Poly with alcoholate

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. 

When dealing with esters of water-soluble, non steam-volatile, poly-hydric alcohols e.g., ethylene glycol or glycerol), the distillate consists of water only (density 1 00). The water soluble, non-volatile alcohol may be isolated by evaporation of the alkahne solution to a thick syrup on a water bath and extraction of the polyhydric alcohol from the salt with cold ethyl alcohol. 

Poly(vinyl alcohol) is a useful water soluble polymer It cannot be prepared directly from vinyl alcohol because of the rapidity with which vinyl alcohol (H2C=CHOH) isomenzes to acetaldehyde Vinyl acetate however does not rearrange and can be polymerized to poly(vinyl acetate) How could you make use of this fact to prepare poly(vinyl alcohol)" ... 

First, we consider the experimental aspects of osmometry. The semiperme-able membrane is the basis for an osmotic pressure experiment and is probably its most troublesome feature in practice. The membrane material must display the required selectivity in permeability-passing solvent and retaining solute-but a membrane that works for one system may not work for another. A wide variety of materials have been used as membranes, with cellophane, poly (vinyl alcohol), polyurethanes, and various animal membranes as typical examples. The membrane must be thin enough for the solvent to pass at a reasonable rate, yet sturdy enough to withstand the pressure difference which can be... 

Acetals are readily formed with alcohols and cycHc acetals with 1,2 and 1,3-diols (19). Furfural reacts with poly(vinyl alcohol) under acid catalysis to effect acetalization of the hydroxyl groups (20,21). Reaction with acetic anhydride under appropriate conditions gives the acylal, furfuryUdene diacetate... 

Dichromated Resists. The first compositions widely used as photoresists combine a photosensitive dichromate salt (usually ammonium dichromate) with a water-soluble polymer of biologic origin such as gelatin, egg albumin (proteins), or gum arabic (a starch). Later, synthetic polymers such as poly(vinyl alcohol) also were used (11,12). Irradiation with uv light (X in the range of 360—380 nm using, for example, a carbon arc lamp) leads to photoinitiated oxidation of the polymer and reduction of dichromate to Ct(III). The photoinduced chemistry renders exposed areas insoluble in aqueous developing solutions. The photochemical mechanism of dichromate sensitization of PVA (summarized in Fig. 3) has been studied in detail (13). 

About half of the wodd production comes from methanol carbonylation and about one-third from acetaldehyde oxidation. Another tenth of the wodd capacity can be attributed to butane—naphtha Hquid-phase oxidation. Appreciable quantities of acetic acid are recovered from reactions involving peracetic acid. Precise statistics on acetic acid production are compHcated by recycling of acid from cellulose acetate and poly(vinyl alcohol) production. Acetic acid that is by-product from peracetic acid [79-21-0] is normally designated as virgin acid, yet acid from hydrolysis of cellulose acetate or poly(vinyl acetate) is designated recycle acid. Indeterrninate quantities of acetic acid are coproduced with acetic anhydride from coal-based carbon monoxide and unknown amounts are bartered or exchanged between corporations as a device to lessen transport costs. 

Many of these reactions are reversible, and for the stronger nucleophiles they usually proceed the fastest. Typical examples are the addition of ammonia, amines, phosphines, and bisulfite. Alkaline conditions permit the addition of mercaptans, sulfides, ketones, nitroalkanes, and alcohols to acrylamide. Good examples of alcohol reactions are those involving polymeric alcohols such as poly(vinyl alcohol), cellulose, and starch. The alkaline conditions employed with these reactions result in partial hydrolysis of the amide, yielding mixed carbamojdethyl and carboxyethyl products. 

Lead azide is not readily dead-pressed, ie, pressed to a point where it can no longer be initiated. However, this condition is somewhat dependent on the output of the mixture used to ignite the lead azide and the degree of confinement of the system. Because lead azide is a nonconductor, it may be mixed with flaked graphite to form a conductive mix for use in low energy electric detonators. A number of different types of lead azide have been prepared to improve its handling characteristics and performance and to decrease sensitivity. In addition to the dextrinated lead azide commonly used in the United States, service lead azide, which contains a minimum of 97% lead azide and no protective colloid, is used in the United Kingdom. Other varieties include colloidal lead azide (3—4 pm), poly(vinyl alcohol)-coated lead azide, and British RE) 1333 and RE) 1343 lead azide which is precipitated in the presence of carboxymethyl cellulose (88—92). 

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. 

Polymer Applications. The reaction of sahcylaldehyde with poly(vinyl alcohol) to form an acetal has been used to provide dye receptor sites on poly(vinyl alcohol) fibers (89) and to improve the light stabihty of blend fibers from vinyl chloride resin and poly(vinyl alcohol) (90) (see Fibers, POLY(VINYL alcohol)). ... 

The resihency and dyeabihty of poly(vinyl alcohol) fibers is improved by a process incorporating -hydroxybenzaldehyde to provide a site for the formation of a stable Mannich base. Hydroxyl groups on the fiber are converted to acetal groups by -hydroxybenzaldehyde. Subsequent reaction with formaldehyde and ammonia or an alkylamine is rapid and forms a stable Mannich base that is attached to the polymer backbone (94). 

Letterpress. This is the oldest printing process stiU in use. It continues to be replaced by newer printing processes. Printing is conducted from a raised image area of the printing plate. Inks in the printing process are transferred directly from a raised area to a substrate. The printing plates contain a thick layer of photopolymer (often a mixture with polymer such as poly(vinyl alcohol) deposited over a plastic or aluminum base. 

Three generations of latices as characterized by the type of surfactant used in manufacture have been defined (53). The first generation includes latices made with conventional (/) anionic surfactants like fatty acid soaps, alkyl carboxylates, alkyl sulfates, and alkyl sulfonates (54) (2) nonionic surfactants like poly(ethylene oxide) or poly(vinyl alcohol) used to improve freeze—thaw and shear stabiUty and (J) cationic surfactants like amines, nitriles, and other nitrogen bases, rarely used because of incompatibiUty problems. Portiand cement latex modifiers are one example where cationic surfactants are used. Anionic surfactants yield smaller particles than nonionic surfactants (55). Often a combination of anionic surfactants or anionic and nonionic surfactants are used to provide improved stabiUty. The stabilizing abiUty of anionic fatty acid soaps diminishes at lower pH as the soaps revert to their acids. First-generation latices also suffer from the presence of soap on the polymer particles at the end of the polymerization. Steam and vacuum stripping methods are often used to remove the soap and unreacted monomer from the final product (56). 

The viscosity of the latex can also be dependent on pH. In the case of some latices, lowering the pH with a weak acid such as glycine is an effective method for raising the viscosity without destabilising the system. Latices made with poly(vinyl alcohol) as the primary emulsifier can be thickened by increasing the pH with a strong alkaU. 

Fig. 41. The pervaporation separation of acetone—water mixtures achieved with a water-selective poly(vinyl alcohol) (PVA) membrane and with an acetone-selective siUcone mbber membrane. The PVA membrane is best suited to removing small amounts of water from a concentrated acetone solution, whereas the siUcone mbber membrane is best suited to removing small amounts of acetone from a dilute acetone stream (89).

The in situ process is simpler because it requires less material handling (35) however, this process has been used only for resole resins. When phenol is used, the reaction system is initially one-phase alkylated phenols and bisphenol A present special problems. As the reaction with formaldehyde progresses at 80—100°C, the resin becomes water-insoluble and phase separation takes place. Catalysts such as hexa produce an early phase separation, whereas NaOH-based resins retain water solubiUty to a higher molecular weight. If the reaction medium contains a protective coUoid at phase separation, a resin-in-water dispersion forms. Alternatively, the protective coUoid can be added later in the reaction sequence, in which case the reaction mass may temporarily be a water-in-resin dispersion. The protective coUoid serves to assist particle formation and stabUizes the final particles against coalescence. Some examples of protective coUoids are poly(vinyl alcohol), gum arabic, and hydroxyethjlceUulose. 

Polymer Blends. The miscibility of poly(ethylene oxide) with a number of other polymers has been studied, eg, with poly (methyl methacrylate) (18—23), poly(vinyl acetate) (24—27), polyvinylpyrroHdinone (28), nylon (29), poly(vinyl alcohol) (30), phenoxy resins (31), cellulose (32), cellulose ethers (33), poly(vinyl chloride) (34), poly(lactic acid) (35), poly(hydroxybutyrate) (36), poly(acryhc acid) (37), polypropylene (38), and polyethylene (39). 

Long-chain alcohols, such as are obtained by the hydrogenation of coconut oil, polymerization of ethylene, or the 0x0 process (qv), are sulfated on a large scale with sulfur thoxide or chlorosulfuhc acid to acid sulfates the alkaU salts are commercially important as surface-active agents (see Surfactants). Poly(vinyl alcohol) can be sulfated in pyhdine with chlorosulfuhc acid to the hydrogen sulfate (84). 

The bonding properties of (Ti02) have been used for size-reinforcing of glass fibers so that they adhere to asphalt or to a PTEE—polysulfide mixture to impart enhanced flex endurance (434—436). Poly(vinyl alcohol) (PVA) solutions mixed with sucrose can be cross-linked with the lactic acid chelate and used generally for glass-fiber sizing (437). 

Vinyl acetal polymers are made by the acid-cataly2ed acetalization of poly(viQyl alcohol) [9002-89-5] with aldehydes (1). 

Analogously, poly(vinyl ketals) can be prepared from ketones, but since poly(vinyl ketals) are not commercially important, they are not discussed here. The acetalization reaction strongly favors formation of the 1,3-dioxane ring, which is a characteristic feature of this class of resins. The first of this family, poly(vinyl ben2al), was prepared in 1924 by the reaction of poly(vinyl alcohol) with ben2aldehyde in concentrated hydrochloric acid (2). Although many members of this class of resins have been made since then, only poly(vinyl formal) [9003-33-2] (PVF) and poly(vinyl butyral) [63148-65-2] (PVB) continue to be made in significant commercial quantities. 

Poly(vinyl alcohol) used to manufacture the poly(vinyl acetal)s is made from poly(vinyl acetate) homopolymer (see Vinyl polymers, vinyl alcohol polymers Vinyl POLYMERS, vinyl acetate polymers). Hydrolysis of poly(vinyl acetate) homopolymer produces a polyol with predominandy 1,3-glycol units. The polyol also contains up to 2 wt % 1,2-glycol units that come from head-to-head bonding during the polymeri2ation of vinyl acetate monomer. Poly(vinyl acetate) hydrolysis is seldom complete, and for some appHcations, not desired. For example, commercial PVF resins may contain up to 13 wt % unhydroly2ed poly(vinyl acetate). Residual vinyl acetate units on the polymer help improve resin solubiHty and processibiHty (15). On the other hand, the poly(vinyl alcohol) preferred for commercial PVB resins has less than 3 wt % residual poly(vinyl acetate) units on the polymer chain. 

The poly(vinyl alcohol) made for commercial acetalization processes is atactic and a mixture of cis- and /n j -l,3-dioxane stereoisomers is formed during acetalization. The precise cis/trans ratio depends strongly on process kinetics (16,17) and small quantities of other system components (23). During formylation of poly(vinyl alcohol), for example, i j -acetalization is more rapid than /ra/ j -acetalization (24). In addition, the rate of hydrolysis of the trans-2iQ. -A is faster than for the <7 -acetal (25). Because hydrolysis competes with acetalization during acetal synthesis, a high cis/trans ratio is favored. The stereochemistry of PVF and PVB resins has been studied by proton and carbon nmr spectroscopy (26—29). 

Manufacture. PVBs are manufactured by a variety of two-stage heterogeneous processes. In one of these an alcohol solution of poly(vinyl acetate) and an acid catalyst are heated to 60—80°C with strong agitation. As the poly(vinyl alcohol) forms, it precipitates from solution (77). Ethyl acetate, the principle by-product, is stripped off and sold. The precipitated poly(vinyl alcohol) is washed to remove by-products and excess acid. The poly(vinyl alcohol) is then suspended in a mixture of ethyl alcohol, butyraldehyde, and mineral acid at temperatures above 70°C. As the reaction approaches completion the reactants go into solution. When the reaction is complete, the catalyst is neutralized and the PVB is precipitated from solution with water, washed, centrifuged, and dried. Resin from this process has very low residual vinyl acetate and very low levels of gel from intermolecular acetalization. 

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