Polyvinyl alcohol
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Polyvinyl alcohol (PVOH, PVA, or PVAl) is a water-soluble synthetic polymer. It has the idealized formula [CH2CH(OH)]n. It is used in papermaking, textile warp sizing, as a thickener and emulsion stabilizer in polyvinyl acetate (PVAc) adhesive formulations, in a variety of coatings, and 3D printing. It is colourless (white) and odorless. It is commonly supplied as beads or as solutions in water.<ref name=Ullmann/><ref>Template:Cite journal</ref> Without an externally added crosslinking agent, PVA solution can be gelled through repeated freezing-thawing, yielding highly strong, ultrapure, biocompatible hydrogels which have been used for a variety of applications such as vascular stents, cartilages, contact lenses, etc.<ref>Template:Cite journal</ref>
Although polyvinyl alcohol is often referred to by the acronym PVA, more generally PVA refers to polyvinyl acetate, which is commonly used as a wood adhesive and sealer.
Uses
PVA is used in a variety of medical applications because of its biocompatibility, low tendency for protein adhesion, and low toxicity. Specific uses include cartilage replacements, contact lenses, laundry detergent pods and eye drops.<ref>Template:Cite journal</ref> Polyvinyl alcohol is used as an aid in suspension polymerizations. Its largest application in China is its use as a protective colloid to make PVAc dispersions. In Japan its major use is the production of Vinylon fiber.<ref name="sri">SRI Consulting CEH Report Polyvinyl Alcohol, published March 2007, abstract retrieved July 30, 2008.</ref> This fiber is also manufactured in North Korea for self-sufficiency reasons, because no oil is required to produce it. Another application is photographic film.<ref>Template:Cite book</ref>
PVA-based polymers are used widely in additive manufacturing. For example, 3D printed oral dosage forms demonstrate great potential in the pharmaceutical industry. It is possible to create drug-loaded tablets with modified drug-release characteristics where PVA is used as a binder substance.<ref>Template:Cite journal</ref>
Medically, PVA-based microparticles have received FDA 510(k) approval to be used as embolisation particles to be used for peripheral hypervascular tumors.<ref>Template:Cite web</ref> It may also used as the embolic agent in a Uterine Fibroid Embolectomy (UFE).<ref>Template:Cite web</ref> In biomedical engineering research, PVA has also been studied for cartilage, orthopaedic applications,<ref>Template:Cite journal</ref> and potential materials for vascular graft.<ref>Template:Cite journal</ref>
PVA is commonly used in household sponges that absorb more water than polyurethane sponges.Template:Citation needed
PVA may be used as an adhesive during preparation of stool samples for microscopic examination in pathology.<ref>Template:Cite journal</ref>
Polyvinyl acetals
Polyvinyl acetals are prepared by treating PVA with aldehydes. Butyraldehyde and formaldehyde afford polyvinyl butyral (PVB) and polyvinyl formal (PVF), respectively. Preparation of polyvinyl butyral is the largest use for polyvinyl alcohol in the US and Western Europe.
Preparation
Unlike most vinyl polymers, PVA is not prepared by polymerization of the corresponding monomer, since the monomer, vinyl alcohol, is thermodynamically unstable with respect to its tautomerization to acetaldehyde. Instead, PVA is prepared by hydrolysis of polyvinyl acetate,<ref name=Ullmann>Template:Ullmann</ref> or sometimes other vinyl ester-derived polymers with formate or chloroacetate groups instead of acetate. The conversion of the polyvinyl esters is usually conducted by base-catalysed transesterification with ethanol:
- [CH2CH(OAc)]n + C2H5OH → [CH2CH(OH)]n + C2H5OAc
The properties of the polymer are affected by the degree of transesterification.
Worldwide consumption of polyvinyl alcohol was over one million metric tons in 2006.<ref name="sri"/>
Structure and properties
PVA is an atactic material that exhibits crystallinity. In terms of microstructure, it is composed mainly of 1,3-diol linkages [−CH2−CH(OH)−CH2−CH(OH)−], but a few percent of 1,2-diols [−CH2−CH(OH)−CH(OH)−CH2−] occur, depending on the conditions for the polymerization of the vinyl ester precursor.<ref name=Ullmann/>
Polyvinyl alcohol has excellent film-forming, emulsifying and adhesive properties. It is also resistant to oil, grease and solvents. It has high tensile strength and flexibility, as well as high oxygen and aroma barrier properties. However, these properties are dependent on humidity: water absorbed at higher humidity levels acts as a plasticiser, which reduces the polymer's tensile strength, but increases its elongation and tear strength.
Safety and environmental considerations
Polyvinyl alcohol is widely used, thus its toxicity and biodegradation are of interest. Tests showed that fish (guppies) are not harmed, even at a poly(vinyl alcohol) concentration of 500 mg/L of water.<ref name=Ullmann/>
The biodegradability of PVA is affected by the molecular weight of the sample.<ref name=Ullmann/> Aqueous solutions of PVA degrade faster, which is why PVA grades that are highly water-soluble tend to have a faster biodegradation.<ref>Template:Cite journal</ref> Not all PVA grades are readily biodegradable, but studies show that high water-soluble PVA grades such as the ones used in detergents can be readily biodegradable according to OECD screening test conditions.<ref>Byrne, Dominic, Boeije, Geert, Croft, Ian, Hüttmann, Gerd, Luijkx, Gerard, Meier, Frank, Parulekar, Yash and Stijntjes, Gerard. "Biodegradability of Polyvinyl Alcohol Based Film Used for Liquid Detergent Capsules: Biologische Abbaubarkeit der für Flüssigwaschmittelkapseln verwendeten Folie auf Polyvinylalkoholbasis." Tenside Surfactants Detergents, vol. 58, no. 2, 2021, pp. 88-96. https://doi.org/10.1515/tsd-2020-2326</ref>
Orally administered PVA is relatively harmless.<ref name="study5">Template:Cite journal</ref> The safety of polyvinyl alcohol is based on some of the following observations:<ref name="study5" />
- The acute oral toxicity of polyvinyl alcohol is very low, with LD(50)s in the range of 15-20 g/kg;
- Orally administered PVA is very poorly absorbed from the gastrointestinal tract;
- PVA does not accumulate in the body when administered orally;
- Polyvinyl alcohol is not mutagenic or clastogenic