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Патент USA US3063962

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United States Patent ()??ce
3,063,950
Patented Nov. 13, 1962
1
2
vanhydride groups esteri?ed with nitrile groups containing
hydroxy compounds. Monomers convenient for the
3,063,950
POLYMERIC AMIDOXIMES AND THEIR DERIVA
TIVES AND A METHOD OF PREPARING SAME
preparation of some of these polymers are for example
acrylonitrile, methacrylonitrile and vinylidene cyanide
Ferdinand Leonard Schouteden, Wilrijk-Antwerp, Bel
gium, assignor to Gevaert Photo-Producten, Mortsel
5
Antwerp, Belgium, a Belgian company
No Drawing. Filed Feb. 26, 1962, Ser. No. 175,790
5 Claims. (Cl. 260—2.1)
hol, polyvinylamine, polyacryl- or methacrylamide, cel
lulose, alginic acid, starch, zein, gelatin, casein as well
The present invention relates to new compositions of
matter viz. to macromolecular substances containing
amidoxime groups and derivatives thereof.
as their derivatives.
In practical applications, one of the most simple pro—
cedures consists in using the reaction mixture directly
The application is a continuation-in-part of our co
after reaction of the macromolecular substances contain
ing nitrile groups with hydroxylamine. After ?ltration
pending application Serial No. 535,295, ?led September
19, 1955, now abandoned.
According to the invention, macromolecular substances
containing amidoxime groups are produced by reacting
macromolecular substances containing nitrile groups with
alone or in combination with other polymerisable mate
rials. Macromolecular substances which may be cyano
ethylated and/ or grafted are for example, polyvinyl alco
15 this reaction mixture is ready for further use.
However,
when preferred, the converted macromolecular substance
may ?rst be precipitated in a non-solvent and redissolved
in proper solvents. The conversion of nitrile groups into
amidoxime groups by the process of the invention has
free hydroxylamine, until at least part of the nitrile
groups have been converted into amidoxime groups, said 20 an in?uence on the solubility characteristics of the macro
macromolecular substances being dissolved, dispersed
molecular substance involved. For instance when poly~
or swelled by an organic liquid.
acrylonitrile of an intrinsic viscosity of 0.5 is reacted be
The scheme of the basic reaction for the preparation
tween 65" C. and 75° C. with hydroxylamine in dimethyl
of macromolecular substances containing amidoxime
formamide, the solubility in dimethylformamide (DMF),
groups according to my invention may be represented by 25 in
acid medium (HCl N), or in alkaline medium
the following general formula:
(NaOH N) of the polymer obtained, depends on the per
centage of ——CN— groups which have been converted
into amidoxime groups.
30
Solubility characteristics in relation to the percentage of
converted —CN— groups
wherein M is the macromolecular part of the molecule,
Solvent
i.e., the macromolecular skeleton which can include ad
Swells
ditional functional groups in addition to nitrile groups; 35
Soluble
between,
Insoluble
percent
2: is the number of nitrile groups in the polymeric starting
material; and y is the number of amidoxime groups in
DMF____ <40% conversion of
40-50 >50% conversion
the ?nal reaction product.
— N- groups.
—CN groups.
Aeld__.___
>90%
conversion
of
90-70 <70% conversion
The reaction is carried out with the macromolecular
substance containing nitrile groups being dissolved, dis
persed or swollen in a non-aqueous organic liquid such as
——ON— groups.
Alkaline" >80%
conversion
—
of
— N- groups
80-60 <60%
of
of
groups.
conversion
0!
—CN groups.
dimethylformamide, dimethylsulfoxide and lower alka
nols such as butanol.
Although the reaction can be carried out at room tem
When copolymers containing nitrile groups are con—
perature, it is advantageous to heat the mixture between 45 verted with hydroxylamine, the solubility characteristics
50 and 100° C. to increase the reaction speed.
of the copolymers are also in?uenced, but the solubility
The reaction is continued until all the nitrile groups
depends not only on the ratio of nitrile groups which are
have reacted with free hydroxylamine or it‘ can be inter
converted into amidoxime groups but also on the ratio
rupted after an arbitrarily chosen period of time. The
between other monomeric units and monomeric acryloni
reaction may be performed either in one operation or 50 trile units present in the original copolymer.
stepwise.
The basic reaction may be preceded, accompanied or
The hydroxylamine can be used in the form of its vari
followed by other reactions with respect to one or more
ous known salts in which case the hydroxylamine is
other functional groups present in the macromolecular
substance.
liberated by the addition of neutralizing substances, i.e.,
suitable alkaline substances.
Typical reactions which may precede or follow the ,
When hydroxylamine is added to the reaction medium
amidoxime formation are, for example, complete or par
in the form of its salts the necessary quantity of neutraliz
tial saponi?cation or esteri?cation of some functional
ing substances for liberating hydroxylarnine may be added
groups, addition of alkylene oxides and/ or acrylonitrile,
stepwise or at once to the reaction medium, whereby the
acetal formation by reaction between polymers of the
hydroxylamine is gradually or substantially immediately
polyvinyl alcohol type and aldehydes, and esteri?cation
liberated. The hydroxylann'ne may be liberated and ?l
of carboxyl or anhydride groups with nitrile groups con
taining hydroxy compounds.
trated in advance and this ?ltrated hydroxylamine used
for the amidoxime reaction.
Typical examples of reactions accompanying the ami
In carrying out the process of the present invention, any
doxime-formation are, for example, inter- and/or intra
macromolecular substance containing nitrile groups may 65 molecular ring-formation, neutralization of acid groups
be used as the starting material; for instance cyano-con
and the splitting out of hydrogen chloride in chlorine
taining polycondensates, or polymers, copolymers, block
copolymers and graft copolymers from polymerisable
nitriles and all combinations thereof, optionally cross
linked, or natural or synthetic macromolecular substances 70
cyano-ethylated with acrylonitrile and/or grafted with a
polymerisable nitrile, or polymers containing carboxyl or
containing copolymers. When the macromolecular part
contains
II
0
groups wherein X=NH2, NHR, NRR', halogen‘ or ‘the
3,063,950
.
_
3
,
4
complement to vform anhydride groups, the hydroxyl
EXAMPLE 1
amine may simultaneously react with these groups with
the formation of hydrox-amic acid. Obviously, the se
quence and the degree of these reactions may be chosen
A. Preparation of Polyacrylonitriie Solution in
Dimethylformamide Medium
groups and their immediate derivatives possess very inter
50 grams of freshly distilled acrylonitrile are mixed
with 500 cm.3 of thiophene free benzene and 0.200 gram
of benzoylperoxide. 150 cm.3 of this solution are intro
esting properties and lend themselves to a Wide variety of
duced into a round bottom ?ask and heated on the water
arbitrarily.
' Macromolecular
5
substances
containing
amidoxime
bath, so that the mixture constantly boils. Introduction
Varying the nature of starting materials, molecular 10 of a supply of oxygen-free and dry nitrogen protects the
reaction mixture from inhibition by oxygen. After 20 to
weight, degree of substitution and consecutive reactions,
30 minutes, polymerization sets in and the remaining
offers the possibility of a considerable number of com~
solution is added dropwise over a period of two hours.
binations. Owing to the presence in the macromolecular
Heating is continued for an additional four hours in order
substance containing admidoxime groups of OH~ and
NHz-groups, the new products are reactive with sub 15 to complete the polymerization. The polyacrylonitrile
syntheses.
stances containing alkaline groups as well as acid groups.
formed is suction ?ltered, repeatedly washed with petro
leum ether and dried. A 10% solution in dimethylform
As non-limiting examples are mentioned the hydrolysis in
amide of the resultant polyacrylonitrile which had an
acid and alkaline medium, the reaction with nitrous acid,
intrinsic viscosity [n] of 0.5 was obtained.
with aniline or with acylating agents; the addition reaction
with carbon disul?de; the formation of heterocyclic rings 20
B. Preparation of Hydroxylamine-Solution
with acetic acid or with ethyl acetylacetate; the addition
reaction of alkylene oxides and/ or of acrylonitrile.
235 grams of anhydrous sodium carbonate are added
Solutions of the modi?ed macromolecular substance ob
in small portions, with stirring to a solution of 250 grams
tained may be cast or subjected to spinning operations and
of hydroxylamine hydrochloride in 500 cm.3 of dimethyl
after evaporation of the solvent, form ?lms and ?bers. 25 formamide. The solution is heated to 80° C. and the mix
I have also noted compatibility of these solutions with
ture reacted for 30 minutes while stirring. Next, the solid
other polymer solutions, i.e., with aqueous solutions of
substance is sucked off and kept and the clear ?ltrate
gelatin, polyvinyl alcohol and polyvinyl pyrrolidone.
maintained overnight at 0-5" C. whereafter the mixture is
Thus, solutions of macromolecular substances contain
?ltered for a second separation of precipitated salts
ing amidoxime groups may be used to alter the properties 30 (sodium chloride). The content of hydroxylamine is
of the above mentioned polymer solutions.
determined by potentiometric titration .
The macromolecular substances according to the proc
C. Prepartion of Polyacrylomidoximes in
ess of my present invention and/ or their derivatives have
Dimethylformamide Medium
very useful ?lm- and ?ber-forming properties. They may
35
be used for the manufacture of photographic ?lm base,
To 500 cm.3 of a 10% polyacrylonitrile solution in
outer and inner layers in graphic- or photographic ele
dimthylforamide obtained according to the procedure de
scribed in A are added 500 cm.3 of a 7.75% solution of
ments, as a raw material in the production of wrapping
material and as a coating on supports of any kind, for
hydroxylamiue in dimethylforamide obtained according
instance in a paint, varnish, lacquer, adhesives or coating
on ?lm, foils, ‘sheets, ?bers and other shaped aritcles.
to (B). While stirring, the mixture is caused to react for
75 minutes at 55—60° C. The liquid, together with the
These macromolecular substances containing amidox
precipitated product, is poured out in methanol while
thoroughly stirring. The precipitate is thoroughly washed
ime groups and derivatives thereof can further be used in
in methanol and dried in vacuum over concentrated
the preparation of paper, either as a modifying agent for
the paper-pulp or as an impregnating agent of the paper 45 sulphurpic acid. Yield: 77 grams or 95% of the theo
band formed. Especially valuable layers are those
formed by chemical reaction of hydroxylamine with
shaped articles made of polymeric materials containing
nitrile groups.
retical amount of a very light yellow colored product,
soluble in alkali and acid and insoluble in dimethylform
amide.
Used in combination with other ?lm
forming polymers, they are capable of altering the prop 50
erties of the ?lm made from these polymers.
vIn the textile ?eld, they may be used equally Well as raw
EXAMPLE 2
A. Preparation of Polyacrylonitrile Solution in
Dimethylsulfoxide
material for the manufacture of new synthetic ?bers, or to
From the polyacrylonitrile obtained in Example 1A
improve the properties of other known ?bers. An appli
and having an intrinsic viscosity of 0.5, a 10% solution
'prove the properties, especially the dyeability, of ?bers
containing nitrile groups.
B. Preparation of Hydroxylam'ine Solution in
cation of outstanding interest consists in their use to im~ 55 in dimethylsulfoxide is made.‘
1 Added to other colloidal solutions, they have a marked
Dimethylsulfoxide
influence on the rheological properties of these solutions. 60
solution in dimethylsulfoxide is made by replacing the
This is of special interest in the manufacture of photo
500 cm.3 of dimethylformamide by 500 cm.3 of dimethyl
graphic elements where it is often desirable to alter the
viscosity and the gelling point of the emulsions. Further
sulfoxide.
more, they may be used as dispersing and/or binding
C. Preparation of Polyacrylamidoxime in
In the same manner as described in Example 1A, a
agents in light-sensitive emulsions. Their ability to bind
or to ?x diiferent chemical substances makes them very
useful particularly in elements where diffusion of chem
ical substances, dyes and color components has a disad
vantageous effect on the quality of the product. An
other application consists in their use as smoke ?lters in
cigarettes. Under certain conditions, this ?xing of other
chemicals is reversible, thus, they may be used as ion
exchange resins preferably in the form of granules or
fabrics.
75
The following examples illustrate my invention.
Dimethyl'sulfoxide Medium
100 cm? of a 7.4% hydroxylamine solution in dimeth
ylsulfoxide obtained according to the method described in
Example 2A are added, while stirring, to a solution of 10
grams of polyacrylonitrile having an extrinsic viscosity of
0.5 obtained according to Example 1A in 100 cm.3 of di
methylsulfoxide. The reaction mixture is heated at 70° C.
After 90 minutes heating, the solution is poured into
methanol, the precipitate is separated and thoroughly
rinsed with methanol, and dried in vacuum over con
8,063,950
ml
53
centrated sulphuric acid. Yield: 12.6 grams of a white
6
Table I‘L-Properties of reaction products otpolyacrylonitrile and by;
product which is soluble in acid, alkali and dimethyl
sulfoxide.
EXAMPLE 3
droxylamine suspended in di?erent portions of butanol
cm.3
A. Emulsion Polymerization of Acrylonitrile
Expt.
A solution containing one liter of Water, one ‘gram of
potassium persulphate, one gram of potassium metabisul
phite and 100 grams of sodium sulphate, is heated in a
round bottom ?ask at 65—70° C.
Solubility
Butanol, Yield poly
acrylarni
doxime, g.
H01,
N/l0
NaOH,
N/lO
A ______________________ __
100
1.3
-—
—
B ______________________ __
20
1. 5
+
+
To this solution are
N orn.—- — equals insoluble; + equals soluble.
added 50 cm.3 of acrylonitrile while stirring. When
polymerization has set in, another 150 cm.3 of acryloni
EXAMPLE 6
trile are added within one hour. Heating is continued
‘for another three hours. The polymer dispersion ob
tained is suction-?ltered, repeatedly washed with warm 15
water and dried. The extrinsic viscosity is 2.9.
Bis-Acrylamide
'
A solution is made of 20 cm.3 acrylonitrile, 0.1 ‘gram
methylene-bis-acrylamide and 0.02 gram benzoylperoxide
B. Preparation of Polyacrylamidoxime From- Emulsion
Polymer
A. Preparation of Copolymer Acrylonitrile/Methylene
in 100 cm.3 thiophene free benzene.
The solution is
20 heated for ?ve hours on a boiling water-bath, while
.One gram of the polymer obtained according to the
method described in Example 3A is dissolved in 20 cm.3
of dimethylformamide. To this solution are added 1.05
grams of hydroxylamine hydrochloride and 0.250 gram
of anhydrous sodium carbonate. The mixture is heated 25
at 95° C. and after 15 and 30 minutes respectively, other
similar sodium carbonate portions are added and heating
is continued for half an hour. The total reaction time
is one hour. The reaction mixture is then suction-?ltered,
maintaining the solution under an inert nitrogen atmos
phere. The precipitate formed is washed with petroleum
ether and dried.
B. Preparation of Amidoxim‘e
Five grams of the above prepared copolymer are swol
len in 150 cm.3 of dimethylformamide, and 10.5 grams
of hydroxylamine hydrochloride and 7.5 grams of an
hydrous sodium carbonate are added to the solution
which is then heated for three hours at 80° C. The
precipitated in methanol, washed with fresh methanol,
isolated and dried. The polymer is insoluble but swells 30 ?nal reaction mixture is poured into water and the in
soluble polymer Washed with Warm water and methanol.
in dimethylformamide, sodium hydroxide and hydrogen
The polymer acts as an ion exchanger; it absorbs ferric
chloride solutions.
ions which may be reversibly exchanged by treatment
with concentrated hydrogen chloride.
EXAMPLE 4
35
EXAMPLE 7
15 grams of polyacrylonitrile prepared by emulsion
polymerization according to the method described in Ex
A. Preparation of Copolymer Acrylonitrile/Vinylacetate
ample 3A and having an extrinsic viscosity of 2.9 are
900 cm? of vinylacetate, 100 cm.3 of acrylonitrile and
dissolved in 300 cm.3 of dimethylformamide.
To individual 50 cm.3 of this stock solution are added
various amounts of hydroxylaminehydrochloride (Table
I, col. 2), and the corresponding quantity of sodium car
bonate (col. 3). The mixtures are uniformly heated for
one gram of benzoyl peroxide are heated on the water
bath for 21/2 hours. On the bottom of the round bottom
?ask, a swollen polymer precipitates. After decantation
of the supernatant liquid, the solid polymer is washed
with methanol, twice dissolved in dimethylformamide
three hours at 75° C. After this, the reaction mixtures
are suction-?ltered, precipitated in methanol, washed with 45 and precipitated in methanol and ?nally dried.
fresh methanol and dried.
B. Preparation of Amidoxime
10 grams of the copolymer according to 7A are dis
solved in 100 cm.3 of dimethylformamide. To this solu
tion are added 21 grams of hydroxylamine hydrochloride
50
and 15 grams of anhydrous sodium carbonate. The solu
Solubilityin—
tion is heated for four hours at 75° C.; the sodium
chloride formed is suction-?ltered and the ?ltrate pre
DMF
H01,
NaOH,
Table I.——Pronerties of reaction products from 2.5 grams polyacrylonltrile
with di?erent amounts of hydroxylamine
Expt. NH1OH.HG1, g. Na1O0a,g.
cipitated with methanol. Further puri?cation by dissolu
tion in dimethylformamide and precipitation in methanol
0
0.65
o
0.5
+
s
-
1.31
1.0
s
s
-
-
1. 97
1.5
s
s
-
2.65
3.28
2.0
2.5
s
s
s
+
+
+
NOTE.—DMF equals dimethyliormamide; + equals soluble; —
equals insoluble; S equals swells.
55 yield a product which is soluble in sodium hydroxide
and 0.1 normal hydrogen chloride.
EXAMPLE 8
Three
grams
of
Dynel
?bers (Dynel is a registered
60
trademark for a copolymer containing 60 mol percent
of vinylchloride and 40 mol percent of acrylonitrile man
ufactured by Carbide and Carbon Chemical Corporation)
EXAMPLE 5
are dissolved in 50 cm.3 of dimethylformamide. 6.3
Two portions, each containing 1 gram of polyacryl 65 grams of hydroxylamine hydrochloride and 4.5 grams of
anhydrous sodium carbonate are added thereto, and the
onitrile having an extrinsic viscosity of 0.5 obtained ac
mixture is heated for two hours at 80° C. After this
cording to the method described in Example 1A are sus
time, the reaction mixture is suction-?ltered and the clear
pended in different quantities of butanol, in amounts
solution precipitated in methanol, repeatedly washed with
given by Table II. To each portion 2.1 grams of hy
droxylaminehydrochloride and 1.5 grams of potassium 70 fresh methanol and dried under vacuum. The polymer
is soluble in aqueous hydrogen chloride- and sodium
hydroxide powder are added while stirring. The mix
hydroxide solutions.
tures are heated for three hours at 90° C., the stirring
being continued. The solid substances obtained are
EXAMPLE 9
sucked o?, washed with water, subsequently washed with
One
gram
of
samples
A and B of Orlon 42 staple ?bers
methanol and dried under vacuum.
75 (registered trademark by Du Pont de Nemours & Co. for
3,063,950
7
B. Preparation of Amidoxim'e
a copolymer containing acrylonitrile) are dissolved in 10
cm.3 of diethylformamide. To these samples are added
different amounts of hydroxylarnine hydrochloride and
anhydrous sodium. carbonate according to the following
One gram of the above polyvinylcyanoethyl ether is dis
solved in 20 cm? of dimethylformamide, and 2.1 grams
of hydroxylamine hydrochloride and 1.5 grams of an
table. Both reaction mixtures are heated for three hours
hydrous sodium carbonate are added. After about three
‘at 75 ° C., ?ltered, precipitated in methanol and dried.
hours heating at 75° C., the reaction mixture is suction
?ltered and the ?ltrate precipitated in methanol. The
Table IIL-Properties of reaction product of Orlon 42 staple ?bers with
different amounts of hydroxylamme
dried product swells in sodium hydroxide and in hydrogen
chloride solution.
Solubility in
10
EXAMPLE 13
E
m
t.
NHOHJICI .
a
‘g
moons.
a
a
DMF
H01,
NaOH,
N110
N/lO
A. Preparation of Cyanoethylated Polyethylene Glycol
50 grams of polyethyleneglycol “600” (a polyethylene
oxide of low molecular weight made by Carbide and
15 Carbon Chemicals Corporation) are mixed with 3.75 cm.3
n .... _065
0.5
s
s
s
of a 40% sodium hydroxide solution. To this solution,
Norm-13MB‘ equals dimethyliormamide; + equals soluble; — equals
cooled to 0° C., 90 cm.3 .of acrylonitrile containing 0.300
A ____ __
1 a
1
‘
__
+
+
insoluble; S equals swells.
gram of dinitrobenzene as polymerization inhibitor are
added dropwise. After three hours, the crude reaction
EXAMPLE 10
20 mixture is poured into methanol. Formed polyacryloni
‘10 grams of a copolymer BMC 11-01B11 of the Bake
trile precipitates while the cyanoethylated polyglycol re
lite Corporation (consisting of nearly 47 mol percent ac
mains in dissolution. The ?ltered solution is neutralized
rylonitrile and 53 mol percent styrene) are dissolved in
with hydrogen chloride, concentrated by evaporation, ?l
250 cm.3 of dimethylformamide. To 25 cm? of samples
tered and ?nally precipitated in ether, wherefrom it is
A and B of this solution are added diiierent amounts of 25
separated as an oil.
hydroxylamine hydrochloride and of anhydrous sodium
carbonate according to the following table.
B. Preparation of Amz'doxime
The two
samples are heated for two hours at 75 ° C. Thereafter
The oil obtained in A above is dissolved in 200 cm.3
they are suction-?ltered, precipitated, washed in methanol
and ?nally dried.
of dimethylformamide and 13.8 grams of hydroxylamine
30 hydrochloride and 8.7 grams of anhydrous sodium car
bonate are successively added thereto. After three hours
reaction at 75° C., the mixture is suction-?ltered and
TABLE IV
Solubility in—
precipitated in ether. The oily layer is separated, washed
Expt. NHzOHHCLg. NazC03,g.
'
A _____ ..
B _____ __
0.250
0.500
DMF
0.190
0.380
with water, redissolved in methanol and precipitated in
petroleum ether. This oil is soluble in 0.1 normal hy
drogen chloride and 0.1 normal sodium hydroxide but
insoluble in water.
EXAMPLE 14
Acetone HOLNIIO
+
+
S
S
-—
-
Nora-DMF equals dimethylformamide; + equals soluble; 40
—- equals insoluble.
EXAMPLE 11
A. Preparation of Graft Polymer of‘ Polyvinylpyrrolidone
‘
A. Preparation of Cyanoethylated Cellulose
Viscose ?bers are cyanoethylated according to the pro
cedure described in Example 3 of United States speci?
cation No. 2,375,847. At the end of the reaction the
homogeneous solution is precipitated in methanol, cen
and Acrylonitrile
45 trifuged, dried, dissolved in acetone, reprecipitated in
methanol, centrifuged and dried again.
described in Example 17 of British speci?cation 715,194.
B. Preparation of Amidoxime
B. Preparation of Amidoxim‘e
100
grams
of this cyanoethylated cellulose are dis
10 grams of the above graft polymer consisting of 45
grams of polyvinylpyrrolidone and 160 cm.3 of acryloni 50 solved in 2000 cm.3 of dimethylformamide, 210 grams of
hydroxylamine hydrochloride and 150 grams of anhydrous
trile are dissolved in 100 cm.3 of diethylformamide, and
sodium
carbonate are added. The mixture is heated at
10.7 grams of hydroxylamine hydrochloride and eight
75° C. while stirring for four hours. After this time, the
grams of anhydrous sodium carbonate are added. The
The graft polymerris prepared according to the method
mixture is heated for two hours at 80° C.
After this
time, the reaction mixture is suction-?ltered, precipitated
sodium chloride formed is suction-?ltered and the solu
55 tion precipitated in methanol, centrifuged and dried. The
freshly prepared product is soluble in 0.1 normal hydro
in methanol, washed with methanol and dried under
vacuum. It is soluble in 0.1 normal aqueous hydrogen
chloride, in 0.1 normal aqueous sodium hydroxide and
in dimethylformamide.
EXAMPLE 12
A. Preparation of Polyvinylcyanoethylether
gen :chloride, but after standing a few days, it becomes
insoluble.
EXAMPLE 15
60
A. Cyanoet‘hylation of Polyacrylamidoxim'e
The polyacrylamidoxime prepared in Example 1C'may
be cyanoethylated by treating 10 grams of this polymer
in 100 cm.3 of water with 1000 cm.3 of acrylonitrile in
by A. De Pauw at the International Congress of Industrial 65 the presence of eight cm.3 of Triton B (a 40% aqueous
According to a method described in a communication
Chemistry, Brussels, September 1954, 22 grams Mowiol
N 70/98 (registered trademark for polyvinyl alcohol of
high molecular weight sold by Farbwerke Hoechst) are
dispersed in 100 cm.3 acrylonitrile containing 0.5 gram
solution of benzyl trimethylammonium hydroxide sold
by Rohm & Haas, Philadelphia) and keeping it gently
dium hydroxide is added. The polyvinylalcohol is fully
drogen chloride.
B. Preparation of Amidoxime
In
the
above
cyanoethylated product, the nitrile groups
75
boiling for three hours. The solution obtained is pre
cipitated in methanol and after several washings cen
dinitrobenzene as a polymerization inhibitor. ' After heat 70 trifuged and dried. This product is soluble in dimethyl
formamide, in 0.1 normal sodium hydroxide and in hy
ing the mixture up to 75° 0, one cm.a of 0.1 normal so
dissolved after eight hours. The reaction mixture is pre
cipitated in water and further puri?ed by redissolution in
acetone and precipitation in diethyl ether.
9
3,063,950
may again be transformed into amidoxime groups by
the following procedure. 10 grams of cyanoethylated
product and 21 grams of hydroxylamine hydrochloride
are dissolved in 200 cm.3 of dimethylformamide. To this
solution are added 15 grams of anhydrous sodium car
bonate and the whole is heated for two hours at 75 ° C.
The sodium chloride which is formed is suction-?ltered
and the solution precipitated in methanol, washed and
dried. This product shows again the characteristics of
amidoximes, that is, being soluble in 0.1 normal sodium
hydroxide and 0.1 normal hydrogen chloride.
EXAMPLE 16
Hydrolysis of a Pvlymeric Amidoxime
One gram of the reaction product from Example 4]‘ is 15
dissolved in 100 cm.3 of one normal sodium hydroxide
and boiled for 60 hours. After neutralizing, the ‘formed
precipitate is suction~?ltered, Washed and dried. The
product is insoluble in 0.1 normal aqueous hydrogen
chloride and soluble in 0.1 normal sodium hydroxide.
20
10
tolerable. Therefore, for purposes of this speci?cation
and claims, “non-aqueous solvent" embraces limited
amounts of Water, not exceeding about seven percent.
It should be appreciated that the instant invention is
not to be construed as being limited by the illustrative
examples. It is possible to produce still other embodi
ments without departing from the inventive concept here
in disclosed. Such embodiments are Within the ability of
one skilled in the art.
What is claimed is:
1. A process for producing high polymers character
ized by a plurality of amidoxime groups which comprises -
heating in a non-aqueous solvent medium a high polymer
selected from the group consisting of a polymer of acry
lonitrile, a polymer of methacrylonitrile, a polymer of
vinylidene cyanide, cyanoethylated polyvinyl alcohol,
cyanoethylated cellulose, cyanoethylated polyvinyl amine,
cyanoethylated polyacrylamide and cyanoethylated poly—
methacrylamide with free hydroxylamine, su?'icient to
transform a substantial amount of the CN groups, with
EXAMPLE 17
One gram of the product from experiment 1C is dis—
solved in 80 cm.3 0.1 normal hydrogen chloride. To this
solution are added 200 cm.3 of a solution containing
0.800 gram “Croceine Brillante” (C. I. 252), a sodium
salt of benzene-azo-benzene-azo-beta-naphthol-6,8-disnl
phonic acid, 0.500 gram sodium sulphate and 2 cm.3 one
the formation of amidoxime groups.
2. The process according to claim 1 wherein the non
aqueous solvent is an alcohol.
3. The process according to claim 1 wherein the non
aqueous solvent is dimethyl formamide.
4. The process according to claim 1 wherein the free
hydroxylamine is formed in situ from its salt.
5. A polymer characterized by a plurality of amidoxime
normal sulphuric acid. The deeply colored polymer pre
cipitates as a ?ne powder which conglomerates on gently 30 groups prepared according to the process of claim 1.
heating for 10 minutes; leaving the solution completely
colorless. The excess of dye is Washed out and the dried
polymer pulverized to a ?ne powder which may be used
References Cited in the ?le of this patent
UNITED STATES PATENTS
as an organic pigment.
In the above examples, to obtain the best results, it is
preferred that the non-aqueous solvent medium be as
completely free from water as possible. However, it is
di?‘icult to completely remove the ?nal traces of water
from certain solvents. Such minor amounts of water are
1,984,417
2,495,286
2,671,066
2,727,835
2,739,136
2,792,276
Mark et a1. ___________ .._ Dec. 18,1934
Brubaker _____________ __ Jan. 24, 1950
Justice _______________ .. Mar. 2, 1954
Barrett ______________ __ Dec. 20, 1955
Kharasch et al _________ __ Mar. 20, 1956
Kaupin et a1 __________ __ May 14, 1957
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