United States Patent [191 [11] 4,357,402

Sheibley et al. [45] Nov. 2; 1982

[54] POLYVINYL ALCOHOL CROSS-LINKED Primary Examiner—Stanford M. Levin

WITH TWO ALDEHYDES Attorney, Agent, or Firm—Normal Musial; John R.
Manning; James Mackin
[75] Inventors: Dean W. Sheibley, Sandusky; Lorra
L. Rieker, Cleveland; Li-Chen Hsu, [57] ABSTRACT
Westlake; Michelle A. Manzo,
Cleveland, all of Ohio A ?lm-forming polyvinyl alcohol resin is admixed, in
aqueous solution, with a dialdehyde cross-linking agent
[73] Assignee: The United States of America as which is capable of cross-linking the polyvinyl alcohol
represented by the Administrator of resin and a water soluble acid aldehyde containing a
the National Aeronautics and Space
reactive aldehyde group capable of reacting with hy
Administration, Washington, DC. droxyl groups in the polyvinyl alcohol resin and an
[21] Appl. No.: 272,234 ionizable acid hydrogen atom. The dialdehyde is pres
Filed: Jun. 10, 1981 ent in an amount sufficient to react with from 1 to 20%
[22] by weight of the theoretical amount required to react
[5 ll Int. Cl.3 ....................... .. C08F 8/28; H01M 2/00; with all of the hydroxyl groups of the polyvinyl alco
H01M 2/16; H01M 2/18 hol. The amount of acid aldehyde is from 1 to 50% by
U.S. Cl. .................................. .. 429/206; 264/104; weight, same basis, and is suf?cient to reduce the pH of
‘ 429/253; 525/61 the aqueous admixture to 5 or less. The admixture is
[58] Field of Search ........................ .. 525/61; 2'64/104; then formed into a desired physical shape, such as by
260/ 17.4 UC; 429/27, 28, 139, 249, 253, 206 casting a sheet or ?lm, and the shaped material is then
[56] References Cited heated to simultaneously dry and cross-link the article.
U.S. PATENT DOCUMENTS
4,272,470 6/1981 Hsu et a1. ............................ .. 525/61 14 Claims, 1 Drawing Figure
US. Patent A Nov. 2, 1982 ' 4,357,402

AQUEOUS ADMlXTURE OF:

POLYVINYL ALCOHOL (PVA);
DIALDEHYDE CROSS LINKING AGENT;
AND AClD-ALDEHYDE.

FORM ADMIXTURE INTO

DESIRED SHAPE

HEAT SHAPED MATERIAL

TO FORM PRODUCT
AND SIMULTANEOUSLY
CROSS-LINK PVA
 4,357,402
1 2
Other features and advantages of the invention will
POLYVINYL ALCOHOL CROSS-LINKED WITH be apparent from the description of preferred embodi
TWO ALDEHYDES ments which follows, including the drawing which is a
block flow diagram of the method of the invention.
ORIGIN OF THE INVENTION
DESCRIPTION OF PREFERRED
The invention described herein was made by employ EMBODIMENTS
ees of the US. Government and may be manufactured
and used by or for the Government for governmental The polyvinyl alcohol resin useful in the invention is
purposes without the payment of any royalties thereon a conventional, ?lm-forming, polymeric material
or therefor. 10 readily available commercially and can be of the type
used heretofore for making separators for alkaline bat
FIELD OF THE INVENTION teries. Commercially available polyvinyl alcohol nor
The present invention relates to a polyvinyl alcohol mally contains about 0.5 to 6% of 1,2-diol units in the
structure and a method for producing such a structure predominantly 1,3-diol structure. The presence of 1,2
and, more speci?cally, to a “one step” method of fabri diol units in the chain results in reduced resistance to
cating cross-linked polyvinyl alcohol articles which are oxidation. Accordingly, it is preferred, in the practice of
particularly useful in producing battery separators. the present invention, to use a polyvinyl alcohol sub
stantially free (i.e. containing less than about 5) of 1,2
BACKGROUND OF THE INVENTION diol units. Polyvinyl alcohol having an essentially head
Earlier processes for preparation of cross-linked pol 20 to-tail structure of this type ‘is readily available. It is
yvinyl alcohol (PVA) sheets and ?lms have involved a made by the alcoholysis of polyvinyl acetate having an
two-step method in which a dry ?lm was ?rst made and essentially head-to-tail structure which is made by low
later cross-linked. Typical processes included treatment temperature polymerization of vinyl acetate. The poly
of a dry PVA ?lm with an aldehyde-containing cross vinyl alcohol is a ?lm-forming resin having, generally, a
25 number average molecular weight of 10,000—200,000
linking solution or treatment with an acid solution of a
dry PVA ?lm in which an aldehyde cross linking agent and is conveniently provided and used in aqueous solu
was incorporated. Thus, these earlier processes require tion such as 10-20% resin by weight. The amount of
two distinct steps: (1) making of the PVA sheet or ?lm; PVA used in the present process is generally from 3 to
and (2) treatment with a solution to effect cross-linking. 20% by weight, based on the total amount of PVA and
Rinsing and drying were also required after the cross water in the aqueous admixture. Preferably, the amount
linking step. of PVA is from 5—l5%, same basis.
It is an object of the present invntion to provide a The cross-linking agent is a dialdehyde. Suitable dial
novel method of producing cross~linked polyvinyl alco dehydes include glyoxal and other dialdehydes which
hol articles. It is a further object to provide such a 35 may be represent by the formula
process in which cross linking of the article is effected
simultaneously with the formation of the article, thus 0 0
avoiding the need of a separate cross linking step. It is a II II
H-C-R-C-H
further object to provide cross-linked polyvinyl alcohol
articles such as battery separators, made by the process. wherein R is a divalent organic radical such as an ali
BRIEF SUMMARY OF THE INVENTION phatic, cycloaliphatic, aromatic, or heterocyclic radi
cal. Preferred dialdehydes include glutaraldehyde and
The foregoing and other objects which will be appar other aliphatic dialdehydes wherein R is a divalent
ent to those having ordinary skill in the art are achieved aliphatic hydrocarbon radical having from 1 to 12 car
in accordance with the present invention by providng a bon atoms, preferably 1 to 6 carbon atoms, and furan
method of producing a cross-linked polyvinyl alcohol aldehydes, e.g. furan dialdehyde, represented by the
element which comprises the steps of: providing an formula:
aqueous admixture comprising a ?lm-forming polyvinyl
alcohol resin, a dialdehyde cross-linking agent capable
of cross-linking the polyvinyl alcohol resin, said cross 0
linking agent being present in an amount of from 1 to
20% by weight of the theoretical amount required to
react with all of the hydroxyl groups of the polyvinyl
alcohol resin, and a water soluble acid-aldehyde con wherein x and y are each 0-2. Other dialdehydes, how
taining a reactive aldehyde group capable of reaction ever, may be used, for example, the polyal
with hydroxyl groups in the polyvinyl alcohol resin and dehydepolysaccharide compounds, such as dialdehyde
an ionizable acid hydrogen atom, said acid aldehyde starch, disclosed in application Ser. No. 145,271, ?led
being present in an amount of from 1 to 50% by weight Apr. 30, 1980, now US. Pat. No. 4,272,470, issued June
of the theoretical amount required to react with all of 9, 1981, the disclosure of which is herein incorporated
the hydroxyl groups of the polyvinyl alcohol resin and 60 by reference. In general, the dialdehyde is one which
suf?cient to reduce the pH of the aqueous admixture to forms a homogeneous admixture with the polyvinyl
not more than 5; forming the admixture into a desired alcohol polymer.
physical shape; and heating the shaped admixture to The dialdehyde cross-linking agent is preferably pro
form a shelf-supporting polymeric article and to simu vided as an aqueous solution or dispersion for ease of
taneously effect a cross linking reaction between the 65 mixing with the polyvinyl alcohol which is also prefera
dialdehyde cross linking agent and the polyvinyl alco bly provided in aqueous solution. In any event, the
hol resin to produce a cross-linked polyvinyl alcohol polymer and cross-linking agent are admixed, prefera
element. bly in aqueous solution. The cross—linking agent is used
 4,357,402
3 4
in an amount of 1 to 20% by weight of the theoretical ?lm is cast at about 50 mils wet thickness onto a glass or
amount required to cross-link all of the available hy stainless steel plate. The plate is then placed in an oven
droxyl groups of the polymer. at 90° C. until dry (about a} hour). The 50 mils wet ?lm
The acid aldehyde used must satisfy four require wil yield about 2 to 3 mils dry. If heating is continued
ments. First, it must have a reactive aldehyde group beyond 45 minutes at 120°-l25° F., globs of gel begin to
capable of reacting with the hydroxyl groups of the form in the solution indicating that cross-linking has
PVA. It is preferred that the aldehyde group reacts started.
with hydroxyl groups in a single polymer chain rather To determine if the dried ?lm is cross-linked, the
than with hydroxyl groups in two different polymer
chains. In the present aqueous system in which the PVA 10 dried ?lm is placed directly into boiling water (neutral
is present in not more than about 20% concentration, it pH). After 20 minutes the ?lm will be recovered intact
is found that the majority of the aldehyde groups of the if it is cross-linked. In the present example, the ?lm is
acid-aldehyde reagent react in this manner. The acid cross-linked and a battery separator having good elec
aldehyde agent is thus incorporated into the polymer trical and physical properties is obtained.
structure. Second, the acid group must contain an ioniz As indicated in Example 1, the ingredients are prefer
able hydrogen. Third, the agent must be suf?ciently ably blended before adding the acid aldehyde. Prior to
acidic to provide a pH of not more than 5, preferably adding the acid aldehyde, the aqueous admixture may
4-5, when used in an amount of 1-50%, preferably be heated to facilitate blending, particularly the intimate
l—20%, by weight of theoretical amount that will react admixture of the dialdehyde and the PVA. It is pre
with all of the hydroxyl groups of the PVA. Fourth, the 20 ferred, however, to keep the temperature low, particu
agent must be water soluble. larly when the acid-aldehyde is added, to prevent pre
Several different acids are suitable including carbox mature cross-linking. Accordingly, it is preferred to
ylic, sulfuric and phosphoric. Glyoxylic acid is pre heat the admixture to not more than about 150° F. and
ferred because it is readily available commercially. Pre that the temperature of the admixture is not more than
ferred acid-aldehydes are those having the formulas 25 about 135° F. when the acid-aldehyde is added.
After addition of the acid-aldehyde, the admixture
‘I? i’
1-1-C-C-OH and H-C-R-C-OH
i? ii may be gently heated to facilitate its admixture. How
ever, temperature should be suf?ciently low to prevent
any substantial cross-linking and, in general, it is pre
and the sulfonic and phosphonic acid analogs thereof, 30 ferred to maintain the temperature at not higher than
wherein R is a divalent organic residue. The divalent about 135° F.
organic residue may be aromatic, aliphatic or cycloali Once the admixture is blended, it is preferred to form
phatic and may be substituted with non-interfering sub it into desired ?nal shape quickly, in order that substan
stituents provided that the four basic requirements set tially all of the cross-linking occurs after shaping. The
forth above are met. Preferred divalent organic radicals 35 permissible time will, of course, depend on the tempera
include phenylene and alkyl of 1 to 6 carbon atoms. The ture and to some extent on the formulation.
acid-aldehyde serves several functions. It functions as Drying of the shaped article can be effected at any
an acetalization reagent. Since it has an aldehyde func temperature suitable to effect drying and cross-linking.
tional group, it reacts with 1,3-diol units in the PVA. It
functions as an acid “catalyst” to induce the cross-link 40
However, the temperature of the article should not be
ing action between the PVA and the dialdehyde and the so high as to dehydrate the PVA. A preferable maxi
reaction between itself and the PVA. The reagent is mum drying temperature is about 205° F. The minimum
incorporated chemically into the PVA structure: it is drying temperature is selected to effect drying and
not present as a soluble or insoluble residue in the ?lm. cross-linking in a desired amount of time. In general, a
45 minimum drying temperature of about 150° F. is pre
EXAMPLE 1 ferred.
A solution mixture for casting or dipping is made COMPARISON EXAMPLE 1
from the following formulation:
The resistivity of a cast ?lm made in accordance with
50 the one step method of the present invention is com
Ingredient Parts by weight pared with a ?lm made in a two step method in which
Medium viscosity PVA (10% aqueous solution) 250 cross-linking is effected by post-treatment of the dry
Dialdehyde of Furan (DAF) 0.5
Water 45 ?lm with acid. In each ?lm, 2% dialdehyde of furan is
Wetting Agent (4 grams Triton X-lOO/ 0.5 incorporated into the ?lm. Results are as follows:
500 ml water) 55
Glyoxylic Acid (50% solution in water) 4.2
Glyoxylic acid in ?lm Resistivity
Experiment Method (Wt. %) (ohm-cm2)
All ingredients, except the GOA, are mixed in a
blender. When blended, the GOA is added and the A Two Step 0 .l4
B Two Step 20 .20
blending is continued for ?ve minutes more. Then the 60 C One Step l0 .10
mixture is heated in a boiling water bath. After 1; hour of
heating, (temperature of the solution about l20°—l25°
P.) if the solution is to be used to dip electrodes, the The comparison with Experiment A illustrates the
electrodes are dipped into the solution, withdrawn, and good electrical properties of the product of the present
dried in an oven at 90° C. until dry (about A hour). If the 65 invention compared with a conventional two-step
solution is to be cast to make a ?lm, the total elapsed cross-linking method. The comparison with Experi
time from addition of the GOA plus heating at ment B illustrates the importance of incorporating the
l20°—125° F. should not exceed about 45 minutes. The acid-aldehyde into the PVA before forming the ?lm.
 4,357,402
5. 6
EXAMPLE 2
mercial ?lm casting techniques. A suitable release agent
in small quantity (0.1%—l.0% by weight) may be used
The procedure of Example 1 is followed except that to obtain release of the dry cross-linked ?lm from the
the dialdehyde of furan is replaced by a dialdehyde of casting belt. The separator solution may be applied to
starch. Results are substantially the same as in Example 5 woven or non-woven substrates such as polypropylene,
1. ; ~ asbestos, nylon, cellulose base, or polyvinyl alcohol in
EXAMPLE 3 one or more coats usingv conventional paper coating
techniques.
A separator ?lm incorporating a ?ller is made in What is claimed is:
accordance with the present invention from the follow 1. A method of producing a cross-linked polyvinyl
ing aqueous admixture: alcohol element which comprises the steps of:
providing an aqueous admixture comprising
Ingredient Parts by weight a ?lm-forming polyvinyl alcohol resin,
a dialdehyde cross-linking agent capable of cross
Medium viscosity PVA (10% solution) 250 15 linking the polyvinyl alcohol resin, said cross
DAF 0.5
Water 50 linking agent being present in an amount of from
Wetting Agent (as in Example 1) 0.5 1 to 20% by weight of the theoretical amount
200 mesh white pine wood flour .69 required to react with all of the hydroxyl groups
Titanium dioxide (Degussa P-25) .56
Tarnol 731 (?ller dispersing agent), of the polyvinyl alcohol resin, and
25% water solution .2 20 a water soluble acid-aldehyde containing a reactive
Glyoxylic acid 4.2 aldehyde group capable of reacting with hy
droxyl groups in the polyvinl alcohol resin and
Following the procedure of Example 1, a cross-linked containing an ionizable acid hydrogen atom, said
PVA battery separator having good electrical and 25 acid-aldehyde being present in an amount of
physical properties is obtained. from 1 to 50% by weight of the theoretical
amount required to react with all of the hydroxyl
EXAMPLE 4 groups of the polyvinyl alcohol resin and suf?
Example 3 is followed except that the ?llers wood cient to reduce the pH of the aqueous admixture
flour and titania are replaced by: to not more than 5;
30 forming the admixture into a desired physical shape;
and
Ingredient Parts by Weight heating the shaped admixture to form a self-support
Calcium Zirconate Silicate ing polymeric article and to simultaneously effect a
(CZS, TAM Products, NL industries) L09 cross-linking reaction between the dialdehyde
Titanium Dioxide (Degussa p-25) .19 35 cross-linking agent and the polyvinyl alcohol resin
to produce a cross-linked polyvinyl alcohol ele
The procedure of Example 1 is followed, and results ment.
are substantially the same as in Example 4. 2. A method according to claim 1 wherein the admix
ture is formed into a desired physical shape by casting a
COMPARISON EXAMPLE 2
?lm of said admixture onto a support.
The resistivity of a cast ?lm, containing 5% ?ller, and 3. A method according to claim 1 wherein the admix
made in accordance with the present invention is com ture is formed into a desired physical shape by immers
pared with a ?lm made with a two step cross-linking ing a support into said admixture and removing the
method, using after-treatment with acid to effect cross support therefrom, whereby a coating of said admixture
linking. Results are as follows: is provided on the support.
4. A method according to claim 1 wherein said acid
aldehyde is selected from the group consisting of those
Experi- Filler Resistivity (Ohm-CmZ) having the formulas
ment Composition Ratio Two Step One Step
D 200 mesh wood flour: 5:4 .31 .15 50
Titania
E calcium zirconate 5:1 .43 .12 ll) 8
H-C-C-OH and H-C-R-C-OH
II II
silicate: titania
and the sulfonic and phosphonic acid analogs thereof
As illustrated in the Examples, the admixture may 55 wherein R is a divalent organic radical.
include conventional addenda such as ?llers, wetting 5. A method according to claim 4 wherein R is se
agents, and the like. Fillers, for example, may be incor lected from the group consisting of a divalent aliphatic
porated in an amount of 5—20% by weight, based on the radical, a divalent cycloaliphatic radical and a divalent
weight of the PVA. Suitable ?llers include titania, tita aromatic radical.
nates, silicates, zirconates, aluminates, wood ?our, and 60 6. A method according to claim 5 wherein R is a
lignin. It is important to note that the admixture may be divalent alkyl radical of from 1 to 6 carbon atoms.
free of any conventional acid catalyst. This is important 7. A method according to claim 5 wherein R is phe
because a conventional acid catalyst, such as sulfuric nylene.
acid, may cause blackening and increased resistance 8. A method according to claim 1 wherein said acidic
when the cross-linked PVA article is subjected to oper 65 aldehyde comprises glyoxylic acid.
ating temperatures of l60°—l80" F. 9. A method according to claim 1 wherein said poly
The present one step method of cross-linking a cast vinyl alcohol resin is present in said admixture in an
?lm while drying is compatible with present PVA com amount of from 3 to 20% by weight, based on the total
 4,357,402
7 8
weight of water and polyvinyl alcohol resin in said wherein R1 is a divalent organic radical of from 1 to 12
carbon atoms.
admixture. 11. A method according to claim 1 wherein said dial
10. A method according to claim 1 wherein said dial dehyde comprises a dialdehyde starch.
dehyde is selected from the group consisting of ethane 5 12. Cross-linked polyvinyl alcohol made by the pro
cess of claim 1.
dial and dialdehydes having the formula 13. In an alkaline battery having a cross-linked poly
vinyl alcohol separator, the improvement wherein the
separator is made by the process of claim 1.
10 14. A method according to claim 1 wherein the
amount of acid aldehyde is 1—20% by weight.
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