Poly vinyl Alcohol Derivatives

General Comment. The foregoing examples clearly show that poly(vinyl alcohol) can be modified readily and that some of these derivatives have potential (and/or actual) biological activity. This survey is definitely not encyclopedic in scope but rather illustrative. No doubt many more examples of potentially biologically active poly(vinyl alcohol) derivatives will be developed in the future and it is entirely possible that some of these may become of value in chemotherapy and other areas where biologically active polymers are now being studied. 

Sato, H., Maeda, M., Nakajima, A. Mechanochemistry and permeability of polyelectrolyte complex membranes composed of poly (vinyl alcohol) derivatives. J. Appl. Polym. Sci. 1979, 23 (6), 1759-1767. 

Most of these azide polymers photocross-link at a faster rate than does poly(vinyl cinnamate), when exposed to light of 260 pm. In addition, they responded well to photosensitization. Also, it was observed [50] that the 4-isomer of azidophthalate shows greater speed increase than does the 3-isomer. In general, the poly(vinyl alcohol) derivatives were reported to exhibit higher cross-linking speeds than do other azide functionalized polymers [176]. 

Scheme 4. Hydrolysis of carboxylated poly(vinyl alcohol) derivatives.

All SCL basically consist of hydrophilic polymers that maintain then-gel structure, with the ability to swell and not dissolve by intermolecular crosslinking. Therefore, natural polymers, such as agarose and gelatin, are potential candidates for its material. However, currently commercially available SCL are made only of copolymers of methacrylic acid derivatives, mainly PHEMA, and several other monomers because of stability and safety concerns. Lenses with a water content of 30-40 % are made mostly of PHEMA and those with water contents of70-80 % are made of copolymers ofN-vinyl pyrrolidone (NVP), acrylamide (AAm), HEMA, and methacrylic acid (MA). There are also poly(vinyl alcohol) derivatives. Table 2 shows the names and chemical structures of various SCL components [6]. 

One of the first PEO chemical gels cmistructed through triazole cross-linking was disclosed by HUbom (Scheme 8) [47]. Poly(vinyl alcohol) derivatives with acetylene 25 and azide side chains 26 were prepared and cross-Unked to produce a hydiogelating network 27. For comparative study, a similar type of hydrogelator 29... 

Resins formed from the reaction of poly(vinyl alcohol) with aldehydes. The formal derivative (from methanal) is used in wire coatings and adhesives and the bulyral (from butanal) is used in metal paints, wood-sealers, adhesives and in safety glass interlayers. 

Suitable protective coUoids for the preparation of acryhc suspension polymers include ceUulose derivatives, polyacrylate salts, starch, poly(vinyl alcohol), gelatin, talc, clay, and clay derivatives (95). These materials are added to prevent the monomer droplets from coalescing during polymerisation (110). Thickeners such as glycerol, glycols, polyglycols, and inorganic salts ate also often added to improve the quahty of acryhc suspension polymers (95). 

Emulsion Adhesives. The most widely used emulsion-based adhesive is that based upon poly(vinyl acetate)—poly(vinyl alcohol) copolymers formed by free-radical polymerization in an emulsion system. Poly(vinyl alcohol) is typically formed by hydrolysis of the poly(vinyl acetate). The properties of the emulsion are derived from the polymer employed in the polymerization as weU as from the system used to emulsify the polymer in water. The emulsion is stabilized by a combination of a surfactant plus a coUoid protection system. The protective coUoids are similar to those used paint (qv) to stabilize latex. For poly(vinyl acetate), the protective coUoids are isolated from natural gums and ceUulosic resins (carboxymethylceUulose or hydroxyethjdceUulose). The hydroHzed polymer may also be used. The physical properties of the poly(vinyl acetate) polymer can be modified by changing the co-monomer used in the polymerization. Any material which is free-radically active and participates in an emulsion polymerization can be employed. Plasticizers (qv), tackifiers, viscosity modifiers, solvents (added to coalesce the emulsion particles), fillers, humectants, and other materials are often added to the adhesive to meet specifications for the intended appHcation. Because the presence of foam in the bond line could decrease performance of the adhesion joint, agents that control the amount of air entrapped in an adhesive bond must be added. Biocides are also necessary many of the materials that are used to stabilize poly(vinyl acetate) emulsions are natural products. Poly(vinyl acetate) adhesives known as "white glue" or "carpenter s glue" are available under a number of different trade names. AppHcations are found mosdy in the area of adhesion to paper and wood (see Vinyl polymers). 

Suspension polymerization of VDE in water are batch processes in autoclaves designed to limit scale formation (91). Most systems operate from 30 to 100°C and are initiated with monomer-soluble organic free-radical initiators such as diisopropyl peroxydicarbonate (92—96), tert-huty peroxypivalate (97), or / fZ-amyl peroxypivalate (98). Usually water-soluble polymers, eg, cellulose derivatives or poly(vinyl alcohol), are used as suspending agents to reduce coalescence of polymer particles. Organic solvents that may act as a reaction accelerator or chain-transfer agent are often employed. The reactor product is a slurry of suspended polymer particles, usually spheres of 30—100 pm in diameter they are separated from the water phase thoroughly washed and dried. Size and internal stmcture of beads, ie, porosity, and dispersant residues affect how the resin performs in appHcations. 

Other thickeners used include derivatives of ceUulose such as methylceUulose, hydroxypropylmethylceUulose, and ceUulose gum natural gums such as tragacanth and xanthan (see Cellulose ethers Gums) the carboxyvinyl polymers and the poly(vinyl alcohol)s. The magnesium aluminum siHcates, glycol stearates, and fatty alcohols in shampoos also can affect viscosity. 

Carbon Cha.in Backbone Polymers. These polymers may be represented by (4) and considered derivatives of polyethylene, where n is the degree of polymeriza tion and R is (an alkyl group or) a functional group hydrogen (polyethylene), methyl (polypropylene), carboxyl (poly(acryhc acid)), chlorine (poly(vinyl chloride)), phenyl (polystyrene) hydroxyl (poly(vinyl alcohol)), ester (poly(vinyl acetate)), nitrile (polyacrylonitrile), vinyl (polybutadiene), etc. The functional groups and the molecular weight of the polymers, control thek properties which vary in hydrophobicity, solubiUty characteristics, glass-transition temperature, and crystallinity. 

Functional derivatives of polyethylene, particularly poly(vinyl alcohol) and poly(acryLic acid) and derivatives, have received attention because of their water-solubility and disposal iato the aqueous environment. Poly(vinyl alcohol) is used ia a wide variety of appHcations, including textiles, paper, plastic films, etc, and poly(acryLic acid) is widely used ia detergents as a builder, a super-absorbent for diapers and feminine hygiene products, for water treatment, ia thickeners, as pigment dispersant, etc (see Vinyl polymers, vinyl alcohol polymers). 

Other typical pyrotechnic fuels include charcoal, sulfur, boron, siUcon, and synthetic polymers such as poly(vinyl alcohol) and poly(vinyl chloride). Extensive use has been made of natural products such as starches and gums, and the use of these materials continues to be substantial in the fireworks industry. MiUtary pyrotechnics have moved away from the use of natural products due to the inherent variabiUty in these materials depending on climatic conditions during the growth of the plants from which the compounds are derived. 

The addition of an a-hydroxycarboxyhc acid to a tetraethylene, propylene, diethjiene, or hexylene glycol titanate gives water-soluble complexes suitable for gelling aqueous solutions of hydroxyl polymers, such as poly(vinyl alcohol) (PVA), or cellulose (qv) derivatives. These are useful as binding agents for glass fibers, clays (qv), and paper coatings (85). 

Solution Polymerization. Solution polymerization of vinyl acetate is carried out mainly as an intermediate step to the manufacture of poly(vinyl alcohol). A small amount of solution-polymerized vinyl acetate is prepared for the merchant market. When solution polymerization is carried out, the solvent acts as a chain-transfer agent, and depending on its transfer constant, has an effect on the molecular weight of the product. The rate of polymerization is also affected by the solvent but not in the same way as the degree of polymerization. The reactivity of the solvent-derived radical plays an important part. Chain-transfer constants for solvents in vinyl acetate polymerizations have been tabulated (13). Continuous solution polymers of poly(vinyl acetate) in tubular reactors have been prepared at high yield and throughput (73,74). 

Poly(vinyl alcohol) can be derived from the hydrolysis of a variety of poly(vinyl esters), such as poly(vinyl acetate), poly(vinyl formate), and poly(vinyl ben2oate), and of poly(vinyl ethers). However, all commercially produced poly(vinyl alcohol) is manufactured by the hydrolysis of poly(vinyl acetate). The manufacturing process can be viewed as one segment that deals with the polymeri2ation of vinyl acetate and another that handles the hydrolysis of poly(vinyl acetate) to poly(vinyl alcohol). 

Some commercial durable antistatic finishes have been Hsted in Table 3 (98). Early patents suggest that amino resins (qv) can impart both antisHp and antistatic properties to nylon, acryUc, and polyester fabrics. CycHc polyurethanes, water-soluble amine salts cross-linked with styrene, and water-soluble amine salts of sulfonated polystyrene have been claimed to confer durable antistatic protection. Later patents included dibydroxyethyl sulfone [2580-77-0] hydroxyalkylated cellulose or starch, poly(vinyl alcohol) [9002-86-2] cross-linked with dimethylolethylene urea, chlorotria2ine derivatives, and epoxy-based products. Other patents claim the use of various acryUc polymers and copolymers. Essentially, durable antistats are polyelectrolytes, and the majority of usehil products involve variations of cross-linked polyamines containing polyethoxy segments (92,99—101). 

Polymeric Calcium Phosphate Cements. Aqueous solutions of polymers such as poly(acryHc acid), poly(vinyl alcohol), gelatin, etc, and/or autopolymerizable monomer systems, eg, 2-hydroxyethyl methacrylate, glycerol dimethacrylate, calcium dimethacrylate, etc, have been used as Hquid vehicles (41,42,76) for the self-setting calcium phosphate cement derived from tetracalcium phosphate and dicalcium phosphate [7757-93-9J. 

Latex Types. Latexes are differentiated both by the nature of the coUoidal system and by the type of polymer present. Nearly aU of the coUoidal systems are similar to those used in the manufacture of dry types. That is, they are anionic and contain either a sodium or potassium salt of a rosin acid or derivative. In addition, they may also contain a strong acid soap to provide additional stabUity. Those having polymer soUds around 60% contain a very finely tuned soap system to avoid excessive emulsion viscosity during polymeri2ation (162—164). Du Pont also offers a carboxylated nonionic latex stabili2ed with poly(vinyl alcohol). This latex type is especiaUy resistant to flocculation by electrolytes, heat, and mechanical shear, surviving conditions which would easUy flocculate ionic latexes. The differences between anionic and nonionic latexes are outlined in Table 11. 

Poly(vinyl alcohol) Polymer derived from the hydrolysis of polyvinyl esters. 

Chitin films can be manufactured from DMAc solutions or by other approaches, for example, blend films of beta-chitin (derived from squid pens) and poly(vinyl alcohol) (PVA) were prepared by a solution casting technique from corresponding solutions of beta-chitin and PVA in concentrated formic acid. Upon evaporation of the solvent, the film having 50/50 composition was found to be cloudy [224]. 

Thermally reversible gels can be prepared from poly (vinyl alcohol) and alkali metal salts of o-hydroxybenzal derivatives having benzenoid groups at both ends 24). Colored gels can be obtained, depending on the type of ketone used (Figure 4). 

Poly(vinyl alcohol) has the structure 10.67. Poly(vinyl acetate) is the fully esterified derivative of polyfvinyl alcohol), in which the -OH groups are replaced by -OCOCH3 groups. As indicated in Table 10.5, commercial polyvinyl sizes are effectively copolymers of polyfvinyl acetate) and polyfvinyl alcohol) that vary in the degree of saponification of the ester groups. These products may comprise 100% of either polymer, or combinations of the two monomers in any proportions. Crotonic acid (2-butenoic acid), widely used in the preparation of resins, may also be a component. This compound exhibits cis-trans isomerism (Scheme 10.17). The solid trans form is produced readily by catalysed rearrangement of the liquid cis isomer. 

The identification of anionic polyfacrylic acid) sizes can be carried out by staining with a fluorescent cationic dye (Cl Basic Orange 14) followed by spectroscopic measurement of excitation wavelength and fluorescence emission [195,196]. Such methods can also be used (with Cl Basic Orange 14 or Cl Basic Red 1) to detect and estimate carboxymethylcellulose, poly(vinyl alcohol) and starch derivatives [197]. 

A strain of yeast and a strain of bacterium were co-immobilized to fabricate a biochemical oxygen demand (BOD) sensor based on sol-gel derived composite materials97. This novel type of biosensor was developed for water monitoring and was used to determine the BOD values of OECD synthetic wastewater, domestic wastewater, and lake waters. The microorganisms Trichosporon cutaneum and Bacillus subtilis were coimmobilized in the sol-gel composite material, which was composed of silica and the grafting copolymer of poly (vinyl alcohol) and 4-vinylpyridine (PVA-g-P(4-VP)). 

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