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Experimental study and kinetic modeling of radical-coordination styrene polymerization with participation of ferrocene

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Abstract

A kinetic model of styrene polymerization with participation of benzoyl peroxide and ferrocene was developed, based on the radical-coordination mechanism. A peculiarity of this mechanism is a parallel functioning of the radical and coordination channels for the macromolecules formation, during the styrene polymerization. The proposed mechanism of the process is confirmed by calculations on the developed kinetic model. This model allows quantitative description of the experimentally determined (1) dependencies of styrene conversion versus the polymerization time, (2) dependencies of number-average and mass-average molar masses of polystyrene versus the styrene conversion, and (3) dependencies of styrene conversion during its polymerization on a polystyrene macroinitiator versus the polymerization time, the macroinitiator obtained by radical-initiated polymerization with participation of ferrocene. The computational experiments were carried out and analyzed to assess the effect of ferrocene concentration and temperature on the process in question.

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Notes

  1. Chain termination by disproportionation was not taken into account in the kinetic scheme, since this reaction is not characteristic for styrene polymerization [52].

Abbreviations

[…]:

is a concentration of species

ΔV :

is a change of styrene volume during polymerization

Ad :

is an adduct

AIBN:

is azobisisobutyronitrile

ATRP:

is Atom Transfer Radical Polymerization

BP:

is benzoyl peroxide

calc :

is a value calculated by the kinetic model

cont :

is a contraction coefficient showing the relative difference between the specific volumes of styrene and polystyrene

C :

is a complex of styrene and ferrocene

DFT:

is density functional theory

exp :

is an experimental value

I :

is an initiator

k :

are rate coefficients

M :

is styrene molecule

Mc :

is ferrocene

M n :

is number-average molar mass of polystyrene

M w :

is mass-average molar mass of polystyrene

n,  z, m :

are chain polymerization degrees

OMRP:

is Organometallic Mediated Radical Polymerization

RCP:

is radical-coordination polymerization

T :

is a temperature

T g :

is a glass transition temperature

T m :

is a melting point

U :

is a conversion of styrene

V0:

is an initial volume of styrene

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Acknowledgements

This study was carried out within the state task No. 075-01261-22-00 for 2020-2022 (scientific project “Catalysis in Oil Refining and Petrochemicals”, Research Funder is Ministry of Science and Higher Education of the Russian Federation).

This study was carried out using the equipment of the Center for Collective Use “Nanomaterials and Nanotechnology” of the Kazan National Research Technological University with the financial support of the Ministry of Science and Higher Education of the Russian Federation under agreement No. 075-15-2021-699.

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Authors and Affiliations

  1. Kazan National Research Technological University, Kazan, Russian Federation

    Konstantin A. Tereshchenko, Daria A. Shiyan & Nikolai V. Ulitin

  2. Ufa Institute of Chemistry – Subdivision of the Ufa Federal Research Centre of the Russian Academy of Sciences, Ufa, Russian Federation

    Sergei V. Kolesov & Sergey L. Khursan

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  1. Konstantin A. Tereshchenko
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Correspondence to Nikolai V. Ulitin.

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Tereshchenko, K.A., Shiyan, D.A., Ulitin, N.V. et al. Experimental study and kinetic modeling of radical-coordination styrene polymerization with participation of ferrocene. J Polym Res 29, 429 (2022). https://doi.org/10.1007/s10965-022-03273-2

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