Computer modeling of radical copolymerization under unusual conditions

Abstract

Although recent years have witnessed an impressive confluence of experiments and kinetic and statistical theories, presently there is no comprehensive understanding of the interrelation between chemical sequences in synthetic copolymers and the conditions of synthesis. For this problem, numerical simulations in conjunction with simple models provide a rather detailed answer. A survey is given of the simulation methods as applied to the design of nontrivial chemical sequences in copolymers obtained via heterogeneous radical polymerization. This review is focused on a recently developed approach, called conformation‐dependent sequence design, which takes into account a strong coupling between the conformation and primary structure of copolymers during their synthesis. We consider some applications of this technique, including the following problems and systems: (1) the design of sequences with long‐range correlations via solution radical copolymerization with simultaneous globule formation, (2) radical copolymerization near a chemically homogeneous surface leading to a copolymer with a gradient primary structure, and (3) template copolymerization near chemically patterned surfaces. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5339–5353, 2004

Approaches to Chemical Synthesis of Protein-Like Copolymers

“…Therefore, the formation of protein-like sequences of these different monomeric units in the macromolecular chains is possible, at least, for part of the resulting chains. The theoretical evaluation of this "mechanism" confirmed, in general, its feasibility [8,13], and in Fig. 1 a typical computer snapshot of the structure of resulting protein-like macromolecules is shown.…”

“…The concept of conformation-dependent computer design of the protein-like copolymers was first formulated in the works by Khokhlov, Khalatur et al [1][2][3][4][5][6][7][8]. This concept is based on the so-called biomimetic approach to computing the sequence of monomeric units in a chain, and also evaluating the conformation adopted in aqueous media by the macromolecules consisting of the amphiphilic comonomers with differing hydrophilicity/hydrophobicity.…”

Energetics and Mechanism of Conformational Transitions of Protein‐Like NIPAM‐Sodium Styrene Sulfonate Copolymers in Aqueous Solutions

“…The necessary condition for such spontaneous folding is the sequence distribution of units. H and P units should be distributed along the chain not randomly but as definite, alternating, enough extended blocks of the units of the same type . Such copolymers received the name “protein‐like” .…”

“…The major challenge in obtaining the protein‐like copolymers remains the generation of nonrandom sequences of the H and P monomers in the course of the copolymer synthesis . One of the possible synthesis procedures is based on the fact that the block sequences can be produced under conditions of segregation of the H and P monomers . Such conditions can be created, in particular, for thermoresponsive copolymer at temperatures higher than LCST of the corresponding H homopolymer .…”

COPOINT – a simple computer program to determine copolymerization parameters by numerical integration

“…Reviews on this important field are given in refs. [13][14][15][16]. Most of the synthetic polymer chemists still prefer closed analytical expressions over computer simulations to describe their copolymerization diagrams.…”