Temperature, polymerization

Polymerization temperature has an influence on polymerization rate, molar mass, MMD and cis- 1,4-content. As molar mass regulation by adjustment of polymerization temperature is important from an industrial point of view this aspect is given special emphasis in this subsection. 

Ranges of polymerization temperatures in Nd-catalyzed diene polymerization which can be found in patents are summarized in Table 20. 

The patents quoted in Table 20 give rather broad temperature ranges. An explanation for this feature is the polymerization mode which is used for the large-scale polymerization of Nd-BR. To the best of our knowledge, adiabatic rather than isothermic modes are used. In the adiabatic mode polymerization heat is neither removed by external nor by evaporation cooling. Therefore, 

The patents quoted in Table 20 do not give information on the effect of polymerization temperature on reaction rates, molar mass, MMD and cis-1,4-contents. This information is scattered in various scientific reports. The reports which are valuable in this context are summarized in Table 21 for binary Nd catalyst systems and in Table 22 for carboxylate-based systems. 

According to Porri et al. the largest effect of polymerization temperature is on reaction rates [50]. Information on the dependence of reaction rates is contained in most of the reports quoted in Tables 21 and 22. Unfortunately, most of these studies do not provide activation energies. 

The vast majority of chemical polymerizations of pyrrole have been carried out between 0°C and room temperature. In one of the few systematic studies of the influence of temperature, Miyata and coworkers77 examined polymerization with FeCl3 

FIGURE 2.9 Poly(terthiophene) from interfacial polymerization using AuC13 in water layer and terthiophene in ionic liquid l-ethyl-3-methylimidazolium bisftrifluoromethanesulfoni-mide), emiNTf2. 

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Many of the reactions listed at the beginning of this section are acid catalyzed, although a number of basic catalysts are also employed. Esterifications are equilibrium reactions, and the reactions are often carried out at elevated temperatures for favorable rate and equilibrium constants and to shift the equilibrium in favor of the polymer by volatilization of the by-product molecules. An undesired feature of higher polymerization temperatures is the increased probability of side reactions such as the dehydration of the diol or the pyrolysis of the ester. Basic catalysts produce less of the undesirable side reactions. 

Dimensional Stability. The wet heat resistance of PVA fiber is indicated by the wet softening temperature (WTS) at which the fiber shrinks to a specified ratio. At one time, the WTS was not more than 95°C for nonacetalized PVA fiber, but improvement of WTS has been achieved by improvement in heat-drawing and -treating techniques other methods proposed include suppression of polymerization temperature of vinyl acetate (36) and employment of alkafi spinning (37). 

Various inorganic, organic, and organometaUic compounds are known to cataly2e this polymerization (4,8,9). Among these, BCl is a very effective catalyst, although proprietary catalysts that signiftcandy lower polymerization temperature from the usual, sealed-tube reaction at 250°C are involved in the industrial manufacture of the polymer. A polycondensation process has also been developed for the synthesis of (4) (10—12). This involves elimination of phosphoryl chloride from a monomer prepared from (NH 2 04 and PCl. ... 

Fig. 5. Activity and isotacticity vs polymerization temperature. Polymerization occurs in hexane at 0.7 MPa (7 bat) for 4 h with a superactive...

Eastman Chemical has utilized a unique, high temperature solution process for propylene polymerization. Polymerization temperatures are maintained above 150°C to prevent precipitation of the isotactic polypropylene product in the hydrocarbon solvent. At these temperatures, the high rate of polymerization decreases rapidly, requiring low residence times (127). Stereoregularity is also adversely affected by high temperatures. Consequentiy, the... 

The rate of ion propagation, is independent of the counterion and has been found to be about 46 X 10 in all cases for CF SO", AsF, SbF, SbCFg, PF g, and BF/ counterions. Conditions were the same for all counterions, ie, 8.0 M of monomer in CCI4 solvent and 25°C polymerization temperature. With less stable counterions such as SbCF and BF at most temperatures, the influence of transfer and termination reactions must be taken into account (71). 

DMSO is an effective solvent for the polymerization as it affords good solubiUty for both the polymer and disodium bisphenol A [2444-90-8]. Typical polymerization temperatures for polysulfone are in the range 130—160°C. At temperatures below 130°C, the polymerization slows down considerably due to poor solubiUty of the disodium bisphenol A salt. 

There has been a marked trend toward concentration of higher styrene (ca 40%) polymers in hot latices, and lower styrene (mostiy 20—30% bound styrene) types in cold latex series. This is a reflection of the fact that lowering the polymerization temperature of high styrene copolymers produces little or no gain in the physical properties of the copolymer. 

The main reason that the decreases as the polymerization temperature increases is the increase in the initiation and termination reactions, which leads to a decrease in the kinetic chain length (Fig. 17). At low temperature, the main termination mechanism is polystyryl radical coupling, but as the temperature increases, radical disproportionation becomes increasingly important. Termination by coupling results in higher PS than any of the other termination modes. 

Isobutjiene was first polymerized ia 1873. High molecular weight polymer was later synthesized at I. G. Farben by decreasiag the polymerization temperature to —75°, but the saturated, unreactive polymer could not be cross-linked iato a useful synthetic elastomer. It was not until 1937 that poly(isobutylene- (9-isoprene) [9010-85-9] or butyl mbber was iavented at the Standard Oil Development Co. (now Exxon Chemical Co.) laboratories (1). 

A living cationic polymeriza tion of isobutylene and copolymeriza tion of isobutylene and isoprene has been demonstrated (22,23). Living copolymerizations, which proceed in the absence of chain transfer and termination reactions, yield the random copolymer with narrow mol wt distribution and well-defined stmcture, and possibly at a higher polymerization temperature than the current commercial process. The isobutylene—isoprene copolymers are prepared by using cumyl acetate BCl complex in CH Cl or CH2CI2 at —30 C. The copolymer contains 1 8 mol % trans 1,4-isoprene... 

The choice of initiator system depends on the polymerization temperature, which is an important factor in determining final product properties. Cold polymers are generally easier to process than hot polymers and in conventional cured mbber parts have superior properties. The hot polymers are more highly branched and have some advantages in solution appHcations such as adhesives, where the branching results in lower solution viscosity and better cohesion in the final adhesive bond. 

Commercial chloroprene polymerization is most often carried out in aqueous emulsion using an anionic soap system. This technique provides a relatively concentrated polymerization mass having low viscosity and good transfer of the heat of polymerization. A water-soluble redox catalyst is normally used to provide high reaction rate at relatively low polymerization temperatures. 

Polymerization temperature, °C trans 1,4 Addition inverted cis 1,2 Addition Isomerized 1,2 3,4 Addition... 

Fig. 2. Effect of polymerization temperature on the crystalline melting point of chloroprene mbbers produced by emulsion polymerization ...

Freeze-Resistant Polymers. Chloroprene homopolymers made at conventional polymerization temperatures of 40—50°C are not sufftcientiy freeze resistant for some appHcations. In particular, automotive parts such as belts, boots, and air springs are used in dynamic appHcations and need... 

An important part of the optimization process is the stabilization of the monomer-template assemblies by thermodynamic considerations (Fig. 6-11). The enthalpic and entropic contributions to the association will determine how the association will respond to changes in the polymerization temperature [18]. The change in free volume of interaction will determine how the association will respond to changes in polymerization pressure [82]. Finally, the solvent s interaction with the monomer-template assemblies relative to the free species indicates how well it will stabilize the monomer-template assemblies in solution [16]. Here each system must be optimized individually. Another option is simply to increase the concentration of the monomer or the template. In the former case, a problem is that the crosslinking as well as the potentially nonselective binding will increase simultaneously. In the... 

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