Methyl acrylate, copolymerization with styrene

Copolymerization of Styrene with Methyl Acrylate (Internal Plasticization)... 

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. 

Acrylonitrile resembles VC, a carcinogen, in structure. It is a flammable, explosive liquid (b.p. 77 C, V.P. 80 mm at 20°C). AN is a component of acrylic and modacrylic fibers produced by copolymerization with other monomers, e.g., with methyl acrylate, Me-methacrylate, vinyl acetate, VC and VDC. Other major uses of AN include copolymerizations with butadiene and styrene to produce ABS polymers, and with styrene to yield SAN resins which are used in the manufacture of plastics. Nitrile elastomers and latexes are also made with AN, as are a number of other chemicals, e.g. acrylamide and adiponitrile. Acrylonitrile is also used as a fumigant. 

The problem of the computation accuracy of these kinetic parameters is dependent first of all on the validity of the copolymer composition determination. As a criterion here one may use the closeness to each other of the values of this composition obtained via the different experimental methods. It is possible to judge about the degree of such a closeness using Tables 6.1 and 6.2 where the data on both chemical analysis and spectroscopy are presented. One can see that, as for the considered cases, the different experimental methods provide quite close values of the copolymer compositions within the accuracy in the range of 5%. Authentic evidence concerning the feasibility to reach such a degree of accuracy is furnished by the data on copolymer composition obtained via independent methods in the different systems, for instance, under the copolymerization of p-chlorstyrene with methyl acrylate [32], of 4-methylstyrene with methyl methacrylate or acrylonitrile [213], and also of styrene with acrylic or methacrylic acids [214],... 

Table 6.3 Summary of reactivity ratios determined by various methods for the bulk copolymerization of styrene with methyl a-hydroxymethyl acrylate at T = 80 °C [226]...

Ferrocenyl acrylate (FMA) and 2-ferrocenylethyl acrylate (FEA) were synthesized and copolymerized with styrene (STY), methyl acrylate (MA), and vinyl acetate (VA) [C. U. Pittman, Jr., Macromolecules, 4, 298 (1971)]. The following monomer reactivity ratios were obtained ... 

Using primarily potentiometric and conductometric titration, several investigators also reported variations in the distribution of the carboxylic acid monomer within the AST emulsion particles. Guziak and Maclay (14) showed that carboxylic acid monomers tended to concentrate near the particle surface of the styrene-acrylic and styrene-butadiene latices studied. Acrylic acid had a greater tendency for surface concentration than did methacrylic acid. Treatment of the latices containing greater than about 20% carboxylic acid monomer with inorganic base produced clear aqueous solutions that were extremely viscous. In an electrophoretic study, Matsumoto and Shimada (16) also found a preferential concentration of acrylic acid near the surface of latices. In contrast, methacrylic acid diffused readily into the particles, where it copolymerized favorably with methyl methacrylate. 

Figure 3.1 Relationship between monomer composition (vlMA corresponding instantaneous polymer composition for various monomers copolymerized with MMA. (5 = styrene, MA = methyl acrylate,...

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. 

Nomura et al. [74,75] proposed an experimental method to study the competitive particle nucleation mechanisms (micellar nucleation versus homogeneous nucleation) in a given emulsion polymerization system. This approach involves the emulsion copolymerization of relatively hydrophobic styrene with relatively hydrophilic monomers such as methyl methacrylate or methyl acrylate. The composition of copolymer produced during the very early stage of polymerization (far lower than 1% monomer conversion), which reflects the characteristic of copolymer at the locus of particle nucleation, is then determined. Emulsion copolymerization of styrene with methyl methacrylate (or methyl acrylate) was carried out, where sodium dodecyl sulfate was used to stabilize the emulsion polymerization system and where the weight ratio of styrene to methyl methacrylate (or methyl acrylate) was kept constant at 1 1. The experimental results show that the compositions of copolymers obtained from emulsion polymerizations in the presence and absence of monomer-swollen micelles are quite different. This provides supporting evidence of the generally accepted Smith-Ewart theory that micellar nucleation controls the particle nucleation process in the emulsion copolymerization of styrene with... 

Suspension Copolymerization of Acrylonitrile with Methyl Acrylate and with Styrene... 

An equimolar mixture of methyl acrylate and styrene is copolymerized. It is found that polymer radicals based on methyl acrylate add methyl acrylate monomer at a rate that is only 18% of the rate at which they add styrene. Polymer radicals based on styrene add methyl acrylate at a rate that is 133% of the rate at which they react with styrene. For what feed composition will a copolymer be produced that is uniform in composition (does not change with conversion) ... 

Copolymerization can be carried out with styrene, acetonitrile, vinyl chloride, methyl acrylate, vinylpyridines, 2-vinylfurans, and so forth. The addition of 2-substituted thiazoles to different dienes or mixtures of dienes with other vinyl compounds often increases the rate of polymeriza tion and improves the tensile strength and the rate of cure of the final polymers. This allows vulcanization at lower temperature, or with reduced amounts of accelerators and vulcanizing agents. 

Fig. 2. Relationship between relative rate and monomer composition in the copolymerization of DAP with vinyl monomers A, styrene or methyl methacrylate B, methyl acrylate or acrylonitrile C, vinyl chloride D, vinyl acetate, and E, ethylene (41).

Graft copolymerization of acrylonitrile with various vinyl comonomers such as methyl acrylate, ethyl acrylate, vinyl acetate, and styrene onto cellulose derivatives using ceric ion was studied [24]. The results showed that... 

---