Академический Документы
Профессиональный Документы
Культура Документы
I, pp 143-152 (1985)
ABSTRACT: Polyvinylpyrrolidone (PVP) having molecular weights (Mwl from 2500 to about
I million is mainly obtained by radical polymerization in solution. The higher molecular weight
type products are polymerized in aqueous solution mostly using hydrogen peroxide as initiator. The
polymers thus obtained have hydroxyl and carbonyl end groups. More stable end groups can be
obtained by polymerization in solvents, which may act as chain transfer agents and which produce
low molecular weight type products. Copolymers especially with monomers such as vinyl acetate
and with various acrylic compounds may also be produced by solution polymerization. Popcorn
polymerization leads to insoluble PVP. Thereby VP is polymerized without initiator in the presence
of small amounts of bifunctional monomers. The polymeric flakes thus formed are highly cross-
linked, mainly due to entanglements. The molecular weight distribution of soluble PVP is broad due
to transfer reactions. An unusual property of PVP is its solubility in water as well as in various
organic solvents. The glass transition temperature of high molecular weight polymers (Mw= I
million) is about l75°C and falls to values under IOOoC with decreasing molecular weight Mw=
2500). PVP forms complexes with various compounds, especially with H-donors such as phenols
and carboxylic acids. The complex formed with cross-linked PVP and polyphenols is used
commercially for the clarification of beverages. Another commercial use is the complexation of
iodine with linear PVP, which leads to effective disinfectants of very low toxicity. Further important
applications of PVP in the pharmaceutical field are their use as binding or film forming agents for
tablets, and as solubilizing agents for injections. The swelling ability of cross-linked PVP in water is
used in disintegrating agents for tablets. In the cosmetic field VP polymers are used as film formers
for hair dressing products. Examples of technical applications are adhesives, textile auxiliaries and
dispersing agents.
KEY WORDS Poly-N-vinylpyrrolidone I Polymerization I Copolymers I
Cross-linked Polymers I Properties I Applications I
Polyvinylpyrrolidone, also called Povidone or pecially in the pharmaceutical, cosmetic and food
briefly PVP, is one of the numerous products 1 •2 of industry as well as for numerous technical appli-
the acetylene chemistry founded by Reppe. By cations. In these various fields PVP has rather
reaction of acetylene with formaldehyde, 1,4-butine different functions. Because there are considerable
diol is obtained which is hydrogenated to butane differences in the requirements, which polymers
diol. After oxidative cyclization to butyrolactone have to meet for these diverse applications, three
and its reaction with ammonia, pyrrolidone is types of PVP are offered, namely homopolymers of
formed by the removal of water. Finally the vinyl different molecular weights, copolymers and cross-
group is introduced to form N-vinylpyrrolidone-2 linked PVP.
(1-(2-oxo-pyrrolidinyl)-ethylene). The course of
these reactions is shown in Figure I.
POLYMERIZATION OF
The polymerization of vinylpyrrolidone produces
VINYLPYRROLIDONE
the polymeric material (Figure 2).
In the course of their 40-year history, vinylpyr- Vinylpyrrolidone can be polymerized either m
rolidone polymers have been extensively used, es- bulk, in solution or in suspension.
143
F. HAAF, A. SANNER and F. STRAUB
lnitiatJon:
Heat
HO• + •OH
H
Uo N H
Uo N
I I I I
HO• + c-c HO -C-C•
I I I I
H H H H
Propagation :
H
Oo
N
+
I I I I
HO- C- C • HO c- c
I I
c - c•
I I
H H H H H H
n
Termination
HO {
HI
c- c
I
I
I
HI
I
CJ=o
c- c• +
I
I
•OH ----.. HO {
H
I
C -
I
c
I
C - C - OH
I
I I I I
toi
H H H H H H H H
n n
H N H
Ho
I
c-c
I
I
I
I
c-c =O
I I
+ Oo N
H H H H I
H
n
Figure 3. Polymerization mechanism of VP in aqueous solution.
-
Initiation:
Heat
ROOR RO· + ·OR
RO· + SH
Solvent - ROH + S·
Uo Oo
S• +
H
I
c=c
I
H
N
I
I
H
- S -C-C•
H
I
I
H
N
H
I
I
Propagation :
HCNJ=o HCNJ=o Oo
s- c- c. + n
H H
C=C
H
- s c- c
'
H H
. c
'
H
'
-C•
N
t01
H
n
Termination by Chain Transfer:
s
H
I
c- c
1
N
I
1
H
I CJ=o
N
I
c -c. + s H '----+ s
1 1
{HV1HCJ=o
c- c
I
I
I
I
I
c- c -
I
I
I
H + S·
HH HH HH HH
n n
Figure 4. Polymerization mechanism of VP in organic solution.
in Toluene
HQ-
H-NMR-S•gnals
of PVP
__}________
t
0 ppm
10 000 35 000 -
Molweight [Dalton]
in Isopropanol
Figure 6. Gel permeation chromatography of PVP.
Conditions: aqueous solution with 0.08 m. Tri(hy-
droxymethyl)aminomethan/HCl, pH 4.65. Flow rate
1 mljmin, 2J'C.
100
'E
Figure 5. NMR-spectra of PVP polymerized in or- E.
ganic solvents. Q)
0
c:
"'
1ii 10
iS 7 Permeability Limit
5 Through the
initiator, show the fragments of isopropanol. "0
w
c: Kidney Capillaries
Polyvinylpyrrolidone produced in organic solution .9 2
"0
in the presence of peroxides contains an end group c: 17 25 30 90 K-Value
w
of the solvent radical and a hydrogen atom from 1 000 10 000 100 000 1 000 000
Molecular Weight Mw
termination due to chain transfer. Since there is no
splitting off of any pyrrolidone at the polymer end, Figure 7. End to end distance of the coiled chains vs.
these polymer products are purer and--due to the K-value and molecular weight. Solvent: 0.9% NaCI in
lack of aldehyde end groups-more stable towards water.
oxidizing agents than those products, which are
polymerized in water with hydrogen peroxide as the formation of the high molecular weight products
initiator. due to grafting of the polymer chain.
In the case of the polymerization in organic Polyvinylpyrrolidone in solution probably exists
solution, low molecular weights are obtained due to as a random coil; suggestions in the literature 6
the transfer reactions of the solvent. In aqueous concerning a possible helix structure have not yet
solution using hydrogen peroxide, medium degrees been proved. Depending on the molecular weight,
of polymerization are obtained. Higher molecular the coil dimensions (average end to end distance)
weight products may also be produced in aqueous are between 1-IOOnm (10-1,000A) in an aqueous
solution, however, in the presence of organic solution of sodium chloride (Figure 7).
initiators. The size of the coil is important for applications
in the medical field. The size is related to the ability
PROPERTIES OF POLY- of the human body to excrete the polymer. The
VINYLPYRROLIDONE diameter of the capillaries of the human kidney 7 is
about 7 nm, i.e., polymers having molecular weights
As it is typical for all radical polymerizations, below 30,000, corresponding to a diameter < 7 nm,
polymerization of vinylpyrrolidone gives a Schulz- are able to pass through the kindey and are ex-
Flory molecular weight distribution (Figure 6). creted. Since all polymers produced by radical
In the case of high molecular weight products, the polymerization have a molecular weight distri-
distribution is broader than in the case of lower bution, only polymers of polyvinylpyrrolidone,
molecular weight polymers. This can be explained which do not contain any significant portion with
by a more intense branching occuring during the molecular weights above 30,000, should be used for
Soluble in:
E1so
Water Di(ethylene glycol)
Methanol Poly(ethylene glycol) 400 "
Ethanol Propylene glycol 8_140
E
Propanol 1,4-Butanediol
Butanol Glycerol 120
Cyclohexanol N- Vinylpyrrolidone
Chloroform Triethanolamine 100 12
Dichloromethane Formic acid 10 000 100 000 1 000 000
I ,2-Dichloroethane Acetic acid Molecular Weight Mw
N- Methylpyrrolidone Propionic acid
Ethylenediamine Figure 8. Glass transition temperature vs. molecular
weight.
Insoluble in:
Ethyl acetate Carbon tetrachloride
Acetone Light petroleum 175°C 10 which corresponds to a molecular weight of
Dioxane Toluene 100,000.
Diethyl ether Xylene At low molecular weights the glass transition
Pentane Mineral oil temperature falls to values below 100°C (Figure 8).
Cyclohexane
The addition of small amounts of water also leads
to lower glass transition temperatures.
injections with human beings in order to secure
good elimination: These are polymers having a VINYLPYRROLIDONE COPOLYMERS
molecular weight average (Mw) of about 2,500.
A special and unusual property of polyvinylpyr- The preparation of vinylpyrrolidone copolymers
rolidone is its solubility in water as well as in various is carried out by copolymerization in solution,
organic solvents. The reason for this is, that PVP whereby in most cases the comonomers are slowly
has hydrophilic as well as hydrophobic functional added to the vinylpyrrolidone monomer to obtain a
groups and therefore interactions with various sol- more homogeneous composition of copolymers,
vents are possible. which otherwise, because of the great disparity of
Aqueous solutions show the unusual behaviour the copolymerization parameters, 11 would not be
that the viscosity in contrast to most other aqueous formed. Copolymers can be formed with numerous
polymer solutions is not affected by electrolytes. 8 monomers by radical polymerization. However,
Polymers with molecular weights (Mw) of more there are only few copolymers, which are produced
than 1 million are generally used as thickening technically in large amounts.
agents. Concerning the solubility of the polyvinyl- The copolymers are produced to alter or to
pyrrolidone a peculiarity has to be pointed out. improve certain properties of the polyvinylpyr-
Commercially used polyvinylpyrrolidone is rolidone. For example, the hygroscopicity of PVP,
it can be seen from Table most which is too high for many applications, is reduced
polar solvents and insoluble in the less polar ones. by copolymerizing vinylpyrrolidone with various
However, if polyvinylpyrrolidone is produced com- amounts of vinyl acetate or vinyl propionate
pletely free of is difficult because of its (Figure 9). Some of these copolymers are no longer
high can also be dissolved in water-soluble, but the water adsorption in the dry
solvents such as dioxane, acetone and toluene. 9 state can be reduced by more than 50%.
Polyvinylpyrrolidone cannot be processed in the Copolymers with cationic functional groups are
melt, because of its low decomposition temperature advantageous for certain applications. For example,
and the extremely poor flow properties of the melt. they generate better adhesion to the hair leading to
Films coated from solution are very brittle, clear a better curl retention (Figure 10).
and glossy. The lactam group in polyvinylpyrrolidone has no
The glass transition temperature increases with measurable cationic activity. Cationic polymers
molecular weight and reaches a plateau at about may be produced with monomers, which carry
CROSS-LINKED POLY-
VINYLPYRROLIDONE
+l+H•
povidone, is of industrial importance. Its main uses
i v
I
CH 2-CH
m
CH 2-y
C=O
I
CH3 n
C=O
I
H,-T
CH 3 0
C=O
I
CH,-y
CH 3 p
are as an agent for clarifying beverages, as a tablet
disintegrant and as an agent against diarrhoea.
A radical mechanism is assumed for the popcorn
polymerization. However, no radical initiator is
required for the popcorn formation. The main
Figure 11. Copolymers of VP with butyl methacrylate, source of radicals comes from the rupture of poly-
Iaury! methacrylate and stearyl methacrylate. mer chains already formed. 18 The radical initiator
is also omitted in the industrial production of the
nitrogen groups of high basicity or which can be crospovidones.
converted to cationic monomers by quaternization The patent literature describes two production
reactions. Examples for monomers of this kind are
aminoalkyl methacrylates and vinylimidazole. The
> t00°C, Alkali
quaternization of the nitrogen group in these
VP
monomers with dimethyl sulphate or alkyl halides +
such as methyl chloride can be carried out before or In Situ Generation of
Bifunctional Monomer
after the polymerization process.
For the production of copolymers having anionic
functional groups, monomers such as acrylic acid, 1Crospovidone 1
Bifunctional Monomers
40 •
r-\
?C-CH3
1-Vinyi-3-Ethylidenepyrrolidone
CH,
'-.N/ (-1.5%)
I
CH=CH2 30
.
\
Popcorn AIBN
PVP PYP
(1.6% B1funclional lllonomer)
Ethylidene-Bis-3-(N-Vinyl-
pyrrolidone)
(- 0.1%)
·'-......_,
------
AIBN-1mt1ated PVP
Table III. T 8 and gel volume of linear Table IV. Applications of VP-polymers
and crosslinked PVP from DSC
Pharmaceuticals: Binder, coating and disintegrant
T" Gel volume for tablets stabilizer, solubilizer
Sample for suspensions and solutions
oc mlg- 1 disinfectant (PVP-I) adsorbent
Cosmetics: Film formers for hair sprays,
Povidone 175 00 setting lotions and conditioning
Crospovidone according to I 190 5 shampoos
Crospovidone according to II 195 5 Food: Stabilization of beverages
Copolymer of VP with Adhesives: Adhesive sticks, water
I. 6 mol% bifunctional monomer 195 42 remoistenable adhesives
(initiator: AIBN) Polymers: Suspending agent in two phase
Copolymer of VP with polymerization systems
16mol% bifunctional monomer 270 12 Textiles: Dye-affinitive stripping and
(initiator: AIBN) levelling agent
Interaction constant•
K/lmol- 1
Compound
Povidone Crospovidone
Active drugs:
Acetylosalicyclic acid 0.7 2.1
Chloramphenicol 0.4
Chlorpromazine 1.0 1.2
Methylparaben 1.8 4.2
Sulfathiazole 0.4 1.0
1------1 Trimethoprime 0.2
10pm
has a much larger degree of swelling due to the lack Solid State
of physical cross-links.
Investigations of the supermolecular structure of
PVP by X-ray studies did not give any evidence of o---H---o ·7 '-(.l:::.o
crystallinity. Since no crystalline domains were ··•. ,..CH---
CH 2 CH 2
--CH ..
•
--CH
CH 2 •••
potassium iodide solutions, called Lugol solution, 5. W. Kern and H. Cherdron, in "Houben Weyl,
and in contrast to the alcoholic solutions, called Methoden der Organische Chemie," Vol. 14, 4th ed.,
iodine tincture, both used in former times. Georg Thieme Verlag, Stuttgart, 1961, p 1106.
Furthermore, PVP is important for adhesive ap- 6. A. E. Tonelli, Polymer, 23, 676 (1982).
7. J. Orloff, "Handbook of Physiology," Section 8:
plications, where it is especially used for adhesive
Renal Physiology, American Physiology Society,
sticks and for remoistenable adehesives. High mo- Washington D.C., 1973.
lecular weight vinylpyrrolidone polymers are also 8. P. Davison and E. Mentzer, SPE, 9300 (1980).
used as protective colloids and particle size reg- 9. R. L. Davidson and M. Sittig, ''Water Soluble
ulators for suspension polymerization of styrene, Resins," 2nd ed., Reinhold Book Corp., New York,
vinyl acetate and vinyl chloride. PVP is used in 1968, S.l37 (Table 7.3).
textile dyeing as a dye affinity stripping and levelling 10. Y. Y. Tau and G. Challa, Polymer, 17, 739 (1976).
II. R. Z. Greenley, J. Macromol. Sci., Chern., A14(4),
agent.
445 (1980).
PVP has found many new applications in recent 17. J. Ferguson and V. S. Ragan, Eur. Polym. J., 15, 627
years due to its unusual properties. By using new (1979).
polymerization techniques and by copolymeriza- 13. A. Henglein, J. Phys. Chern., 63, 1852 (1959).
tion, the polymer properties can be further mod- 14. C. C. Anderson et al., J. Appl. Polym. Sci., 23, 2453
ified and improved, so that completely new fields (1979).
of application are opened up. In most cases PVP is 15. GAF, U.S. Patent 2658045, November 3, 1953.
16. GAF, U.S. Patent 3350366, October 31, 1967.
usually present as an essential auxiliary and not as
17. DOW, U.S. Patent 3669103, June 13, 1972.
the active substance itself. The continuing interest in 18. J. W. Breitenbach, "Encyclopedia of Polymer
PVP is shown by ca. 20 publications and ca. 25 Science and Technology," Vol. II, 1969, p 587-597.
patents per year on this subject, which demonstrates 19. GAF, U.S. Patent 2 938 017, May 24, 1960; GAF,
the still growing potential of the polyvinyl- U.S. Patent 3277066, October 4, 1966; GAF, U.S.
pyrrolidones. Patent 3 306 866, February 28, 1967.
20. BASF, Ger. Patent 2255 263, June 5, 1975.
21. D. Horn and W. Ditter, a) J. Pharm. Sci., 71, 1021
REFERENCES ( 1982); b) "Proceedings of the International
Symposium on Povidone," University of Kentucky,
I. BASF, Deutsches Reichspatent 757 355, 1944. Aprill7-20, 1983, Lexington, U.S.A., p 80-100.
2. W. Reppe, "Polyvinylpyrrolidon," Verlag Chemie, 22. D. Horn and W. Ditter, a) See ref 2lb, ppl20-140;
Weinheim, 1954. b) "PVP-Iod in der operativen Medizin,"
3. N. Tsubokawa, N. Takeda, and A. Kanamaru, J. Herausgegeben von G. Hierholzer, und G. Gi:irtz,
Polym. Sci., Polym. Lett. Ed., 18, 625 (1980). Springer Verlag, Berlin-Heidelberg, 1984.
4. M. Biswas and P. Mishra, Polymer, 16, 621 (1975). 23. W. Gottardi, Hyg. Med., 8, 203 (1983).