Poly acetal solvents

Batch and Semibatch Polymerization. The reactor is normally operated in a semicontinuous mode by delaying vinyl acetate, solvent, and initiator. The same reactor can be used for stripping the poly(vinyl acetate) solution, provided that careful addition of methanol is used in order to prevent the viscosity in the reactor from becoming excessive (249). The disadvantages of batch polymerization are lack of product consistency and unsatisfactory economics in large scale production (250,251). The true batch reaction, where all the reactants are added to the reactor at time zero, yields a product having a very broad molecular weight distribution of limited commercial value. 

Figure 1. A two-dimensional compatibility diagram for poly(vinyl acetate). Solvents represented by closed circles dissolve the polymer open circles designate solvents swelling the polymer solvents not visibly affecting the polymer are designated by crosses (after Scigliano (34)).

In fact, all solvent-sensitive or soluble material will be either dissolved or swollen on exposure to the liquid adhesive the hard adhesive is, however, inert. Some thermoplastic m rials are unaffected by the liquid adhesives. These are Poly acetal. Polyethylene, Polypropylene, Nylon (polyamide) and Teflon (PTFE). 

Uses Plasticizer for cellulose nitrate, ethyl cellulose, chlorinated rubber, cellulosic coatings, PVAc, PVB, PVC, PVP, PVdC, poly(acrylate/methacrylate) defoamer in proteinaceous sol ns. improves It. stability in cellulose acetate solvent for household, l l cleaners solvent, film-former, plasticizer in inks, adhesives, coatings food-pkg. adhesives lubricant Reguiatory FDA 21CFR 175.105 kosher... 

Polyacetaldehyde, a mbbery polymer with an acetal stmcture, was first discovered in 1936 (49,50). More recentiy, it has been shown that a white, nontacky, and highly elastic polymer can be formed by cationic polymerization using BF in Hquid ethylene (51). At temperatures below —75° C using anionic initiators, such as metal alkyls in a hydrocarbon solvent, a crystalline, isotactic polymer is obtained (52). This polymer also has an acetal [poly(oxymethylene)] stmcture. Molecular weights in the range of 800,000—3,000,000 have been reported. Polyacetaldehyde is unstable and depolymerizes in a few days to acetaldehyde. The methods used for stabilizing polyformaldehyde have not been successful with poly acetaldehyde and the polymer has no practical significance (see Acetalresins). 

Cellulosics. CeUulosic adhesives are obtained by modification of cellulose [9004-34-6] (qv) which comes from cotton linters and wood pulp. Cellulose can be nitrated to provide cellulose nitrate [9004-70-0] which is soluble in organic solvents. When cellulose nitrate is dissolved in amyl acetate [628-63-7] for example, a general purpose solvent-based adhesive which is both waterproof and flexible is formed. Cellulose esterification leads to materials such as cellulose acetate [9004-35-7], which has been used as a pressure-sensitive adhesive tape backing. Cellulose can also be ethoxylated, providing hydroxyethylceUulose which is useful as a thickening agent for poly(vinyl acetate) emulsion adhesives. Etherification leads to materials such as methylceUulose [9004-67-5] which are soluble in water and can be modified with glyceral [56-81-5] to produce adhesives used as wallpaper paste (see Cellulose esters Cellulose ethers). 

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). 

In the case of solvent spinning, ie, secondary acetate, polyacrylonitrile, and poly(vinyl chloride), the FWA is added to the polymer solution. An exception is gel-whitening of polyacrylonitrile, where the wet tow is treated after spinning in a washbath containing FWA. 

A solubihty parameter of 24.5-24.7 MPa / [12.0-12.1 (cal/cm ) ] has been calculated for PVF using room temperature swelling data (69). The polymer lost solvent to evaporation more rapidly than free solvent alone when exposed to air. This was ascribed to reestabUshment of favorable dipole—dipole interactions within the polymer. Infrared spectral shifts for poly(methyl methacrylate) in PVF have been interpreted as evidence of favorable acid—base interactions involving the H from CHF units (70). This is consistent with the greater absorption of pyridine than methyl acetate despite a closer solubihty parameter match with methyl acetate. 

Vinyl Acetate—Ethylene Copolymers. In these random copolymers, the ratio of ethylene to vinyl acetate (EVA) is varied from 30—60%. As the vinyl acetate content increases, the oil and heat resistance increases. With higher ethylene content the physical strength, tensile, and tear increases. The polymers are cured with peroxide. The main properties of these elastomers include heat resistance, moderate oil and solvent resistance, low compression set, good weather resistance, high damping, exceUent o2one resistance, and they can be easily colored (see Vinyl polymers, poly(VINYL acetate)). 

Membrane stmcture is a function of the materials used (polymer composition, molecular weight distribution, solvent system, etc) and the mode of preparation (solution viscosity, evaporation time, humidity, etc). Commonly used polymers include cellulose acetates, polyamides, polysulfones, dynels (vinyl chloride-acrylonitrile copolymers) and poly(vinyhdene fluoride). 

The use of poly(vinyl acetate) or copolymer emulsions eliminates the need for expensive, flammable, odorous, or toxic solvents and the need for the recovery of such solvents. They are easy to apply and the equipment is easy to clean with water, if done promptly. Emulsions also offer the advantage of high sohds content with fluidity, siace the viscosity of emulsions are iadependent of the molecular weight of the resia iu the particles. 

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 acetate) latex paints are the first choice for interior use (149). Their abihty to protect and decorate is reinforced by several advantages belonging exclusively to latex paints they do not contain solvents so that physiological harm and fire ha2ards are eliminated they are odorless they are easy to apply with spray gun, roUer-coater, or bmsh and they dry rapidly. The paint can be thinned with water, and bmshes or coaters can be cleaned with soap and tepid water. The paint is usually dry in 20 minutes to two hours, and two coats may be applied the same day. 

Commercial Hydrolysis Process. The process of converting poly(vinyl acetate) to poly(vinyl alcohol) on a commercial scale is compHcated on account of the significant physical changes that accompany the conversion. The viscosity of the poly(vinyl acetate) solution increases rapidly as the conversion proceeds, because the resulting poly(vinyl alcohol) is insoluble in the most common solvents used for the polymeri2ation of vinyl acetate. The outcome is the formation of a gel swollen with the resulting acetic acid ester and the alcohol used to effect the transesterification. 

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