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Patented Dec. 24, 1946
_ 2,413,275
UNITED STATES PATENT ~ OFFICE ‘_
POLYVINYL ACETAL MALEATES AND‘
METHOD OF MAKING SAME‘
FrankE. Wilson, Ashland, Gustavus J. Esselen,
Swampscott, and Gaetano F. D’Alelio, North
ampton, Mass., assignors, by mesne assign
ments, to Pro-Phy-Lac-Tic Brush Company,
Northampton, Mass, a corporation of Delaware
No Drawing. Application August 27, 1943,
SerialNo. 500,278
7 Claims.
(01. 260-73)
1
r
2
.
The ?nal product retains the double bonds of
The present invention relates to a novel syn—
thetic material and to a process of making the
the acyl radical of the component maleic acid,
and therefore may be capable of- reaction with
‘other substances with valuable results.
polyvinyl alcohol is condensed with an aldehyde
We are aware that it has been proposed to,
in the presence of maleic acid, preferably in the 5
copolymerize monomeric vinyl methyl formal
form of maleic anhydride, and in a substantially
(which is a mixed methyl vinyl acetal of form
anhydrous medium and under conditions such
aldehyde) with maleic anhydride, but this causes
that the polyvinyl alcohol and the ?nal product
the disappearance of the double bonds and‘ the
are always in the solid state and the water formed
by the reaction is removed from the reaction zone, 10 molecule contains no ester groups, We are also
aware that it has been proposed to copolymerize
the maleic acid not only acts as a catalyst for
same. It is based on the discovery that when a
the acetal reaction but also as a reactant so that a
a vinyl ester and a maleic dimethyl ester with the .
there is produced what may be called a polyvinyl
disappearance of the double bondsof the maleic
acid, then saponify the resulting product to pro
duce a polyvinyl‘ alcohol containing carboxyl
acetal maleate.
.
.
Determination of the acid and saponi?cation
numbers of the resulting products indicatesthat
groups derived from maleic acid and ?nally ace
talize with an aldehyde. This product can be de
there are present in the ?nal product uncombined
scribed as containing residues of polyvinyl acetal
free carboxyl groups, also that some of the di
carboxylic acid groups have formed a ring while
and residues of malice anhydride or acid, but
others have formed a bridge or cross-linkage. 20 contains no ester groups and the double bond of
the maleic acid has disappeared. In contrast,
These tests indicate that in one portion of the
the present process is the esteri?cation and ace
molecule only one of the carboxyl groups reacts
talization of previously formed‘polymers and re-‘
with an hydroxyl group of the polyvinyl alcohol
sults in a product containing ester groups of poly
while in another part of the molecule both of the
carboxyl groups have reacted with one polyvinyl 25 vinyl alcohol and maleic acid and retains the
double bonds of maleic acid.
alcohol chain producing a ring structure, and
The copending application of Joseph Dahle
that in another part of the molecule both car
Serial No. 343.439. ?led July 1, 1940, describes the
boxyl groups have reacted with two polyvinyl
treatment of a ?lament of polyvinyl alcohol with
alcohol chains producing a bridge structure.
Such a material may be represented as con 30 an aldehyde in the presence of maleic anhydride
and water. In this reaction, the maleic anhydride
taining the following ?ve residues:
acts solely as a catalyst and does not form an
ester with the polyvinyl alcohol.
'
The novel products described herein and pro
duced by our novel processes are characterized
by different solubility characteristics from similar
products made by known pro‘esses, and, not
withstanding the large amount of cross linkage,
may be hot molded under relatively high tem
peratures and pressures. For instance. it’ is pos
sible to hot mold the product made with maleic
anhydride as described hereafter under tempera
tures of from 130° to 150° C, and pressures of
from 5000 to 10.000 lbs. per square inch. This is
exceptional when one considers that a cross:
linked copolymer of approximately‘ 99 to 99.5
parts of vinyl acetate and 0.5 to 1 part of di-allyl
maleate. which acts as a cross linking agent, can
not be successfully molded, although the amount
50 of the cross linking agent is extremely small.
In the new maleic anhydride product herein de
scribed, the percentage of the cross linking com
ponent as shown by the saponi?cation numbers
is very much larger yet it is possible to hot mold
where R is an alkylene or arylene radical.
55
the product successfully.
2,418,875
3
Example 2
The novel products herein described are made
Powdered polyvinyl alcohol ______ __grams__ 44
Heptane ______________ __cubic centimeters__ 700
by treating a solid polyvinyl alcohol with maleic ,
acid or its equivalent anhydride and an aldehyde
. simultaneously.
Paraformaldehyde _______________ _..grams__
Maleic anhydride _________________ __do____
This is done preferably in a vol
atile liquid which is a non-solvent for the poly
30
5
Reaction temperature _____________ __°C-_ 84-95
Reaction ttime ___________________ __hours__ 2.5
vinyl alcohol and for the resulting final product, a
and is not miscible with water. A part at least ‘
of the reaction is carried out at or above the
The procedure was otherwise as in Example 1.
vaporization temperature of‘ the reaction mixture .
The product analyzed 21.1 percent unreacted
10
so that the water formed by the reaction is re
hydroxyl‘groups calculated as vinyl alcohol. The
moved from the zone of the reaction and carried
acid number was 14 and the saponiflcation num
o? with the vapors of the non-solvent liquid. In
ber was 25. The per cent of acetal was 73.8, and
practice, it is convenient to condense the vapors
the degree of reaction 95.6.
to separate the water from the distillate and re
Example 3
15
turn the distillate to the reaction chamber. This
process has the advantage that the polyvinyl al-,
Powdered polyvinyl alcohol ______ __grams__ 44‘
cohol and the resultant product are in the solid
Heptane __________ __'__-cubic centimeters__,500
state throughout the process, and, therefore, it
Butyraldehyde __________________ __grams_.. 54
is not necessary to dissolve the polyvinyl alcohol,
"Maleic anhydride ________ -L _______ __do____
5
or precipitate the product from a solution.
Reaction temperature __________ __°C__ 76 to 87.5
The term “a polyvinyl alcohol” is used herein
Reaction time; _________________ __hours__
3
to include pure polyvinyl alcohol or polyvinyl ma
Acid
number
17;
saponi?cation
number
31;
vinyl
terials containing unreacted- hydroxyl groups, for
alcohol 11.7; acetal 82.0; degree of reaction 84.5.
instance, a partially esteri?ed polyvinyl alcohol,
25
‘
Example 4
a partial polyvinyl acetal ‘or the hydrolyzed in
terpolymer of vinyl chloride and vinyl acetate,
etc.
' Powdered polyvinyl alcohol ____ ___._grams__
Various inert liquids may be employed. We
prefer to use inert hydrocarbons such as benzene,
heptane, octane and mixed hydrocarbon frac
Crotonaldehyde _________________ "grams" 52.5
an Maleic anhydride _________________ .._do____
non-solvent for the polyvinyl alcohol and for the‘
resulting acetal, and that it be immiscible with
water, and preferably miscible with the aldehyde
.
‘
Reaction time____-, _____________ __hours__
alcohol 38.1; acetal 52.1; degree of reaction 56.7.
Example 5
The polyvinyl alcohol or other polyvinyl sub
Powdered polyvinyl alcohol ______ __grams__ 44
Heptane _____________ __cubic centimeters__ 600
stance may be in different solid forms, such for
instance,‘ as a powder, a ?lament, a sheet, a'rod
Furfuraldehyde _________________ __grams__
' or a tube. Filaments are polyvinyl alcohol which 40
Maleic anhydride _________________ __do__.._
72
5
Reaction temperature _________ __°C__ 78 to 94.5
have been stretched to increase the. tensile
strength and fabric: woven‘ therefrom may be
Reaction time ___________________ _-hours__
treated as described without great loss of tensile
strength. Such, ?laments or ‘cloth retain their
original softness and ?exibility to a high degree.
The invention will be fully understood from
the following examples which are given as illus
3
Acid number 9; saponi?cation number 59; vinyl
alcohol 74.3; acetal 16; degree of reaction‘ 56.7.
Example 6
'
Powdered polyvinyl alcohol ______ __grams__ 44
Heptane _____________ -.cubic centimeters__ 500
Benzaldehyde ___________________ -_grams__ 79.5
Maleic anhydride ________________ __do____
5
Reaction temperature _________ __°C__ 88 to 95.5
trations of the way the novel process maybe
practiced and the product produced.
Example 1
Powdered polyvinyl alcohol ______ __grams__ 44
Heptane___ ___________ __cubic centimeters__ 'mo
Reaction time ___________________ __hours__
3
Acid number 17; saponification number 58; vinyl
alcohol 16.2; acetal 73.4; degree of reaction 51.2.
30 -
Maleic anhydride____'_ ____________ __v_do__.._
Example 7
The heptane and polyvinyl alcohol were heated,
with stirring, to 70° C.‘ The maleic anhydride
was melted and added to the mixture. The heat
ing was continue! for 15 minutes then the para~
formaldehyde was added and the mixture heated
Powdered polyvinyl alcohol ______ "grams"
44
Varnoline (a heavy benzine)
cubic centimeters__ 500
Paraformaldehyde ______________ “grams” 22.5
in a vessel equipped with a reflux condenser and
' a water trap.
3
' Acid number 23; saponi?cation number 50; vinyl
'
Paraformaldehyde _______ __' ______ __grams__
5
Reaction temperature _____ __'__‘____°C__ 81 to 92
tions, etc., it being requisite that the liquid be a '
and catalyst.‘
44
Heptane _____________ __cubic centimeters-_ 500
'
Maleic anhydride _______ __' ________ __do____
During the continued heating, the
5
. Reaction temperature __________ __°C__ 70 to 148
water‘ as it was produced by the reaction was
vaporized with the heptane and was then con
Reaction time _'_ ____________ __\__minutes__'
70
Acid number 8; saponi?cationl'number 57; vinyl
densed and caught in the trap while the con 65 alcohol 17.4; acetal 73.2; degree of reaction 90.0.
densed heptane was returned to the reaction ves
Example 8
sel. In this way, the water produced by the
reaction was removed from the reaction bath and
prevented from combining in substantial amounts
with the ‘unreacted polyvinyl alcohol. The heating as described was continued for two and one
half hours, after which the polyvinyl acetal was
separated by ?ltering and was washed and neu
tralized to remove any traces of uncombined ma
lelc acid.
-
'
“
Cloth woven from polyvinyl alcohol yarn
grams__
23
Heptane ____________ __cubic centimeters” 1200
Paraformaldehyde ______________ _-grams-_
l5
Maleic anhydride ________________ __do____
5
Reaction temperature__________ __°C__ 84 to 90
75 Reaction time ____________ .._' .... "hours"
3
2,413,275
‘ 6
Example 9
Cloth woven from polyvinyl alcohol yarn
grams__
compound in a liquid hydrocarbon in the pres
ence of an aldehyde and a compound selected
from the group consisting of maleic acid and
maleic anhydride, and conducting the reaction
under anhydrous conditions by removing water
5
Heptane ___________ __'_-cubic centimeters__ 700
Paraiormaldehyde _______________ __grams__
15
Maleic anhydride _________________ __do____
5
Reaction temperature ____________ __°C__ 84 to 92
Reaction time"; ______________ __minutes_- '75
Example 10
Polyvinyl alcohol sheeting-—thickness 0.004"
grams__
from the zone of the reaction, the maleic com
pound serving as the sole acetalization catalyst
and also simultaneously as an esteriiying agent
thereby producing a polyvinyl acetal maleate
10 which is not soluble in said hydrocarbon.
4. The process of acetalizing a solid polyvinyl
compound containing repeating
l5
Heptane _____________ __cubic centimeters__ 500
Paraformaldehyde _______________ __grams__
Maleic anhydride ________ -7 _______ __do____
15
v5
15
Reaction temperature ___________ __°C__ 86 to 91
Reaction time __________________ __1hours__
1
No'rn.——'l‘he center of the sheet was not reacted.
Example 11
Polyvinyl alcohol as a coating on cotton
cloth, approximately __________ __grams__
15
Heptane _____________ __cubic centimeters__ 1500
Butyraldehyde _________________ __grams__
75
Maleic anhydride ________________ __do____
5
Reaction temperature ___________ __°C__ 85 to 91
Reaction time __________________ __hours__
3
units which comprises heating such a polyvinyl
compound in heptane in the presence of an alde
hyde and a compound selected from the group
consisting of maleic acid and maleic anhydride,'
and conducting the reaction under anhydrous
conditions by removing water from the zone of
the reaction, the maleic compound serving as the
sole acetalization catalyst and also simultaneous
ly as an esterifying agent thereby producing a
polyvinyl acetal maleate which is not soluble in
the heptane.
5. The process of acetalizing a solid polyvinyl
compound containing repeating
It will be apparent from the above examples
that the degree of reaction will depend in part 30
at least on the temperature and time.
“Cm-cu
ta
In each
units which comprises heating such a polyvinyl
compound in a liquid hydrocarbon in the pres
re?ux condenser with a trap for separation of
ence of an aldehyde and maleic anhydride, and
the water, the condensed inert liquid being re
conducting the reaction under anhydrous condi
turned to the reaction mixture.
tions by removing water from the zone. of the
We claim:
1. In the process of acetalizing a solid poly
reaction, the maleic anhydride serving as the sole
vinyl compound containing repeating
acetalization catalyst and also simultaneously as
an esterifying agent thereby producing a poly
—cm-cH
40 vinyl acetal maleate which is not soluble in said
on
instance the reaction was carried on under a
hydrocarbon.
units with an aldehyde in an inert reaction me
6. The process of acetalizing a solid polyvinyl
dium whereby the polyvinyl compound and the
resulting polyvinyl acetal remain in the solid
state throughout the process, the improvement
which consists in conducting the acetalization
compound containing repeating
under anhydrous conditions and in the presence
of a single catalyst selected from the group con
units which comprises heating such a polyvinyl
compound in a liquid hydrocarbon in the presence
of butyraldehyde and maleic anhydride, and con
ducting the reaction under anhydrous conditions
by removing water from'the zone of the reaction,
the maleic anhydride serving as the sole ace
talization catalyst and also simultaneously as an
sisting of maleic acid and maleic anhydride, the
maleic compound also acting simultaneously as
an esterifying agent. ’
2. In the process of acetalizing a solid poly
vinyl compound containing repeating
esterifying agent thereby producing a polyvinyl
butyral maleate which is not soluble in said hy-
units with an aldehyde in an inert reaction me
drocarbon.
7. In the process of acetalizing a polyvinyl
dium whereby the polyvinyl compound and the
resulting polyvinyl acetal remain in the solid state
throughout the process, the improvement which,
consists in conducting the acetalization under
compound containing repeating
anhydrous conditions in the presence of maleic
anhydride as the sole acetalization catalyst, the
maleic anhydride also acting simultaneously as
an esterifying agent.
3. The process of acetalizing ,a solid polyvinyl
units with an aldehyde, the improvement which
compound containing repeating
Mir-cue
011
units which comprises heating such a polyvinyl 70
-
-—(.‘Hg——(EH-—
on
comprises conducting the acetalization under an
hydrous conditions and in the presence of a single
catalyst selected from the group consisting of
maleic acid and maleic anhydride, the maleic
compound also acting simultaneously as an ester
ifying agent.
FRANK E. WILSON.
GUSTAVUS J. ESSELEN.
GAETANO F. D’ALELIO.
'
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