PolyvinylpyrrolidonePolymers

I

POLYMERSPERFORMANCE-ENHANCING PRODUCTS

PVP(POLYVINYLPYRROLIDONEj

. film former

. protective colloid and suspending agent

. dye-receptive resin

. binder and stabilizer

. adhesive

. complexing agent

. physiologically inert

OF CONT TS

COMMERCIAL TYPES OF pVPPage

2

PHYSICAL AND CHEMICAL PROPERTIESMolecular Weight DeterminationViscositySolubilityFilm-Forming PropertiesCompatibilityProtective-Colloid ActionComplex FormationStability

333566888

INDUSTRIALAPPLICATIONS OF PVP 9

PHYSIOLOGICAL PROPERTIESAcute ToxicityChronic Toxicity

121212

REFERENCES 13

1

COMMERCIAL TYPES OF PVP

. Linear nonionic polymer

. High polarity / proton acceptor

. Amphiphilic

. Compatible with a variety of resins andeJectrolytes

. Solublein water and polar solvents,insolubleinesters, ethers, ketones and hydrocarbons

. Unsuitable for thermoplastic processing

PVP polymers are available in several viscosity and as a polymerization additive.grades, ranging from low to high molecular PVP polymer is supplied in five viscosityweight. This range,coupled withsolubility in aque- grades as a powder and/or aqueous solution.ous and organic solvent systems combined with The full line of PVP polymers is also available forits nontoxic character, gives PVP great flexibility. personal care applications such as film forming,Its industrial applications include, for example, in emulsion stabilization, colorant dispersion, etc.adhesives to improve strength and toughness; in ISP also offers pharmaceutical grades of PVP;paper manufacture to increase strength and as a our Plasdone@and Polyplasdone@polymer prod-coating resin; and in synthetic fibers to improve ucts are used in the pharmaceutical industry, anddye receptivity. It is also widely employed in inks, our Polycla~ stabilizers are used in the beverageimaging, lithography, detergents and soaps, the industry. Information on these polymers is avail-textile, ceramic, electrical, metallurgical industries able in separate brochures.

Tables I and II illustrate the PVPpolymers commercially availableand some typical properties.Table I

General PVP Properties.jrlard, glossy, transparent, oxygenperroeable.films. which.adhere to a varietyof substrates.Hygroscopic

..Adhesive and cohesive properties.Cross-linkable.

. PhysiologicaHylnert

Table"PVP Solution and Powder Products

a 5% aqueous solutionNOTE: These data are typical of current production,but are not necessarily specifications.

2

Property PVP K-1.5 PVP K-30 PVP K..60 PVP K-90 PVP K-120

Appearance @25C Pale yellow Off-white,Colorlessto Off-white, Yellow Yellow, Off-white, Colorless to \Jf.white,aqueous amorphous pale yellow amorphousaqueous viscous,amorphous yellow amorphoussolution powder aqueous powder solution aqueous pOWder aqueous powder

solution solution solution

K-Value (Viscosity of 1% 13-19" 13C19" 27-33 26-35 50-.62 80c100 90-100 110-130 108-130solution)

Co.lor(APHA) 4max. 100 max! 150 max.80 max." 100 max."40 max. 60max! 25 max! 50 max,'(VCS)

%Residual VP O.1max. 0.1 max. .001max.

PHYSICAL AND CHEMICAL PROPERTIES

MOLECULAR WEIGHT DETERMINATION

There have been many studies that have beendevoted to the determination of the molecular

weight of PVP. The low molecular weight polymershave narrower distribution curves of molecularentities than the high molecular weight compounds.Some of the techniques for measuringthe molecularweight of various PVP products are based on mea-suring sedimentation, light scattering, osmometry,NMR spectroscopy, ebullimometry, and size exclu-sion chromatography for determining absolutemolecular weight distribution. By the use of thesemethods, anyone of three molecular weightparameters can be measured, namely the numberaverage (Mn), viscosity average (Mv), and weightaverage (Mw). Each of these characteristics canyield a different answer for the same polymer asillustrated by using these measurement techniquesin the analysis of the same PVP K-30 sample. Thefollowing results are reported:

Numberaverage(Mn)- 10,000Viscosity average (Mv) - 40,000Weight average (Mw) - 55,000

Therefore, in any review of the literature, one mustknow which molecular average is cited.Conventionally, molecular weights are expressed bytheir "K-values," which are derived from relative vis-cosity measurements.

VISCOSITY

The K-values assigned to various grades of PVPrepresent a function of the average molecularweight, the degree of polymerizationand the intrinsicviscosity. The K-values are derived from viscositymeasurements and are calculated according toFikentscher's formula:

11 75Ko2log rei 1 + 1.5Ko2 +Ko

C where c = concentration in9/100 ml solution11rei = viscosity of the solution

compared with solventK = 1000Ko

The K-value accepted for PVP by pharmacopoeiasand other authoritative bodies worldwide is mea-sured by the viscosity technique and calculated bythe use of the Fikentscher's equation.

In aqueous solution PVP K-15and K-30,particularlyin concentrations below 10%, have little effect onviscosity, whereas K-60 and K-90 considerablyinfluence flow properties (Figure 1). In organic sol-vents the viscosity of the solution is related, ofcourse, to that of the solvent, Table III.

Figure 1Effect of Concentration of Different

Grades of PVP on Viscosity ofAqueous Solutions at 25C

100000

10000

1/1

1000

100

10

1

0 10 20 30

%PVP

40 50 60

3

Table III

Viscosities of PVP K-30 in Various Organic Solvents

Solvent 20/0PVP 100/0PVP SolventKinematic Viscosities (in centistokes)

20/0PVP

4804321

280

Note: Kinematic Viscosity in centistokes = Absolute Viscosity in centistokes

Density

PVP solution viscosity does not change appreciablyover a wide pH range, but increases in concentratedHC!. Strongcausticsolutions precipitate the polymer,but this precipitate solution redissolves on dilutionwith water (Table IV).

Table IVEffect of pH on Viscosity of 5% Aqueous

PVP K-30at 25C

10

Viscosity (cp)I2.4

The densities of PVP water solutions are only slight-ly changed despite a significant increase in the con-centration of PVP K-30, Table V.

Table VEffect of PVP K-30 Concentration on

Density in Water

PVP Concentration (%Density at 25'C (glml)

101.02

201.04

The effect of temperature and concentration onviscosity is shown in Figures 1 and 3 for PVP K-30and K-90 respectively. Any possible effect of hightemperatures and concentrations on finished formu-lations should be determined experimentally.

Figure 2Brookfield Viscosity of Aqueous PVP K-30

D..(,)

:;; 10'iij0(,)'"'S:'tIQj;;::...00Ii

100

-+- 1D'C--- 25'C-.- 40'C-e- 6D'C

0.1a 5 10 15 20 25

Concentration (w/w),%

Figure 3Brookfield Viscosity of Aqueous PVP K-90

100000

4

-+- 1D'C--- 25'C-.- 4D'C-e-6D'C

5 10 15 20 25

Concentration (w/w),%

10000D..(,)

:;;'iij 10000(,)'"'S:'tI

100...00Ii

10

10

SOLUBILITY

PVP is readily soluble in cold water and the con-centration is limited only by viscosity. It is possibleto prepare free-flowing solutions of PVP K-30 inconcentrations up to 60% with only moderateeffect on density. PVP K-60 and K-90are availablecommercially as 45 and 20 percent aqueoussolutions, respectively. .

Roughly 0.5 mol water per monomer unit isassociated with the polymer molecule in solution.This is of the same order of magnitude as thehydration reported in the literature for various pro-teins.

PVP K-30 is also freely soluble in manyorganic solvents, including alcohols, some chlori-nated compounds such as chloroform, methylene

chloride and ethylene dichloride, nitroparaffins,and amines. It is essentially insoluble in hydrocar-bons, ethers, some chlorinated hydrocarbons,ketones and esters.

Dilute solutions of PVP in hydrocarbonsmay be prepared by the use of a cosolvent, e.g.,butanol, N-methyl-2-pyrrolidone, or nonylphenol.Clear 3-5% PVPsolutions in aliphatic hydrocarbonsmay be readily prepared by adding the hydrocar-bon to a butyl alcohol solution of the polymer. Inoil-based products, solubilization in an alkylphenol,e.g., octyl- or nonylphenol, is useful. The alkylphe-nol is first heated to about 100C and the PVP

added slowly with stirring. Then the temperaturemay be raisedtoapproximately 200Cto acceleratesolution.

Table VI

PVP K-30Solubility

The following representative organic solvents will dissolve 10% or more PVP at room temperature:

Alcoholsmethanolethanolpropanolisopropanolbutanolsec-butanolamyl alcohol2-ethyl-l-hexanolcyclohexanoJ

nol (50'C)Iycol

1,3-butanediol

1 ,4-butanediol

glycerin

Ketone-Alcoholdiacetone alcohol

Acidsformic acidacetic acidpropionic acid

Ketonemethylcyclohexanone

anline

ethylenediaminepyridinemorpholine2-aminoethanoldiethanolaminetriethanolamine

aminoethylethanolamine2-hyd roxyethylmorpholi ne2-amino-2-methvl-1-propanol

Ether-Alcohols

glycol ethersdie

Chlorinated Hydrocarbonsmethylene dichloridechloroform

ethylene dichloride01

- - :01hexamethylene glycolpolyethylene glycol 4002,21 -thiodiethanol

Lactams

2-pyrrolidoneN-methyl-2-pyrrolidoneN-vinyl-2-pyrrolidone

Lactone'Y-butyrolactone

Aminesbutylaminecyclohexylamine

Nitroparaffinsnitromethanenitroethane

Esterethyl lactate

Hydrocarbonsbenzenetoluene*xyleneTetralin**petroleum etherhexaneheptane*Stoddard solvent*kerosene*

Ketonesmethylethylketoneacetonecyclohexanone

s

Ethersdioxaneethyl ether

Chlorinated Hydrocarbonscarbon tetrachloridechlorobenzene

Estersethyl acetatesec-butyl acetate

*pvp is soluble in these hydrocarbons in about 5% concentration when added to the solvent as a 25% butanol solution.

**Tetralin is a registered trademark of DuPont

5

FILM FORMING PROPERTIES

Dried unmodified films of PVP are clear, transpar-ent, glossy, and hard. Appearance does not varywhenfilms are cast from different solvent systems,such as water, ethanol, chloroform, or ethylenedichloride.

Compatible plasticizers may be added withoutaffecting clarity or luster of the film. Moisturetaken up from the air by PVP can also act as aplasticizer. Among the several commercial modi-fiers that may be used inconcentrations of 10-50%(based on PVP) to control tack and / or brittlenessor to decrease hygroscopicity are:

carboxymethylcellulosecellulose acetate

cellulose acetate propionatedibutyl tartratediethylene glycoldimethyl phthalateDytol 8-35, J-68, and L-79

(Rohm and Haas)2-ethylhexanediol-1, 3glyceringlycerylmonoricinoleateHyprin GP-25 (Dow)Igepal CQ-430 (Rhone Poulenc)Lorol (DuPont)oleyl alcoholResoflex R-363 (Cambridge)Santicizer 141, 8-16, and E-35

(Monsanto)shellacsorbitol

Carboxymethycellulose, cellulose acetate, cellu-lose acetate propionate, and shellac effectivelydecrease tackiness. Dimethyl phthalate is lesseffective, whereas glycerin, diethylene glycol, andsorbitol increase tackiness. Films essentiallytack-free over all ranges of relative humidity maybe obtained with 10% arylsulfonamide-formalde-hyde resin.

In comparative tests for plasticity at 33% relativehumidity, PVP films containing 10% diethyleneglycol show an "elongation at break" twice that ofPVP films containing 10% glycerin, polyethyleneglycol 400, sorbitol, or urea, and four times that ofPVP films containing 10% ethylene glycol,dimethyl phthalate, or Santicizer E-35. At 50%relative humidity, 10% Santicizer E-G5,25% glyc-erin, and 25% diethylene glycol are effective plas-ticizers. At 70% relative humidity, 25% sorbitoland 25% dimethylphthalate may be used suc-cessfully.

COMPA TlBILlTY

PVP shows a high degree of compatibility, both insolution and film form, with most inorganic saltsolutions and with many natural and syntheticresins, as well as with other chemicals (TableVII).

At 25C the addition of 100 ml of a 10% solution

of any of the following salts to 10% PVP K-30aqueous solution (Le., 10 parts of the test salt to1 part of PVP)does not change the appearance ofthe solution:

aluminum potassium sulfatealuminum sulfateammonium chlorideammonium sulfatebarium chloridecalcium chloridechromium sulfate

copper sulfateferric chloride

magnesium chloridemercuric acetatenickel nitratelead acetate

potassium chloridepotassium sulfatepotassium dichromatesodium bicarbonate*sodium chloridesodium nitrate

sodium phosphate (primary)sodium pyrophosphatesodium sulfatesodium sulfitesodium thiosulfatesilver nitratezinc sulfate

*200 ml if a 5% solution

6

AIK (S04b,12H2OA12(S04h,18H20NH4CI(NH4bS04BaCl2,H20CaCI2Cr2(S04h,nH20CuS04,5H2OFeCI3,6H2OMgCI2,6H2OHg(C2H302bNi(N03)2,6H2OPb(C2H302b,3H2OKCI

K2S04K2Cr207NaHC03NaCI

NaN03NaH2P04,H2ONa4P2O7

Na2S04Na2S03,7H20Na2S203,5H20AgN03ZnS04,7H20

CLASS

Ether-Alcohols

Gums

Glycerides

Esters

Phenols

Misc.Resins.

SyntheticPolymers

S urfactants

QUatemaryAmmoniumCompounds

Table VIICompatibility of PVP

in Solutions and Films

COMPOUNDTESTED"

polyethylene glycolUcon Oil@50-HB 5100 (polyalkylene glycol, Union Carbide)Ucon Oil@75-HB 90,000 (Union Carbide)arabickarayatragacanthsodium alginateolive oilcastor oillanolinlecithinbeeswaxdiethylene glycol stearate

Flexo@300 (triethylene glycol bis-alpha-ethylcaproate,Union Carbide)

cellulose acetate propionatecellulose acetate

phenol)~ethylene-bisrophenol)]

shellacethyl cellulosemethylcellulosecarboxylmethylcellulose

(low viscosity grade)com dex1rin**

Saran@B-1155 (vinylidene chloride polymer, Dow)

PVI-C poly ( isobutyl ether)PVM poly ( ethyl ether)polystyrenepolyvinyl alcoholAlipal@CO-436 (ammonium salt of sulfated

n xypoly (ethylenoxy) ethanol,Rhone ulenc)

Duponol@(sodium lauryl sulfate, DuPont)Nekal@BX-78 (sodium alkylnaphthalene. sulfonate, Rhone-Poulenc)

Hyamine@ 2389 (Rhom and Haas)Tetrosar'" (Onyx)BTC@(alkylidmethylbenzyl ammonium

chloride, Onyx)Isothar'" (Lauryl isoquinolinium bromide,

Onyx)cetylpyridinium chloride

*Ratio of PVP to compound 1:3, 1:1, 3:1

"Ratio of PVP to compound 1:19

Colloidal suspensions are formed by 10% solutions ofthe following salts when addedlQ 10% aqueous PVPsolutions in the amounts shown:

sodium carbonate

sodium phosphate, dibasicsodium phosophate, tribasicsodium metasilicate

Na2COsNa2HP04*7H20NaSP04*12H20

Na2SiOs*5H2O

RatioTest Salt: PVP

1:85:13.7:1

1.28:13:1

SOLVENT %TTLSOLIDS

ethanolethanolethanolwaterwaterwaterwater

chloroformpropargyl

alcoholethanol

ethanolethanolwater

waterwater

N-methyl-2-pyrrolidone 3

chloroform 4hot meltchloroform

water

waterwater

waterwaterwater

water

water

Abbreviations:SPSIINHC

SOLUTION OR MELTAPPEARANCE

55

ItP~S

S clear, light yellowS clear, colorlessS yellowI 0 ogeneous INS clear, colorless

35

44

S clear, yellowS clear, colorless

SS

66

54

SISS clear,colonessS

35

3210

S clear, CS clear, col ,ss

S hazy, light yellowS clear, colorlessS clear, coloness

10

1010

S clear, colorless

S clear, colorlessS clear, colorless

Soluble

Partially solubleInsoluble

IncompatibleHomogenousCompatible

FILMCOMPATIBILITY

CINHCHHC

cC

cCC

C

ININCINC

C

When reviewing Table VII, one should note the gener-al procedure followed in determining compatibility wasto dissolve PVP K-30 and the test material separatelyin a mutual solvent. After mixing the two solutions,appearance was observed. The solution was thencast onto a glass plate and the resulting film examinedafter evapordtion of the solvent.

7

I

PVP powder can be stored under ordinaryconditions without undergoing decomposition ordegradation. However, since the powder is hygro-scopic, suitable precautions should be taken toprevent excessive moisture pickup. Bulk polymeris supplied in tied polyethylene bags enclosed infiber packs. When not in use, the polyethylenebag should be kept closed at all times in the cov-ered container.

On PVPfilms, moisture acts as a plasticizer.These films are otherwise chemically stable.

The equilibrium water content of ,PVPsolidor films varies in a linear fashion with relative

humidity and is equal to approximately one-thirdthe relative humidity. Samples of dried, powderedPVP, subjected to 20, 52, and 80 percent relativehumidity until equilibrium is reached, show a 10, 19,and 31 percent moisture weight gain, respectively.

Exposure to extreme elevated tempera-tures should be avoided, though PVP powder isquite stable to heat. Some darkening in color anddecreased water solubility are evident on heatingin air at 150.C. However, PVP appears to be quitestable when heated repeatedly at 110-130.C forrelatively short intervals.

Aqueous PVP is stable for extended periodsif protected from molds. The usual preservatives-benzoic acid, sorbic acid, esters of p-hydroxyben-zoic acid-are quite effective. However,appropriatetests should be made with finished productscontaining PVP before deciding on a preservative.Steam sterilization (15 lb. pressure for 15 min.)can also be used and this treatment does not

appear to change the properties of the solutions.The polymer has no buffering power, and

large changes in the pH of solutions are observedupon addition of small amounts of acids or bases.For example, the pH of 100 ml of 3.5% PVP K-30

Resorcinol and pyrogallol also precipitate solution is raised from pH 4 to pH 7 by the additionPVP from aqueous solution, but these complexes of 1-2 ml 0.1 N sodium hydroxide.

8

PROTECTIVE-COLLOID ACTION

Small amounts of PVP effectively stabilize emul-sions, dispersions, and suspensions. Evenlyophobic colloids, which exist without significantaffinity for the medium, can be protected by PVP.The polymer is adsorbed in a thin molecular layeron the surface of the individual colloidal particles toprevent contact and overcome any tendency toform a continuous solid phase.

The best viscosity grade to use depends, ofcourse, on the application. In some cases, thelower molecular weight polymers, PVP K-15 orPVP K-30, are more efficient than high molecularweight material. For example, PVP K-15 is partic-ularly effective as a dispersant for carbon blackand low-bulk density solids in aqueous media. It isused in detergent formulations to prevent soil rede-position on synthetic fibers and as a protectivecolloid for certain pigments. In viscous systems,on the other hand, PVP K-90 is most suitable, e.g.,as a dispersant for titanium dioxide or organic pig-ments and latex polymers in emulsion paints. Alsoin the suspension polymerization of styrene, PVPK-90 is preferred as the protective colloid to gen-erate the desired particle size.

COMPLEX FORMATlON/CROSSLlNKING

PVP forms molecular adducts with many othersubstances. This can result in a solubilizing actionin some cases orin precipitation in others.

PVP crosslinks with polyacids like poly-acrylic or tannic acid to form complexes which areinsoluble in water or alcohol but dissolve in dilutealkali. Gantre~ AN (ISP), methyl vinyl ether/male-ic anhydride copolymer, will also insolubilize PVPwhen aqueous solutions of polymers are mixed inapproximately equal parts at low pH. An increasein pH will solubilize the complex.

Ammonium persulfate will gel PVP in 30minutes at about 90.C. These gels are not ther-moreversible and are substantially insoluble inlarge amounts of water or salt solution. The morealkaline sodium phosphates will have the sameeffect. When dried under mild conditions, PVPgels retain their uniform structure and capacity toswell again by absorption of large amounts ofwater.

~

redissolve in additional water. In alcoholic solu-tion, no precipitation takes place.

Under the influence of actinic light, diazocompounds and oxidizing agents, such as dichro-mate, render PVP insoluble.

Heating in air to 150.C will crosslink PVPand strong alkali at 100.C will permanently insolu-bilize the polymer.

j

I

JSTABILITY

J

INDUSTRIAL APPLICATIONS OF POLYVINYLPYRROLIDONE

Polyvinylpyrrolidone is widely used in a broadvariety of industries. This is due to its unique phys-ical and chemical properties, particularly becauseof its good solubility in both water and manyorganicsolvents, its chemical stability, itsaffinity to complex

AREA OF USE

Adhesives...pressure-sensitive and water-remoist-enable types... food packaging (indi rect food contact). .. metal adhesives. . .abrasives. ..sandcore binder...

rubber to metal adhesives...glue sticks.

Ceramics...binder in high temperature fire preparedproducts such as clay, pottery, porcelain, brick prod-ucts...dispersant for ceramic media slurries...andviscosity modifier.

Glass and Glass Fibers.. .acts as a binder, lubricant

and coating agent.

Coatingsllnks.. .digital printing coating...ball-poinftive colloid and levelling agentymers! coatings! printing inks...pigment

dispersanL.water-colors for commercial art...tem-porary protective coatings...paper coatingsmwaxesand polishes.

both hydrophobic and hydrophilic substances andits nontoxic character. Several hundreds of papershave been published describing the advantages ofusing PVP in formulas for the following productareas.

ADVANTAGES OF PVP

Specific adhesive for glass, metal, plastics.Imparts high initial tack, strength, hardness.

Particularly suitable for remoistenable adhesiveapplications.

Forms grease-resistant films.

Films can be cast from water or organic solvents.

Modifies viscosity of polymer-based adhesives.

Raises cold-flow temperature.

Raises softening point of thermoplastics.

Binder is completely combustible in the firingprocess and therefore exerts no influence on theceramic and product and in addition, is compatiblewith inorganic materials.

Aids in processing and helps to prevent abrasion ofglass.

Suspending agent, flow promoter in inks.

Nonthixotropic.

Promotes better gloss, high tinctorial strength,more uniform shades.

Antiblock agent.

Grease resistant.

Inkjet dye fixative.

9

AREAOF USE

HI & I... dye transfer inhibitor... liquid and powderlaundry products...detergent briquettes and bars...detergent encapsulating agent...soap sheets...waterless hand cleaners...industrial sanitizers...auto cleaning solutions...grease remover...foamstabilizer for bubble baths...dirt deposition inhibitorfor synthetic fibers and resin-treated fabrics...binderfor tabletformulations...enzymestabilization.

ElectricalApplications...storage batteries...print-ed circuits...cathode ray tubes...binder for metalsalts or amalgams in batteries...gold, nickel,copperand zinc plating...a thickener for solar gel pondsand as an adhesive to prevent leakage of batteries...serves as an expander in cadmium-type elec-trodes...binder in sintered-nickel powder plates.

Lithographyand Photography...foil emulsions...etch coatings...plate storage...gumming of litho-graphic plates...dampener roll solutions...photoand laser imaging processes...microencapsulation...thermal recording...carrier, finisher preserver oflithographic plates...thermal transfer recordingribbons and optical recording discs.

Fibers and Textiles...synthetic fibers...dyeing andprinting...fugitivetinting...dyestrippinganddispersant...scouring...delustering...sizing and finishing...greaseproofing aid...soil release agent. Widelyused as dye dispersant and to disperse titaniumdioxide.

""1:

ADVANTAGES OF PVP

Compatible in clear liquid, heavy-duty detergents.

Loose-color scavenger during laundering.

Improves emollient action and detergent storagestability.

Stabilizes foam.

Reduces irritation.

In enzyme containing products used to coat andbind the enzyme thereby minimizing dusting.

HYdrophilic material in electrode separators ofmicroporous Jilmtype.

Compatible dispersant in printed circuits toimprove uniformity.

Shadow masks and protects light sensitive materialin CRT.

Compatible dispersant for solar collection heattransfer liquids, for gold, nickel, copper and zincplating baths and cathode ray tubes.

Light-hardenable, water-soluble colloid tor diazo,dichromate, or silver emulsion layers..

Obviates deep-etching of metal plates.

Offers uniform viscosity, temperature stability.

Nonthixotropic. Defoggant.

Adheres tightly to plates in nonimage areas.

Grease-proof and water receptive.

Chemically inert to ink ingredients.

Binder, dispersant carrier and improves adhesionfor light absorber dyes and antistick agent.

Increases covering power density and contrast aswell as speed of emulsions used in photography.

Backbone for grafting monomers.

Improves dye receptivity of such hydrophobicfibers as polyolefins, viscoses, rubber latices, poly-acrylonitriles and acrylics.

Dye fixation improver and dye vehicle in wooltransfer printing. Thickener for heat activated tex-tile adhesives, textile finishes and print parts forvarious types of fabrics.

Textile dye stripping and strike rate control throughdye complexion.

Acts as a dye scavenger in print washing.

Contributes enhanced adhesives to glass-fibersizes.

10

'!o

AREA OF USE

Membranes...macroporous, multiporous, desalina-

tion,gas separating, liquid ultrafiltration, hemodialysis,selective permeability types of membranes, hollowfiber membranes.

Metallurgy...processing for both ferrous and non-ferrous metals...coating ingredient to aid or removematerial from metal surfaces such as copper, nickel,zinc and aluminum.

Paper...inorganic papers, cellulose papers, ragstock...rag stripping...coloring and beating opera-tions...copying paper, printing paper and electricinsulating papers...paper adhesives.

Polymerizations... acryl ic monomers... unsatu ratedpolyesters...olefins, including PVC...styrene beads...substrate for graft polymerization...template inacrylic polymerization.

Water andWasteTreatment, andHygiene...scaleinhibitor, prevention of corrosion in water transfersystems, clogging of reverse osmosis membranes,water treatment in fish hatchery ponds...removal ofoil, dyes from waste water and as an oil-ball formingagent in oil spill removal...flocculant in waste watertreatment...waste water clarifier in papermaking...in deodorants for neutralization of irritant and poi-sonous gas, in air conditioning filters.

Oil/Gas...additive to cement used in the oil industry...viscosity modifier...gas hydrate inhibitor.

ADVANTAGES OF PVP

Good compatibility and crosslinking properties

Ability to complex with a broad variety of com-pounds.

Strong polar character and hydrophilicity improvesselective material separation properties.

Steel quenching bath media.

Coating to facilitate the cold forming of metals.

Binder for casting molds and cores.

Thickener, viscosity. controlling agent, adhesionimprover, water soluble flux.

Improves strength and stability.

Prevents sliding.

Fluorescent whitening agent carrier.

Improves luster, binding, absorbency, whiteningand gloss.

Solubilizes dyes for coloring, dyestripping:

Fiber and pigment dispersant.

Helps in preventing deposition of pitch.

Complexing agent for modifying resins.

Binder for inorganic flakes and fibers.

Acts as particle-sIze regulator, suspending agentand viscosity modifier of emulsion polymers. Inpolymerization products, improves strength, clarity,color receptivity.

Post-polymerization additive to improve dyeabilityand stability oflatices..

Pigment dispersant.

Complexes and gels in water to react with unde-sired water products.

Cement set-time retarder, reduces speed of fluidloss and improves the sealant properties of thewell casing.

Used as a viscosity modifier in drilling muds.

Kinetic inhibitor of pipeline gas hydrate formation.

I...

11

PHYSIOLOGICAL PROPERTIES

PVP IS SAFE

In the half century since the invention of PVP, avery extensive body of toxicological data in animaland man has been developed. It is perhaps themost intense body of toxicological informationavailable on any pharmaceutical excipient or foodadditive in use today.

The data supports the conclusions reached byindividual workers, as well as numerous regulatorybodies, that PVP is safe.

Contributing to this favorable safety profile are thefollowing:

BiologicalActivity:Becauseof its uniquechemicalnature, PVP would be expected to be biologicallyinert apart from exerting osmotic activity. A largenumber of animal and human studies support themetabolic inertness of this polymer and hence thesafety of PVP.

Absorption: The absorption of PVP from thegastro-intestinal tract is very limited and proceedsprimarily by fluid-phase pinocytosis.

Metabolism: PVP is not metabolized.

Pharmacological Effects: With normal use, PVPdoes not modify physiological activity.

More Specifically:

Acute Toxicity:Studies in rodents, dogs andprimates have shown that PVP is a substancewith a very low acute toxicity. It is essentiallyimpossible to kill animals by administration of PVPexcept by gross osmotic imbalance. Thus, theLO50 of PVP orally is reported to exceed 100g/kgand be over 10g/kg intravenously or intraperi-toneally.

Subchronic Toxicity:Repeat dose oral studies inrodents and dogs have shown apart from loosestool at high doses, which is related to the bulkpurgative actions of PVP, there is no evidence of

~

any toxicity as judged by clinical chemistry, hema-tology and histopathology. The no-adverse effectlevel (NOEL) in subchronic studies in rodents and

dogs exceeds 5g/kg/day.

Chronic Toxicity:In two well conducted chronicstudies using PVP K-25 and PVP K-90 in the dietat dose levels as high at 10%and 5% respectively,over a two-year period, there was no evidence ofany substance-related toxicity in clinical chem-istry,hematology,urineanalysis and histopathologyreview. There was no evidence of any carcino-genic effect or evidence of PVP storage in anyorgan. There was no evidence of any cumulativedamage over the two-year studies.

Teratology:Teratogenicity studies on PVP givenorally, intravenously and intra-aminiotically in ratsand/or rabbits have shown no evidence ofembryo-toxicity or teratogenicity.

Mutagenicity:In vitro and in vivo mutagenicitystudies have shown that PVP does not have anygenotoxic or clastogenic acitivity.

In Summary:

An extensive body of toxicological data in animalssupports the biological inertness of PVP. Theacute, subchronic and chronic toxicity of orallyadministered PVP is extremely low. It is not asensitizer or irritant. There are no reportedadverse effects following oral administration inhumans. The currently permitted United Nations'World Health Organization's Food and AgricultureOrganizations joint expert committee on foodadditives established an allowable daily intake of50mg/kg/day for food use provides an adequatemargin of safety. There would appear to be noreason to restrict its oral pharmaceutical use inany way. There have been no reports of adverseeffects following its use intravenously as a plasmaexpander, even after the administration of verylarge amounts.

Based on the available data, PVP should provesafe in normal industrial applications.

12

REFERENCESThere is a sizable listing of technical literature that deals with the various aspects of PVP and its applications. Thefollowing listing is a representative, not comprehensive, sampling of this literature.

General Chemistry1. L.Senak,C.S.Wu,and E.G.Malawer,"SizeExclusionChromatographyof Poly(Vinylpyrrolidone).IIAbsolute

MolecularWeightDistributionby Sec/LallsandSecWithUniversalCalibration,"J. Liq. Chromatogr.,10 (6):1127-1150(1987). -

2. B.V. Robinson, EM. Sullivan, J.F. Borzelleca, and S.L. Schwartz, "PVP-A Critical Review of the Kinetics andToxicology of Polyvinylpyrrolidone (Povidone)," (Chelsea, MI:CRC Press, 1990).

Ceramics1. EP 294,208 (Dec. 7, 1988), TE. Wood, D.M. Wilson, H.G. Sowman (to Minnesota Mining & Mfg. Co.).2. P.K.Bajpai, C.M. Fuchs and D.E. McCullum, "Development of Tricalcium Phosphate Ceramic Cements,"ASTM Spec.

Tech. Publ, 953:337-88(1987).

Electrical1. US Pat. 4,904,526 (Feb. 27, 1990), D.C. Koskenmaki (to Minnesota Mining and Mfg. Co.).2. GB Pat. 2,217,333 (Oct. 25,1989), Y.Tamida, S. Yuasa and M. Sakuran (to Canon KK).3. JP Pat. 01,220,426 (Feb. 29, 1988), R Nagai, T. Sugiura (to Hitachi Condenser Co, Ltd).4. R Narasimha, V., A Kalpalatha, "Thermally Stimulated Discharge Currents in Polyvinylpyrrolidone Polymer Films."

Materials, Chemicals& Physics17:317-24 (1987).5. V. Rao, K. Narasimha, "Electrical Conduction Mechanism in Poly (vinylpyrrolidone) Films,"Polymer28:648-50(1987).

Fibers and Textiles1. K. Nishida, Y.Ando, S. Toriumi, "The DesorbingAction of Polyvinylpyrrolidone," J.Soc. Dyers Colour,104:96-9 (1988).2. EP 247,539 (Dec. 2, 1987), EV. Distefano (to Air Products and Chemicals, Inc.).3. US Pat 4,698,384 (Oct. 6, 1987), C.L. Mao (to Air Products and Chemicals, Inc.).4. W.B.Achwal and R Samvatsarkar, "Preparation of Polymer-Dye Complexes and Their Application as Tinting Agents,"

Indian J. Text Res12:6-12 (1987).5. EP 0,368,370 (May 16, 1990),H.G. Sowman (Minnesota Mining and ManufacturingCo.).

HI&I1. EP 350,449 (Jan. 10, 1990),M. Joellenback and C. Eckhardt (to Ciba Geigy AG.).2. EP 342,997 (Nov. 23, 1989), GK Rennie, P.Bernardi (to Unilever N.V.).3. US Pat. 4,842,761 (June 27, 1989), H.J. Rutherford (to International Flavors and Fragrances Inc.).4. US Pat.4,764,289 (Aug. 16, 1988),T. Trinh (to Procter and Gamble Co.).5. EP 265,257 (April 27, 1988),AH. Clements, G.A. Catton, A.PAE Rocourt (to UnileverN.V.).

Lithography and Photography1. US Pat. 4,877,698 (Oct. 31, 1989), PK Watson, I.D. Morrison and M.D. Crouch (to Xerox Corp.).2. JP Pat. 01,193,845 (Aug. 3, 1989), K. Kumashiro and H. Shimazaki (to Konica Co.).3. US Pat. 4,849,286 (July 18, 1989), M.H. Milne (to James River Graphics, Inc.).4. EP 326,715 (Aug. 9,1989), M.S. Dhillon, S. Hsieh and DA Seeley (to Hoechst Celanese Corp.).5. US Pat. 4,914,451 (Sept. 27, 1989), P.C. Morris and M.S. Hickman (to Hewlett-PackardCo.).

Metallurgy1. US Pat. 4,826,545 (May 2, 1989), R W. Foreman and AG. Meszaros (to Foreman).2. US Pat.4,738,731(April 19, 1988), RW. Foreman, RW. and AG. Meszaros (to Parke Davis & Co.).3. US Pat. 4,528,044 (July 9, 1985), J.E Warchol (to E.E Houghton & Co.).4. US Pat. 4,595,425 (June17, 1986),RH. Harding (to Union Carbide Corp.).

Oil I Gas1. US Pat. 4,825,950 (May 2, 1989), B. Kalpakci and TG. Arf (to Standard Oil Co.).2. US Pat. 4,792,412 (Dec. 20,1988), I.J. Heilweil (to Mobil Oil Corp.).3. US Pat. 4,498,994 (Feb. 12, 1985), I.J. Heilweil (to Mobil Oil Corp.).

Paper1. US Pat 4,600,462 (Apr. 30, 1985), W.R Watt (to James River Dixie Northern, Inc.).2. US Pat.4,673,704(Feb. 5,1986),P. Flesher and D. Farrer (to Allied Colloids Ltd.).3. JP Pat. 01,139,812 (Jun. 1, 1989), T Kanda and T Matsuda (to Toray Industries Inc.).4. JP Pat. 63,006,169 (Jan.12, 1988), T Tanaka and M. Okita (to Toho Rayon Co., Ltd.).

13

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