Monomer unreacted

Chain lifetimes are small and the concentration of free radicals is low. To a reasonable approximation, the system consists of unreacted monomer, unreacted initiator, and dead polymer. The quasi-steady hypothesis gives... 

Balance over reactor-filter-dryer subsystem gives flows to recovery column, water, 44,892 + 10,101 — 532 = 54,461 kg monomer, unreacted monomer = 1122 kg... 

Methyltosylate initiated polymerization In order to determine if the PEG part plays any significant role in initiation, a polymerization was carried out with methyl tosylate as initiator using M/I of 5.92. At complete consumption of monomer, unreacted methyl tosylate was still present (see Figure 4). The polymer produced had a broad molecular weight distribution, 1.39. kp/kl was estimated by... 

The polymer is withdrawn continuously from a specially designed outlet at the bottom of the reactor and sent to a degassing vessel where monomer unreacted, comonomer and hydrogen are removed from the polymer with the help of a counter-current propane gas flow. 

There is high molecular weight polymer present at any time during the polymerization, so the contents of the reaction at any time are unreacted monomer, unreacted initiator, and high molecular weight polymer. There are no significant amounts of intermediate size species (dimer, trimers, etc.). 

The half-life of the initial benzoyloxy radicals from decompositions of benzoyl peroxide is estimated to be 10 to 10 seconds. Past that time, they decompose into phenyl radicals and carbon dioxideThis is sufficient time for the benzoyloxy radicals to be trapped by reactive monomers. Unreactive monomers, however, are more likely to react with the phenyl radicals that form from the elimination reaction. In effect there are two competing reactions. ... 

In contrast to a living polymer, the lifetime of a growing chain in free radical polymerizations is very short, typically on the order of milliseconds. Free radical concentrations - which include all the growing chain - are very low, typically 10" to 10" mole m"To a reasonable approximation, the system consists of unreacted monomer, unreacted initiator, and dead polymer. The free radicals are formed spontaneously in some systems such as polystyrene, but chemical initiation is more common ... 

The fraction of unreacted B groups is rp, so this gives the probability of reaction for B. Since p is the fraction of A groups on multifunctional monomers, rp must be multiplied by 1 - p to give the probability of B reacting with an AA monomer. The total probability for the chain shown is the product of the probabilities considered until now ... 

In Chap. 5 all molecules—whether monomer or n-mers of any n—carry functional groups hence the fraction described by Eq. (5.24) applies to the entire reaction mixture. Equation (6.67), by contrast, applies only to the radical population. Since the radicals eventually end up as polymers, the equation also describes the polymer produced. Unreacted monomer is specifically excluded, however. 

Elimination of unreacted monomers can be accompHshed by two methods dual initiators to enhance conversion of monomers to product (73—75) and steam stripping (70,76). Several process improvements have been claimed for dewatering beads (77), to reduce ha2e (78—81), improve color (82—86), remove monomer (87,88), and maintain homogeneous copolymer compositions (71,72,89). 

A schematic of a continuous bulk SAN polymerization process is shown in Figure 4 (90). The monomers are continuously fed into a screw reactor where copolymerization is carried out at 150°C to 73% conversion in 55 min. Heat of polymerization is removed through cooling of both the screw and the barrel walls. The polymeric melt is removed and fed to the devolatilizer to remove unreacted monomers under reduced pressure (4 kPa or 30 mm Hg) and high temperature (220°C). The final product is claimed to contain less than 0.7% volatiles. Two devolatilizers in series are found to yield a better quaUty product as well as better operational control (91,92). 

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. 

Since adipic acid has been produced in commercial quantities for almost 50 years, it is not surprising that many variations and improvements have been made to the basic cyclohexane process. In general, however, the commercially important processes stiU employ two major reaction stages. The first reaction stage is the production of the intermediates cyclohexanone [108-94-1] and cyclohexanol [108-93-0], usuaHy abbreviated as KA, KA oil, ol-one, or anone-anol. The KA (ketone, alcohol), after separation from unreacted cyclohexane (which is recycled) and reaction by-products, is then converted to adipic acid by oxidation with nitric acid. An important alternative to this use of KA is its use as an intermediate in the manufacture of caprolactam, the monomer for production of nylon-6 [25038-54-4]. The latter use of KA predominates by a substantial margin on a worldwide basis, but not in the United States. 

An example of a commercial semibatch polymerization process is the early Union Carbide process for Dynel, one of the first flame-retardant modacryhc fibers (23,24). Dynel, a staple fiber that was wet spun from acetone, was introduced in 1951. The polymer is made up of 40% acrylonitrile and 60% vinyl chloride. The reactivity ratios for this monomer pair are 3.7 and 0.074 for acrylonitrile and vinyl chloride in solution at 60°C. Thus acrylonitrile is much more reactive than vinyl chloride in this copolymerization. In addition, vinyl chloride is a strong chain-transfer agent. To make the Dynel composition of 60% vinyl chloride, the monomer composition must be maintained at 82% vinyl chloride. Since acrylonitrile is consumed much more rapidly than vinyl chloride, if no control is exercised over the monomer composition, the acrylonitrile content of the monomer decreases to approximately 1% after only 25% conversion. The low acrylonitrile content of the monomer required for this process introduces yet another problem. That is, with an acrylonitrile weight fraction of only 0.18 in the unreacted monomer mixture, the low concentration of acrylonitrile becomes a rate-limiting reaction step. Therefore, the overall rate of chain growth is low and under normal conditions, with chain transfer and radical recombination, the molecular weight of the polymer is very low. 

The monomer recovery process may vary ia commercial practice. A less desirable sequence is to filter or centrifuge the slurry to recover the polymer and then pass the filtrate through a conventional distillation tower to recover the unreacted monomer. The need for monomer recovery may be minimized by usiag two-stage filtration with filtrate recycle after the first stage. Nonvolatile monomers, such as sodium styrene sulfonate, can be partially recovered ia this manner. This often makes process control more difficult because some reaction by-products can affect the rate of polymerization and often the composition may vary. When recycle is used it is often done to control discharges iato the environment rather than to reduce monomer losses. 

The presence of additives or unreacted monomers ia certaia plastic foams can limit their use where food or human contact is anticipated. Heavy metals can also be found ia various additives. The manufacturers recommendations or existing regulations again should be foUowed for such appHcations. 

Three generations of latices as characterized by the type of surfactant used in manufacture have been defined (53). The first generation includes latices made with conventional (/) anionic surfactants like fatty acid soaps, alkyl carboxylates, alkyl sulfates, and alkyl sulfonates (54) (2) nonionic surfactants like poly(ethylene oxide) or poly(vinyl alcohol) used to improve freeze—thaw and shear stabiUty and (J) cationic surfactants like amines, nitriles, and other nitrogen bases, rarely used because of incompatibiUty problems. Portiand cement latex modifiers are one example where cationic surfactants are used. Anionic surfactants yield smaller particles than nonionic surfactants (55). Often a combination of anionic surfactants or anionic and nonionic surfactants are used to provide improved stabiUty. The stabilizing abiUty of anionic fatty acid soaps diminishes at lower pH as the soaps revert to their acids. First-generation latices also suffer from the presence of soap on the polymer particles at the end of the polymerization. Steam and vacuum stripping methods are often used to remove the soap and unreacted monomer from the final product (56). 

Recycle and Polymer Collection. Due to the incomplete conversion of monomer to polymer, it is necessary to incorporate a system for the recovery and recycling of the unreacted monomer. Both tubular and autoclave reactors have similar recycle systems (Fig. 1). The high pressure separator partitions most of the polymers from the unreacted monomer. The separator overhead stream, composed of monomer and a trace of low molecular weight polymer, enters a series of coolers and separators where both the reaction heat and waxy polymers are removed. Subsequendy, this stream is combined with fresh as well as recycled monomers from the low pressure separator together they supply feed to the secondary compressor. 

Gas-phase polymerization of propylene was pioneered by BASF, who developed the Novolen process which uses stirred-bed reactors (Fig. 8) (125). Unreacted monomer is condensed and recycled to the polymerizer, providing additional removal of the heat of reaction. As in the early Hquid-phase systems, post-reactor treatment of the polymer is required to remove catalyst residues (126). The high content of atactic polymer in the final product limits its usefiilness in many markets. 

Gas chromatography (gc) has been used extensively to analyze phenoHc resins for unreacted phenol monomer as weU as certain two- and three-ring constituents in both novolak and resole resins (61). It is also used in monitoring the production processes of the monomers, eg, when phenol is alkylated with isobutylene to produce butylphenol. Usually, the phenoHc hydroxyl must be derivatized before analysis to provide a more volatile compound. The gc analysis of complex systems, such as resoles, provides distinct resolution of over 20 one- and two-ring compounds having various degrees of methylolation. In some cases, hemiformals may be detected if they have been properly capped (53). 

---