Oligomerization and polymer

The decomposition of initiator produces the initial radicals which initiate the polymerization and the formation of oligomeric and polymer radicals, polymers and graft copolymers in the continuous phase. The solubility of these polymers decreases with the polymer molecular weight (MW) and above a certain critical value of MW they precipitate from the continuous phase and form unstable primary particles. 

Cuprous salts catalyze the oligomerization of acetylene to vinylacetylene and divinylacetylene (38). The former compound is the raw material for the production of chloroprene monomer and polymers derived from it. Nickel catalysts with the appropriate ligands smoothly convert acetylene to benzene (39) or 1,3,5,7-cyclooctatetraene (40—42). Polymer formation accompanies these transition-metal catalyzed syntheses. 

Polymerization was carried out in NaOH aqueous solution. Table 4 summarizes the reaction conditions and polymer yields. The first step of the polymerization was hydrolysis and oligomerization of the silylethers at low temperatures from 90°C to 150 °C. In order to increase the polymer yield and the softening point of the polymers, the second step was carried out at higher temperatures under reduced pressure, removing alcohol and water, 1H-NMR, 13CNMR and IR spectroscopy of each polymer show that these polymers have the polysiloxane structure substituted with a phenol group. 

Oligomerization and polymerization of terminal alkynes may provide materials with interesting conductivity and (nonlinear) optical properties. Phenylacetylene and 4-ethynyltoluene were polymerized in water/methanol homogeneous solutions and in water/chloroform biphasic systems using [RhCl(CO)(TPPTS)2] and [IrCl(CO)(TPPTS)2] as catalysts [37], The complexes themselves were rather inefficient, however, the catalytic activity could be substantially increased by addition of MesNO in order to remove the carbonyl ligand from the coordination sphere of the metals. The polymers obtained had an average molecular mass of = 3150-16300. The rhodium catalyst worked at room temperature providing polymers with cis-transoid structure, while [IrCl(CO)(TPPTS)2] required 80 °C and led to the formation of frani -polymers. 

The activation barrier for the oligomerization of alkynes may be overcome thermally or catalytically. Because the classical thermal transformation of ethyne into benzene in a hot tube is rather ineffective (47), more emphasis has been placed on working out catalytic routes for the synthesis of linear oligomers, cyclooligomers, and polymers. Transition metal compounds have proved to act as effective catalysts in homogeneous as well as in heterogeneous processes (48). 

A mechanism for explaining how oligomeric and polymeric forms of a protein or polypeptide can arise by three-dimensional swapping of internal domains in monomers. The basic idea is that a protein s ternary structure is stabilized by the contacts between its domains, and under certain circumstances, the domains of several polypeptide chains may bind in a way that gives rise to nonphysiologic oligomers, polymers, and aggregates. 

Many, but not all, macromolecules are created by the mutual chemical chain reactions of small molecules called monomers and the arising species contain repeated small units, mers. In that case they are designated oligomers or polymers depending on their molar mass. This means that all oligomers and polymers can be called macromolecular substances but not all macromolecular substances are of oligomeric or polymeric nature (lignin, humin substances, etc.). Properties of macromolecular systems depend on... 

In Figure 11.2.1A the process of dispersion polymerization is shown focusing on the formation process of particles. Dispersion polymerization starts from a homogeneous solution, and when oligomeric radicals and polymer, formed in the monomer solution, do not have affinity for the medium, they become insoluble and precipitate. The precipitate is unstable and homoaggregates to become primary particles. Primary particles homoaggregate further until they become stable secondary particles. The mechanism to keep the particles stable depends on what type of stabilizer is used. The propagation processes from nuclei to primaiy particles and from primary to secondary ones does not have to be considered as discontinuous steps. However, it... 

Figure 11.2.IB describes the propagation process of particles. When a sufficient amount of stabilized particles is formed, all the oligomeric radicals and polymer or primary particles are captured by existing stable particles before they precipitate and form new particles by themselves. This is what is called the growth process of particles by heteroaggregation.

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