PVA

PVA resins as piNYL POLYMERS - VINYL ALCOHOL POLYMERS] pol 24)... 

VINYLPOLYTffiRS - VINYL ALCOHOLPOLYTffiRS] (Vol 24) PVA. See Poly(vinyl alcohol). 

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). 

Most of the polymer s characteristics stem from its molecular stmcture, which like POE, promotes solubiUty in a variety of solvents in addition to water. It exhibits Newtonian rheology and is mechanically stable relative to other thermoplastics. It also forms miscible blends with a variety of other polymers. The water solubiUty and hot meltable characteristics promote adhesion in a number of appHcations. PEOX has been observed to promote adhesion comparable with PVP and PVA on aluminum foil, cellophane, nylon, poly(methyl methacrylate), and poly(ethylene terephthalate), and in composite systems improved tensile strength and Izod impact properties have been noted. 

Four other groups of synthetic adhesives find uses in secondary processing, ie, overlaying, assembly gluing, etc, and in furniture and cabinet manufacture. Poly(vinyl acetate) (PVA) adhesives are widely used in appHcation of veneers and other overlays to panel substrates and in some unit-assembly operations. PVA adhesives are an emulsion of polyvinyl acetate in water and cure by loss of water. The PVA adhesives are somewhat... 

Vinyl alcohol does not exist as a monomer, but Herrmann and Haehnel (1) were able to obtain the desired product poly(vinyl alcohol) [9002-89-5] (PVA), by polymerizing vinyl acetate and then hydrolyzing the resultant poly(vinyl acetate). This process is employed for the commercial production of PVA even now. The principal concern of the discoverers was development of a suture for surgical operations the fiber then obtained was not suited for clothing use (2). 

Commercial production of PVA fiber was thus started in Japan, at as early a period as that for nylon. However, compared with various other synthetic fibers which appeared after that period, the properties of which have continuously been improved, PVA fiber is not very well suited for clothing and interior uses because of its characteristic properties. The fiber, however, is widely used in the world because of unique features such as high affinity for water due to the —OH groups present in PVA, excellent mechanical properties because of high crystallinity, and high resistance to chemicals including alkah and natural conditions. 

The People s RepubHc of China introduced Kuraray technology and started production of PVA fiber by a wet spinning process in 1965. Its annual capacity reached 165,000 tons in 1986 (9). The Democratic People s RepubHc of Korea produce PVA and reportedly have an annual production capacity of 50,000 tons (9). 

Raw Material. PVA is synthesized from acetjiene [74-86-2] or ethylene [74-85-1] by reaction with acetic acid (and oxygen in the case of ethylene), in the presence of a catalyst such as zinc acetate, to form vinyl acetate [108-05-4] which is then polymerized in methanol. The polymer obtained is subjected to methanolysis with sodium hydroxide, whereby PVA precipitates from the methanol solution. 

PVA used for the manufacture of fiber generally has a degree of polymerization of about 1700 and, for general-purpose fiber, a high degree of hydrolysis of vinyl acetate units of at least 99 mol %. 

Pure PVA dissolves in water but does not fluidize by melting. Commercial production of PVA fiber is therefore carried out by wet spinning or dry spinning, utilizing aqueous PVA solution. In either case, purified PVA is dissolved in hot water and the solution is extmded through fine holes of a spinneret the extmded streams are coagulated to form continuous filaments, which are then heat-treated to have adequate mechanical properties. 

Since PVA fiber as spun is soluble in water, it is necessary to improve the water resistance of the as-spun fiber (10). Heat treatment followed by acetalization is a classic method to provide high water resistance. 

Fig. 2. Pliotogiapli of the cross sections of PVA fiber manufactured by wet spinning with a coagulating bath of sodium sulfate (a) and sodium hydroxide...

An aqueous PVA solution containing a small amount of boric acid may be extmded into an aqueous alkaline salt solution to form a gel-like fiber (15,16). In this process, sodium hydroxide penetrates rapidly into the aqueous PVA solution extmded through orifices to make it alkaline, whereby boric acid cross-links PVA molecules with each other. The resulting fiber is provided with sufficient strength to withstand transportation to the next process step and its cross section does not show a distinct skin/core stmcture. 

Fig. 3. Schematic comparison of the stmctures of PVA fibers formed by salt coagulation and alkaU coagulation, (a) Low orientation, low crystallinity (b)...

Boric acid/alkaU spinning has been commercialized in Kuraray Co. and Unitika Co. in Japan, and is reportedly under research and development also in the People s RepubHc of China as a process for producing high strength PVA fiber to be used for replacing asbestos (9). 

Fine adjusting and optimization of each step of this process is stiU underway, and a PVA fiber having a single fiber strength as high as 2 N/tex (21 gf/dtex), which is close to that of aramid fiber, has been reported (18). 

Moisture Absorbency. PVA fiber is more hygroscopic than any other synthetic fiber. The hygroscopicity varies depending on how the fiber is processed after spinning, ie, in heat-drawing, he at-treatment, acetalization, and the like. 

Dimensional Stability. The wet heat resistance of PVA fiber is indicated by the wet softening temperature (WTS) at which the fiber shrinks to a specified ratio. At one time, the WTS was not more than 95°C for nonacetalized PVA fiber, but improvement of WTS has been achieved by improvement in heat-drawing and -treating techniques other methods proposed include suppression of polymerization temperature of vinyl acetate (36) and employment of alkafi spinning (37). 

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