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Pseudokinetics for the copolymerization of butadiene and styrene produced using n-butyl lithium and N,N,N′,N′-tetramethylethylenediamine, considering different reactivities of the structural units

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Abstract

The anionic solution copolymerization of butadiene and styrene prepared by anionic living polymerization using an initiator composed of n-butyl lithium, and N,N,N′,N′-tetramethylethylenediamine as active center modifier was modeled as a tetrapolymerization. The kinetic model proposed considering that the reactivity of the active sites is different because of varying configurations cis, trans, vinyl, and styryl. From the reaction scheme expressions to rate of monomers consumption, microstructure and dyad formation were obtained. With the first-order Markov model, the expressions for the fraction of active sites and dyad distribution as a function of the conditional probabilities were obtained. Therefore, the model proposed is different to kinetic models previously reported, because it allows obtaining the parameters kinetic in order to know the distribution of the isomeric species presents in the copolymerization of butadiene and styrene, and the intrinsic reactivity of configurational active sites. The rate constants were determined by fitting to the conversion and dyad experimental data using the nonlinear least square method. The experimental data reported in the literature, monomer conversion and microstructure, in addition to dyad sequence distribution were correctly predicted.

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Abbreviations

(C):

active sites cis

FC :

cis isomer formation

FT :

trans isomer formation

FV :

vinyl isomer formation

FS :

styrene isomer formation

FCC :

dyad formation cis-cis

FCT :

dyad formation cis-trans

FCV :

dyad formation cis-vinyl

FCSV :

dyad formation cis-styrene

FTC :

dyad formation trans-cis

FTT :

dyad formation trans-trans

FTV :

dyad formation trans-vinyl

FTS :

dyad formation trans-styrene

FVC :

dyad formation vinyl-cis

FVT :

dyad formation vinyl-trans

FVV :

dyad formation vinyl-vinyl

FVS :

dyad formation vinyl-styrene

FSC :

dyad formation styrene-cis

FST :

dyad formation styrene-trans

FSV :

dyad formation styrene-vinyl

FSS :

dyad formation styrene-styrene

Fij :

total quantity of the ij dyad

i:

active site that reacts with a butadiene molecule

[I]:

initiator concentration

j:

ending live isomer resulting from this reaction

kij :

rate constant

kiC, kiT, kiV, and kiS :

rate constants of the initiation

M1 :

butadiene monomer

M2 :

styrene monomer

Р:

\( {\hbox{matrix }} = \left[ {\begin{array}{*{20}{c}} {{P_{CC}}} & {{P_{CT}}} & {{P_{CV}}} \\{{P_{TC}}} & {{P_{TT}}} & {{P_{TV}}} \\{{P_{VC}}} & {{P_{VT}}} & {{P_{VV}}} \\\end{array} } \right] \)

Pij :

conditional probability of the active sites

[Pc], [PT] [PV], [PS]:

concentration of active sites

Pc1,0,0,0, PT 0,1,0,0, PV 0,0,1,0 :

active sites with one monomeric unit with the negative

PS 0,0,0,1 :

charge located in the cis, trans and vinyl isomer respectively

PX a,b,d,m :

living polymer with the negative charge located in the isomer X, (X = C, T, V or S) with a, b and d units of cis, trans, vinyl and styryl respectively

val:

equality: rCT rTV rVC = rTC rCV rVT

rij :

reactivity ratios

Wi :

fraction of active sites

W :

vector (Wc, WT, Wv, Ws)

XCj, XTj, XVj, XSj :

butadiene conversion converted to the dyad Cj, Tj, Vj, Sj.

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Authors and Affiliations

  1. Facultad de Ciencias Químicas, Universidad Veracruzana, Av. Universidad Veracruzana Km. 7.5, Coatzacoalcos, Veracruz, Mexico

    José Alfredo Tenorio-López & María del Carmen Cuevas-Díaz

  2. Unidad de Desarrollo de Productos y Procesos, Resirene, S.A. de C.V. Carr. Federal Puebla-Tlaxcala Km. 15.5, Tlaxcala, Mexico

    Juan José Benvenuta-Tapia

  3. Centro de Investigación y de Estudios Avanzados, Instituto politécnico Nacional, Av. Instituto Politécnico Nacional 2508, Mexico City, Mexico, DF

    Nancy Edith Castillo-Hernández

Authors
  1. José Alfredo Tenorio-López
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  2. Juan José Benvenuta-Tapia
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  3. Nancy Edith Castillo-Hernández
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  4. María del Carmen Cuevas-Díaz
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Correspondence to Juan José Benvenuta-Tapia.

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Tenorio-López, J.A., Benvenuta-Tapia, J.J., Castillo-Hernández, N.E. et al. Pseudokinetics for the copolymerization of butadiene and styrene produced using n-butyl lithium and N,N,N′,N′-tetramethylethylenediamine, considering different reactivities of the structural units. J Polym Res 18, 927–938 (2011). https://doi.org/10.1007/s10965-010-9490-5

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