Poly partially hydrolyzed

Pyrotechnic mixtures may also contain additional components that are added to modify the bum rate, enhance the pyrotechnic effect, or serve as a binder to maintain the homogeneity of the blended mixture and provide mechanical strength when the composition is pressed or consoHdated into a tube or other container. These additional components may also function as oxidizers or fuels in the composition, and it can be anticipated that the heat output, bum rate, and ignition sensitivity may all be affected by the addition of another component to a pyrotechnic composition. An example of an additional component is the use of a catalyst, such as iron oxide, to enhance the decomposition rate of ammonium perchlorate. Diatomaceous earth or coarse sawdust may be used to slow up the bum rate of a composition, or magnesium carbonate (an acid neutralizer) may be added to help stabilize mixtures that contain an acid-sensitive component such as potassium chlorate. Binders include such materials as dextrin (partially hydrolyzed starch), various gums, and assorted polymers such as poly(vinyl alcohol), epoxies, and polyesters. Polybutadiene mbber binders are widely used as fuels and binders in the soHd propellant industry. The production of colored flames is enhanced by the presence of chlorine atoms in the pyrotechnic flame, so chlorine donors such as poly(vinyl chloride) or chlorinated mbber are often added to color-producing compositions, where they also serve as fuels. 

Solubility. Poly(vinyl alcohol) is only soluble in highly polar solvents, such as water, dimethyl sulfoxide, acetamide, glycols, and dimethylformamide. The solubiUty in water is a function of degree of polymerization (DP) and hydrolysis (Fig. 4). Fully hydrolyzed poly(vinyl alcohol) is only completely soluble in hot to boiling water. However, once in solution, it remains soluble even at room temperature. Partially hydrolyzed grades are soluble at room temperature, although grades with a hydrolysis of 70—80% are only soluble at water temperatures of 10—40°C. Above 40°C, the solution first becomes cloudy (cloud point), followed by precipitation of poly(vinyl alcohol). 

The hydroxyl groups in poly(vinyl alcohol) contribute to strong hydrogen bonding both intra- and intermolecularly, which reduces solubiUty in water. The presence of the residual acetate groups in partially hydrolyzed poly(vinyl alcohol) weakens these hydrogen bonds and allow solubiUty at lower temperatures. 

Adhesives. Poly(vinyl alcohol) is used as a component in a wide variety of general-purpose adhesives to bond ceUulosic materials, such as paper and paperboard, wood textiles, some metal foils, and porous ceramic surfaces, to each other. It is also an effective binder for pigments and other finely divided powders. Both fully and partially hydrolyzed grades are used. Sensitivity to water increases with decreasing degree of hydrolysis and the addition of plasticizer. Poly(vinyl alcohol) in many appHcations is employed as an additive to other polymer systems to improve the cohesive strength, film flexibiUty, moisture resistance, and other properties. It is incorporated into a wide variety of adhesives through its use as a protective coUoid in emulsion p olymerization. 

Partially hydrolyzed poly(vinyl alcohol) grades are preferred because they have a hydrophobic /hydrophilic balance that make them uniquely suited for emulsion polymerization. The compatibUity of the residual acetate units with the poly(vinyl acetate) latex particles partly explains the observed stabilization effect. The amount of PVA employed is normally 4—10% on the weight of vinyl acetate monomer. The viscosity of the resulting latex increases with increasing molecular weight and decreasing hydrolysis of the PVA (318). 

Poly(vinyl alcohol) is used as an additive to dry-wall joint cements and stucco finish compounds. Rapid cold-water solubiUty, which can be achieved with finely ground PVA, is important in many dry mixed products. Partially hydrolyzed grades are commercially available in fine-particle size under the name S-grades. The main purpose of the poly(vinyl alcohol) is to improve adhesion and act as a water-retention aid. 

Partially hydrolyzed grades are used in many cosmetic appHcations for their emulsifying, thickening, and film-forming properties. Poly(vinyl alcohol) is also used as a viscosity builder for aqueous solutions and dispersions. 

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... 

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. 

Poly(starch-g-(l-amidoethylene)) copolymer is not a polyelectrolyte and will be a smaller molecule in water than an equal molecular weight, partially hydrolyzed poly(l-amidoethylene). Polyelectrolyte effect should, however, cause the graft copolymer to expand in solution in the same way it causes poly(l -amidoethylene) to expand, so a series of hydrolyzed graft copolymers were prepared from poly(starch-g-(l-amidoethylene))(41-43) and these derivatives were tested to determine the effect of hydrolysis on copolymer properties in solution. 

Electrolyte Effect on Polymer Solution Rheology. As salt concentration in an aqueous poly(1-amidoethylene) solution increases, the resulting brine becomes a more Theta-solvent for the polymer and the polymer coil compresses(47) This effect is particularly pronounced for partially hydrolyzed poly(l-amidoethylene). The... 

Poly(starch-g-(1-amidoethylene)) copolymers can be formed by ceric-ion- initiated, free-radical polymerization of 2-propenamide on starch. Poly(starch- g-[partially hydrolyzed 1-amidoethylene]) can be formed by treatment of an aqueous solution of the copolymer with 0.5 M sodium hydroxide at 40UC under anaerobic conditions. Treatment of the copolymer under these conditions for 10 minutes produces a hydrolyzed copolymer with a degree of hydrolysis between 9 5 and 14 5 percent. 

Complexes with Iodine. One of the simplest "reactions" of poly(vinyl alcohol) is the formation of a blue complex with iodine. This complex formation, which requires the presence of KI, has been studied extensively by many workers (26-31). This complex also forms with partially hydrolyzed poly(vinyl acetates) (26) and is known to be affected by the 1,2-glycol content and the isotacticity of the polymer both of which tend to reduce complex formation (31). The complex also depends on the molecular weight of the poly(vinyl alcohol) and the iodine concentration. 

Starch (1), Cellulose (2), Cellulose Methyl Ether (3), Oxy-cellulose (4), PVA (5), Partially Hydrolyzed PVAc (6), Silk (.2), Wool (7), Hide-Powder (8), Natural Rubber Latex ( ), Synthesized Poly-(ot-Amino Acids) (10), Nylon-6 (11), Nylon-3 (12), Ot-Amylase (13), Lysozyme (14), RNA (15), Polyacrylonitrile (16), Polyvinyl-sulfonate (17) ... 

A partially hydrolyzed head-to-tail poly(vinyl acetate) ... 

Poly(acrylic acid) and partially hydrolyzed polyacrylamide are used for the prevention of scale in water used for boilers and for flocculating agents in water purification. 

Bakalik and Kowalski investigated the sulfomethylation reaction in some detail using C-13 NMR.9 They found there was no detectable amount of amidomethylsulfonate under the condition described by Schiller and Suen. The major products are partially hydrolyzed poly(acrylamide) and the mono, bis, and tris sulfomethylamines. Since the sulfomethylamines are not titratable by the redox titration, the iodometric titration results are not a good indicator for the formation of amidomethylsulfonate product. 

Poly(vinyl acetate) emulsions are excellent bases for water-resistant paper adhesives destined for use in manufacturing bags, tubes, and cartons. Glue-lap adhesives, which require moderate-to-high resistance to water, exemplify this type. When routine water resistance is required, a homopolymer vinyl acetate emulsion containing a cellulosic protective colloid is effective for most purposes. Next effective are emulsions containing fully hydrolyzed poly(vinyl alcohol) as a protective colloid, followed by those containing partially hydrolyzed poly(vinyl acetate). 

In the slurry process, the hydrolysis is accomplished using two stirred-tank reactors in series (266). Solutions of poly (vinyl acetate) and catalyst are continuously added to the first reactor, where 90% of the conversion occur, and then transferred to the second reactor to reach full conversion. Alkyl acetate and alcohols are continuously distilled off in order to drive the equihbrium of the reaction. The resulting poly (vinyl alcohol) particles tend to be very fine, resulting in a dusty product. The process has been modified to yield a less dusty product through process changes (267,268) and the use of additives (269). Partially hydrolyzed products having a narrow hydrolysis distribution cannot be prepared by this method. 

Poly(vinyl alcohol) is utilized as a component of starch-based adhesives.11121114 Other patents report the use of partially oxidized starch,1115 dextrins,1116 dextrins and urea,1117 borax,1118 boric acid,1119 and vinyl methyl ether-maleic acid copolymers.1120 Other patents indicate the use of poly (vinyl alcohol) with partially hydrolyzed poly(vinyl acetate),1121 nonhy-drolyzed poly(vinyl acetate),1122 and poly(vinyl chloride).1123 A few patents have reported such poly acrylic additives as poly (acrylic acid)1124 and its salts,1125 poly(acrylamide),1126 1127 A-methylacrylamide or poly(A-acryl-amide),1128 and polyethyleneimine.1129 Polystyrene has also been used,1130 as well as more complex copolymers such as a maleic acid monobutyl ester-methyl vinyl ether copolymer, together with dextrin and polyacrylamide),1131 carboxylated ethyl acrylate-styrene zinc salt copolymer,1132 ethylene-methyl acrylate-vinyl acetate copolymer,1133 vinyl acetate-vinyl pyr-rolidone copolymer,1134 and ethylene-vinyl acetate copolymer.1135 Some adhesives are compounded with SBR latex1136 1138 and phenol-formaldehyde resins.1139... 

Poly(N-acylethyleneimine)s are also a source for production of totally unsubstituted or partially N-acylated linear poly(ethyleneimine)s. In that case acid hydrolysis is preferred. The physical properties of obtained polymers depend on the degree of hydrolysis. Below 70% of deacylation the polymers are amorphous otherwise they are crystalline. Partially hydrolyzed polymers have applications in paper manufacture, adhesives, coatings, ion-exchange resins, textile manufacture, and water treatment. 

Most research into the study of dispersion polymerization involves common vinyl monomers such as styrene, (meth)acrylates, and their copolymers with stabilizers like polyvinylpyrrolidone (PVP) [33-40], poly(acrylic acid) (PAA) [18,41],poly(methacrylicacid) [42],or hydroxypropylcellulose (HPC) [43,44] in polar media (usually alcohols). However, dispersion polymerization is also used widely to prepare functional microspheres in different media [45, 46]. Some recent examples of these preparations include the (co-)polymerization of 2-hydroxyethyl methacrylate (HEMA) [47,48],4-vinylpyridine (4VP) [49], glycidyl methacrylate (GMA) [50-53], acrylamide (AAm) [54, 55], chloro-methylstyrene (CMS) [56, 57], vinylpyrrolidone (VPy) [58], Boc-p-amino-styrene (Boc-AMST) [59],andAT-vinylcarbazole (NVC) [60] (Table 1). Dispersion polymerization is usually carried out in organic liquids such as alcohols and cyclohexane, or mixed solvent-nonsolvents such as 2-butanol-toluene, alcohol-toluene, DMF-toluene, DMF-methanol, and ethanol-DMSO. In addition to conventional PVP, PAA, and PHC as dispersant, poly(vinyl methyl ether) (PVME) [54], partially hydrolyzed poly(vinyl alcohol) (hydrolysis=35%) [61], and poly(2-(dimethylamino)ethyl methacrylate-fo-butyl methacrylate)... 

The group of Abetz [77] used polystyrene-fcZocA -poly(l,2-butadiene)-block-polyitert-hutyl methacrylate) triblock copolymers with partially hydrolyzed poly(tert-butyl methacrylate) blocks, together with polystyrene-... 

Goodall, A. R., Greenhill-Hopper, M. J., Characterization of partially hydrolyzed poly(vinyl acetates) for use as stabilizers in suspension polymerization, Macromol. Chem., Macromol. Symp. 35-36 (1990) 499. 

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