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Патент USA US2130451

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Patented Sept. 20, 1938
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12,130,451
PATENT QOFFIC'E'
UNITED STATES
2-130A51
PROCESS FOR THE PREPARATION 0
VINYL DERIVATIVES
'
Georges E. Zelger, Montrenil-sous-Bois, Seine,
France, assignor, by mesne- ' assignments, to
Eastman Kodak Company, Jersey City, N. 1., a
corporation of New Jersey
>
No Drawing. Application May 16,1935, Serial
No. 21,878._ In France May 23, 1934
16 Claims.
This invention relates to a process for the prep
aration of condensation products of a polyvinyl
alcohol and an aldehyde, in the presence of a cat
'
(Cl. 260-2)
1
1% of the weight of the total reaction mass. (See
alyst. In particular, this invention relates to a
5 process for the preparation of condensation prod
Example 1.)
It has proven more satisfactory to approach the
transition point, solubility-insolubility, from the
‘insoluble side. As the amount of catalyst is in
creased
for the successive trial condensations, the
ucts of a polyvinyl alcohol and an aldehyde which
condensation products become softer andv softer
gives solutions of high, practically maximum vis
when in contact with the solvent and tend to dis
cosity in suitable organic solvents.
'
This application is a continuation-in-part of my ‘ perse more and more therein, until ?nally a prod
10
is obtained which appears to give a homogene
10 copending application Serial No. 706,099, ?led " uct
ous dispersion in the solvent. Close examination
January 10, 1934.
\
.
however, that this mixture is not homo
Condensation products of a polyvinyl alcohol reveals,
but rather is made up of small swollen
and an aldehyde obtained according to known geneous
particles of the condensation product dispersed
processes have various disadvantages. For ex
throughout the solvent.‘ If now, the amount of .15
15 ample, certain of these condensation products are catalyst is but slightly increased for the next
insoluble in all solvents, while others are soluble,
but give rise to solutions of relatively low viscosi
ty. Such solutions of lower viscosity are unsatis
factory for many purposes. In fact, it is essential,‘
in the manufacture of ?lms, ?laments, threads
and the like from these condensation products, to
employ condensation products which are entirely
soluble in suitable solvents and in addition give
solutions of high viscosity with these solvents.
Now, I have found that condensation products
of a polyvinyl alcohol and an aldehyde which give
solutions of high, practically maximum viscosity
with suitable organic solvents, such as a mixture
of four volumes of methylene chloride and one
volume of pure ethyl alcohol, ethylene chloride,
3 tetrachlorethane chloroform or, other suitable or
ganic solvents, preferably mixed with a small
amount of alcohol, can be prepared by effecting
the condensation in the presence of an amount of
catalyst slightly in excess of that amount neces
3 GI sary to produce a condensation product just in‘
soluble in the suitable organic solvent, previously
selected. I have also found that this amount of
catalyst can be varied only within narrow limits,
40 if the resulting condensation product is to form
solutions of high, practically maximum viscosity.
The object of this invention, therefore, is to pro
vide condensation products of a polyvinyl alco
hol and an aldehyde which give solutions of high,
practically maximum viscosity with suitable or'
45 ganic solvents. A further object is to provide a
process for the preparation of such vinyl conden
sation products. Other objects will appear here
inafter.
50
.
According to my invention, the maximum
amount of catalyst, which gives a condensation
product just‘ insoluble in the chosen organic sol
vent, is determined by trial condensations, using
progressively larger amounts of catalyst. Then
55 for the desired condensation product, an amount
of catalyst just slightly in excess of that amount
previously determined is employed. If the cata
lyst is hydrogen chloride and if the condensation
is e?ected at ordinary temperatures, that is, about
60 20° C., the excess of catalyst is equal to less than
condensation, a product is obtained which is en
tirely soluble and the resulting solution is. ofa
high, practically maximum viscosity. Larger
amounts of catalyst give rise to condensation 20
products which form solutions of de?nitely lower
viscosity. If‘ the catalyst employed is hydrogen
chloride, I have found the excess to be employed
in the ?nal condensation to vary between about
0.3% and about 1% of the weight of the total re-. 26'
action mass.
'
g
The following examples serve to illustrate my
invention, but are not intended to be limiting.
In these examples, the polyvinyl alcohols are de
?ned by indicating the Engler viscosity of their 30
4% aqueous solutions at 15° C. and the concen
tration of catalyst is expressed as a percent of the
weight of the total reaction mass. (See Exam
ple 1.)
‘
,
Example 1.-—100 g. of a polyvinyl alcohol (Engler
viscosity 63) were dissolved in 1 liter of water, 35
grams of trioxymethylene were added and to the _
resulting mixture, 300 cc. of hydrochloric acid (sp.
gr. 1.19) were introduced. This quantity ‘of hy
drochloric acid weighed 357 g. and since 37% of 40
the acid was hydrogen chloride,,132‘g. of hydro-'
gen- chloride had been introduced. Thus the
amount of hydrogen chloride (132 g.) was equal to
8.8%‘ of the total reacting mass (1492 g.). The
mixture was stirred or otherwise agitated and al 45
lowed to react at about 20‘? C. At the end of from
one to two hours, the trioxymethylene went into
solution, giving a transparent ‘liquid. At the end
of several hours a white compact mass of the
vinyl condensation product'precipitated. This
50
product was washed and dried. It .was completely
soluble in a mixture of four volumes of methyl
ene chloride and one volume of pure ethyl a1‘
cohol, a 2% solution having an Engler viscosity
of 61 at.14° C.
.
-
55
With a concentration of hydrogen chloride
equal to 10% of the total reacting mass, the
vinyl condensation product gives a solution in a
mixture of four volumes of methylene chloride
and one volume of pure ethyl alcohol which is very
do
2
2,180,451
?uid and of lower viscosity. With a concentration
condensation product of a particular polyvinyl
.alcohol and an aldehyde which dissolved com
pletely in a suitable, previously selected organic
Example 2.-—10‘0"g_.,>0f polyvinyl alcohol (Engler solvent
and gives therewith a solution' of high
viscosity 97) were treated as in Example 1, but in
of 8%, the product is incompletely soluble, giving
a gel which is notv homogeneous.
the presence of 12% hydrogen chloride. The
vinyl condensation produchgave a 2% solution in
practically maximum viscosity is Just slightly in
excess of that necessary to produce a condensa
a mixture of four volumes of methylene chloride tion product just insoluble in the previously se
and one volume of pure ethyl alcohol having an lected organic solvent. Further, it can be seen
10 Engler viscosity of 65 at 15° C., such a viscosity that the absolute amount of catalyst which gives
rise to the desirable condensation product can be 10
being the maximum obtained with a polyvinyl varied
within but narrow limits.
alcohol of this degree of polymerization.
It is to be noted that my invention is not limited
With a‘ concentration of hydrogen chloride
equal to 11% of the total reacting mass, the vinyl to the above examples, nor to the choice 01' the
15 condensation product was quite insoluble in a bodies employed, nor to catalysts, the proportions
mixture of four volumes of methylene chloride indicated for catalysts falling according to the 15
and one volume of pure ethyl alcohol.
‘
f
Example 3.—100 g. of a polyvinyl alcohol (En
gler viscosity 38) were treated as in Example 1,
20 but in the presence of 7% hydrogen chloride.
The vinyl condensation product gave a 2% solu
tion in a mixture of four-volumes of methylene
chloride and one volume of pure ethyl alcohol
having an Engler viscosity of 30 at 15° C., such
' a viscosity being the maximum obtained with a
polyvinyl alcohol of this degree of polymerization.
With a concentration of hydrogen chloride
equal to 6.7% of the total reacting mass, the vinyl
condensation product was insoluble in a mixture
30 of four volumes of methylene chloride and one
volume of pure ethyl alcohol, giving rise to swollen
particles which dispersed but did not dissolve to
give a solution.
-
Example 4.—100 g. of a polyvinyl alcohol (En
. gler viscosity 63) were treated as in Example '1,
but at a temperature of 60° to 80° C., and in the
bodies employed and according to the nature of
the catalysts. At ordinary temperatures 1. e.
about 20° C. where A% represents the amount of
hydrogen chloride, based on the weight of the
total reacting mass, necessary to produce a con 20
densation product of a polyvinyl alcohol and an
aldehyde just insoluble in a previously selected
organic solvent, from about (A+0.3) % to about
(A+1.0)% of hydrogen chloride, based on the
weight of the total reactingv mass, produces a 25
condensation product of a polyvinyl alcohol and
an aldehyde which gives a solution of high, prac
tically maximum viscosity in the previously se
lected organic solvent.
,
In the claims, the polyvinyl alcohols are de
?ned by indicating the Engler viscosities of their
4% aqueous solutions at 15° C. and the amounts
of catalyst are indicated as a percent of the
weight of the total reaction mass. (See Exam
ple 1.) The term aldehyde is intended to mean 35
presence of 15.5% hydrogen chloride. The vinyl 1 an aldehyde in either its monomeric or its poly
condensation product gave a 2% solution in a meric form e. g. formaldehyde is intended to
mixture of four volumes of methylene chloride
and one volume of pure ethyl alcohol having an
Engler viscosity of 48 at 15° C.
With a concentration of hydrogen chloride
equal to 12.5% of the total reacting mass, thev
vinyl condensation product is incompletely sol-.
45 uble in a mixture of four volumes oi’ methylene‘
chloride and one volume of pure ethyl alcohol. 1
mean either monomeric formaldehyde or one 01'
its polymers such as trioxymethylene.
What I claim as my invention and desire to be
secured by 'LetterslPatent of the United States .
is:
1..A process for the preparation of a conden
sation product of a polyvinyl alcohol and an al
dehyde which gives a solution of high viscosity
Example 5.—100 g. of a polyvinyl alcohol in a previously selected organic solvent compris
(Engler viscosity 63) were treated as in Example ing condensing a polyvinyl alcohol with an al
1, but in the presence of 25% of hydrogen sul-" dehyde, in the presence of about (A+0.3) per
cent to about (Ii-+1) per cent by weight of a
50 fate. The vinyl condensation product gave a 2%
solution in a mixture 01' four volumes of methyl~ catalyst, based on the total weight of the reacene chloride and one volume of pure ethyl alcohol tion mass, where A percent represents the amount
of catalyst necessary to produce a condensation
having an Engler viscosity of 45 at 15° C.
just‘insoluble in the previously selected
With a concentration of hydrogen sulfate equal product
organic solvent.
.
55 to 23.5% of the ‘total reacting mass, the vinyl
2. A ‘process for the preparation of a condensa
condensation product is incompletely soluble in
a mixture of four volumes of methylene chloride tion product of a polyvinyl alcohol and formalde
hyde which gives a solution of high viscosity in
and one volume of pure ethyl alcohol. '
From these examples it can be seen that the a previously selected organic solvent compris
absolute amount of hydrogen chloride necessary
to produce a condensation product of a polyvinyl
alcohol and an aldehyde which gives a solu
tion of high practically maximum viscosity with
a mixture of four volumes of methylene chloride
and one volume‘ of pure ethyl alcohol varies be
tween about 7% and 12% 01' the .weight of the
total reaction mass, depending upon the particu
lar polyvinyl alcohol 'employed and when the
condensation is effected at ordinary temperatures.
‘ At higher temperatures, that is from about 60° C.
to about 80° C., the absolute'amount of hydrogen
chloride is somewhat higher varying from about
14% to about 20%.
From these examples, it can also be seen that
75 the amount of catalyst necessary to produce a
30
ing condensing a polyvinyl alcohol with formal
dehyde, in the presence of about (A+0.3) per 60
cent to about (A+1) percent by weight of a
catalyst, based on the total weight of the reac
tion mass, where A. per cent represents the
amount of catalyst necessary to produce-a con
densation product just insoluble in the previous 65
ly selected organic solvent.
3. A process for the preparation of a condensav~
tion product of a polyvinyl alcohol and an aide
hyde which gives a solution of high viscosity in
a previously selected organic solvent comprising 70
condensing a polyvinyl alcohol with an aldehyde,
in the presence of about (A+0.3) percent to
about (A+1)‘ percent by weight of acid catalyst,
based on the total weight of the reaction mass,
where A percent represents the amount of acid
75
3
2,130,451
about (A+0.3) per cent to about _(A+l) per cent
catalyst necessary to produce a condensation ‘by weight of hydrogen chloride, based on the
product just insoluble in the previously selected. total weight of- the reaction mass,‘where A per
organic solvent.
_
cent represents the amount of hydrogen chloride
necessary to produce a condensation product just
4. A process for the preparation of a condensa
tion product of a polyvinyl alcohol and formalde
hyde which gives a solution of high viscosity in a
previously selected organic solvent comprising
condensing a polyvinyl alcohol with formalde
hyde, inthe presence of about (A+0.3) percent to
about (A+1) percent by weight of acid catalyst,
10
based on the total weight of the reaction mass,
insoluble in the mixture of about four volumes of
methylene chloride and about one volume of ethyl
alcohol.
where A percent represents the amount of acid
catalyst necessary to produce a condensation
product just insoluble in the previously selected
organic solvent.
-
5. A process for the preparation of a condensa
tion product of a polyvinyl alcohol and an alde
hyde which gives a solution of high viscosity in
a previously selected organic solvent comprising
20
.
.
10. A process for the preparation of a conden
sation product of a polyvinyl alcohol and an alde
hyde which gives a solution of high viscosity in a
condensing a polyvinyl alcohol with an aldehyde,
in the presence of from about (A+0.3) percent to
about (A+1) percent by vweight of hydrogen
chloride, based on the total weight of the reaction
mass, where A percent represents the amount of
hydrogen chloride necessary to produce a conden
25 sation product just insoluble in the previously
selected organic solvent.
6. A process for the preparation of a condensa
mixture of about four volumes of methylene chlo
ride and about one volume of ethyl alcohol com
prising condensing, at about 20° C., a polyvinyl
alcohol with formaldehyde in the presence'of
from about (A+0.3) per cent to about (A+1)
per cent by weight of hydrogen chloride, based
on the total weight of the reaction mass, where
A per cent represents the amount of hydrogen
chloride necessary to produce a- condensation 20
product just insoluble in the mixture of about
four volumes of methylene chloride and about one
volume of ethyl alcohol.
'
I
11. A process for the preparation of a con
densation product of a polyvinyl alcohol and an 26
aldehyde comprising condensing a polyvinyl al-.
cohol of Engler viscosity about 38 with an alde
hyde, in the presence of about 7 per cent by
weight of hydrogen chloride,'based on the weight
tion product of a polyvinyl alcohol and formalde
30
the total reaction mass, at about 20° C.
hyde which gives a solution of high viscosity in of 12.
A process for the preparation of a con
30
a previously selected organic solvent comprising densation product of a polyvinyl alcohol and
condensing a polyvinyl alcohol with formalde
formaldehyde comprising condensing a polyvinyl
hyde, in the presence of from about (AA-0.3) per
alcohol of Engler viscosity about 38 with formal
cent to about (A-i-l) percent by weight of hydro dehyde,
the presence of about '7 per cent by
gen chloride, based on the totalweight of the weight ofinhydrogen
chloride, based on the total
35 reaction mass, where A percent represents the
weight of the reaction mass, at about 20° C. '
amount of hydrogen chloride necessary to pro
13. A process for the preparation of a‘con
duce a condensation product just insoluble in the densation product of a polyvinyl alcohol and an
previously selected organic solvent.
aldehyde comprising condensing a polyvinyl al 40.
'7. A process for the preparation of a condensa
cohol of Engler viscosity of about63 with an alde
40
tion product of a polyvinyl alcohol and an aide
hyde, in the presence of about 8.8 per cent by
hyde which gives, a solution of high viscosity in a weight of hydrogen chloride, based on the total
mixture of about four volumes of methylene chlo
weight of the reaction mass, at a temperature of
ride and about one volume of ethyl alcohol com
prising condensing a polyvinyl alcohol with an
45 aldehyde, in the presence of from about (Ag-0.3)
about 20° C., and in the presence or about 15.5
per cent by weight of hydrogen chloride, based
on the total weight of the reaction mixture/at
per cent to about (A+l) per cent by weight of
about 60° C. to about 80° C.
hydrogen chloride, based on the total weight of \_ from
14. A process for the preparation of a con
the reaction mass, where A per cent represents densation product of a polyvinyl alcohol and
’ the amount of hydrogen chloride necessary to formaldehyde comprising condensing a polyvinyl
50
produce a condensation product just insoluble in alcohol oi Engler viscosity of about 63 with form‘
the mixture of about four volumes of methylene . aldehyde, in the presence of about 8.8 per cent by,
chloride and about one volume of ethyl alcohol. weight of hydrogen chloride, based on the total
8. A process for the preparation of_a ‘condensa
weight of the reaction mass, at a temperature or 55
tion‘product
of a polyvinyl alcohol and an alde
55
about 20° C. and in the presence of about 15.5 per
hyde which gives a solution of high viscosity in cent
by weight of hydrogen chloride, based on
a mixture of about four volumes of methylene
chloride and about one volume of ethyl alcohol the total weight of the reaction mixture, at from
comprising condensing a polyvinyl alcohol with about 60° C. to about 80° C.
15. A process for the preparation of a con 60
formaldehyde,
in the presence of from about densation
60
product of a polyvinyl alcohol and an
(_A+0.3) per cent to about (AH-1) per cent by aldehyde comprising condensing a polyvinyl al
weight of hydrogen chloride, based on the total cohol of Engler viscosity of about 9'7 with an al.
weight of the reaction mass, where A per cent dehyde, in the presence of about 12 per cent‘ by
represents the amount of hydrogen chloride nec
weight of hydrogen chloride, based on the total 65
65 essary to produce a condensation product just _ weight of the reaction mass, at about 20° C.
insoluble in the mixture of about four volumes of
16. A process for the preparation of a con
methylene chloride and about one volume of ethyl densation product of a polyvinyl alcohol and
alcohol.
9. A process for the preparation of a condensa
70 tion product of a polyvinyl alcohol and an aide
hyde which gives a solution of high viscosity in a
{mixture of about four volumes of methylene chlo
ride and about one volume of ethyl alcohol com
prising condensing, at about 20° 0.‘, a polyvinyl
75 alcohol with an aldehyde, in the presence of-Irom
formaldehyde comprising condensing a polyvinyl
alcohol of Engler viscosity about 97 with form 70
aldehyde, in the presence of about 12 per cent by
weight of hydrogen chloride, based on the total
weight or the reaction mixture,
at about 20° C. .
GEGRGES E. znmm.
75
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