SODIUM ACRYLAMIDE SULFONATE

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. 

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)... 

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. 

General. Aqueous solutions of hydrophilic monomers were emulsified in xylene using water-in-oil emulsifiers, and polymerized using oil-soluble initiators. Typical hydrophilic monomers were sodium p-vinylbenzene sulfonate, sodium vinylbenzyl sulfonate, 2-sulfoethyl acrylate, acrylic acid, acrylamide, vinylbenzyl-trimethylammonium chloride, and 2-aminoethyl methacrylate hydrochloride. Typical oil-soluble initiators were benzoyl and lauroyl peroxides. In some cases, water-soluble potassium persulfate was used, both separately and in mixtures with oil-soluble peroxides. Of the water-in-oil emulsifiers, one of the most effective was Span 60 (technical sorbitan monostearate. Atlas Chemical Industries, Inc.). 

Emulsion polymerization typically refers to the polymerization of a nonaqueous material in water. The polymerization of a water-soluble material in a nonaqueous continuum has been called inverse emulsion polymerization. The inverse emulsion polymerization technique is used to synthesize a wide range of polymers for a variety of applications such as wall paper adhesive, waste water fiocculant, additives for oil recovery fluids, and retention aids. The emulsion polymerization technique involves water-soluble polymer, usually in aqueous solution, emulsified in continuous oil phase using water in oil emulsifier. The inverse emulsion is polymerized using an oil- or water-soluble initiator. The product is a colloidal dispersion of sub-microscopic particles with particle size ranging from 0.05 to 0.3 pm. The typical water-soluble monomers used are sodium p-vinyl benzene sulfonate, sodium vinyl sulfonate, 2-sulfo ethyl acrylate, acrylic acid, and acrylamide. The preferred emulsifiers are Sorbitan monostearate and the oil phase is xylene. The proposed kinetics involve initiation in polymer swollen micelles, which results in the production of high molecular weight colloidal dispersion of water-swollen polymer particles in oil. 

Fig 1. Viscosity ratio, with/without added salt as a function of added salt. 0 is a copolymer of acrylamide and sodium styrene sulfonate (5%), a polyelectrolyte control. H is a copolymer of acrylamide and SPE, a zwitterionic polymer. is a copolymer of acrylamide and. Cg-alkyl acryl unide, a hydrophobe containing polymer. Q is a terpolymer of acylamide, Cs-alkyl acylamide and SPE, a polymer containing both hydrophobic and zwitterionic groups. 

See Styrene/butadiene polymer Ethenylbenzene, polymer with 2-propenamide. See Styrene/acrylamide copolymer Ethenylbenzenesulfonic acid, sodium salt, homopolymer 4-Ethenylbenzenesulfonic acid sodium salt, homopolymer. See Sodium polystyrene sulfonate 4-Ethenylcyclohexene 4-EthenyM -cyclohexene. See 4-Vinylcyclohexene Ethenyidimethoxymethylsilane. See Vinylmethyidimethoxysilane 1 -Ethenyl-1,5-dimethyl-4-hexenyl benzeneacetate. See Linalyl phenylacetate 1 -Ethenyl-1,5-dimethyl-4-hexenyl 3-phenyl-2-propenoate. See Linalyl cinnamate Ethenyl ethanoate. See Vinyl acetate 6-Ethenyl-6-(methoxyethoxy)-2,5,7,10-tetraoxa-6-silaundecane. SeeVinyltris(2-methoxyethoxy) silane... 

Propanesulfonic acid-3-hydroxy-y-sultone. See 1,3-Propane sultone 1-Propanesulfonic acid, 3-mercapto-, monosodium salt. See Sodium mercaptopropane sulfonate 1-Propanesulfonic acid, 2-methyl-2-[(1-oxo-2-orpoenyl) amino]-, monosodium salt, polymer with N,N-dimethyl-N-2-propenyl-2-propen-1-aminium chloride and 2-proepnamide. See Poly (acrylamide-[2-acrylamide-2-methylpropylsulfonate]-dimethyldiallyl ammonium chloride) sodium salt 1-Propanesulfonic acid, 3-(2-propynyloxy)-, sodium salt. See Sodium 3-(2-propynyloxy)-1-propanesulfonate... 

Texin DP7-3006, Texin DP7-3008. See Polyurethane, thermoplastic Texin OSS 50. See Sodium oleic sulfonate Texipol 63-001, Texipol 63-002, Texipol 63-514 Texipol 67-5024, Texipol 67-5026, Texipol 67-5028. See Acrylamides copolymer Texlin 300. See Triethylenetetramine Texlin 400. See Tetraethylenepentamine Texlin 500. See Polyethylenepolyamine Texofor A1P. See Ceteth-20 Tex Sil 42BP. See Sodium silicate TexsolveB. See Hexane TexsolveC. See Heptane Texsoive S Texsolve S-66 Texsolve S-LO. See Mineral spirits... 

Sodium DVB/acrylates copolymer Sodium hyaluronate Sodium polyacrylate starch Sodium polymethacrylate Sodium polystyrene sulfonate Sodium PVM/MA/decadiene crosspolymer Sodium styrene/acrylates copolymer Sodium tauride acrylates/acrylic acid/acrylonitrogens copolymer Soluble collagen Starch/acrylates/acrylamide copolymer Starch diethylaminoethyl ether Steareth-10 allyl ether/acrylates copolymer Stearylvinyl ether/MA copolymer ... 

Sodium polyacrylate-acrylamide resin scale control agent, soil removal Acrylic acid/sulfonic acid/sodium styrene sulfonate terpolymer sodium salt scale control agent, water treatment Acrylic acid/sulfonic acid/sodium styrene sulfonate terpolymer sodium salt scale inhibitor... 

Probably the most important factor for the future of NMP will be the development of new compounds that allow polymerization and copolymerization of a broader range of monomers under milder reaction conditions we should however note that nitroxide mediated polymerization has already been applied to styrene [92], acrylates [93], acrylamides [94], acrylonitrile [67], dienes [95], and recently polymerization of ethylene has been claimed to be controlled [96,97]. NMP has also been extended to functional monomers such as sodium styrene sulfonate [98], 2-vinylpyridine [99,100], 3-vinyl pyridine [101,102], and 4-vinylpyridine [103]. However, since a nitroxide residue ends up at the end of each chain, these new compounds should be inexpensive, and introduce no adverse properties (color, poor thermal stability, etc.) to the final material. 

PVOH miscibility has been noted with poly(N, N-dimethyl acrylamide) [962] and partial miscibility noted with methyl cellulose [963]. With poly(N, N-dimethyl acrylamide), vinyl alcohol-vinyl acetate copolymers are miscible above 12 mole% vinyl alcohol. Fully hydrolyzed PVOH is not miscible with poly(2-ethyl oxazoline)(PEOx), but ethylene-vinyl alcohol copolymers (68 and 78 mole% vinyl alcohol) are miscible with PEOx [964]. Vinyl acetate-vinyl alcohol copolymers were shown to be miscible with PEOx over a wide range of copolymer compositions [965]. The immiscibility of fully hydrolyzed PVOH was attributed to the hydroxyl self-association dominating the competing hydroxyl-amide association. PVOH blends with sodium polystyrene sulfonate gave flexible, transparent films with good electrical conductivity [966]. Phase separation of PVOH/PEO [967] and PVOH/hydroxypropylmethyl cellulose blends [968] has been reported. PVOH/polyethyleneimine blends have been studied for membrane separations involving isomer separation [969]. PVOH/poly(ethyl oxazoline) blends have noted in a series of patent applications related to proton-conducting membranes [970]. 

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). 

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. 

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]. 

Acrylamide copolymers designed to reduce undesired amide group hydrolysis, increase thermal stability, and improve solubility in saline media have been synthesized and studied for EOR applications. These polymers still tend to be shear sensitive. Acrylamide comonomers that have been used include 2-acrylamido-2-methylpropane sulfonate, abbreviated AMPS, (1,321-324), 2-sulfo-ethylmethacrylate (325,326), diacetone acrylamide (324, 326), and vinylpyrrolidinone (327,328). Acrylamide terpolymers include those with sodium acrylate and acrylamido-N-dodecyl-N-butyl sulfonate (329), with AMPS and N,N-dimethylacrylamide (330), with AMPS and N-vinylpyrrolidinone (331), and with sodium acrylate and sodium methacrylate (332). While most copolymers tested have been random copolymers, block copolymers of acrylamide and AMPS also have utility in this application (333). 

Most polymers used in oil field operations and resource recovery are synthetic. The man-made materials in common use are polyO-amidoethylene) ( = polyacrylamide ), poly( 1-amidoethylene-r-( sodium 1-carboxylatoethylene ) ( = partially hydrolyzed polyacrylamide ), poly(l-amidoethylene-r-( sodium 1-(2-methylprop-1N-yl-1-sulfonate)amidoethylene) (AMPS-acrylamide copolymer), and xanthan gum. Xanthan gum is a synthetic because no one finds a pool or river contaminated with Xanthomonas compestris that experiences the right sequence of solute to naturally produce the exocellular gum polymer. A fermenter is a man made object, a tree is not. 

The first type is a standard polysoap derived from a polymerizable surfactant leading to poly(sodium 11-acryloyloxyundecane-l-sulfonate) PSl whereas the second polysoap is an alternating copolymer of maleic acid anhydride and acrylamide leading to a polymer with carboxylic acid groups and hydrophobic n-alkylamide groups PS2 (see Fig. 6.9). The organometaUic catalyst was not covalently bound to the polysoaps in the catalytic experiments. 

Tumoko and coworkers [485] showed that polymers based on acrylamide, methyl propane sulfonic acid and butyl methacrylate in conjunction with poly(2 methacryloyloxyethyl phosphorylcholine-co-butyl methacrylate) are capable of suppressing platelet adherence. Similar results [486] were found on poly(gamma benzyl 1 glutamate-co-leucine) neutralized with sodium. 

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