Styrene efficiency

Biscyclopentadienyl complexes and bridged metallocene complexes of titanium show lower polymerization activities than the monocyclopentadienyl complexes (39). The catalytic activity and S5nidiospecificity for bridged metallocenes does increase by decreasing the bite-angle (51). Although ansa-monocyclopentadienyl-amido titanium complexes are essentially inactive for homopolymerization of styrene, efficient sPS formation with nonbridged amido cylcopentadienyl complexes of titanium has been reported (52). 

The sequential block copolymerization of la with styrene efficiently proceeded to afford an objective AB diblock copolymer, poly(la)- 7/ocfe-polystyrene, with well-defined structures. This success further confirms the living nature of the anionic polymerization of la. Similarly, a well-defined BA diblock copolymer, polystyrene-l7/ocfe-poly(la), was synthesized by reversing the sequence of monomer addition, namely styrene followed by la. Thus, the possible crossover copolymerization indicates that the electrophilicities of la and styrene as well as the nucleophilicities of both living polymers are very similar. 

Aromatic radical anions, such as lithium naphthalene or sodium naphthalene, are efficient difunctional initiators (eqs. 6,7) (3,20,64). However, the necessity of using polar solvents for their formation and use limits their utility for diene polymerization, since the unique abiUty of lithium to provide high 1,4-polydiene microstmcture is lost in polar media (1,33,34,57,63,64). Consequentiy, a significant research challenge has been to discover a hydrocarbon-soluble dilithium initiator which would initiate the polymerization of styrene and diene monomers to form monomodal a, CO-dianionic polymers at rates which are faster or comparable to the rates of polymerization, ie, to form narrow molecular weight distribution polymers (61,65,66). 

Methyl methacrylate is often used in combination with styrene to improve light transmission and uv stabiUty in fiame-retardant glazing appHcations. Phosphate ester (triethyl phosphate) additives are also included to supplement fiame-retardant efficiency benzophenone uv stabilizers are required to prevent yellowing of these uv-sensitive resins. 

Example 8 Calculation of Rate-Based Distillation The separation of 655 lb mol/h of a bubble-point mixture of 16 mol % toluene, 9.5 mol % methanol, 53.3 mol % styrene, and 21.2 mol % ethylbenzene is to be earned out in a 9.84-ft diameter sieve-tray column having 40 sieve trays with 2-inch high weirs and on 24-inch tray spacing. The column is equipped with a total condenser and a partial reboiler. The feed wiU enter the column on the 21st tray from the top, where the column pressure will be 93 kPa, The bottom-tray pressure is 101 kPa and the top-tray pressure is 86 kPa. The distillate rate wiU be set at 167 lb mol/h in an attempt to obtain a sharp separation between toluene-methanol, which will tend to accumulate in the distillate, and styrene and ethylbenzene. A reflux ratio of 4.8 wiU be used. Plug flow of vapor and complete mixing of liquid wiU be assumed on each tray. K values will be computed from the UNIFAC activity-coefficient method and the Chan-Fair correlation will be used to estimate mass-transfer coefficients. Predict, with a rate-based model, the separation that will be achieved and back-calciilate from the computed tray compositions, the component vapor-phase Miirphree-tray efficiencies. 

The rate-based model gave a distillate with 0.023 mol % ethylbenzene and 0.0003 mol % styrene, and a bottoms product with essentially no methanol and 0.008 mol % toluene. Miirphree tray efficiencies for toluene, styrene, and ethylbenzene varied somewhat from tray to tray, but were confined mainly between 86 and 93 percent. Methanol tray efficiencies varied widely, mainly from 19 to 105 percent, with high values in the rectifying section and low values in the stripping section. Temperature differences between vapor and liquid phases leaving a tray were not larger than 5 F. 

Based on an average tray efficiency of 90 percent for the hydrocarbons, the eqiiilibniim-based model calculations were made with 36 equilibrium stages. The results for the distillate and bottoms compositions, which were very close to those computed by the rate-based method, were a distillate with 0.018 mol % ethylbenzene and less than 0.0006 mol % styrene, and a bottoms product with only a trace of methanol and 0.006 mol % toluene. 

FIG. 14-42 Overall (Murphree) efficiency and pressure drop data for several devices using the same test mixture (ethylbenzene/styrene). See text for details. [Billet, Conrad, and Giuhh, Instn. Chem. Engrs. Symp. Ser. No. 32, 5, 111 (1979).]... 

Efficiency and pressure drop data for Siilzer BX metal gauze structured packing and for three test mixtures are shown in Fig. 14-7.5. For the ethyl benzene/styrene test mixture, the effect of operating pressure is shown. The high viscosity mixture, propylene glycoL/ethylene... 

Polypropylene block and graft copolymers are efficient blend compatibilizers. These materials allow the formation of alloys, for example, isotactic polypropylene with styrene-acrylonitrile polymer or polyamides, by enhancing the dispersion of incompatible polymers and improving their interfacial adhesion. Polyolefinic materials of such types afford property synergisms such as improved stiffness combined with greater toughness. 

Photoinitiation of polymerization of MMA and styrene by Mn(facac)3 was also investigated, and it was shown that the mechanism of photoinitiation is different [33] from that of Mn(acac)3 and is subject to the marked solvent effect, being less efficient in benzene than in ethyl acetate solutions. The mechanism shown in Schemes (15) and (16) illustrate the photodecomposition scheme of Mn(facac)3 in monomer-ethyl acetate and monomer-benzene solutions, respectively. (C = manganese chelate complex.)... 

Kaeriyama and Shimura [34] have reported the photoinitiation of polymerization of MMA and styrene by 12 metal acetylacetonate complex. These are Mn(acac)3, Mo02(acac)2, Al(acac)3, Cu(bzac)2, Mg(acac)2, Co(a-cac)2, Co(acac)3, Cr(acac)3, Zn(acac)2, Fe(acac)3, Ni(a-cac)2, and (Ti(acac)2) - TiCU. It was found that Mn(a-cac)3 and Co(acac)3 are the most efficient initiators. The intraredox reaction with production of acac radicals is proposed as a general route for the photodecomposition of these chelates. 

This photoinitiating system is also used for the polymerization of other vinyl monomers such as styrene (St), acrylonitrile (AN), and vinylacetate (VA). The efficiency of photoinitiation by this system follows the order ... 

Wang and Chen [41] studied the compatibility problems of incompatible NBR-PVC blends. Poly(vinyl-idene chloride-covinyl chloride) is reported to act as an efficient interfacial agent. Blends of PVC, NBR, and the copolymer were prepared by the solution casting technique using THE as a solvent. Improvement in mechanical properties can be achieved in NBR-PVC blend by the addition of different types of rubbers [42]. Different rubbers include NR, styrene butadiene (SBR) and butadiene (BR). Replacement of a few percent of NBR by other rubbers will improve the mechanical properties and at the same time reduce the cost of the blend. 

The addition of living poly(styrene) to AIBN leads finally, especially for high coupling efficiencies, to the elimination of one nitrile group [72]. More recently, Ren et al. [73] have used bis(2-chloroethyl)2,2 -azodiisobu-tyrate (see scheme 19) to terminate anionically initiated poly(butadiene) chains. Since the azo transfer agent possesses two functional groups (Cl) that are able to termi-... 

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