Diluents, polymerizations

The first sulfur curable copolymer was prepared ia ethyl chloride usiag AlCl coinitiator and 1,3-butadiene as comonomer however, it was soon found that isoprene was a better diene comonomer and methyl chloride was a better polymerization diluent. With the advent of World War II, there was a critical need to produce synthetic elastomers in North America because the supply of natural mbber was drastically curtailed. This resulted in an enormous scientific and engineering effort that resulted in commercial production of butyl mbber in 1943. 

This is an important consideration in the selection of an optimum polymerization diluent, which is very easily neglected in laboratory investigations. Also, since little is known cd>out particle coalescence in the presence of mechanical agitation, extreme care must be taken in mixing scale-up. 

The homopolymerization and copolymerization of 4-methyl-l-pent-ene is generally carried out in a batch polymerization process (5). Batch polymerization refers to a polymerization method in which a quantity of the monomers are polymerized in a reaction vessel and then the resulting polymer is recovered from that reaction vessel upon the desired level of polymerization of the monomers. It is desirable to carry out such processes under conditions, which result in a slurry of particles of the desired polymer or copolymer in the polymerization diluent rather than a solution of the polymer or copolymer. The formation of such a slurry aids in the separation and purification of the resulting polymer. 

The compatibility of blends of poly (vinyl chloride) (PVC) and a terpolymer (TP) of ethylene, vinyl acetate, and carbon monoxide was investigated by dynamic mechanical, dielectric, and calorimetric studies. Each technique showed a single glass transition and that transition temperature, as defined by the initial rise in E" at 110 Hz, c" at 100 Hz, and Cp at 20°C/min, agreed to within 5°C. PVC acted as a polymeric diluent which lowered the crystallization temperature, Tc, of the terpolymer such that Tc decreased with increasing PVC content while Tg increased. In this manner, terpolymer crystallization is inhibited in blends whose value of (Tc — Tg) was negative. Thus, all blends which contained 60% or more PVC showed little or no crystallinity unless solvent was added. 

Although the terpolymer plasticized PVC, the latter was found to act as a polymeric diluent which lowered the crystallization temperature, Tc, of the former. In this maner, the crystallization of the terpolymer could be retarded or inhibited in blends whose value of (Tc — Tg) was near or below 0°C. Mixtures containing 60% or more PVC were found to be in this category and showed little or no sign of bulk crystallization. However mixtures containing 80 and 90% PVC which were completely amorphous in the bulk, crystallized when solvent was added. Though we believe crystallization occurred because of a lowering of Tg, separation of this from the possibility of crystallization from solution would require further studies. 

One way of obtaining a network swollen with diluent is to form the network in a first step and then absorb an unreactive diluent into it. Alternatively, the same diluent can be mixed into the reactive chains prior to end linking. In either case, oligomeric and polymeric diluents are of greatest interest. The diluent must be functionally inactive for it to reptate through the network rather than being bonded to it. Both types of networks can then be extracted to determine the ease with which various diluents can be removed, as a function of Mj and M. ... 

From literature, the melting and recrystallisation temperamres of a semi-crystalline polymer is depressed in the presence of a polymeric diluent and is governed by the equation [64],... 

Two typical examples of the overall crystallization rate, expressed as either fo s or peak time, are given in Fig. 11.7 for poly(ethylene oxide)-poly(vinyl phenol) (18) and for poly(aryl ether ether ketone)-poly(ether imide) (19) in Fig. 11.8. The dependence of the crystallization rates on composition are similar to one another and are closely related to the results for other binary mixtures. The overall crystallization rates follow the pattern established for spherulite growth rates. At the higher crystallization temperatures only a modest decrease in the rate is observed with the addition of the noncrystallizing component However, with a decrease in the crystallization temperature the polymeric diluent becomes more effective in reducing the rate. Because of the retardation in the rate with dilution a much wider range in isothermal crystallization temperatures can be studied. Thus, for the more dilute blends a maximum in the rates with temperature can be observed. This is... 

Tetrahydrofurfuryl alcohol is used in elastomer production. As a solvent for the polymerization initiator, it finds appHcation in the manufacture of chlorohydrin mbber. Additionally, tetrahydrofurfuryl alcohol is used as a catalyst solvent-activator and reactive diluent in epoxy formulations for a variety of apphcations. Where exceptional moisture resistance is needed, as for outdoor appHcations, furfuryl alcohol is used jointly with tetrahydrofurfuryl alcohol in epoxy adhesive formulations. 

If a linear mbber is used as a feedstock for the mass process (85), the mbber becomes insoluble in the mixture of monomers and SAN polymer which is formed in the reactors, and discrete mbber particles are formed. This is referred to as phase inversion since the continuous phase shifts from mbber to SAN. Grafting of some of the SAN onto the mbber particles occurs as in the emulsion process. Typically, the mass-produced mbber particles are larger (0.5 to 5 llm) than those of emulsion-based ABS (0.1 to 1 llm) and contain much larger internal occlusions of SAN polymer. The reaction recipe can include polymerization initiators, chain-transfer agents, and other additives. Diluents are sometimes used to reduce the viscosity of the monomer and polymer mixture to faciUtate processing at high conversion. The product from the reactor system is devolatilized to remove the unreacted monomers and is then pelletized. Equipment used for devolatilization includes single- and twin-screw extmders, and flash and thin film evaporators. Unreacted monomers are recovered for recycle to the reactors to improve the process yield. 

In this pyrolysis, sub atmospheric partial pressures are achieved by employing a diluent such as steam. Because of the corrosive nature of the acids (HE and HCl) formed, the reactor design should include a platinum-lined tubular reactor made of nickel to allow atmospheric pressure reactions to be mn in the presence of a diluent. Because the pyrolysate contains numerous by-products that adversely affect polymerization, the TFE must be purified. Refinement of TFE is an extremely complex process, which contributes to the high cost of the monomer. Inhibitors are added to the purified monomer to avoid polymerization during storage terpenes such as t7-limonene and terpene B are effective (10). 

In order to faciUtate heat transfer of the exothermic polymerization reaction, and to control polymerizate viscosity, percent reactives are adjusted through the use of inert aromatic or aUphatic diluents, such as toluene or heptane, or higher boiling mixed aromatic or mixed aUphatic diluents. Process feed streams are typically adjusted to 30—50% polymerizable monomers. 

Some slurry processes use continuous stirred tank reactors and relatively heavy solvents (57) these ate employed by such companies as Hoechst, Montedison, Mitsubishi, Dow, and Nissan. In the Hoechst process (Eig. 4), hexane is used as the diluent. Reactors usually operate at 80—90°C and a total pressure of 1—3 MPa (10—30 psi). The solvent, ethylene, catalyst components, and hydrogen are all continuously fed into the reactor. The residence time of catalyst particles in the reactor is two to three hours. The polymer slurry may be transferred into a smaller reactor for post-polymerization. In most cases, molecular weight of polymer is controlled by the addition of hydrogen to both reactors. After the slurry exits the second reactor, the total charge is separated by a centrifuge into a Hquid stream and soHd polymer. The solvent is then steam-stripped from wet polymer, purified, and returned to the main reactor the wet polymer is dried and pelletized. Variations of this process are widely used throughout the world. 

Most commercial processes produce polypropylene by a Hquid-phase slurry process. Hexane or heptane are the most commonly used diluents. However, there are a few examples in which Hquid propylene is used as the diluent. The leading companies involved in propylene processes are Amoco Chemicals (Standard OH, Indiana), El Paso (formerly Dart Industries), Exxon Chemical, Hercules, Hoechst, ICl, Mitsubishi Chemical Industries, Mitsubishi Petrochemical, Mitsui Petrochemical, Mitsui Toatsu, Montedison, Phillips Petroleum, SheU, Solvay, and Sumimoto Chemical. Eastman Kodak has developed and commercialized a Hquid-phase solution process. BASE has developed and commercialized a gas-phase process, and Amoco has developed a vapor-phase polymerization process that has been in commercial operation since early 1980. 

Install automatic or manual activation of bottom discharge valve to drop batch into a dump tank with diluent, poison, or inhibitor, or to an emergency containment area (May not be effective for systems such as polymerization reactions where there is a significant increase in viscosity.)... 

Plasticizers are substances (usually low molecular weight diluents) that are incorporated into polymeric materials to improve their workability and increase flexibility. Polymeric plasticizers are low glass transition temperature (Tg) poly-... 

The pore size, the pore-size distribution, and the surface area of organic polymeric supports can be controlled easily during production by precipitation processes that take place during the conversion of liquid microdroplets to solid microbeads. For example, polystyrene beads produced without cross-linked agents or diluent are nonporous or contain very small pores. However, by using bigb divinylbenzene (DVB) concentrations and monomer diluents, polymer beads with wide porosities and pore sizes can be produced, depending on the proportion of DVB and monomer diluent. Control of porosity by means of monomer diluent has been extensively studied for polystyrene (3-6) and polymethacrylate (7-10). 

In addition to monomers and the initiator, an inert liquid (diluent) must be added to the monomer phase to influence the pore structure and swelling behavior of the beaded resin. The monomer diluent is usually a hydrophobic liquid such as toluene, heptane, or pentanol. It is noteworthy that the namre and the percentage of the monomer diluent also influence the rate of polymerization. This may be mainly a concentration or precipitation effect, depending on whether the diluent is a solvent or precipitant for the polymer. For example, when the diluent is a good solvent such as toluene to polystyrene, the polymerizations proceed at a correspondingly slow rate, whereas with a nonsolvent such as pentanol to polystyrene the opposite is true. 

Following the completion of the polymerization process, the beaded polymer is recovered from the suspension mixture and freed from the stabilizer, diluents, and traces of monomers and initiators. For laboratory and small-scale preparation, repeated washings with water, methanol, or acetone are appropriate. Complete removal of the monomer diluent, solvents, and initiator, especially from macroporous resin, may require a long equilibration time with warm methanol or acetone. In industry, this is usually accomplished by stream stripping. 

A porous polystyrene-divinylbenzene gel is produced by suspension polymerization in an aqueous system with incorporation of more than 5 mol% initiator to a total amount of styrene and divinylbenzene with an inert organic solvent as diluent and porogen (24). 

A process for the preparation of porous polyvinyl alcohol gels in three steps is (1) suspension polymerization of vinyl acetate with diethylene glycol dimethacrylate in the presence of a diluent as porogen, (2) saponifying of the resulting porous polyvinyl acetate gel with an alkali, and then (3) subjecting... 

Continuous porous polymer rods have been prepared by an in situ polymerization within the confines of a chromatographic column. The column is filled with glycidyl methacrylate and ethylene dimethacrylate monomer mixtures, cyclo-hexanol and dodecanol diluents, and AIBN initiator. They are then purged with nitrogen, stopped, and closed with a silicon rubber septum. The polymerization is allowed to proceed for 6 hr at 70°C with the column acting as a mold (47). 

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