22

PolyNinyl Alcohol) for Adhesives

HAROLD L. JAFFE
Chemical Consultant
Millburn, New Jersey
and
FRANKLIN M. ROSENBLUM
Air Products and Chemicals, Inc.
Allentown, Pennsylvania

Poly(vinyl alcohol) (PVOH) is a water-soluble Poly(vinyl alcohol) also contributes to emulsi-

synthetic resin. It is produced by the hydrolysis fication and stabilization of aqueous disper-
of poly(vinyl acetate); the theoretical mon- sions.
omer, CH2 =CHOH, does not exist. Discovery The main uses of PVOH in the United States
of PVOH was credited to German scientists W. are in textile and paper sizing, adhesives, and
O. Herrmann and W. Haehnel in 1924, and the emulsion polymerization. Significant volumes
polymer was commercially introduced into the are also used in such diverse applications as
United States in 1939. I joint cements for building construction, water-
Poly(vinyl alcohol), also known as polyvinyl soluble film for hospital laundry bags, emulsi-
alcohol, is a dry solid and is available in gran- fiers in cosmetics, temporary protective films
ular or powdered form. Grades include both the to prevent scratching of highly polished sur-
fully hydrolyzed form on poly(vinyl acetate) faces, and soil binding to control erosion.
and products containing residual, i.e., unhy- Poly(vinyl alcohol) is an intermediate in the
drolyzed, acetate groups. Resin properties vary production of poly(vinyl butyral), the adhesive
according to the molecular weight of the parent interlayer in laminated safety glass. Outside the
poly(vinyl acetate) and the degree of hydroly- United States, PVOH is also used for textile
sis. A wide range of grades is offered by PVOH fiber, although it must be chemically treated to
manufacturers . become water-insoluble. 2 Poly(vinyl alcohol)
The wide range of chemical and physical fiber is produced in Japan and the People's Re-
properties ofPVOH resins has led to their broad public of China for captive use.
industrial use. They are excellent adhesives and
highly resistant to solvents, oil, and grease.
PHYSICAL PROPERTIES
Poly(vinyl alcohol) forms tough, clear films
that have high tensile strength and abrasion re- The physical properties of PVOH are con-
sistance. Its oxygen-barrier qualities are supe- trolled by molecular weight and the degree of
rior to those of any known polymer; however, hydrolysis. The upper portion of Fig. 1 shows
PVOH must be protected from moisture, which the variation in properties with molecular
greatly increased its gas permeability. weight at a constant degree of hydrolysis. 3 Hy-

I. Skeist (ed.), Handbook of Adhesives

401
© Van Nostrand Reinhold, New York, NY 1990
402 HANDBOOK OF ADHESIVES
'nc...... flexlbI'lty
'nc...... Iftl• • en.lllvlty
'nc...." .... of .otv.1Jon
MoIecu'ar weight
% Hydroly.'.
'ncr. . . . flexlbl'lty
'nc...... d'.per.'ng poww
'nc...... wa"" .en.lllvlty
'nc...... adhe.,on 10
hydrophobic .urfac••
Fig. I. Properties of poly(vinyl alcohol).
Table 1. Physical Properties of
Poly(Vinyl Alcohol).
Property
Appearance
Specific gravity;
of solid
of 10 wt % solution at
25°C
Thennal stability
Refractive index (film) at
20°C
Thennal conductivity,
W/(m . K)'
Electrical resistivity,
ohm-cm
Specific heat, J / (g . K)b
Melting point (unplasti-
cized), °C
Tg,OC
Storage stability (solid)
Flammability
Stability in sunlight
'To convert W/(m . K) to (Btu· in.)/(h . ft2 . OF), divide by
0.1441.
"To convert J to cal. divide by 4.184.
given in the lower portion of the figure. Since
, _• • v'.coalty
hydrolysis and molecular weight can be inde-
'nc...... block re.'alenc. pendently controlled in the manufacturing pro-
'nc...... 1M.'" alrengI/I cess, a product matrix has evolved that provides
'nc...... l1/li""re.,m_
the property balance needed for different appli-
'nc.......he.1IIe aIrengI/I
Inc...... • ofvenI ,..,mnc. cations. The PVOH product matrix has four
'nc...... d'.per.'ng poww important molecular weight ranges and three
key hydrolysis levels, although intermediate
products are available (see Specifications).
Various physical properties are listed in Table
1.
'ncr. . . . wal. re.'.lance
'ncr..... len.ne alreng!h
'nc...... block re.'alance
SOLUBILITY
'nc...." aofvenI ,..,mnce All commercial PVOH grades are soluble in
'nc...... adhe.1on 10
hydrophilic surface.
water, the only practical solvent. The ease with
which PVOH can be dissolved is controlled
primarily by the degree of hydrolysis. Fig. 2
shows the effect of degree of hydrolysis on sol-
ubility with other variables held constant. Fully
hydrolyzed products must be heated close to the
atmospheric boiling point of water to dissolve
completely. Lower temperatures are required
as the degree of hydrolysis is decreased until
Value 75-80% hydrolysis is reached, at which point
White-to-cream granular
powder
1.27-1.31
1.02
Gradual discoloration
above 100°C; darkens
rapidly above 150°C; w
rapid decomposition ~
above 200°C g
en
1.55 is
12
0.2 :g
(3.1-3.8) X 107 8en
w
1.5
230 for fully hydrolyzed
grades; 180-190 for
partially hydrolyzed
grades
75-85
Indefinite when protected
from moisture
Burns similarly to paper 30 40 50 60 70 60 90
Excellent
TEMPERATURE,oC
Fig. 2. Solubility of O.4-rnm poly(vinyl alcohol) cast film.
 POLY(VINYL ALCOHOL) FOR ADHESIVES 403

the product is fully cold-water soluble but pre- col, acetone, and methyl acetate. 5 It has limited
cipitates upon heating. The hydrolysis range of solubility in dimethyl sulfoxide; the solubility
87-89% is considered optimum for both cold is in proportion to the residual acetate content.
and hot water solubility. Products with this op- Although there are no good solvents for PVOH
timum degree of hydrolysis are commonly re- other than water, up to 50% of lower alcohols
ferred to as partially hydrolyzed poly(vinyl can be added to PVOH solutions without caus-
alcohol). Regardless of the degree of hydroly- ing precipitation.
sis, all commercial PVOH grades remain dis-
solved upon cooling. SOLUTION VISCOSITY
Solubility is also influenced by particle size,
The viscosity of a PVOH solution is controlled
i.e., surface area, molecular weight, and crys-
by molecular weight, concentration, and to
tallinity. Decreasing particle size and molecu-
lesser degree, temperature. Degree of hydrol-
lar weight improves the solubility weight.
ysis does not strongly affect viscosity, although
Crystallinity is induced by heat treatment and
the viscosity is proportional to degree of hy-
retards the solubility rate. 4 Because the pres-
drolysis at constant molecular weight. Viscos-
ence of residual acetate groups reduces the ex-
ity relationships for low, medium, and high
tent of crystallinity, low hydrolysis grades are
molecular weight grades are shown in Fig. 3.
much less sensitive to heat treatment.
Viscosity, rather than solubility, limits the con-
Poly(vinyl alcohol) solutions show a high
centration of PVOH solutions. With conven-
tolerance toward many electrolytes, as shown
tional batch-mixing equipment, the practical
in Table 2. Small additions of strong inorganic
concentration limits for low, medium and high
acids and bases do not precipitate PVOH from
molecular weight resins are ca 30 wt %, 20 wt
solution, but the hydrolysis reaction continues
%, and 15 wt %, respectively.
to completion at extreme pH.
Poly(vinyl alcohol) cannot be dissolved by
most common organic solvents, e.g., gasoline,
kerosene, benzene, xylene, trichloroethylene,
carbon tetrachloride, methanol, ethylene gly-

Table 2. Maximum Salt Concentration

in which PVA is Soluble, % in Water. B,b
A
PYA degree of
hydrolysis ,A
/
Electrolyte 95% 88% /
/
Na2S04 5 4 /
(NH4hS04 6 5 //
Na2HP04 . 7H 2O 8 5 /
Na3P04 . 12H2O 8 6 /
NA2HP04 . H2O 9 6 /
/
NaHC03 9 7
Alz{S04h . 16H2O 10 6
Na2S203 . 5H2O 10 8
ZnS04 . 7H 2O 13 10
NaCl; KCl 14 10
CUS04' 5H2O 15 10
CH 3COONa . 3H 2O 23 15
NaN0 3 24 20 Concentration in water. WI %
'Courtesy of Air Products and Chemicals, Inc. Degree of polymerization: A, 800; B. 2000; and C. 2400.
bDetermined by adding a 10% solution of PVA dropwise to 50 ml Solid line, at 20·C; broken line, at 65"C.
of the salt solution at increasing concentration until precipitation is
observed. Fig. 3. Solution viscosity of poly (vinyl alcohol).
404 HANDBOOK OF ADHESIVES
The viscosities of partially hydrolyzed PVOH
solutions remain stable if the solutions are
stored at high temperatures over a wide range
of concentrations. However, viscosities of con-
centrated solutions of fully hydrolyzed PV A
gradually increase over a period of days when
stored at room temperature, and gelation oc-
curs in products that contains < 1 mol % ace-
tate groups. This viscosity increase or gelation
can be reversed by reheating. 6 Lower solution
concentrations and lower degrees of hydrolysis
eliminate viscosity instability associated with
long-term solution storage.
MANUFACTURE
All PVOH manufacture involves poly (vinyl
acetate) as the starting material. The theoretical
monomer, vinyl alcohol (CH2 =CHOH), does
not exist. Conversion of poly(vinyl acetate) to
PVOH is generally accomplished by base-cat-
alyzed methanolysis; 10 sodium hydroxide is the
usual base.
Poly(vinyl acetate) polymerization is accom-
plished by conventional processes, e.g., solu-
tion, bulk, or emulsion polymerization.
Solution polymerization is favored because the
subsequent alcoholysis reaction requires sol-
vent addition. 10 The polymerization step deter-
mines the ultimate molecular weight of the
PVOH. Catalyst concentration, temperature,
and solvent control the degree of polymeriza-
tion; acetaldehyde is an effective chain-transfer
agent. It is the agent commonly used.
The degree of hydrolysis of PVOH is con-
trolled during the alcoholysis and is indepen-
dent of molecular-weight control. Fully
hydrolyzed PVOH is obtained if methanolysis
is allowed to go to completion. The reaction
can be terminated by neutralizing or removing
the sodium hydroxide catalyst. The addition of
small amounts of water to the reactants pro-
motes saponification of poly(vinyl acetate),
which consumes sodium hydroxide. The extent
of hydrolysis is inversely proportional to the
amount of water added. A disadvantage of
water addition is an increase in byproduct so-
dium acetate, which is present as ash in all
commercially available grades of PVOH. The
alcoholysis reaction can be carried out in a
highly agitated slurry process; a fine precipitate
forms as the poly (vinyl acetate) converts into
PVOH. The product is then washed with meth-
anol and is filtered and dried. A moving belt
process allows the PVOH to form a gel and
subsequently to be cut into granular form. II
The alcoholysis process yields methyl ace-
tate as a byproduct. The methyl acetate can be
used as a solvent or it can be processed to re-
cover methanol and acetic acid. One such pro-
cess involves mixing the methyl acetate with
water and passing them through a cation-ex-
change resin to catalyze the hydrolysis reac-
tion. lo
Methanol recovered from this process can be
totally recycled to the methanolysis step, and
the acetic acid is sold as a byproduct.
POLYVINYL ALCOHOL IN POLYVINYL
ACETATE EMULSION ADHESIVES
Polyvinyl alcohol is a first-class adhesive in its
own right. It also serves as an excellent addi-
tive for modifying the properties of polyvinyl
acetate emulsion adhesives.
Polyvinyl alcohol adheres particularly well
to cellulosic substrates such as wood or paper.
Adding it to a polyvinyl acetate emulsion will
increase the affinity as well as the tensile
strength of the formulation.
Because it is a hydrophilic polymer, polyvi-
nyl alcohol functions as a humectant to retard
the loss of water from the formulation and pro-
long open time of the adhesive film. Wet tack
is increased and can be enhanced further by
adding tackified (borated) polyvinyl alcohols.
Polyvinyl alcohol is used as a thickener to
increase viscosity and control the solids con-
tent. When a high viscosity but low solids for-
mulation is needed, a small amount of a high
viscosity polyvinyl alcohol should be added.
When both high viscosity and high solids are
desired, a medium viscosity grade should be
added. All grades impart smooth flow from ap-
plicator reservoirs and shear resistance at high
machine speeds. Polyvinyl alcohol affords the
best means of balancing the viscosity and sol-
ids content of an emulsion adhesive.
Partially hydrolyzed polyvinyl alcohols in-
crease the stability of emulsion adhesives by
functioning as emulsifiers and protective col-
loids. 8 These alcohols increase water sensitiv-

ity of adhesive films, making them useful in
emulsions designed for remoistenable adhe-
sives or in those requiring easy clean up. Par-
tially hydrolyzed resin types are also used to
preemulsify organic solvent solutions before
adding them to emulsions adhesives. Fully hy-
drolyzed polyvinyl alcohols, however, increase
the water resistance of adhesive films, partic-
ularly the medium and high molecular weight
grades. 12
All polyvinyl alcohols improve the machin-
ability of emulsion adhesives; spitting and
throwing are reduced on high speed equipment.
All types have surface-active properties that
promote thorough wetting of roller applicators
and adherends. Wetting and penetration into the
adherend are improved by using polyvinyl al-
cohols with lower molecular weight and hy-
drolysis. Since polyvinyl alcohol has a higher
melting point (200°C) than the emulsion to
which it is being added, it raises the heat-seal-
ing and blocking temperature of the film and
increases its overall heat resistance. All poly-
vinyl alcohol resins facilitate the incorporation
of water-immiscible substances into the for-
mulation and stabilize the adhesive. In addi-
tion, solvent and oil resistance are increased
and creep is decreased by polyvinyl alcohol. 12
CROSSLINKING
Poly(vinyl alcohol) can be readily crosslinked
for improved water resistance. 9 The most prac-
tical means of crosslinking PVOH is with
chemical additives, e.g., glyoxal, urea-formal-
dehydes, and melamine-formaldehyde. Tri-
methylolmelamine is often preferred if a low
temperature is required. An acid catalyst, e.g.,
ammonium sulfate or ammonium chloride, is
necessary with the formaldehyde crosslinkers.
Metal compounds can also be effective insolu-
bilizers for PVOH. These additives include
strongly chelating metal salts of copper and
nickel, e.g., cupric ammonium complexes,
chromium complexes, organic titanates, and
dichromates. The heat treatment during drying
of PVOH films or coating is generally sufficient
to complete the crosslinking reaction, although
when dichromates are used the reaction is best
catalyzed by ultraviolet light. Crosslinking
slowly takes place even at room temperature,
POLYIVINYL ALCOHOl) FOR ADHESIVES 405
and prolonged storage of the treated PVOH so-
lution should be avoided. Crosslinking can also
be accomplished by simply heating dry PVOH
above 100°C; this dehydrates the polymer and
yields an unsaturated carbon backbone. Inter-
molecular reactions between unsaturated groups
in adjacent polymer chains form permanent
crosslinks. However, thermal crosslinking is
not considered a practical reaction because it is
also accompanied by polymer decomposi-
tion. 13
Although PVOH film can be rendered insol-
uble by crosslinking, it swells in water and
loses strength upon extended exposure. Com-
plete water insensitivity cannot be achieved, al-
though it improves with degree of hydrolysis.
Fiber-grade PVOH has a degree of hydrolysis
of at least 99.9%; it exhibits negligible swell-
ing in water, although it absorbs moisture, like
many natural fibers.
GELATION
The controlled gelation of PVOH solutions is
important where penetration into a porous sub-
strate is undesirable, e.g., paper coatings and
adhesives. Boric acid and borax react strongly
with PVOH and are widely used industrially as
gelling agents. Poly(vinyl alcohol) is extremely
sensitive to borax, which causes gelation by
forming a bisdiol complex as shown below:
As little as 0.1 % borax, based on solution
weight, can cause thermally irreversible gela-
tion. Boric acid forms a weaker monodiol com-
plex and is preferred for controlled, partial
gelation of PVOH. 7 The reaction is very sen-
sitive to pH, and full gelation occurs above pH
6.
Boration causes aqueous solutions of PVOH
to develop strong wet tack after cooking. Ad-
hesives based on tackified (borated) poly (vinyl
alcohol) work particularly well where they can
be applied as a very thin film and then the sub-
406 HANDBOOK OF ADHESIVES

strates mated using very high pressures. These The PVOH process is highly capital inten-
conditions are found in spiral tube winding and sive, requiring separate facilities for polymer-
solid fiber laminating. These adhesives are usu- ization, alcoholysis and recovery of acetic acid
ally prepared at solid content levels of 18-25 %. and methanol from the byproduct methyl ace-
The poly(vinyl alcohol) content varies from 5 tate.
to 9 %; the remainder of the solids is comprised Some major producers and announced capac-
of kaolin clay. The liquid adhesive is applied ities:
at rates of 40-45 grams per 1000 square me- Capacity (thousand
ters, which results in a dry application of 8-12 metric tons/yr)
grams per 1000 square feet. U.S.
The tackified polyvinyl alcohols, introduced Air Products and 48
in the early 1960s, rapidly replaced starch/urea Chemicals, Inc.
formaldehyde adhesives in solid fiber laminat- duPont 60
ing and dextrine, compounded polyvinyl ace- Japan
tate and sodium silicate adhesives in spiral tube Kuraray 110
winding. The new adhesives demonstrated su- Nippon Goshei 50
perior adhesion over silicates and dextrines to Denka 25
a wide variety of paper substrates. These ad- Unitiken 25
hesives reduce warp in solid fiber laminating Total Japan 210
and shrinkage in spiral tubes because of the low Europe
adhesive application rate and, thus, low amount Hoechst 30
of water added to the laminations. The low ap- Taiwan
plication rate and low resin level also made Chang Chun 34
these adhesives very economical.
Another advantage of these adhesives is that SPECIFICATIONS AND REGULATIONS
they permit rapid bond formation when applied Three important commercially available types
properly. Tubes and board bound with fully or of PVOH are distinguished by the mole percent
superhydrolyzed polyvinyl alcohol and clay ad- residual acetate groups in the resin: fully hy-
hesives also have excellent water resistance, drolyzed (1-2 mol % acetate), intermediately
and are used where the box or tube may be ex- hydrolyzed (3-7 mol %), and partially hydro-
posed to water for an extended period, as is the lyzed (10-15 mol %) PVOH. Poly(vinyl alco-
case with military packages and composite cans hol)s with other degrees of hydrolysis are
or dynamite tubes. produced, but collectively, they have a much
The adhesive properties of polyvinyl alcohol smaller market share than any of the three prin-
also appeared attractive for the manufacture of cipal grades. When no reference is made to the
corrugated board. Adhesives based on the su- degree of hydrolysis in describing PVOH, it is
perbydrolyzed grades of tackified polyvinyl al- generally assumed to be a fully hydrolyzed
cohol were demonstrated at both the single face grade.
and double backer sections of modem corru- Poly(vinyl alcohol) is produced in four gen-
gated machines which were run at full speed. eral molecular weight ranges, as shown in Ta-
The board had strong dry bonds, high water re- ble 3. Several other molecular weight resins are
sistance and showed excellent nonwarp prop-
erties. But while the polyvinyl alcohol Table 3. Molecular Weight of Main
adhesives were a technical success, they were Commercial Poly(Vinyl Alcohol) Grades. a
unable to compete economically against starch Nominal 4% solution viscosity,
adhesives. Viscosity grade Ma mPa . s (= CP)b

Low 25,000 5-7

PRODUCTION Intennediate 40,000 13-16
Medium 60,000 28-32
There are two producers of PVOH in the U.S., High 100,000 55-65
four in Japan, and several in Europe, where 'Courtesy of Air Products and Chemicals. Inc.
Hoechst is the dominant one. "Measured at 20·C with Brookfield viscometer.

Table 4. FDA Regulations Applicable to
Poly(Vinyl Alcohol) as an Indirect Food
Additive.
Regulation Description
181.30 Prior sanctioned substances used in
manufacture of paper and paperboard
products used in food packaging for
fatty foods only
175.105 Adhesives, no limitations
176.170 Components of paper and paperboard
in contact with aqueous and fatty
foods, extractive limitations
176.180 Components of paper and paperboard
in contact with dry food, no limita-
tions
177.1200 Cellophane coating, no limitations
177.1670 Poly(vinyl alcohol) film
177.2260 Filters, resin-bonded where filter fiber
is cellulose
177.2600 Filters, resin-bonded; extractables must
be less than 0.08 mg/cm2 (0.5 mg/
sq. in.)
175.300 Resinous and polymeric coatings
175.320 Resinous and polymeric coatings for
polyolefin films; net extractable less
than 0.08 mg/cm2 (0.5 mg/sq. in.)
177.2800 Textiles and textile fibers, for dry
foods only
178.3910 Surface lubricants in the manufacture
of metallic articles
produced, but they have only a minor market
share. Industry practice expresses the molecu-
lar weight of a particular grade in terms of its
4 % aqueous solution viscosity. Intermediate
viscosities can be achieved by blending. Prod-
ucts of different degree of hydrolysis can also
be blended to develop, e.g., intermediate sol-
ubility. Blended products have a broad distri-
POL YIVINYL ALCOHOl) FOR ADHESIVES 407
bution in molecular weight and degree of
hydrolysis, which may be undesirable in some
applications.
FDA regulations applicable to the use of
PVOH as an indirect food additive are listed in
Table 4.
BIBLIOGRAPHY
1. Herrman, W.O., and Haehnel, W., U.S. Patent
1,672,156 (1928) (to Wacker Chimie).
2. Ave, H., and Ono, Y., U.S. Patent 3,084,989 (1963)
(to Kuraray and Air Products).
3. "Vinol" Product Handbook, Air Products and Chem-
icals, Inc., Allentown PA 1980.
4. Tubbs, R. K., Inskip, J. K., and Subramanian, P. M.,
Soc. Chern. Ind., Monograph 30, London (1968) pp.
88-103.
5. Peirerls, E. S., Mod. Pfost., 18(6) (1941).
6. Toyoshina, K., in "Polyvinyl Alcohol," C. A. Finch
(ed.), pp. 17-67, New York, John Wiley and Sons,
(1973).
7. Hawkins, R. L., U.S. Patent 3,135,648 (1964) (to Air
Products and Chemicals).
8. Hulbekian, E. V., and Reynolds, O. E. D., in "Poly-
vinyl Alcohol," C. A. Finch (ed.), pp. 427-461, New
York, John Wiley & Sons, (1973).
9. Finch, C. A., in "Polyvinyl Alcohol," C. A. Finch
(ed.), pp. 183-302, New York, John Wiley and Sons,
(1973).
10. Chin, Y., "Polyvinyl Acetate and Polyvinyl Alco-
hoi," private report No. 57A by Process Economics
Program, Stanford Res. Inst., Menlo Park, CA (1970).
11. Demny, R., "Polyvinyl Acetate and Polyvinyl Alco-
hoI," private report No. 57 by Process Economics
Program, Stanford Res. Inst., Menlo Park, CA (1970).
12. Daniels, W. E., "Polyvinyl Acetate," in "Kirk-Oth-
mer Encyclopedia of Chemical Technology," 3rd Ed.,
pp. 839-843, New York, John Wiley and Sons, 1983.
13. Tubbs, R. K., and Wu, T. K., in "Polyvinyl Alco-
hol," C. A. Finch (ed.), pp. 167-183, New York,
John Wiley and Sons, 1973.