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Vinyl Alcohol Polymers

Vinyl Alcohol Polymers

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Vol. 8 VINYL ALCOHOL POLYMERS 399
VINYL ALCOHOL POLYMERS
Introduction
Poly(vinyl alcohol) (PVA), a polyhydroxy polymer, is the largest volume, syn-thetic water-soluble resin produced in the world. It is commercially manufac-tured by the hydrolysis of poly(vinyl acetate), because monomeric vinyl alcoholcannot be obtained in quantities and purity that makes polymerization to PVAfeasible (1–3).Poly(vinyl alcohol) was discovered by Haehnel and Herrmann who, throughtheadditionofalkalitoaclearalcoholicsolutionofpoly(vinylacetate),wereabletoobtaintheivory-coloredPVA(4).ThefirstscientificreportsonPVAwerepublishedin 1927 (5,6).TheexcellentchemicalresistanceandphysicalpropertiesofPVAresinshaveresulted in broad industrial use. The polymer is an excellent adhesive and pos-sesses solvent, oil, and grease resistance, properties matched by few other poly-mers. Poly(vinyl alcohol) films exhibit high tensile strength, abrasion resistance,and oxygen barrier properties which under dry conditions are superior to those of most polymers. The polymer’s low surface tension provides for excellent emulsifi-cation and protective colloid properties.The main uses of PVA are in textile sizing, adhesives, protective colloids foremulsion polymerization, fibers, production of poly(vinyl butyral), and paper siz-ing. Significant volumes are also used in the production of concrete additives and joint cements for building construction and water-soluble films for containmentbags for hospital laundry, pesticides, herbicides, and fertilizers. Smaller volumesareconsumedasemulsifiersforcosmetics,temporaryprotectivefilmcoatings,soilbinding to control erosion, and photoprinting plates.
 Encyclopedia of Polymer Science and Technology
. Copyright John Wiley & Sons, Inc. All rights reserved.
 
400 VINYL ALCOHOL POLYMERS Vol. 8
Fig. 1.
Effect of molecular weight and hydrolysis on the properties of PVA (7).
Physical Properties
The physical properties of PVA are highly correlated with the method of prepa-ration. The final properties are affected by the polymerization conditions of theparent poly(vinyl acetate), the hydrolysis conditions, drying, and grinding. Fur-ther, the term PVA refers to an array of products that can be considered to becopolymers of vinyl acetate and vinyl alcohol.The effect of hydrolysis and molecular weight is illustrated in Figure 1. Thevariations in properties with molecular weight are for a constant degree of hy-drolysis (mol%) (7), and the effect of hydrolysis is at a constant molecular weight.Representative properties are shown in Table 1.
Crystallization and Melting Point.
The ability of PVA to crystallize isthe single most important physical property of PVA as it controls water solubility,water sensitivity, tensile strength, oxygen barrier properties, and thermoplasticproperties. Thus, this feature has been and continues to be the focal point of aca-demic and industrial research (8–37). The degree of crystallinity as measured byx-ray diffraction can be directly correlated to the products density or the swellingcharacteristic of the insoluble part (Fig. 2).The size of the crystals determines the melting point. Reported values forthe melting point of PVA range between 220 and 267
C for fully hydrolyzed PVA(38–42). Exact determination of the crystalline melting point using normal datatechniques is difficult as decomposition takes place above 140
C. The divergencein melting point may be ascribed to decomposition or prior treatment history. Themelting point of PVA containing an appropriate amount of diluent or comonomeris less influenced by decomposition. Thus, the melting point of fully hydrolyzedPVAcanbedeterminedbytheextrapolationofthemeasuredvaluesto0%diluent.
 
Vol. 8 VINYL ALCOHOL POLYMERS 401
Table 1. Physical Properties of Poly(vinyl alcohol)
Property Value Remarks Appearance White to ivory white granu-lar powderSpecic gravity 1.271.31 Increases with degree ocrystallinityTensile strength, MPa
a
(98–99% hydrolyzed)67110 Increases with degree ocrystallinity (heat treat-ment), and molecularweight, decreases withincreasing humidityTensile strength, MPa(87–89% hydrolyzed)2479 Increases with molecularweight and decreaseswith increasing humidityElongation, % 0300 Increases with increasinghumidityThermal coefficient of expansion per
C7–12
×
10
5
Specific heat, J/(g
·
K)
b
1.67Thermal conductivity,W/(m
·
K)0.2Glass-transitiontemperature, K 358 9899% hydrolyzed331 8789% hydrolyzedMelting point, K 503 9899% hydrolyzed453 8789% hydrolyzedElectrical resistivity,
·
cm(3.1–3.8)
×
10
7
Thermal stability Gradual discoloration above100
C; darkens rapidlyabove 150
C; rapid decom-position above 200
CRefractive index
n
D
(20
C)1.55Degree of crystallinity 00.54 Increases with heat treat-ment and degree of hy-drolysisStoragestability(solid) Indefinite when protectedfrom moistureFlammability Burns similarly to paperStability in sunlight Excellent
a
To convert MPa to psi, multiply by 145.
b
To convert J to cal, divide by 4.184.
 A more reliable melting point is obtained in this manner. The melting points de-termined by the diluent method are 255–267
C for commercial superhydrolyzedPVA (greater than 99% hydrolysis). The melting point determined by meltingpoint depression caused by noncrystallizing comonomer units assumes as a firstapproximation that the vinyl acetate units are randomly distributed. This as-sumption usually does not apply to commercial PVA. The extrapolated values of 

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