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POLYMERS
PERFORMANCE-ENHANCING PRODUCTS
PVP
(POL YVINYLPYRROLIDONEj
. film former
. protective colloid and suspending agent
. dye-receptive resin
. adhesive
. complexing agent
. physiologically inert
OF CONT
TS
Page
2
3
3
3
5
6
6
8
8
8
PHYSIOLOGICAL PROPERTIES
Acute Toxicity
Chronic Toxicity
12
12
12
REFERENCES
13
Tables I and II illustrate the PVPpolymers commercially available and some typical properties.
Table I
General PVP Properties
.jrlard, glossy, transparent, oxygenperroeable.films. which.
adhere to a variety of substrates
Hygroscopic
.
.
.
.
.
.
.
Cross-linkable.
. PhysiologicaHylnert
Table"
PVP Solution and Powder Products
PVP K-1.5
Property
PVP K-30
PVP K..60
Yellow
Pale yellow Off-white, Colorlessto Off-white,
aqueous amorphous pale yellow amorphous aqueous
solution
solution
powder
aqueous
powder
solution
13-19"
13C19"
27-33
26-35
50-.62
K-Value (Viscosity of 1%
solution)
4max.
100 max!
150 max.
80 max."
100 max."
Co.lor(APHA)
(VCS)
O.1max.
0.1 max.
%Residual VP
.001max.
<0.1
<0.1
28 -32
%Active
29"31
95rnin.
4549
.95 min.
68 72
%Moisture
5max
69-71
5max.
51- 55
0.012
5. max
0.02 max
0.044
0,01?
%Ash (combustion)
6-9
3 7
6-9
3 7
3-7
PH (5% aqueous sOlUtion)
Appearance @ 25C
MW Range
6,000
(measured by LALLS)
Brookfield Viscosity, cps
(5% soHds@)25C)
SpecificGravity@25'C
Bulk Density (g/cc)
FilmDensity (g/cc)
Freezihg Point C
Specific
Heat (callg/KC)
Tg CC)
- 15,000
40,000" 80,000
1.061
1.203
-4.1
0.819
-
0.6- 0.7
-
1.062
.76- 80
0.016
5max.
-
0.1 maXi
95 min.
5tJ'lax.
4-9
3'7
<0.1
H13
87-89
0.018
6 9
2,000,000"
freezecdried
<0.1
95.min.
1.051
"2.2
0.738
170
a 5% aqueous solution
NOTE: These data are typical of current production,
but are not necessarily specifications.
<0..1
20 -24
1.122
163
50 max,'
150
25 max!
O.4i-0.6
130
60 max!
1,500,000
1.207
-g,T
0.803
40 max.
900,000-
PVP K-120
240,00"
450,000
10
PVP K-90
1.216
-0.9
0.827
-
0;3 0.4
-
A8
3,000,000
350
-
1.024
-
.O,.? 0.3
-
0.3
0.884
174
176
100000
Numberaverage(Mn)-
10,000
Viscosity average (Mv) - 40,000
Weight average (Mw) - 55,000
10000
1/1
<II
..\I::
0
1/1
:;:;
C
<II
U
:>;
.iij
0
(,)
1/1
VISCOSITY
1000
100
:>
10
1
0
11
log rei
75Ko2
1 + 1.5Ko2 +Ko
K = 1000Ko
10
20
30
%PVP
40
50
60
Table
III
Solvent
20/0PVP
100/0PVP
Solvent
20/0PVP
480
4
3
2
1
2
80
Note: Kinematic
Viscosity
in centistokes
= Absolute
Viscosity
in centistokes
Density
Figure 2
Brookfield Viscosity of Aqueous PVP K-30
100
D..
(,)
:;; 10
'iij
0
(,)
Table IV
Effect of pH on Viscosity of 5% Aqueous
PVP K-30 at 25C
10
Viscosity (cp)
-+- 1D'C
--- 25'C
'"
'S:
'tI
Qj
;;::
...
0
0
Ii
-.- 40'C
-e- 6D'C
0.1
a
I 2.4
10
Concentration
The densities of PVP water solutions are only slightly changed despite a significant increase in the concentration of PVP K-30, Table V.
15
20
25
(w/w), %
Figure 3
Brookfield Viscosity of Aqueous PVP K-90
100000
Table V
Effect of PVP K-30 Concentration on
Density in Water
10000
D..
(,)
:;;
'iij
0
(,)
PVP Concentration (%
Density at 25'C (glml)
10
1.02
1000
-+- 1D'C
--- 25'C
'"
'S:
'tI
20
1.04
...
0
0
Ii
-.- 4D'C
-e- 6D'C
100
10
1
0
10
Concentration
15
(w/w), %
20
25
SOLUBILITY
PVP is readily soluble in cold water and the concentration is limited only by viscosity. It is possible
to prepare free-flowing solutions of PVP K-30 in
concentrations up to 60% with only moderate
effect on density. PVP K-60 and K-90 are available
commercially as 45 and 20 percent aqueous
solutions, respectively.
.
Roughly 0.5 mol water per monomer unit is
associated with the polymer molecule in solution.
This is of the same order of magnitude as the
hydration reported in the literature for various proteins.
PVP K-30 is also freely soluble in many
organic solvents, including alcohols, some chlorinated compounds such as chloroform, methylene
Table VI
PVP K-30 Solubility
The following representative organic solvents will dissolve 10% or more PVP at room temperature:
Alcohols
methanol
ethanol
propanol
isopropanol
butanol
sec-butanol
amyl alcohol
2-ethyl-l-hexanol
cyclohexanoJ
nol (50'C)
Iycol
Acids
formic acid
acetic acid
propionic acid
Ketone
methylcyclohexanone
Chlorinated Hydrocarbons
methylene dichloride
chloroform
Ether-Alcohols
glycol ethers
die
ethylene dichloride
01
- :01
hexamethylene glycol
polyethylene glycol 400
2,21 -thiodiethanol
Lactams
2-pyrrolidone
N-methyl-2-pyrrolidone
N-vinyl-2-pyrrolidone
1 ,3-butanediol
glycerin
Lactone
'Y-butyrolactone
Ketone-Alcohol
diacetone alcohol
Ester
ethyl lactate
1 ,4-butanediol
Hydrocarbons
benzene
toluene*
xylene
Tetralin**
petroleum ether
hexane
heptane*
Stoddard solvent*
kerosene*
Amines
butylamine
cyclohexylamine
Ethers
dioxane
ethyl ether
anline
ethylenediamine
pyridine
morpholine
2-aminoethanol
diethanolamine
triethanolamine
aminoethylethanolamine
2-hyd roxyethylmorpholi ne
2-amino-2-methvl-1-propanol
Nitroparaffins
nitromethane
nitroethane
Ketones
methylethylketone
acetone
cyclohexanone
Chlorinated Hydrocarbons
carbon tetrachloride
chlorobenzene
Esters
ethyl acetate
sec-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
COMPA TlBILlTY
carboxymethylcellulose
cellulose acetate
cellulose acetate propionate
dibutyl tartrate
diethylene glycol
dimethyl phthalate
Dytol 8-35, J-68, and L-79
(Rohm and Haas)
2-ethylhexanediol-1, 3
glycerin
glycerylmonoricinoleate
Hyprin GP-25 (Dow)
Igepal CQ-430 (Rhone Poulenc)
Lorol (DuPont)
oleyl alcohol
Resoflex R-363 (Cambridge)
Santicizer 141, 8-16, and E-35
(Monsanto)
shellac
sorbitol
AIK (S04b,12H2O
A12(S04h,18H20
NH4CI
(NH4bS04
BaCl2,H20
CaCI2
Cr2(S04h,nH20
CuS04,5H2O
FeCI3,6H2O
MgCI2,6H2O
Hg(C2H302b
Ni(N03)2,6H2O
Pb(C2H302b,3H2O
KCI
K2S04
K2Cr 207
NaHC03
NaCI
NaN03
NaH2P04,H2O
Na4P2O7
Na2S04
Na2S03,7H20
Na2S203,5H20
AgN03
ZnS04,7H20
Table VII
Compatibility of PVP
in Solutions and Films
SOLVENT
CLASS
COMPOUNDTESTED"
Ether-Alcohols
polyethylene glycol
Ucon Oil@50-HB 5100 (polyalkylene glycol, Union Carbide)
Ucon Oil@75-HB 90,000 (Union Carbide)
arabic
karaya
tragacanth
sodium alginate
olive oil
castor oil
lanolin
lecithin
beeswax
diethylene glycol stearate
Gums
Glycerides
Esters
Phenols
Misc.
Resins.
Synthetic
Polymers
S urfactants
QUatemary
Ammonium
Compounds
%TTL
SOLIDS
ethanol
ethanol
ethanol
water
water
water
water
chloroform
propargyl
alcohol
ethanol
shellac
ethyl cellulose
methylcellulose
carboxylmethylcellulose
(low viscosity grade)
com dex1rin**
ethanol
ethanol
water
N-methyl2-pyrrolidone
chloroform
hot melt
chloroform
water
water
water
water
water
H
H
C
3
5
S clear, yellow
S clear, colorless
4
4
S
S
c
C
5
4
C
C
C
3
4
S
I
S
S clear,coloness
S
IN
IN
C
IN
C
3
5
S clear, C
S clear, col
3
2
10
10
S clear, colorless
10
10
S clear, colorless
S clear, colorless
,ss
water
water
Abbreviations:
S
PS
I
IN
H
C
Na2SiOs*5H2O
C
It
P~
S
water
Na2COs
Na2HP04*7H20
NaSP04*12H20
C
IN
H
5
5
water
water
PVI-C poly (
isobutyl ether)
PVM poly (
ethyl ether)
polystyrene
polyvinyl alcohol
Alipal@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)
FILM
COMPATIBILITY
6
6
phenol)
~ethylene-bis
rophenol)]
sodium carbonate
SOLUTION OR MELT
APPEARANCE
Soluble
Partially soluble
Insoluble
Incompatible
Homogenous
Compatible
When reviewing Table VII, one should note the general procedure followed in determining compatibility was
to dissolve PVP K-30 and the test material separately
in a mutual solvent. After mixing the two solutions,
appearance was observed. The solution was then
cast onto a glass plate and the resulting film examined
after evapordtion of the solvent.
Ratio
Test Salt: PVP
1:85:1
3.7:1
1.28:1
3:1
PROTECTIVE-COLLOID ACTION
j
I
AREA OF USE
ADVANTAGES OF PVP
Adhesives...pressure-sensitive
and water-remoistenable types... food packaging (indi rect food contact)
. .. metal adhesives. . .abrasives. ..sandcore binder...
films.
""1:
AREA OF USE
ADVANTAGES OF PVP
Compatible dispersant
improve uniformity.
in printed circuits to
emulsions
...etch coatings...plate storage...gumming of lithographic plates...dampener roll solutions...photo
and laser imaging processes...microencapsulation
...thermal recording...carrier, finisher preserver of
lithographic plates...thermal transfer recording
ribbons and optical recording discs.
'!
AREA OF USE
ADVANTAGES OF PVP
Membranes...macroporous,
multiporous, desalination, gas separating, liquid ultrafiltration, hemodialysis,
selective permeability types of membranes, hollow
fiber membranes.
Metallurgy...processing
for both ferrous and nonferrous metals...coating ingredient to aid or remove
material from metal surfaces such as copper, nickel,
zinc and aluminum.
I.
PHYSIOLOGICAL PROPERTIES
PVP IS SAFE
any toxicity as judged by clinical chemistry, hematology and histopathology. The no-adverse effect
level (NOEL) in subchronic studies in rodents and
dogs exceeds 5g/kg/day.
Absorption:
In Summary:
12
REFERENCES
There is a sizable listing of technical literature that deals with the various aspects of PVP and its applications. The
following listing is a representative, not comprehensive, sampling of this literature.
General Chemistry
1. L. Senak,C.S. Wu,and E.G.Malawer,"SizeExclusionChromatographyof Poly(Vinylpyrrolidone).II Absolute
MolecularWeightDistributionby Sec/Lallsand Sec With UniversalCalibration,"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 and
Toxicology of Polyvinylpyrrolidone (Povidone)," (Chelsea, MI:CRC Press, 1990).
Ceramics
1. 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).
Electrical
1. 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 & Physics 17:317-24 (1987).
5. V. Rao, K. Narasimha, "Electrical Conduction Mechanism in Poly (vinylpyrrolidone) Films," Polymer28:648-50 (1987).
Fibers and Textiles
1. 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 Res 12:6-12 (1987).
5. EP 0,368,370 (May 16, 1990), H.G. Sowman (Minnesota Mining and Manufacturing Co.).
HI&I
1. 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 Unilever N.V.).
Lithography and Photography
1. 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-Packard Co.).
Metallurgy
1. US Pat. 4,826,545
2. US Pat. 4,738,731
3. US Pat. 4,528,044
4. US Pat. 4,595,425
Oil I Gas
1. 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.).
Paper
1. 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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