Polyethylene oxide-benzene

To illustrate the application of corresponding-states theory to polymer solution calculations, we consider two cases of sol-vent/polymer vapor-liquid equilibria. The first case we consider is that of the chloroform/polystyrene solution. The second is that of benzene/polyethylene oxide. 

Figure 6, Variation of p 12 u)ith temperature for benzene/polyethylene oxide...

ACPA azobis(4-cyanopentanoic acid) AIBN azobis isobutyronitrile) BPO benzoyl peroxide DVB divinyl benzene, EGA 2-ethylcyano-acrylate HPC hydroxypropyl cellulose MMA methyl methacrylate PAAc polyacrylic acid PEI polyethyleneimine, PEO/PPO polyethylene oxide/polypyropylene oxide copolymer PVME polyvinylmethylether PVP polyvinylpyrrolidone K-30 DMSO dimethylsulfoxide PGA polyglutaraldehyde CMS chloromethylstyrene PMMA-g-OSA polymethylmethacrylate grafted oligostearic acid. 

Synthesis of comb (regular graft) copolymers having a PDMS backbone and polyethylene oxide) teeth was reported 344). These copolymers were obtained by the reaction of poly(hydrogen,methyl)siloxane and monohydroxy-terminated polyethylene oxide) in benzene or toluene solution using triethylamine as catalyst. All the polymers obtained were reported to be liquids at room temperature. The copolymers were then thermally crosslinked at 150 °C. Conductivities of the lithium salts of the copolymers and the networks were determined. 

Polystyrene/polyethylene oxide dendrimers were prepared by ATRP using tri- and tetra (bromomethyl) benzene as the initiators [207]. Each bromine end-group of the resulting stars was transformed first to two - OH groups and subsequently to potassium alcholate, as shown in Scheme 114. These - OK sites served to initiate the anionic polymerization of EO. The synthesized dendritic copolymers were found to display monomodal and narrow molecular weight distribution. 

Ethylene is obtained by catalytic cracking of naphtha. It is one of the key petrochemical commodities worldwide used mostly in the production of polyethylene, ethyl benzene, ethylene oxide and others. The consumption of ethylene for the production of alcohols and other surfactant raw materials represents less than 10% of the total end uses of ethylene on a worldwide basis. 

If a mechanical degradation of a solution of two polymers is carried out by high speed stirring, the formation of a block copolymer is not probable as the scission of polymer molecules at low concentration is not caused mainly by intermolecular interaction, such as by collision of molecules and through entanglements, but by displacements due to hydrodynamic forces in velocity gradients. Nakamo and Minoura (98) did obtain reaction by stirring a benzene solution of polyethylene oxide and poly(methyl methacrylate). 

Fig. 30a-d. Polymerization of methyl methacrylate by high speed stirring of polyethylene oxide solution, a) effect of monomer concentration on polymerization rate (PEO 4 g/100 ml, stirring speed 30000 rpm. b) effect of monomer (MMA) concentration on intrinsic viscosity of reaction mixture (PEO 4 g/100 ml, stirring speed 30000 rpm, solvent benzene, c) effect of PEO concentration on polymerization rate, d) effect of PEO concentration on intrinsic viscosity of reaction mixture (Stirring speed 30000 rpm)... 

The kinetics of the reaction of solid sodium iodide with 1-bromooctane were studied with a 95 % RS graft of polyethylene oxide) 6-mer methyl ether on 3 % CL polystyrene as catalyst (51)176). The rates were approximately first order in 1-bromooctane and independent of the amount of excess sodium iodide. The rates varied with the amount of the solid catalyst used, but there was not enough data to establish the exact functional dependence. All experiments employed powdered sodium iodide, magnetic stirring, and 75-150 pm catalyst beads. Thus the variables stirring speed and particle size, which normally are affected by mass transfer and intraparticle diffusion, were not studied. Yanagida 177) favors a mechanism of transfer of the sodium iodide by dissolution in the solvent (benzene) and diffusion to the catalyst particle... 

The block-polymers containing a middle block of polystyrene and two blocks of polyethylene oxide have some unusual properties. They are soluble in methyl ethyl ketone and cannot be precipitated from this solvent by methanol. Addition of water produces a slight cloudiness but still no precipitation although the block polymer is not soluble in pure water. The polymer is also soluble in benzene, but addition of water to this solution causes its precipitation. On the other hand, neither homopolystyrene nor homo-polyethylene oxide or their mixtures are precipitated from benzene solution by addition of water. This strange behaviour is explained by Richards and Szwarc (45) in terms of hydrogen bonding which depends on the chemical potential of water in the aqueous layer and therefore also in the benzene solution. 

Sadron and Rempp (223) have recently investigated in various solvents the viscosity behavior of polyethylene oxide) with low molecular weights ranging from 62 (ethylene glycol) to about 2 104. Fig. 25 shows the result of application of the present method to these data. It is clear from the figure that the data in benzene and in carbon tetrachloride fit the present theory well and give a common intercept, from which K is evaluated as (11 1) 10-4. Another series of data obtained in cyclohexane... 

Booth, C. Devoy, C. J., "Thermodynamics of Mixtures of Polyethylene oxide) and Benzene," Polymer, 12, 309 (1971a). 

Chang, Y. H. Bonner, D. C., "Sorption of Solutes by Polyethylene oxide). II. Benzene at Finite Concentrations," J. Appl. Polym. Sci., 19, 2457 (1975b). 

As a result of the recommendation of the Petrochemical Advisory Committee, several petrochemical complexes were planned, each with a naphtha throughput on the order of 200,000 tons/yr. The first of these complexes, set up by National Organic Chemicals in Bombay, went into production in 1967. This complex mainly produces polyethylene oxide (20,000 tons), butanol, butadiene, and benzene. Another complex at Koy-ali near Baroda (1974) produces aromatics and has a capacity of 24,000 tons of DMT, 21,000 tons ofo-xylene, and 25,000 tons of mixed xylene. A... 

The mechanism and kinetics of the degradation of polyethylene oxide (PEO) in water, benzene, and chloroform and its copolymerization with sodium methacrylate (NaMA) in water under sonication were studied using a 21-kHz ultrasonic probe [26]. The degradation rates were directly proportional to the vaporization enthalpy and viscosity of solvent. In a further study [27], the kinetics and mechanism of block copolymerization of PEO with NaMA in water under 21.5-kHz ultrasonic irradiation was studied. The ultrasonic copolymerization of PEO-NaMA in aqueous solution follows the kinetic relationship ... 

Table 8. Weight fraction (Wj) and activity coefficient (Ci/wj) of benzene in solutions of polyethylene oxide) (PEO) 73)...

Typically, the oil phase contained 78% monomer/co-monomer, 8% divinyl benzene (cross-linking agent), and 14% non-ionic surfactant Span 80 (Sorbitan monooleate), while the aqueous phase contained 1% potassium persulfate as the initiator. In most cases studied here, monomer is styrene and when elasticity of the polymer is required, 2-ethylhexyl acrylate (2EHA) was used (styrene/2EHA ratio is 1 4). Whenever additives/fillers are placed in the aqueous phase their amounts are stated as weight percent while the phase volume of the aqueous phase remains constant. In some cases, the aqueous phase contains 0.5% hydroxyapatite and 15% phosphoric acid which is used to dissolve the hydroxyapatite, or alternatively, the aqueous phase may contain varying amounts of water-soluble polymer, such as polyethylene glycol or polyethylene oxide. If the styrene-based PHP is to be sulfonated to obtain ionic-hydrophilic foam, the pre-dispersion of sulfuric acid within the pores is useful, if not essential, and in that case, acids (typically 10%) can be used as the internal phaseP . ... 

The regioselectivity of nitration of toluene with nitronium salts has been successfully altered by their prior complexation with crown ethers. Complexation of NO2 BFJ by 18-C-6 crown ether substantially altered the selectivity in nitration of toluene and benzene as reported by Elsenbaumet and Wasserraan [128]. Similar effect was observed with polyethylene oxides. Savoie al. reported isolation of the IS-C-b-NOa BFJ complex and its characterization [129], Masci carried out the yet most detailed study on the effect of crown ethers on the selectivity of electrophilic aromatic nitration [130]. 

Skirda, et al. [92] used PFGNMR to study polyethylene oxides (M = 2, 20, 40, and 3000 kDa) and polystyrenes (M = 240 and 1300 kDa) in chloroform, benzene, dioxane, and carbon tetrachloride over a full range of polymer volume fractions . M /M was ss 1.1 for polyethylene oxides (except M /M 2 for the 3000 kDa polymer) and 1.2 for polystyrenes. Figures 10 and 11 show the data. For each polymer.solvent combination, a stretched-exponential fit as shown describes the data well. 

Figure 3. Influence of polymer concentrations on the relative viscosity of solutions containing polyethylene oxide and anionic sodium dodecyl benzene sulfonate micelles.

Electrical properties have been reported on numerous carbon fiber-reinforced polymers, including carbon nanoflber-modified thermotropic liquid crystalline polymers [53], low-density polyethylene [54], ethylene vinyl acetate [55], wire coating varnishes [56], polydimethyl siloxane polypyrrole composites [50], polyacrylonitrile [59], polycarbonate [58], polyacrylonitrile-polycarbonate composites [58], modified chrome polymers [59], lithium trifluoromethane sulfonamide-doped polystyrene-block copolymer [60], boron-containing polyvinyl alcohols [71], lanthanum tetrafluoride complexed ethylene oxide [151, 72, 73], polycarbonate-acrylonitrile diene [44], polyethylene deoxythiophe-nel, blends of polystyrene sulfonate, polyvinyl chloride and polyethylene oxide [43], poly-pyrrole [61], polypyrrole-polypropylene-montmorillonite composites [62], polydimethyl siloxane-polypyrrole composites [63], polyaniline [46], epoxy resin-polyaniline dodecyl benzene sulfonic acid blends [64], and polyaniline-polyamide 6 composites [49]. 

Figure 8.14 Ds of (a) polystyrenes in CCI4 and CeDe (measurements and symbols same as Figure 8.2), (b) polystyrene benzene and polystyrene cyclohexane (measurements and symbols same as Figure 8.3), (c) toluene solutions of (O) 15, ( ) 530, and ( ) 730 kDa polydimethylsiloxanes with single-Af (sohd line) and all-M (dashed line) fits, using PFGNMR measurements of Giebel, et al.(24) and Skirda, et al. 25), and (d) polyethylene oxide water (measurements and symbols same as Figure 8.1). Lines represent fits, one for each polymer solvent, to a joint stretched exponential in c and M.

Double bonds characterize the basic building blocks of the petrochemical business. Ethylene, for example, is the chemical compound used to make vinyl chloride, ethylene oxide, acetaldehyde, ethyl alcohol, styrene, alpha olefins, and polyethylene, to name only a few. Propylene and benzene, the other big-volume building blocks, also have the characteristic double bonds. 

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