SODIUM ACRYLAMIDE

The reaction with sodium sulfite or bisulfite (5,11) to yield sodium-P-sulfopropionamide [19298-89-6] (C3H7N04S-Na) is very useful since it can be used as a scavenger for acrylamide monomer. The reaction proceeds very rapidly even at room temperature, and the product has low toxicity. Reactions with phosphines and phosphine oxides have been studied (12), and the products are potentially useful because of thek fire retardant properties. Reactions with sulfide and dithiocarbamates proceed readily but have no appHcations (5). However, the reaction with mercaptide ions has been used for analytical purposes (13)). Water reacts with the amide group (5) to form hydrolysis products, and other hydroxy compounds, such as alcohols and phenols, react readily to form ether compounds. Primary aUphatic alcohols are the most reactive and the reactions are compHcated by partial hydrolysis of the amide groups by any water present. 

In a typical adiabatic polymerization, approximately 20 wt % aqueous acrylamide is charged into a stainless steel reactor equipped with agitation, condenser, and cooling jacket or coils. To initiate the polymerization, an aqueous solution of sodium bisulfite [7631-90-5] is added, followed by the addition of a solution of ammonium persulfate [7727-54-0] N2HgS20g. As the polymerization proceeds, the temperature rises to about 90°C, and then begins to fall at the end of the polymerization. The molecular weight obtained depends primarily on the initiator concentration employed. 

Isothermal polymerizations are carried out in thin films so that heat removal is efficient. In a typical isothermal polymerization, aqueous acrylamide is sparged with nitrogen for 1 h at 25°C and EDTA (C2QH2 N20g) is then added to complex the copper inhibitor. Polymerization can then be initiated as above with the ammonium persulfate—sodium bisulfite redox couple. The batch temperature is allowed to rise slowly to 40°C and is then cooled to maintain the temperature at 40°C. The polymerization is complete after several hours, at which time additional sodium bisulfite is added to reduce residual acrylamide. 

Starch is a polysaccharide found in many plant species. Com and potatoes are two common sources of industrial starch. The composition of starch varies somewhat in terms of the amount of branching of the polymer chains (11). Its principal use as a flocculant is in the Bayer process for extracting aluminum from bauxite ore. The digestion of bauxite in sodium hydroxide solution produces a suspension of finely divided iron minerals and siUcates, called red mud, in a highly alkaline Hquor. Starch is used to settle the red mud so that relatively pure alumina can be produced from the clarified Hquor. It has been largely replaced by acryHc acid and acrylamide-based (11,12) polymers, although a number of plants stiH add some starch in addition to synthetic polymers to reduce the level of residual suspended soHds in the Hquor. Starch [9005-25-8] can be modified with various reagents to produce semisynthetic polymers. The principal one of these is cationic starch, which is used as a retention aid in paper production as a component of a dual system (13,14) or a microparticle system (15). 

Reaction conditions depend on the reactants and usually involve acid or base catalysis. Examples of X include sulfate, acid sulfate, alkane- or arenesulfonate, chloride, bromide, hydroxyl, alkoxide, perchlorate, etc. RX can also be an alkyl orthoformate or alkyl carboxylate. The reaction of cycHc alkylating agents, eg, epoxides and a2iridines, with sodium or potassium salts of alkyl hydroperoxides also promotes formation of dialkyl peroxides (44,66). Olefinic alkylating agents include acycHc and cycHc olefinic hydrocarbons, vinyl and isopropenyl ethers, enamines, A[-vinylamides, vinyl sulfonates, divinyl sulfone, and a, P-unsaturated compounds, eg, methyl acrylate, mesityl oxide, acrylamide, and acrylonitrile (44,66). 

Acrylate and acrylamide polymers have several uses in drilling fluids, one of which is for filtration control. Sodium polyacrylates [9003-04-7] having molecular weights near 250,000 are exceUent temperature-stable filtration control agents for both fresh- and salt water muds, provided the concentration of water-soluble calcium is <400 mg/L (83). The calcium ions are precipitated using a carbonate such as soda ash, before adding the polyacrylate at concentrations up to ca 6 kg/m (3 Ib/bbl). 

The simplest monomer, ethylenesulfonic acid, is made by elimination from sodium hydroxyethyl sulfonate and polyphosphoric acid. Ethylenesulfonic acid is readily polymerized alone or can be incorporated as a copolymer using such monomers as acrylamide, aHyl acrylamide, sodium acrylate, acrylonitrile, methylacrylic acid, and vinyl acetate (222). Styrene and isobutene fail to copolymerize with ethylene sulfonic acid. 

Poly(vinyl alcohol) undergoes Michaels addition with compounds containing activated double bonds, including acrylonitrile (145—150), acrylamide (151—153), A/-methylolacrylamide (154—156), methyl vinyl ketone (157,158), acrolein (157), and sodium 2-acrylamido-2-methylpropanesulfonate (159). The reactions have been carried out under conditions spanning from homogeneous reactions in solvent to heterogeneous reactions occurring in the swollen powder or fiber. 

For copolymers of acrylamide with sodium acrylate, the preexponential factor K and exponent a of [tj] = KM depend on copolymer composition (Table 3). 

Table 3 Dependence of Constants K and a of [T7] = KM° on Mole Fraction of Sodium Acrylate (Xsa) for Copolymer Acrylamide with Sodium Acrylate in 0.5 M NaCl at 25°C [9]...

Anionic polyacrylamide was prepared by gamma radiation-initiated copolymerization of acrylamid with sodium acrylate in aqueous solution at optimum conditions for the copolymerization [17]. The copolymerization process produces water-soluble poly (acrylamide-sodium acrylate [pAM-AANa] of high molecular weight [17,54]. 

Poly (acrylamide-sodium aery late-d ia 11 y idiet hy lammonium-... 

In previous works [18-20,23,102] water-soluble polymers such as polyacrylamide (pAM), polysodium acrylate (pAA Na), poly(acrylamide-sodium acrylate) (pAM-AA Na), poly(acrylamide-diallyethylamine-hy-drochloride) (pAM-DAEA-HCl), and poly(acrylamide-sodium acrylate-diallyethylamine-hydrochloride) (pAM-AANa-DAEA-HCl) were used in the recovery of cations and some radioactive isotopes from aqueous solutions. It was found that the floe is formed between the added polymer and ions of the solution in the flocculation process with the formation of a crosslinked structure. The formed cross-linked structure is characterized by [103-105] ... 

T. Siyam, Studies on Gamma Radiation Induced Copolymerization of Acrylamide Sodium Acrylate as Floccu-lant, M. Sc. Thesis, Fac. Sci., Cairo Univ. (1982). 

Cotton linters and viscose grade wood pulp were partially xanthated under different conditions to study the effect of the degree of substitution on the acrylamide grafting of these pulps. Sodium hydroxide solutions of 2%, 4%, and 6% were used and the vapor phase xantha-tion process was applied for 0.5, 1.0, 1.5, and 2.0 h for... 

The base materials include acrylic acid (ethylenecarboxylic acid, propenoic acid, vinylformic acid, CH2 CHCOOH) and its sodium salt, methacrylic acid [2-methylpropenoic acid, CH2 C(CH3)COOH], acrylamide (acrylic amide, propenamide, CH2 CH-CONH2), and methacrylamide. 

Acrylic acid terpolymers have appeared on the market in recent years. With their broad spectrum of functions, they offer the potential for excellent waterside conditions. In particular, the terpolymers have proved to be very effective particulate iron oxides dispersants and colloidal iron stabilizers. Examples include acrylic acid/sulfonic acid/sodium styrene sulfonate (AA/SA/SSS), such as Good-Rite K781, K797, K798. A further example is acrylic acid/ sulfonic acid/substituted acrylamide (AA/SA/NI), such as Acumer 3100. 

Acrylic add/sulfonic acid/sodium styrene sulfonate 447 Acrylic add/sulfonic acid/substituted acrylamide 447... 

AA/SA AA/SA/NI AA/SA/SSS sulfonate (polymer) aciylic acid/sulfonic acid aciylic acid/sulfonic acid/ nonionic (polymer) aciylic acid/sulfonic acid/sodium styrene sulfonate acrylic acid/sulfonic acid/substituted acrylamide (polymer)... 

Carboxymethylcellulose, polyethylene glycol Combination of a cellulose ether with clay Amide-modified carboxyl-containing polysaccharide Sodium aluminate and magnesium oxide Thermally stable hydroxyethylcellulose 30% ammonium or sodium thiosulfate and 20% hydroxyethylcellulose (HEC) Acrylic acid copolymer and oxyalkylene with hydrophobic group Copolymers acrylamide-acrylate and vinyl sulfonate-vinylamide Cationic polygalactomannans and anionic xanthan gum Copolymer from vinyl urethanes and acrylic acid or alkyl acrylates 2-Nitroalkyl ether-modified starch Polymer of glucuronic acid... 

Homopolymers and copolymers from amido-sulfonic acid or salt containing monomers can be prepared by reactive extrusion, preferably in a twin screw extruder [1660]. The process produces a solid polymer. Copolymers of acrylamide, N-vinyl-2-pyrrolidone, and sodium-2-acrylamido-2-methyl-propane sulfonate have been proposed to be active as fluid loss agents. Another component of the formulations is the sodium salt of naphthalene formaldehyde sulfonate [207]. The fluid loss additive is mixed with hydraulic cements in suitable amounts. 

A fluid loss additive for hard brine environments has been developed [1685], which consists of hydrocarbon, an anionic surfactant, an alcohol, a sulfonated asphalt, a biopolymer, and optionally an organophilic clay, a copolymer of N-vinyl-2-pyrrolidone and sodium-2-acrylamido-2-methylpropane sulfonate. Methylene-bis-acrylamide can be used as a crosslinker [1398]. Crosslinking imparts thermal stability and resistance to alkaline hydrolysis. 

The nonionic monomer can be acrylamide, N,N-dimethylacrylamide, N-vinyl-2-pyrrolidone, N-vinyl acetamide, or dimethylamino ethyl methacrylate. Ionic monomers are AMPS, sodium vinyl sulfonate, and vinylbenzene sulfonate. The terpolymer should have a molecular weight between 200,000 to 1,000,000 Dalton. 

A fluid loss additive useful in cementing oil and gas wells is a blend [423,424,1015] of a copolymer of acrylamide/vinyl imidazole. The second component in the blend is a copolymer of vinylpyrrolidone and the sodium salt of vinyl sulfonate. Details are given in Table 2-2. The copolymers are mixed together in the range of 20 80 to 80 20. Sodium or potassium salts or a sulfonated naphthalene formaldehyde condensate can be used as a dispersant. 

An N-vinylpyrrolidone/acrylamide random copolymer (0.05% to 5.0% by weight) is used for cementing compositions [371, 1076]. Furthermore, a sulfonate-containing cement dispersant is necessary. The additive can be used in wells with a bottom-hole temperature of 80° to 300° F. The fluid loss additive mixture is especially effective at low temperatures, for example, below 100° F and in sodium silicate-extended slurries. 

Ethoxylated methylcarboxylates Propoxyethoxy glyceryl sulfonate Alkylpropoxyethoxy sulfate as surfactant, xanthan, and a copolymer of acrylamide and sodium 2-acrylamido-2-methylpropane sulfonate Carboxymethylated ethoxylated surfactants (CME) Polyethylene oxide (PEG) as a sacrificial adsorbate Polyethylene glycols, propoxylated/ethoxylated alkyl sulfates Mixtures of sulfonates and nonionic alcohols Combination of lignosulfonates and fatty amines Alkyl xylene sulfonates, polyethoxylated alkyl phenols, octaethylene glycol mono n-decyl ether, and tetradecyl trimethyl ammonium chloride Anionic sodium dodecyl sulfate (SDS), cationic tetradecyl trimethyl ammonium chloride (TTAC), nonionic pentadecylethoxylated nonylphenol (NP-15), and nonionic octaethylene glycol N-dodecyl ether Dimethylalkylamine oxides as cosurfactants and viscosifiers (N-Dodecyl)trimethylammonium bromide Petrochemical sulfonate and propane sulfonate of an ethoxylated alcohol or phenol Petrochemical sulfonate and a-olefin sulfonate... 

Associative copolymers of acrylamide with N-alkylacrylamides, terpoly-mers of acrylamide, N-decylacrylamide, and sodium-2-acrylamido-2-methyl-propane sulfonate (NaAMPS), sodium acrylate (NaA), or sodium-3-acrylamido-3-methylbutanoate (NaAMB) have been shown to possess the required rheologic behavior to be suitable for enhanced oil-recovery processes [1184]. 

The addition of hydrogenated castor oil to a copolymer of acrylamide and sodium acrylate formulation will suspend the copolymer and retard the settling process [1657]. 

Many synthetic water-soluble polymers are easily analyzed by GPC. These include polyacrylamide,130 sodium poly(styrenesulfonate),131 and poly (2-vinyl pyridine).132 An important issue in aqueous GPC of synthetic polymers is the effect of solvent conditions on hydrodynamic volume and therefore retention. Ion inclusion and ion exclusion effects may also be important. In one interesting case, samples of polyacrylamide in which the amide side chain was partially hydrolyzed to generate a random copolymer of acrylic acid and acrylamide exhibited pH-dependent GPC fractionation.130 At a pH so low that the side chain would be expected to be protonated, hydrolyzed samples eluted later than untreated samples, perhaps suggesting intramolecular hydrogen bonding. At neutral pH, the hydrolyzed samples eluted earlier than untreated samples, an effect that was ascribed to enlargement... 

Figure 6 The stress-strain behavior predicted by Eq. (16) is observed for /V-isopropyl acrylamide-co-sodium acrylate gel.

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