Acrylic acid solution polymerization

Scott, R. A., Peppas, N. A. (1997). Kinetic study of acrylic acid solution polymerization. 

Polymerization of a monomer in a solvent overcomes many of the disadvantages of the bulk process. The solvent acts as diluent and aids in the transfer of the heat of polymerization. The solvent also allows easier stirring, since the viscosity of the reaction mixture is decreased. Thermal control is much easier in solution polymerization compared to bulk polymerization. On the other hand, the presence of solvent may present new difficulties. Unless the solvent is chosen with appropriate consideration, chain transfer to solvent can become a problem. Further, the purity of the polymer may be affected if there are difficulties in removal of the solvent. Vinyl acetate, acrylonitrile, and esters of acrylic acid are polymerized in solution. 

Under the extreme conditions employed by Saegusa acrylic acid will polymerize in the presence of pyridine. However, nitroethylene is the least reactive of the olefins so far polymerized by this amine in solution at room temperature. 

Fibrils of polyaniline were prepared by the polymerization of aniline in a gel of poly(acrylic acid) using FeCl3 as oxidant [81]. Fibrils with a diameter of approximately 50 nm and 1-5 fim long were observed by scanning electron micrography. Colloidal suspensions of the fibrils in the poly(acrylic acid) solutions could be also obtained by this method. The colloidal suspension shows optical spectrum changes with a pH similar to pure polyaniline. 

Another type of initiation of acrylic acid polymerization is the initiation by redox systems. Some redox systems investigated for the polymerization of acrylic and methacrylic acid are listed in Table 11. W. Kem obtained poly(acrylic add) on the cathode during electrolysis of an aqueous acrylic acid solution with KCN or BaCl2. Active initiator is the freshly generated hydrogen. The electrode material can be platinum, lead, iron, or mercury [508]. 

A more recent development is template polymerization [520 522]. When acrylic acid was polymerized in aqueous solution using potassium persulfate as initiator, the polymerization proceeded very slowly. In the presence of poly(vinylpyrrolidone) but under otherwise identical reaction conditions, the rate of polymerization increased dramatically, depending on the amount of PVP. At nearly equimolar concentrations of PVP and monomer, the rate of polymerization reaches a maximum value, because of the strong interaction between poly(vinylpyrrolidone) and acrylic acid in aqueous solution (Scheme 40) [523]. 

Procedure 2-14 is an example of the polymerization of methacrylic acid initiated by ammonium persulfate in a single batch operation, while Procedure 2-15 makes use of the gradual monomer addition technique. This latter approach potentially permits the preparation of poly(meth-acrylic acid) solutions of concentration levels greater than the usual 20-25% level. 

Finally the development of the shear viscosity diulng polymerization is calculated by (20.39), representing the result of the rheokinetics (compare Fig. 20.18 left) with an addend, that considers the temperature dependency of the viscosity of the aqueous acrylic acid solution. Equations (20.37) and (20.38) can also be calculated by the Runge-Kutta method, whereby (20.41) is calculated separately and with the resulting conversion of (20.39). 

Poly(acrylic acid) and Poly(methacrylic acid). Poly(acryHc acid) (8) (PAA) may be prepared by polymerization of the monomer with conventional free-radical initiators using the monomer either undiluted (36) (with cross-linker for superadsorber appHcations) or in aqueous solution. Photochemical polymerization (sensitized by benzoin) of methyl acrylate in ethanol solution at —78° C provides a syndiotactic form (37) that can be hydrolyzed to syndiotactic PAA. From academic studies, alkaline hydrolysis of the methyl ester requires a lower time than acid hydrolysis of the polymeric ester, and can lead to oxidative degradation of the polymer (38). Po1y(meth acrylic acid) (PMAA) (9) is prepared only by the direct polymerization of the acid monomer it is not readily obtained by the hydrolysis of methyl methacrylate. 

The amide group is readily hydrolyzed to acrylic acid, and this reaction is kinetically faster in base than in acid solutions (5,32,33). However, hydrolysis of N-alkyl derivatives proceeds at slower rates. The presence of an electron-with-drawing group on nitrogen not only facilitates hydrolysis but also affects the polymerization behavior of these derivatives (34,35). With concentrated sulfuric acid, acrylamide forms acrylamide sulfate salt, the intermediate of the former sulfuric acid process for producing acrylamide commercially. Further reaction of the salt with alcohols produces acrylate esters (5). In strongly alkaline anhydrous solutions a potassium salt can be formed by reaction with potassium / /-butoxide in tert-huty alcohol at room temperature (36). 

The furfuryl esters of acrylic and methacrylic acid polymerize via a free-radical mechanism without apparent retardation problems arising from the presence of the furan ring. Early reports on these systems described hard insoluble polymers formed in bulk polymerizations and the cross-linking ability of as little as 2% of furfuryl acrylate in the solution polymerization of methylacrylate121. ... 

The most common poly(alkenoic acid) used in polyalkenoate, ionomer or polycarboxylate cements is poly(acrylic acid), PAA. In addition, copolymers of acrylic acid with other alkenoic acids - maleic and itaconic and 3-butene 1,2,3-tricarboxylic acid - may be employed (Crisp Wilson, 1974c, 1977 Crisp et al, 1980). These polyacids are prepared by free-radical polymerization in aqueous solution using ammonium persulphate as the initiator and propan-2-ol (isopropyl alcohol) as the chain transfer agent (Smith, 1969). The concentration of poly(alkenoic add) is kept below 25 % to avoid the danger of explosion. After polymerization the solution is concentrated to 40-50 % for use. 

Monofunctional and difunctional xanthates, shown in Scheme 30, were employed as chain transfer agents in the synthesis of block and triblock copolymers of acrylic acid, AA and acrylamide, AAm PAA-fr-PAAm, PAAm-fr-PAA-fo-PAAm and P(AA-sfaf-AAm)-fr-PAAm [81]. The polymerizations were conducted in aqueous solutions at 70 °C with 4,4 -azobis(4-cyanopentanoic acid) as the initiator. The yields were almost quantitative,... 

Figure 1. Conversion curves of the polymerization of acrylic acid in toluene solutions (4). Monomer concentrations (volume per cent) (1) 100% (2) 95% (3) 90% (4) 85% (5) 80% (6) 65% (7) 50% (8) 27%. The polymer precipitates as a fine powder at all concentrations. Initiation by gamma-rays at 20°C and...

Abstract. Auto-accelerated polymerization is known to occur in viscous reaction media ("gel-effect") and also when the polymer precipitates as it forms. It is generally assumed that the cause of auto-acceleration is the arising of non-steady-state kinetics created by a diffusion controlled termination step. Recent work has shown that the polymerization of acrylic acid in bulk and in solution proceeds under steady or auto-accelered conditions irrespective of the precipitation of the polymer. On the other hand, a close correlation is established between auto-acceleration and the type of H-bonded molecular association involving acrylic acid in the system. On the basis of numerous data it is concluded that auto-acceleration is determined by the formation of an oriented monomer-polymer association complex which favors an ultra-fast propagation process. Similar conclusions are derived for the polymerization of methacrylic acid and acrylonitrile based on studies of polymerization kinetics in bulk and in solution and on evidence of molecular associations. In the case of acrylonitrile a dipole-dipole complex involving the nitrile groups is assumed to be responsible for the observed auto-acceleration. 

Note Acrylamide may contain the following impurities acetamide, acrylic acid, acrylonitrile, copper, formaldehyde, hydroquinone, methylacrylamide, hydroquinone monomethyl ether, peroxide, propanamide, and sulfate. When acrylamide is produced using a copper catalyt, copper salts may be added to aqueous solutions at concentrations >2 ppm (NICNAS, 2002). Commercial solutions 30-50%) are usually inhibited with copper salts to prevent polymerization. In addition, solutions containing oxygen will prevent polymerization. 

Carboxylated polymers can be prepared by mechanical treatment of frozen polymer solutions in acrylic acid (Heinicke 1984). The reaction mechanism is based on the initiation of polymerization of the frozen monomer by free macroradicals formed during mechanolysis of the starting polymer. Depending on the type of polymer, mixed, grafted, and block polymers with a linear or spatial structure are obtained. What is important is that the solid-phase reaction runs with a relatively high rate. For instance, in the polyamide reactive system with acrylic acid, the tribochemical reaction leading to the copolymer is completed after a treatment time of 60 s. As a rule, the mechanical activation of polymers is mainly carried out in a dry state, because the structural imperfections appear most likely here. 

Monomer and initiator must be soluble in the liquid and the solvent must have the desired chain-transfer characteristics, boiling point (above the temperature necessary to carry out the polymerization and low enough to allow for ready removal if the polymer is recovered by solvent evaporation). The presence of the solvent assists in heat removal and control (as it also does for suspension and emulsion polymerization systems). Polymer yield per reaction volume is lower than for bulk reactions. Also, solvent recovery and removal (from the polymer) is necessary. Many free radical and ionic polymerizations are carried out utilizing solution polymerization including water-soluble polymers prepared in aqueous solution (namely poly(acrylic acid), polyacrylamide, and poly(A-vinylpyrrolidinone). Polystyrene, poly(methyl methacrylate), poly(vinyl chloride), and polybutadiene are prepared from organic solution polymerizations. 

The heat of an emulsion polymerization is the same as that for the corresponding bulk or solution polymerization, since AH is essentially the enthalpy change of the propagation step. Thus, the heats of emulsion polymerization for acrylic acid, methyl acrylate, and methyl methacrylate are —67, —77, and —58 kJ mol-1, respectively [McCurdy and Laidler, 1964], in excellent agreement with the AH values for the corresponding homogeneous polymerizations (Table 3-14). 

These superabsorbents are synthesized via free radical polymerization of acrylic acid or its salts in presence of a crosslinker (crosslinking copolymerization). Initiators are commonly used, water-soluble compounds (e.g., peroxodi-sulfates, redox systems). As crosslinking comonomers bis-methacrylates or N,hT-methylenebis-(acrylamide) are mostly applied. The copolymerization can be carried out in aqueous solution (see Example 5-11 or as dispersion of aqueous drops in a hydrocarbon (inverse emulsion polymerization, see Sect. 2.2.4.2). 

A very interesting phenomenon was observed when a small amount of methanol was added to the solution of acrylic acid in n-hexane. In such system, the auto-accelera-tion of the polymerization is very high. It was suggested that the complex (acrylic acid)2 MeOH is formed. This complex associates very rapidly with the polymer formed at the early stages of the reaction to produce a structure in which ultrafast propagation occurs. 

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