Styrene copolymerization with methyl

Uses Copolymerized with methyl acrylate, methyl methacrylate, vinyl acetate, vinyl chloride, or 1,1-dichloroethylene to produce acrylic and modacrylic fibers and high-strength fibers ABS (acrylonitrile-butadiene-styrene) and acrylonitrile-styrene copolymers nitrile rubber cyano-ethylation of cotton synthetic soil block (acrylonitrile polymerized in wood pulp) manufacture of adhesives organic synthesis grain fumigant pesticide monomer for a semi-conductive polymer that can be used similar to inorganic oxide catalysts in dehydrogenation of tert-butyl alcohol to isobutylene and water pharmaceuticals antioxidants dyes and surfactants. 

Table 6.6 Comparison of theoretical and experimental triad distributions in copolymer of styrene Mt with methyl methacrylate M2 prepared in bulk copolymerization (T = 60 °C) at conversions p = 0.03 -0.05 [281]...

To synthesize water-soluble or swellable copolymers, inverse heterophase polymerization processes are of special interest. The inverse macroemulsion polymerization is only reported for the copolymerization of two hydrophilic monomers. Hernandez-Barajas and Hunkeler [62] investigated the copolymerization of AAm with quaternary ammonium cationic monomers in the presence of block copoly-meric surfactants by batch and semi-batch inverse emulsion copolymerization. Glukhikh et al. [63] reported the copolymerization of AAm and methacrylic acid using an inverse emulsion system. Amphiphilic copolymers from inverse systems are also successfully obtained in microemulsion polymerization. For example, Vaskova et al. [64-66] copolymerized the hydrophilic AAm with more hydrophobic methyl methacrylate (MMA) or styrene in a water-in-oil microemulsion initiated by radical initiators with different solubilities in water. However, not only copolymer, but also homopolymer was formed. The total conversion of MMA was rather limited (<10%) and the composition of the copolymer was almost independent of the comonomer ratio. This was probably due to a constant molar ratio of the monomers in the water phase or at the interface as the possible locus of polymerization. Also, in the case of styrene copolymerizing with AAm, the molar fraction of AAm in homopolymer compared to copolymer is about 45-55 wt% [67], which is still too high for a meaningful technical application. 

The simple linear relation between and x shown in Figure 15.3 is found only for a few copolymers composed of compatible monomer pairs, such as styrene copolymerized with either methyl acrylate or butadiene. A simple ideal mixing rule can be applied to these systems, but when the comonomer properties differ markedly, the linear dependence is lost and a nonlinear equation has to be developed. 

In the same fashion, methacrylate groups have also been incorporated in soybean oils to generate similar polymer architectures. Acrylated epoxidized soybean oil and maleinated acrylated epoxidized soybean oil were reacted with methacrylated lauric acid as a method of reducing styrene input [41]. This increased both the visocosity and the glass transition temperature when compared with the styrene analogue as well as having the benefits of improving the environmental properties of the polymer even further. Acrylated, epoxidized soybean oil was copolymerized with methyl methacrylate in a polymerization initiated by benzoyl peroxide to produce a clear bioplastic [42]. 

Figure 22-7. Change in mole fraction of monomeric unit, of the reversibly polymerizing a-methyl styrene in the free radical copolymerization with methyl methacrylate at 60 C (above) or with acrylonitrile at 80 C (below) as a function of the overall monomer concentration. In the former case, reversibly depolymerizing disequences (—), and in the latter case, nondepolymerizing disequences (—), were found. (After data from P. Wittmer.)...

A bromine-terminated monofunctional poly(rerr-butyl acrylate) resulting from ATRP of rBA catalyzed by the CuBr/At, At,At, iV, lV"-pentamethyldiethylenetriamine (PMDETA) system (initial mole concentration ratios tBA methyl bromopropionate (MBrP) CuBr PMDETA CuBr2 = 50 1 0.5 0.525 0.025, 25% acetone, 60°C conversion = 96% after 6.5 h) was used as macroinitiator for block copolymerization with styrene (St) with the initial mole concentration ratios of St P(rBA) CuBr PMDETA = 100 1 1 1 at 100°C (conversion 94%). The monofunctional bromo-terminated copolymer P(rBA)-A-P(St) formed was subsequently used as a macroinitiator for a further copolymerization with methyl acrylate (MA). The polymerization was also catalyzed by CuBr/PMDETA (initial concentration ratios MA P(rBA-i>-P(St) CuBr PMDETA = 392 1 1 1), under high dilution in toluene and reached 23% monomer conversion after 3.5 h at 70°C. The experimental molecular weight (M ) of the resulting triblock copolymer P(tBA)-fo-P(St)-fr-P(MA) was 24,800 with a PDI = 1.10. Calculate the theoretical M to compare with the experimental value. 

The copolymerization of a,p-unsaturated ketones has been studied extensively in order to improve the poor chemical and thermal stability exhibited by the homopolymers. The vinyl ketones have been copolymerized with most of the common vinyl and diene monomers. The data are given in Ref. [326]. For initiation, the same reagents could be used as for free-radical homopolymerization. Copolymerization was carried out in bulk [371] and in emulsion systems [372]. In copolymerization with methyl methacrylate, vinyl acetate [373], and styrene [371] it was concluded that the relative reactivities of the vinyl ketones increase with the increasing electron-withdrawing nature of the vinyl ketone substituent. Polar and steric effects are not observed. Most of the work has been directed toward the preparation of oil- and solvent-resistant rubbers to replaee styrene-butadiene rubber. Emulsion eopolymerization of butadiene with methyl isopropenyl ketone yielded rubbers with good solvent resistance and low temperature flexibility, but the products tended to harden on storage and were not compatible with natural rubber [374]. The reactive earbonyl function caused sensitivity to alkine reagents. Copolymers of butylacrylate and methyl vinyl ketone, for example, can be erosslinked by treatment with hydrazine [375]. 

The repeat unit for poly(ethylene terephthalate) ([I] Reaction (1.2) above) is built up from two chemical units, but the polymer is a continuous repeat of this structure. In many cases, the structure of a polymer is modified by the addition of another monomer unit during the polymerization process, a process known as copolymerization. This for a vinyl polymer system, for example, styrene could be copolymerized with methyl methacrylate. Such copolymers can be arranged in different as shown in Fig. 1.2 and each type of material may show interesting or... 

The decay of radicals produced by photo-irradiation of cellulose at room temperature, and the characteristics of photo-irradiated cellulose for the initiation of graft copolymerization with methyl methacrylate have been investigated. The e.s.r. spectra of irradiated samples of untreated, swollen, oximated, or ferric-ion-sensitized celluloses were examined. The decay of radicals was accelerated by solvents (water — methanol > acetone > p-dioxan) and was retarded by methacrylic acid > methyl methacrylate styrene. Graft copolymerization of methyl methacrylate with photo-irradiated cellulose was effectively initiated by water or methanol, but not by either acetone or p-dioxan. It appears that initiation of the graft copolymerization onto pre-irradiated cellulose is promoted by radicals exhibiting a singlet in the e.s.r. spectrum. 

Poly(p-tnercaptostyrene) was prepared by the polymerization of p-vinylphenyl thioacetate 24,25) (III) which was synthesized from p-aminoacetophenone (IV) (Scheme I). Conversitsi of FV via a diazonium salt to xanthate (V), followed by reduction with NaBH4 introduced a thiophenol group (VI). Pyrolysis of the corresponding diacetate produced III in 10% overall yield This styrene derivative polymerized readily and saponification of the resultant homopolymer yielded an alkaU soluble polymer. Copolymerization with methyl methacrylate gave, upon saponification, another synthetic mercaptan-containing copolymer. 

Styrene Copolymers, Copolymerization is another way to improve the mechanical properties and chemical resistance of polystyrene. Acrylonitrile, butadiene, alphamethylstyrene, methyl methacrylate, divinyl-benzene, maleic anhydride, and other monomers have been copolymerized with styrene to produce commercially important copolymers. Some of the most widely used of these are those prepared with acrylonitrile and butadiene. Styrene copolymerized with butadiene (SBR) is one of the more important elastomeric materials used today. (See Chapter 18.)... 

Parallel approaches have been described for the preparation of polyacrylate-protease conjugates [396-400]. Acryloylation of subtilisin and a-chymotrypsin, followed by mixed polymerization with methyl methacrylate, vinyl acetate, styrene, or ethylvinyl ether, provides insoluble, doped polymethyl methacrylate, polyvinyl acetate, polystyrene, and polyethyl vinyl ether polymers [396]. These biocatalytic plastics perform especially well in hydrophilic and hydrophobic solvents, and have been used for peptide synthesis and the regioselective acylation of sugars and nucleosides. Similarly, modification of subtilisin and thermolysin with PEG monomethacrylate, then copolymerization with methyl methacrylate and trimethylolpropane trimethacrylate furnishes protease-polymethyl methacrylate plastics, which show good activities and stabilities in aqueous, mixed, and low-water and anhydrous organic media [397-400]. The protein-acrylate composites are unique in that they enable catalytic densities as high as 50% w/w. 

Styrene and methyl methacylate have been used as comonomers in many investigations of copolymerization. Use the following listj of ri values for each of these copolymerizing with the monomers listed below to rank the latter with respect to reactivity ... 

Styrene monomer was also copolymerized with a series of functional monomers by using a single-step dispersion copolymerization procedure carried out in ethanol as the dispersion medium by using azobisizobu-tyronitrile and polyvinylpyrollidone as the initiator and the stabilizer, respectively [84]. The comonomers were methyl methacrylate, hydroxyethyl acrylate, metha-crylic acid, acrylamide, allyltrietoxyl silane, vinyl poly-dimethylsiloxane, vinylsilacrown, and dimethylamino-... 

In contrast to /3-PCPY, ICPY did not initiate copolymerization of MMA with styrene [39] and AN with styrene [40]. However, it accelerated radical polymerization by increasing the rate of initiation in the former case and decreasing the rate of termination in the latter case. The studies on photocopolymerization of MMA with styrene in the presence of ICPY has also been reported [41], /8-PCPY also initiated radical copolymerization of 4-vinylpyridine with methyl methacrylate [42]. However, the ylide retarded the polymerization of N-vinylpyrrolidone, initiated by AIBN at 60°C in benzene [44]. (See also Table 2.)... 

Kondo maintained his interest in this area, and with his collaborators [62] he recently made detailed investigations on the polymerization and preparation of methyl-4-vinylphenyl-sulfonium bis-(methoxycarbonyl) meth-ylide (Scheme 27) as a new kind of stable vinyl monomer containing the sulfonium ylide structure. It was prepared by heating a solution of 4-methylthiostyrene, dimethyl-diazomalonate, and /-butyl catechol in chlorobenzene at 90°C for 10 h in the presence of anhydride cupric sulfate, and Scheme 27 was polymerized by using a, a -azobisi-sobutyronitrile (AIBN) as the initiator and dimethylsulf-oxide as the solvent at 60°C. The structure of the polymer was confirmed by IR and NMR spectra and elemental analysis. In addition, this monomeric ylide was copolymerized with vinyl monomers such as methyl methacrylate (MMA) and styrene. 

Vinylidene Chloride CH2=CC12. Monomer forms unstable peroxides by autooxidation therefore, no oxidg agents or w Air Vap Monomer In Air 7.0 to 16.0% > Ambient > Ambient Inhibitor—Methyl Ether of Hy droquino ne (100 ppm) Transport store under. inert gas in a cool, dry place. No sparks -18.0 570 Self-polymerizing, easily copolymerizes with with Acrylates Styrene. Polymerization catalyzed by light or w... 

Ring-opening polymerization of 2-methylene-l,3-dioxepane (Fig. 6) represents the single example of a free radical polymerization route to PCL (51). Initiation with AIBN at SO C afforded PCL with a of 42,000 in 59% yield. While this monomer is not commercially available, the advantage of this method is that it may be used to obtain otherwise inaccessible copolymers. As an example, copolymerization with vinyl monomers has afforded copolymers of e-caprolactone with styrene, 4-vinylanisole, methyl methacrylate, and vinyl acetate. 

In the copolymerization of isopropenylferrocene with a-methyl-styrene at 0°C, using varying molar ratios of isopropenylferrocene and a-methylstyrene, traces of polymer formation were obtained only at a 30/70 ratio of the two monomers, as shown in the data in Table III. Because a-methylstyrene has a much lower ceiling temperature than styrene, we also decided to use styrene as a comonomer under conditions similar to those employed with a-methylstyrene. The reaction temperature for the copolymerization with a-methylstyrene was 20°C. 

To improve the polymerizability of organotin monomers, a convenient method for the production of trialkylstannyl-1,3-alkadienes has been developed 54 57) and their copolymerization with styrene and methyl methacrylate studied 58 59). 

Homopolymerization of ethyl 4-vinyl-a-cyano-p-phenylcinnamate with AIBN in benzene gave a soluble polymer of inherent viscosity 0.2 djf,/g. There was no evidence for involvement of the tetra-substituted double bond in the polymerization. Copolymerizations with styrene and methyl methacrylate were also successful. 

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