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Radical Polymerization modeling

RadicalPoly — Repository Overview & Project Notes

Created: 2026-06-26

This folder contains three separate tools for modeling radical polymerization. Here is an orientation to all three and how they relate to each other.

Repos at a Glance

Repo Type Language Approach Scope
MatLab\Emulsion-Polymerization-Modeling/ Tancev (GitHub) MATLAB Deterministic ODE Seeded emulsion, single monomer
MatLab\Copolymerization-Reaction-Modeling/ Tancev (GitHub) MATLAB Deterministic ODE Batch bulk, two monomers
mcPolymer/ TU Clausthal (GitLab) C++ Kinetic Monte Carlo General radical polymerization
slimmc/ slimmc A Monte Carlo simulation program of radical polymerization kinetics

Tancev Models (Emulsion + Copolymerization)

Both repos are written by Georgi Tancev, PhD and share the same monomer system: styrene / MMA with AIBN initiator at ~60°C. The parameters are consistent across both and provide a natural starting point for combining the two models into an emulsion copolymerization simulation.

Shared Model Architecture

main.m          ← sets parameters, calls ODE solver, plots
  └── batch.m / emulsion1.m / emulsion2.m   ← ODE right-hand side
        └── cumulative.m (copolymerization only)  ← post-processing

Key Connection Point

The copolymerization model (batch.m) provides the kinetics inside the particle (Mayo-Lewis terminal model). The emulsion model provides the particle phase mass balance (monomer partitioning, particle swelling, n̄). Combining them:

Particle interior:  Mayo-Lewis copolymerization kinetics (kp_AA, kp_BB, kp_AB, kp_BA)
Particle exterior:  Emulsion ODE framework (n_s, v_p, phi, rho, n_bar)
Water phase:        Initiator decay, radical generation, entry rate rho

This combination yields an emulsion copolymerization model — a significant and industrially relevant extension.

mcPolymer (Monte Carlo Simulator)

mcPolymer/ is an independent open-source C++ kinetic Monte Carlo (kMC) simulator from TU Clausthal. It is not from Tancev.

What it adds over the Tancev ODE models:

  • Full chain length distribution (CLD), not just averages Mn/Mw
  • Microstructure: sequence distribution, branching (backbiting for acrylates)
  • Reversible-deactivation radical polymerization: ATRP, NMP, RAFT
  • Stochastic simulation — naturally handles statistical fluctuations

Role in this project: Use mcPolymer as a reference/validation tool. Run the same monomer system in mcPolymer and compare Mn, Mw, PDI, and composition vs. conversion to the Tancev deterministic model. Discrepancies reveal where the ODE moment-method approximations break down.

Included examples relevant to this project:

  • examples/styrene/ — styrene homopolymerization
  • examples/mma-s-sg1/ — MMA/styrene copolymerization (NMP-controlled)

Known Issues Across the Repos

Critical Bug: Emulsion function name typos

In emulsion1.m and emulsion2.m, the function declaration uses emuslion (transposed letters) instead of emulsion. MATLAB requires the function name to match the filename. These files will fail to run as-is.

Fix:

% emulsion1.m line 1:
function [ dm ] = emulsion1( t,n,n_s,n_M_0,V_p_0 )   % was: emuslion1

% emulsion2.m line 1:
function [ dm ] = emulsion2( t,n,n_s,n_M_0,V_p_0,V )  % was: emuslion2

Parameter duplication

Rate constants and physical properties are hardcoded independently in each .m file. Changing a parameter (e.g., kp, temperature) requires edits in multiple places. Any Python or MATLAB refactor should centralize parameters in a single struct or config dict.

Recommended Development Path

  1. Fix the typo bugs in the emulsion functions (5 min fix)
  2. Run the copolymerization model (Copolymerization-Reaction-Modeling/main.m) — it should work as-is, produces Mayo-Lewis diagram, composition profile, and MWD moments
  3. Port copolymerization model to Python — cleaner for further development (see NOTES.md in that folder)
  4. Run mcPolymer (styrene example) for validation
  5. Combine emulsion + copolymerization into a unified emulsion copolymerization ODE model

Quick Literature Map

Topic Key Reference
Mayo-Lewis copolymerization Odian, Principles of Polymerization, Ch. 6-7
Gel effect (free volume) O'Neil et al., Macromolecules 1999
Gel effect (Trommsdorff, semibatch) Ray et al., Polym. Eng. Sci. 1995
Smith-Ewart theory, n̄ Tiwari, 2021; Gilbert Emulsion Polymerization 1995
Radical entry mechanisms Herrera-Ordonez, Macromol. React. Eng. 2025
kMC for emulsion Marien et al., Macromolecules 2019
MWD moment method Dotson et al., Polymerization Process Modeling, VCH 1996

See individual NOTES.md files in each repo folder for detailed analysis.