is relatively small. As a result, we could estimate that it was the polyethylene oxide which has an end group of C18H37/OH.

No. End group composition formula Monomer n Adduct ion Mass DBE Mass error
(modulus; mDa)		 Mass error
(mDa)		 Mass error
(modulus; ppm)		 Mass error
(ppm)
1 C16H34 C2H4O 22 Na 1217.83200 -0.5 2.2767 -2.2767 1.8695 -1.8695
2 C18H38O C2H4O 21 Na 1217.83200 -0.5 2.2767 -2.2767 1.8695 -1.8695
3 C20H42O2 C2H4O 20 Na 1217.83200 -0.5 2.2767 -2.2767 1.8695 -1.8695
4 C22H46O3 C2H4O 19 Na 1217.83200 -0.5 2.2767 -2.2767 1.8695 -1.8695
Product-ion mass spectrum and RKM plot of group ④

Analysis of Copolymers

It is important to use high mass-resolution to analyze copolymers, which consist of two or more species of monomer. JMS-S3000 SpiralTOF™-plus 3.0 can separate many isobaric ion peaks (which have the same nominal mass but different accurate mass) on a mass spectrum. Since the mass spectra of copolymers are complicated, it is not practical to assign the peaks one by one. KMD analysis using msRepeatFinder makes it possible to visualize the distribution of polymer species. Below is the analysis example of an EO-PO block copolymer. The enlarged mass spectrum shows that peaks that are less than 0.03 u apart are clearly separated by a high mass-resolution. Visualizing the mass spectrum using a KMD plot (base unit: PO), a lattice is seen reflecting the PO distribution on the horizontal axis and the EO distribution in a diagonal direction. In addition, Fraction Base KMD plots provide a clearer visualization of the polymer series than conventional KMD plots.

Mass spectrum of EO-PO block copolymer

Mass spectrum of EO-PO block copolymer

KMD plot (left) / Fraction base KMD plot (right)

KMD plot (left) / Fraction base KMD plot (right)
From the pattern on the KMD plot, it is possible to know the ratio of the two monomers contained in the binary copolymer, or the difference in the synthetic process of the copolymers. Below are the mass spectra and KMD plots (base unit: PO) of two EO-PO copolymers with approximately equal average molecular weights. A small amount of PO homopolymer was detected on the mass spectrum and the KMD plot of the PO-EO-PO block copolymer. This is considered to be one of the proofs that this sample is a block copolymer, as the residual EO or PO homopolymers in the randomly polymerized EO-PO copolymers are unlikely given the process of synthesizing the copolymers.
On the other hand, for the EO-PO random copolymer, the KMD plot shows that the numeric distribution of EO monomers is wide. In addition, by specifying the end groups, the DP (degree of polymerization) plot can be generated, and the molar ratio and weight ratio of EO and PO can be calculated. The weight ratio of the PO-EO-PO block copolymers are in good agreement with the published values. It is possible to estimate the EO/PO composition ratios of the EO/PO random copolymer whose EO/PO ratio is not disclosed.
Mass Spectra of EO-PO random copolymer and PO-EO-PO block copolymer
Mass Spectra of EO-PO random copolymer and PO-EO-PO block copolymer
Overlaid KMD plot of EO-PO random copolymer and PO-EO-PO block copolymer
Overlaid KMD plot of EO-PO random copolymer and PO-EO-PO block copolymer
DP plot of the EO-PO random copolymer
DP plot of the EO-PO random copolymer
Molar ratio % Wight ratio %
EO PO EO PO
79.8 20.2 75.0 25.0
DP plot of the EO-PO block copolymer
DP plot of the EO-PO block copolymer
Molar ratio % Wight ratio %
EO PO EO PO
46.8 53.2 40.1 59.9

Differential analysis of 2 polymer samples

The differential analysis of the end groups and molecular weight distributions of polymer samples is very important for checking the degradation of a sample, the difference between production lots, and the difference in the synthesis processes. msRepeatFinder (optional) can perform the differential analysis of two samples. Below is an application example used for the degradation analysis of polyethylene terephthalate. The bottom left shows the mass spectrum before and after degradation. Before degradation, cyclic oligomers, and after the degradation, the series having the COOH/COOH end groups were observed as major components respectively. In performing differential analysis, each sample was measured three times. The bottom right is the result of the differential analysis shown in the KMD plots. The red shows stronger peaks before degradation, while the green shows the stronger peaks after the degradation. In addition, a volcano plot can be created to confirm the components that differ with statistical significance between the 2 samples.
Mass spectra of PET samples before and after degradation
Mass spectra of PET samples before and after degradation
KMD plot of differential analysis result
KMD plot of differential analysis result
Volcano plot of differential analysis result
Volcano plot of differential analysis result
msRepeatFinder (Option)

msRepeatFinder (Option)

The Kendrick Mass Defect (KMD) plot and the Kendrick Mass Remainder (KMR) plot are used to estimate the polymer species and end groups contained in polymer materials from a complex mass spectrum and clarify their identity. In addition, the differential analysis function between two samples is effective in verifying sample degradation, lot-to-lot differences, and differences in the synthesis process.

Mass Imaging Analysis

MALDI MS imaging was initially developed to focus on high molecular weight compounds such as proteins and peptides. However, with the expanding applications of MALDI MS imaging, the interests have shifted to include smaller molecules such as lipids, pharmaceuticals, and pharmaceutical metabolites. Conventional MALDI - reflectron TOFMS has difficulty discerning small molecule signals from those of matrix. In the case of MALDI MS imaging, signals from unwanted molecules on the specimen surface will often interfere with signals from the target analytes. High selectivity by means of high mass-resolving power is essential for obtaining reliable target analyte spatial distributions. It is also important to maintain high mass-resolution and mass-accuracy for a long time even when measuring a sample surface with a large area and non-uniformity. SpiralTOF™-plus 3.0 is the only MALDI-TOFMS that meets imaging requirements with ultra-high mass-resolution and long flight distance to minimize loss of mass resolution due to sample surface non-uniformity. In addition, it also supports high-speed mass imaging analysis.

FINE-AI Filter: Noise Filtering Using AI (Machine Learning) Technology

Our newest MS imaging data processing software msMicroImagerTM version 3 (optional) is now equipped with FINE-AI Filter, a noise filtering technology that uses AI (machine learning). This new FINE-AI Filter originates from the JEOL LIVE-AI (Live Image Visual Enhancer-AI) technology developed for our scanning electron microscopes (SEM), which was re-optimized for MS imaging and implemented to achieve significant improvements to the quality of MS images.
FINE-AI Filter: Noise Filtering Using AI (Machine Learning) Technology

Mass spectrometry imaging of polymers

Mass spectrometry imaging can be applied to polymers. Two spots are prepared by adding two antioxidants - Irgafos 168 (BASF) and Irganox 1010 (BASF) - to polymethylmethacrylate (PMMA). The ultraviolet irradiation was performed to the right spot only and its degradation was visualized by using mass spectrometry imaging. For polymers, it is possible to visualize the quantitative change in both polymers and additives. It is also possible to capture the changes in the average molecular weight and polydispersity.
MS imaging of PMMA, Irgafos 168, and Irganox 1010
MS imaging of PMMA, Irgafos 168, and Irganox 1010

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