Polymers molecular weight, controlling

High molecular weight polymers or gums are made from cyclotrisdoxane monomer and base catalyst. In order to achieve a good peroxide-curable gum, vinyl groups are added at 0.1 to 0.6% by copolymerization with methylvinylcyclosiloxanes. Gum polymers have a degree of polymerization (DP) of about 5000 and are useful for manufacture of fluorosiUcone mbber. In order to achieve the gum state, the polymerization must be conducted in a kineticaHy controlled manner because of the rapid depolymerization rate of fluorosiUcone. The expected thermodynamic end point of such a process is the conversion of cyclotrisdoxane to polymer and then rapid reversion of the polymer to cyclotetrasdoxane [429-67 ]. Careful control of the monomer purity, reaction time, reaction temperature, and method for quenching the base catalyst are essential for rehable gum production. 

The kinetics of vinyl acetate emulsion polymeriza tion in the presence of alkyl phenyl ethoxylate surfactants of various chain lengths indicate that part of the emulsion polymerization occurs in the aqueous phase and part in the particles (115). A study of the emulsion polymerization of vinyl acetate in the presence of sodium lauryl sulfate reveals that a water-soluble poly(vinyl acetate)—sodium dodecyl sulfate polyelectrolyte complex forms, and that latex stabihty, polymer hydrolysis, and molecular weight are controlled by this phenomenon (116). 

Monovalent cations are good deflocculants for clay—water sHps and produce deflocculation by a cation exchange process, eg, Na" for Ca ". Low molecular weight polymer electrolytes and polyelectrolytes such as ammonium salts (see Ammonium compounds) are also good deflocculants for polar Hquids. Acids and bases can be used to control pH, surface charge, and the interparticle forces in most oxide ceramic—water suspensions. 

Controlled polymerisation of ethylene oxide under alkaline conditions will produce a range of polymers marketed under the trade name Carbowax. These have molecular weights in the range 1500-20000 and are greases or waxes according to their degree of polymerisation. Lower molecular weight polymers... 

To obtain high molecular weight polymers the tetramer is equilibrated with a trace of alkaline catalyst for several hours at 150-200°C. The product is a viscous gum with no elastic properties. The molecular weight is controlled by CcU eful addition of monofunctional material. 

The refining of oil produces the monomer feed streams for tackifiers as byproducts of the process. Tackifiers are low molecular weight polymers, typically 300-5000 g/mol, most often 500-1000 g/mol. Generally molecular weights are well below Mg and thus, within a given class of resins, softening points are controlled primarily by molecular weight (see Fig. 1). 

In solution polymerization, an organic solvent dissolves the monomer. Solvents should have low chain transfer activity to minimize chain transfer reactions that produce low-molecular-weight polymers. The presence of a solvent makes heat and viscosity control easier than in bulk polymerization. Removal of the solvent may not be necessary in certain applications such as coatings and adhesives. 

Thus, the polymers have a regular structure and can attain high molecular weights under controlled reaction conditions. 

The polymerization rate is controlled by the slowest process. Thus it is important to establish the rate controlling steps. The starting material for the (SPP) can be the dry nylonsalt Z 4) but mostly a low or middle molecular weight polymer is used. The polyamide-salts have the disadvantage of high amine losses 3 4). 

Thermal Effects in Addition Polymerizations. Table 13.2 shows the heats of reaction (per mole of monomer reacted) and nominal values of the adiabatic temperature rise for complete polymerization. The point made by Table 13.2 is clear even though the calculated values for T dia should not be taken literally for the vinyl addition polymers. All of these pol5Tners have ceiling temperatures where polymerization stops. Some, like polyvinyl chloride, will dramatically decompose, but most will approach equilibrium between monomer and low-molecular-weight polymer. A controlled polymerization yielding high-molecular-weight pol)mier requires substantial removal of heat or operation at low conversions. Both approaches are used industrially. 

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