# Determination of Copolymer Block-Length Distributions Using Fragmentation Data Obtained from Tandem Mass Spectrometry

## TL;DR

This paper shows how tandem mass spectrometry can be used to determine the block-length distribution of copolymers, offering more detailed insights than traditional methods.

## Contribution

A new algorithm was developed to determine copolymer block-length distributions from MS/MS fragmentation data.

## Key findings

- The algorithm successfully derived block-length distributions that matched NMR results.
- Distinct synthesis methods produced discernible trends in block-length distributions.
- The method provides detailed insights into copolymer chemistry and functional properties.

## Abstract

The block-length distribution (BLD) of polyamide and
polyurethane
copolymers was determined from mass spectrometry (MS) data. While
nuclear magnetic resonance (NMR) traditionally determines the number-average
block length, this work demonstrates that MS/MS is a viable option
for the characterization of the distribution. An algorithm was implemented
and modified to accurately determine copolymer BLDs from fragmentation
data. The algorithm incorporates preferences in bond fragmentation.
Evaluation of the algorithm encompassed the use of polyamide and polyurethane
model systems. In both scenarios, the algorithm successfully derived
BLDs, that corresponded well with the average block lengths obtained
with 13C NMR. The newly developed algorithm enabled the
characterization of BLDs based on MS/MS data. Typical trends in BLDs
corresponding to distinct synthesis methods were discernible. These
BLDs offer uniquely detailed insights into copolymer chemistry, potentially
elucidating variations in functional properties of copolymers despite
overall identical compositions.