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Kinetics of polymerization processes

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Polymerization Processes

Part of the book series: Advances in Polymer Science ((POLYMER,volume 38))

Abstract

Works pertaining to the following problem areas have been reviewed:

  1. 1)

    Radical polymerization, including the question of the dependence of chain termination rate constant on the length of the macroradical chain, the possibility for continuous radical polymerization to be achieved through the complexing and stabilization of free radicals and of catalytic chain transfer in radical polymerization.

  2. 2)

    Ionic polymerization, including the thermodynamic aspects of heterogeneous polymerization kinetics, kinetic features of the ionic polymerization of heterocyclic compounds and the zwitterionic polymerization.

  3. 3)

    Mathematical modeling of polymerization kinetics, including its application for the verification of kinetic schemes and the values of kinetic constants, as well as in the design of industrial processes.

Investigations summed up in this review are mainly those carried out by kinetics schools in the Soviet Union over the past 5 years. The review contains 145 references to original works.

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Abbreviations

[A]:

concentration of active centres of polymerization

Ac:

acceptor monomer

a:

cross-section area of monomeric unit in polymer

C:

complex of comonomers

c:

heat capacity

C p :

constant of chain transfer to polymer

C m :

constant of chain transfer to monomer

C s :

constant of chain transfer

D:

donor monomer

D 1 :

diffusion constant of monomer

E:

activation energy

f:

initiation efficiency

i, j:

degree of polymerization

l, n:

length and number of segments in polymer zwitterion

k ij :

termination rate constant of radicals Ri and Rj

k t :

termination rate constant

k p :

propagation rate constant

k 0AA , k 0AD , k 0DD :

termination rate constants

k s :

chain transfer rate constant

k d :

depolymerization rate constant

k i :

initiation rate constant

k (−) :

rate constant of propagation on free ions

k (±) :

rate constant of propagation on cyclic ion pairs

k m :

rate constant of chain transfer to monomer

k tp :

cross-termination rate constant

k tl :

entangled radical termination rate constant

k AD :

rate constant of copolymerization A and D

k AC :

rate constant of copolymerization A and C

k DA :

rate constant of copolymerization D and A

k DC :

rate constant of copolymerization D and C

k f :

rate constant of chain transfer to polymer

k′ d :

rate constant of deactivation

K (n)p :

equilibrium constant of ion pairs with degree of polymerization “n”

K p :

equilibrium constant

[M]:

concentration of monomer

[M] liqlim :

equilibrium concentration of monomer in relation to dissolved polymer

[M] sollim :

equilibrium concentration of monomer in relation to solid polymer

[p]:

polymer concentration

P n :

number average degree of polymerization

P w :

weight average degree of polymerization

q:

conversion of monomer

Q:

heat of reaction

[R]:

concentration of radicals

[Rn]:

concentration of “free” ions with degree of polymerization “n”

[rn]:

concentration of ion pairs with degree of polymerization “n”

[S]:

concentration of chain transfer agent

[T]:

concentration of 1,3,5-trioxane

[Tr]:

concentration of 1,3,5,7-tetraoxane

V p :

molar volume of polymer

V m :

molar volume of monomer

V s :

effective volume of ion pair

W:

rate of reaction

W i :

rate of initiation

W cr :

rate of crystallization

α:

kAD/kDA

ΔF:

change in free energy

λ′:

length of monomeric unit in polymer

λ:

heat conductivity coefficient

δ:

Frank-Kamentsky's parameter

μ:

kinematic viscosity

μ M :

chemical potential of monomer

μ 0 :

chemical potential in standard state

μ Mdiss :

chemical potential of dissolved monomer

μ pdiss :

chemical potential of dissolved polymer

μ Tdiss :

chemical potential of dissolved trioxane

μ TCpdiss :

chemical potential of trioxane units in the dissolved copolymer

ρ:

density

η:

viscosity

Φ p :

volume fraction of polymer

ν liq :

average degree of polymerization of dissolved portion of polymer chain

τ:

induction period

χ:

thermal diffusivity

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Authors and Affiliations

  1. Institute of Chemical Physics, USSR Academy of Sciences, Vorobyovskoye shosse 2b, B-334, Moscow, USSR

    Alexander A. Berlin, Stanislav A. Volfson & Nikolai S. Enikolopian

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  1. Alexander A. Berlin
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  2. Stanislav A. Volfson
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  3. Nikolai S. Enikolopian
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Berlin, A.A., Volfson, S.A., Enikolopian, N.S. (1981). Kinetics of polymerization processes. In: Polymerization Processes. Advances in Polymer Science, vol 38. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-10217-5_4

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