Sulfonate monomers

With as httie as 0.5% hydrolysis of the sulfone monomer, the polymerization stoichiometric balance is sufficientiy upset to prevent high molecular weight polymer from being achieved. The dependence of maximum attainable PSF molecular weight on water content during polymerization can be inferred from Figure 1. 

An additive described as reducing the water loss and enhancing other properties of well-treating fluids in high-temperature subterranean environments consists of polymers or copolymers from N-vinyl lactam monomers or vinyl-containing sulfonate monomers. Organic compounds like lignites, tannins, and asphaltic materials are added as dispersants [175]. 

Polymer from N- Vinyl Lactams and Vinyl Sulfonates. A water-soluble polymer from N-vinyl lactam monomers or vinyl-containing sulfonate monomers... 

In copolymers containing the styrene sulfonate moiety and maleic anhydride units, the maleic anhydride units can be functionalized with alkyl amine [1411-1416]. The water-soluble polymers impart enhanced deflocculation characteristics to the mud. Typically, the deflocculants are relatively low-molecular-weight polymers composed of styrene sodium sulfonate monomer maleic anhydride, as the anhydride and/or the diacid and a zwitterionic functionalized maleic anhydride. Typically the molar ratio of styrene sulfonate units to total maleic anhydride units ranges from 3 1 to 1 1. The level of alkyl amine functionalization of the maleic anhydride units is 75 to 100 mole-percent. The molar concentrations of sulfonate and zwitterionic units are not necessarily equivalent, because the deflocculation properties of these water-soluble polymers can be controlled via changes in their ratio. 

Procedure To a dry Erlenmeyer flask of appropriate size, add one half of the reaction solvent. All reactants, including the dry mass of the hydroperoxide, should not constitute more than 23 weight percent of the reaction mixture or an insoluble product may be produced. Add dry lignin and dry calcium chloride to the reaction vessel and cap with a septum or rubber stopper. In a separate vessel, dissolve 2-propenamide in about one quarter of the DMSO solvent and, in a third vessel, dissolve the sulfonated monomer in the final one quarter of the solvent. Saturate both monomer solutions with by bubbling with the gas for 10 minutes. Saturate the lignin solution with for 10 minutes. Add the hydroperoxide to... 

Brominated Monomer/Oligomer Mixtures from IV (V). The brominated sulfone monomer/oligomer mixtures were preparedby two different methods. Method A A mixture of pyridine (70mL), IV (11.5 mmol), dibromobenzene (26.96g, 115 mmol), anhydrous potassium carbonate (7.94g, 57.5 mmol) and cuprous iodide (0.13g, 0.7 mmol) was heated at reflux under nitrogen for 24h. After cooling to room temperature, the reaction mixture was acidified with IN HC1 and the aqueous solution extracted with ether. The organic phase was reduced in volume to a brown gum which was washed several times with hexane and then dried to give a 75-95% yield of the dibromo product. 

Direct Copoiymerization of Sulfonated Monomers To Afford Random (Statistical) Copolymers 4595... 

Directly copolymerized sulfonated poly(arylene ether ketone) PEMs are also possible by employing a sulfonated dihalide ketone monomer (sodium 5,5 -carbonylbis(2-fluorobenzenesulfonate)), as first reported by Wang. ° The sulfonated monomer chemical structure is shown in Figure 20. 

Direct copolymerization of sulfonated monomers has been used to synthesize sulfonated poly (benzimidazoles), poly(benzoxazole)s, and poly(benzothia-zole)s. As an example, Kim et al. synthesized poly-(benzthiazole)s from 2,5-diamino-1,4-benzenedithiol dihydrochloride and either 2-sulfoterethphthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, or 2,4-disulfoisophthalic acid potassium salt in poly-phosphoric acid (PPA), as shown in Figure 34. Similar sulfonated poly(benzimidazole) and sulfonated poly(benzoxazole) ° structures have also been synthesized. A general synthetic scheme for each is shown in Figure 35. The stability of these polymers in aqueous acidic environments appears... 

Postsulfonation of polymers to form PEMs can lead to undesirable side reactions and may be hard to control on a repeatable basis. Synthesis of sulfonated macromolecules for use in PEMs by the direct reaction of sulfonated comonomers has gained attention as a rigorous method of controlling the chemical structure, acid content, and even molecular weight of these materials. While more challenging synthetically than postsulfonation, the control of the chemical nature of the polymer afforded by direct copolymerization of sulfonated monomers and the repeatability of the reactions allows researchers to gain a more systematic understanding of these materials properties. Sulfonated poly(arylene ether)s, sulfonated poly-(imide)s, and sulfonated poly(styrene) derivatives have been the most prevalent of the directly copolymerized materials. 

Bis(phenoxy) and Bis(phenylthio) Sulfone Monomers Soluble aromatic polyethers were obtained by the oxidative polymerization of 4,4 -bis(phenoxy)diphenyl sulfone, of its substituted derivatives and 4,4 -bis(phenylthio)diphenyl sulfone [Eq. (65)] [210]. The solubility and yield of the polymers was increased by the presence of methyl, tert-butyl, and methoxy group substituents on the phenoxy group of 365 (Fig. 50). 

A modification of the condensation copolymer compounds involves incorporating anionic character into the polymer chain by use of sulfonated monomers. The necessary hydrophilicity is provided by the sulfonated blocks (Fig. 7.8). Like the other polyester condensation polymers, these anionic products can be applied by exhaust or padding. The exhaustion efficiency can be significantly improved by adding small amounts of magnesium chloride to the application bath. 

The sodium salts and the acids of poly-3(2-ethanesul-fonate) thiophene and poly-3-(4-butanesulfonate) thiophene are the first known examples of water soluble CPs many other examples of water-soluble, self-doped CPs are given in recent reviews. Indeed, it is well known that the incorporation of highly soluble sulfonate groups on the CP backbone is a common method of achieving water solubility in a doped CP. The two most popular routes are the use of sulfonated polymeric dopants and the polymerization of sulfonated monomers. 

Typically, carboxylate ionomers are prepared by direct copolymerization of acrylic or methacrylic acid with ethylene, styrene or similar comonomers by free radical copolymerization (65). More recently, a number of copolymerizations involving sulfonated monomers have been described. For example, Weiss et al. (66-69) prepared ionomers by a free-radical, emulsion copolymerization of sodium sulfonated styrene with butadiene or styrene. Similarly, Allen et al. (70) copolymerized n-butyl acrylate with salts of sulfonated styrene. The ionomers prepared by this route, however, were reported to be "blocky" with regard to the incorporation of the sulfonated styrene monomer. Salamone et al. (71-76) prepared ionomers based on the copolymerization of a neutral monomer, such as styrene, methyl methacrylate, or n-butyl acrylate, with a cationic-anionic monomer pair, 3-methacrylamidopropyl-trimethylammonium 2-acrylamlde-2-methylpropane sulfonate. 

The Q-parameter for the sulfonate monomer, which is indicative of its general reactivity13, did not change in the range of pH 7-1.5, but the e-parameter, in which the polar effect of the substituent group on the reactivity of the monomer (as well as that of the radical derived from it) is reflected, increased threefold at the low pH value. This was attributed to suppression of ionization at pH 1.5, causing a shift in the e-parameter towards a more positive value. 

This chapter describes the synthesis, kinetics, and solution properties for copolymers ofN-vinylpyrrolidone (NVP) with sulfonate ionic and zwitterionic monomers. Examples of the sulfonate ionic monomers are sodium styrenesulfonate (NaSS) and sodium acrylamido-2-meth-ylpropanesulfonate (NaAMPS) an example of the zwitterionic sulfonate monomer is 2-hydroxyethyt)dimethyl(3-sulfopropyt)-ammonium inner salt, methacrylate (SPE). The NVP-NaAMPS monomer pair was exceptional, showing evidence for donor-acceptor character and an alternating tendency in copolymerization. The NVP copolymers containing simple sulfonate ionic monomers e.g., NaAMPS) showed polyelectrolyte solution properties. On the other hand, the NVP copolymers with zwitterionic sulfonate monomers showed antipoly electrolyte solution behavior. 

I EW SULFONATE MONOMERS, both the simple ionic [e.g., sodium styrenesulfonate (NaSS) and sodium acrylamido-2-methylpropanesulfonate (NaAMPS) (i)], and zwitterionic [e.g., (2-hydroxyethyl)dimethyl(3-sulfopro-pyl)ammonium, inner salt, methacrylate (SPE) (2)] types, have recently become available. Homopolymers of such simple sulfonate monomers are characterized by good thermal and hydrolytic stability however, their so-... 

Poly(N-vinylpyrrolidone), P(NVP), is a nonionic, water-soluble polymer with high thermal and hydrolytic stability (7-9). Copolymers of N-vinylpyr-rolidone (NVP) with various carboxylate and carboxylate-precursor monomers (e.g., acrylic acid, sodium acrylate, crotonic acid, itaconic acid, and maleic anhydride) are also well-known (10). In addition, the homo- and copolymerization kinetics of these monomers are well-established. On the other hand, reports of copolymerizations of NVP with sulfonate monomers are sparse 11, 12). This chapter describes the synthesis, kinetics, and reactivity ratios for the copolymerization of NVP and some of the newer sulfonate monomers. A comparison of some of the solution properties for such copolymers is also included. 

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