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Патент USA US3099663

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United States Patent 0 ”IC€
3,099,553
Patented July 39, 1963
2
l
non-metallized azo compounds to their metallized form
3,ll99,653
if ‘desired. Also the metallizing agent can be incorporated
in the spinning dope, the ?ber spun as usual and then
NAPHTHQEC A€ll® AMEDE EYES
James M. i’ltraley and Raymond ‘C- Harris, Kingsport,
Tenn, assignors to Eastman Kodak Company, Roch
ester, N.Y., a corporation of New dersey
N0 Drawing. Filed Jan. 21, 196d, Ser. No. 3,723
5 Claims, (Cl. 2ee_1ss)
treated in a dyebath containing one or more of the non
rnetallized azo compounds to form the metal complex on
BENZOTHIAZGLE AZQ 2,3~HYDR®XY
the ?ber.
~
The non-metallized monoazo compounds yield orange
to red shades on poly-acrylonitrile materials. The metal
lized compounds yield violet to blue shades, which have
T[his invention relates to new azo compounds and their 10 good fastness to light, washing and gas, on polyacryloni
trile materials, such as ‘acrylic ?bers. The metallized
application to the art of dyeing or coloring. More par
dyeings have better ‘fastness to washing than the corre—
ticularly, it relates to certain metallized and nonmetal
sponding
non-metallized dyeings and frequently have im
lized benzothiazole azo compounds and their applica
proved tastness to light. Among the acrylonitrile poly
tion to the dyeing or coloring of acrylonitrile polymeric
materials, especially polyacrylonitrile textile materials.
The azo compounds of our invention consist of the
15 were that can be dyed or colored with the non—rnetallized
and metallized azo compounds of our invention are those
disclosed in Straley and Giles U.S. Patent 2,857,372‘, is
sued October 21, 1958.
mono-azo compounds, devoid of a water-so-lubilizing
group, having the formula:
20
25
wherein Ar represents an ortho~arylene radical of the
benzene series, R represents an alkylene radical having 2
to 3 carbon atoms, R’ represents an alkyl radical having
1 to 4 carbon atoms and wherein N(R’)2 collectively
represents a member selected from the group consisting
of a morpholinyl radical and a piperidyl radical and their
metal complexes ‘containing a metal selected from the
group consisting of nickel, cobalt and chromium.
2~aminobenzothiazole,
2-amino-6-methylsul-fonylbenzothiazole,
Z-amino-6-ethylsullfonylbenzothiazole,
2-amino-6-n-propylsulfonylbenzothiazole,
2-amino-G-n-butylsulfonylbenzothiazole,
2-arnin'ob enzothiazole-6-N-methylsul?onamide,
Z-aminobenzothiazole-6-N-ethylsulfonamide,
Z-a-minobenzothiazole-o-N-n-propylsulfonamide,
2-aminobenzothiazole-6~N-n-butylsulfonamide,
Z-amino-6-rnethoxybenzothiazole,
2~amino-6-ethoxybenzothiazole,
The non-metallized monoazo compounds: of our inven
tion are prepared by diazotizing a Z-aminobenzothiazole 35
compound having the formula:
wherein Ar represents an or-tho-arylene radical of the
Z-amino-6-n-propoxybenzothiazole,
Z-amino-6-n~butoxybenzothiazole,
2-amino-6-methylbenzothiazole,
Z-amino-6-ethylbenzothiazole,
2-amino-6-n-propylbenzothiazole,
Z-amino-6-n-butylbenzothiazole,
Z-amino-o-p-hydroxyethylbenzothiazole,
Z-amino-6-y-l1ydroxypropylbenzothiazole,
2-amino-6-6-hydroxybutylbenzothiazole,
2-amino-6-acetylaminobenzothiazole,
2-arnino-6-n-propionylaminobenzothiazole,
Z-amin0-6-n-butyrylarninobenzothiazole, '
benzene series devoid of a water-solubilizing group and
coupling the diazoninm compound obtained with a naph
thalene compound having the formula:
45
Z-amino~6-thiomethylbenzothiazole,
2-amino-6-thiocyanobenzothiazole,
2-amino~6-tri-?uoromethylbenzothiazole,
2-amino-6-chlorobenzothiazole,
2~amino-6-nitrobenzothiazole,
2-amino-4,7=dimethoxybenzothiazole,
Z-amino-S,6-dimethoxybenzothiazole,
50
2-amino-4,7~diethoxybenzothiazole, and
2-arninoell,6-di-methylbenzothiazole
wherein R, R’ and N(R')2 have the meaning previously
assigned to them. The metallized azo compounds of our
are representative of the Z-aminobenzothiazole com
invention are prepared by metallizing the non-metallized
pounds used in the preparation or" the azo compounds of
azo compounds with appropirate metallizing agents in ac 55 our invention.
cordance with known metallizing procedures. The man
ner in which metallization can be carried out is fully de
2~hydroXy-N-3 - (B-dimethylaminoethyl ) naphthamide,
scribed hereinafter.
2-hydr0xy-N-3-‘( ?-diethylaminoethyl) naphthamide,
Nickel chloride, nickel bromide, nickel sulfate, nickel
acetate, nickel formate, nickel thiocyanate [Ni(SCN)2],
cobaltous bromide, \cobaltic chloride, cobaltous chloride,
cobaltous acetate, cobalt thiocyanate [Co(SCN)2], chro
mium trichloride, chromium tribromide, chromic sulfate,
chromic acetate and chromium thiocyanate [Cr(SCN)3],
60
2-hydroxy-N-3 -( l8-di-n-propylaminoethyl) naphthamide,
2-hydroxy-N-3 - ( ?-di-n-butylamino ethyl) naphth amide,
2-‘hydroxy-N-3 - ('y-dimethylaminopropyl) naphthamide,
2-‘hydroxy-N-3- (ry-diethylaminopropyl ) naphthamide,
24hydroxy-N-3 - ('y-di-n-butylarninopropyl) naphthamide,
for example, are illustrative of the metallizing agents that 65 2-hydroxy-N-3 — ( B-morpholinylethyl ) naphthamide,
Z-hydroXy-N-B - ( 'y-morpholinylpropyl) naphthamide,
can be employed.
2-hydroxy~N-3 - ( p-piperidylethyl ) naphthamide and
Both the non-‘metallized and the metallized azo com
Z-‘hydroxy-N-S - (e/epip eridylp-ropyl) naphthamide
pounds ‘of our invention can ‘be applied to polyacrylo
nitrile textile materials in the form of an aqueous disper
are illustrative of the coupling components used in pre
sion. Coloration can also be effected by incorporating the 70
paring the 2.20 compounds of our invention.
non-metallized or metallized azo compounds into the spin
The coupling components can be prepared by reacting
ning dope, spinning the ?ber as usual and converting the
3,099,653
.
d
3
2-hydroxy-3-naphthoic acid chloride or 2-acetoxy-3-naph
thoic acid chloride with an amine having the formula:
wherein R, R’ and N(R’)2 have the meaning previously
5.5 grams of 2-hydroxy-N-3-('y-dimethylaminopropyl)
' naphthamide in 100 cc. of 5% ‘aqueous acetic acid and
enough crushed ice was added to maintain the tempera
ture below 5° C. After stirring for an additional two
hours, the reaction mixture was made neutral to Congo
red paper by the addition of sodium carbonate and the
dye compound which precipitated was recovered by ?ltra
tion, washed well with water and dried. It dyes poly
assigned to them. When 2-acetoxy-3-naphthoic acid chlo
ride is employed the acetyl group is split off by known
methods after the reaction with the amine is complete.
The following examples illustrate the invention.
acrylonitrile orange shades. The nickel, cobalt and
10 chromium complexes yield slightly greener shades on
Example 1
acrylic ?bers, such as Orlon 42 and Verel, which are
15 grams of Z-aminobenzothiazole were dissolved in
:fast to light, gas and washing.
240 cc. of water and 140 cc. of 96% sulfuric acid, cooled
Example 4
to 0° C., and diazotized by the addition of a nitrosyl sul
furic acid solution previously prepared from 7.2 grams 15
23 grams of 2~arnino-6-methylsulfonylbenzothiazole
of sodium nitrite and 50 cc. of 96% sulfuric acid. Diazo
tization was carried out at a temperature below 5° C.,
with stirring. A coupling solution was prepared by dis
solving 27 grams of .2-hydroxy-N-3-(y-dimethylamino
propyl)naphthamide in 400 cc. of water and 15 cc. of
glacial acetic acid and the temperature was brought to
5° C. by the addition of crushed ice. The diazonium
solution was added over a period of about 20 minutes,
were diazotized and the diazonium compound obtained
was coupled with 28 grams of 2-hydroxy-N-3-(?-diethyl
aminoethyl)naphthamide.
Diazotization, coupling and
recovery of the dye compound formed were carried out
in accordance with the procedure described in Example 1.
The dye compound obtained dyes polyacrylonitrile tex
tile materials orange shades. The nickel, cobalt and
chromium complexes yield blue-violet shades on acrylic
with stirring, and stirring was continued for 45 minutes
?bers such as Orlon 42 and Verel which are fast to light,
longer, adding ice as necessary to maintain the tempera 25 washing and gas.
ture of the reaction mixture at 5° C. or below. Upon
Example 5
completion of the coupling reaction the reaction mixture
3.3 grams of 2-amino-é-methylbenzothiazole were di
was made neutral to Congo red paper by the addition of
azotized and the diazonium compound obtained was
sodium carbonate and the dye compound which precipi
tated was recovered by ?ltration, Washed well with water 30 coupled with 5.3 grams of 2-hydroxy-N-3-(?-dimethyl
aminoethyhuaphthamide. Diazotization, coupling and
and air-dried. The dye compound thus obtained has the
recovery of the dye compound formed were carried out
formula:
in accordance \m'th the procedure described in Example 3.
H
(EONOHzCHzCHzN
CH3
The dye compound obtained dyes polyacrylonitrile tex
CH3
tile materials red shades. The nickel, cobalt and chro
rnium complexes yield blue shades on acrylic ?bers, such
as Verel and Orion 42, which are vfast to light, washing
and ‘gas.
Example6
and dyes polyacrylonitrile ?bers red shades. The nickel,
cobalt and chromium complexes yield blue shades on
15 grams of '2-aminobenzothiazole were diazotized and
the diazon-ium compound obtained was coupled with 28
acrylic ?bers such as Orlon 42 and Verel which are fast
grams of 2-hydroxy-N-3-(?-diethylaminoethyl)naphtha
to light, washing and gas.
mide. Diazotization, coupling and recovery of the dye
Example 2
1.08 grams of the non-metallized monazo dye com~
pound of Example 1, 15 cc. of acetone and 2 cc. of 28%
compound formed were carried out in accordance with
45 the procedure described in Example 1. The dye com
pound obtained dyes polyacrylonitrile textile materials
red shades. The nickel, cobalt and chromium complexes
aqueous ammonium hydroxide were re?uxed together
yield blue shades on acrylic ?bers, such as Verel and
Orlon 42, which are fast to light, washing and gas.
and a solution of 0.7 gram of Ni(OOCCH3)2-4H2O in
15 cc. of 50% aqueous acetone was added over a period 50
Example 7
of 15 minutes. Re?uxing was continued for three hours
after which the reaction mixture was poured into 400 cc.
of water and the temperature brought to 80° C. 10‘ grams
of sodium chloride were ‘added, with stirring, and then the
grams of 2 - hydroxy-N-3-(B - dimethylaminoethyl)naph
reaction mixture was allowed to cool to room tempera
ture. The metallized dye product, a so-called 1:2 com
compound formed were carried out in accordance wit-hthe
plex in which nickel and the monoazo compound are
combined in the ratio of about one atom of nickel to
procedure described in Example )1. The dye compound
obtained dyes polyacrylonitrile textile materials red shades.
The nickel, cobalt and chromium complexes yield blue
15 grams of Z-aminobenzothiazole were diazotized and
the diazonium compound obtained was coupled with 25.5
thamide. Diazotization, coupling and recovery of the dye
2 molecules of the monoazo compound, which precipi
tated was recovered by ?ltration, washed with a 2% 60 shades on acrylic ?bers, such as Verel and Orlon 42,
which are fast to light, washing and gas.
aqueous sodium chloride solution and air-dried. lt colors
polyacrylonitrile textile ?bers, such as Orlon 42 and Verel,
Example 8
blue shades which have good fastness to light, washing
and gas.
Example 3
A solution of nitrosyl sulfuric acid was prepared from
4.21 grams of the non-metallized dye of Example 1
65 were added in small portions to a solution of 5.4 grams
of \CrCl3-6H2O in 50 cc. of ethyleneglycol at 140° C.
The reaction mixture was stirred at 140° C. for one hour
1.52 grams of sodium nitrite and 20 cc. of 96% sulfuric
longer, cooled to 80° VC. and then poured into 120 cc. of a
acid. 20 cc. of propionic-acetic (1:5 ) acid were added
10% aqueous sodium chloride solution. Impurities were
below 8° C. and then a solution of 3.6 grams of 2-ami-no 70 removed by ?ltration and the dye product was precipitated
6-methoxybenzothiazole in 20 cc. of propionic-acetic
from the ?ltrate by making it basic with 10% NHQOH
(1:5) acid was added at a temperature below 5° C. The
The chromium complex, a so-called 1:2 complex in
reaction mixture thus obtained was stirred at 5° C. for
which chromium and the monoazo compound are com
two hours. The diazonium solution thus prepared was
bined in the ratio of about one atom of chromium to 2
stirred into a coupler solution prepared by dissolving 75 molecules of the monoazo compound, of the dye of
3,099,653
5
Example 1 was recovered by ?ltration, washed with a
10% aqueous ‘sodium chloride solution and air-dried. It
yields reddish-blue shades on polyacrylonitrile textile ma
terials made of Verel or Orlon 42 acrylic ?bers which
have good fastness to light, gas and washing.
6
in which the non-metallized azo compounds can be used
to dye an acrylonitrile polymer textile material. .1 gram
of dye is dissolved by warming in 5 cc. of methyl Cello
solve.
A 2% aqueous solution- of a nonionic surfactant,
such as .Igepal CA (a polymerized ethylene oxide-alkyl
phenol condensation product), is ‘added slowly until a ?ne
emulsion is obtained and then the dye mixture is brought
Example 9
to a volume of 200 cc. with warm water.
188 grams of Z-hydroxy - 3 - naphthoio acid were
5 cc. of a 5%
aqueous solution of formic acid or ace-tic acid are added
slurn'ed in ‘1000 cc. of dry benzene. A solution of 122
grams of SoCl2 in 500 cc. of dry benzene was added over 10 and then 10 grams of fabric made ‘from an acrylic ?ber
is entered and in the case of Orlon 42 the dyeing is car
a period of 30‘ to 45‘ minutes. The reaction mixture re
ried out at the boil for one hour. ‘In the case of mate
sulting was stirred for 2.5 hours at room temperature, then
rials made of Verel acrylic ?ber the dyebath temperature
raised slowly to 60° C. and held at this temperature until
should not exceed 90° C. in order to avoid damage to the
a clear solution resulted (about 2 hours). The excess
SOCIZ, S02 and HCl was removed under vacuum while 15 ?ber. The dyed material is then washed well with water
and dried. The metallized dyeing, in which the 1:2 metal
keeping the pot temperature at 60° ‘C. or below. The
complex is formed in situ on the material being dyed, can
be obtained, for example, in accordance with the proce
dure described in Example 10. A 3% solution of a salt,
mixture for about 15 minutes. The reaction mixture was
cooled to 25° C. and 138 grams of anhydrous K2CO3 were 20 other than the thiocyanate salt, can be used. However,
last traces of $00,, S02 and HCl were removed by
passing a slow stream of dry air through the reaction
we have found the use of the thiocyanates of nickel, co
added, after which a solution of 110 grams of 3-dimethyl
balt and chromium to be particularly advantageous.
aminopropylamine in 300 cc. of dry, benzene was added
The premetallized azo dyes can be applied in the same
dropwise while keeping the pot temperature at 60° C. or
general manner as the non-metallized azo dyes. How
below. The reaction mixture was stirred 6 hours longer
at room temperature, then raised to 65° vC. and ?ltered 25 ever, in order to mitigate the possibility of demetallization
during dyeing 5 cc. of a 5% aqueous solution of a weak
hot. The material collected on the ?lter was washed with
acid such as boric acid is used instead of formic acid or
three 2-liter portions of hot benzene. The combined
?ltrates were concentrated under vacuum to 1/3 their
acetic acid. Except for this change the dyeing conditions
volume below 70° C. The reaction mixture was cooled
to room temperature. The desired product which pre
are the same.
cipitated was recovered by ?ltration.
Example 10
A yield of 240
A polyacrylonitrile textile fabric dyed red with a 1%
grams of N-('y-dimethylaminopropyl) _ 2 - hydroxy-3
dyeing (by Weight of pure dye) of the dye product of
naphthamide was obtained.
Example 1 was padded with a 3% aqueous solution of
Following the general procedure described in the ex
nickel thiocyanate under conditions such that a 60 to
ample just given the other naphthamide coupling com 35 100% pick up, based on the weight of the fabric, was
ponents are readily prepared.
obtained. The polyacrylonitrile fabric was then aged
The following tabulation further illustrates the azo
in a steam chest under 5 p.s.i. pressure for 10 minutes
compounds of our invention and sets forth (1) the colors
after which it was scoured at 60° C. with soap» and water,
the non-metallized azo compounds yield on polyacryl
rinsed well with water and dried. The polyacrylom'trile
40
onitrile textile fabrics made of Verel or Orlon 4J2 acrylic
fabric was dyed a blue shade having good fastuess to light,
?ber and (2) the colors obtained when the non-metallized
washing and gas.
dyeings are metallized with nickel thiocyanate. “Original”
The non-metallized and metallized azo compounds de
refers to the non-metallized dyeing and “Final” refers to
scribed herein are devoid of water-solubilizing groups such
the metallized dyeing.
as the carboxylic acid and the sulfonic acid groups. Any
45 other suitable method known to the art can be used to
Coupler
2-aminobenzothi~
azole compound
R
G-Nitro ________ _6,7-Dichloro ____ __
—(CH2)a__
-—-(CH2)2__
?-thiocyano ____ __
—(CHz)a__
—-(OH:2)3__
Color
R’
Original
apply them to acrylonitrile polymeric materials.
The invention has been described in detail with particu
Final
lar reference to preferred embodiments thereof, but it
50
5,6-dimethoxy____ —(GHz)a__
_
The expression “propionic-acetic (1:5) acid” refers to
-(CH2)2-_
--(CH2)3_-
Il-CrHe ______ __
55
R
N(R’)z
G-mcthoxy _____ __ —(CH2)3._
morpholiny1__
o-methoxy _____ __
piperidyl ____ __
—~(CH2)3__
—(CHZ)2__
a mixture of propionic and acetic acids in which there are
?ve parts by volume of acetic acid to 1 part by volume
of propionic acid.
_
Unsubstitutcd___ —(OH2)2__ morpholinyl.-.
?-ethoxy _______ __
will be understood that variations ‘and modi?cations can
be effected within the spirit and scope of the invention
as described hereinabove and as de?ned in the ‘appended
claims.
piperidyl ____ __
We claim:
1. The monoazo compounds, devoid of a water
60 solubilizing group, having the formula:
The non-metallized azo compounds disclosed in the fore
going tabulation can also be metallized with a suitable
cobalt or chromium metallizing agent, especially cobalt
thiocyanate and chromium thiocyanate, to form the cobalt 65
and chromium complexes thereof. The cobalt complexes
yield about the same colors as the corresponding nickel
wherein X represents a member selected from the class
complexes. In the case of the chromium complexes the
consisting of a hydrogen atom, lower alkyl, lower alkoxy,
color tends to be redder. As shown hereinbefore metal
nitro
and thiocyano radicals, R represents an ‘alkylene rad
70
lization can also be effected off the ?ber.
ical having 2 to 3 carbon ‘atoms, R’ represents an alkyl rad
The non-metallized and metallized azo compounds de
ical having 1 to 4 carbon atoms and wherein N(R’)2 col~
scribed herein can be applied to acrylonitrile polymers,
lecti-vely represents a member selected from the group
such as polyacrylonitrile and acrylonitrile graft polymers,
consisting of a morpholinyl radical and a piperidyl
in the form of an aqueous dispersion.
The following example illustrates one satisfactory Way 75 radical.
3,099,653
8
2. The monoazo compound having the formula: ‘
4. The monoazo compound having the formula:
02135
HO
01
10
5. The monoazo compound having the formula:
.3. The monoazo compound having the formula:
/S \
CH3OH
3
H10
H
0 ONCHzOHzCHzN
/
CH3
CH
/O-—-N=N—
15
N/
References Cited in the ?le of this patent
UNITED STATES PATENTS
20
2,128,256
2,402,538
2,408,421
2,868,774
Krzikalla et a1. _______ __ Aug. 30,
Dreyfus ____________ __ June 25,
Grimmel et a1. _______ __ Oct. 1,
:Straley et a1. ________ __‘__ Jan. 13,
1938
1946
1946
1959
2,916,482
Straley et a1. ________ __ Dec. 8, 1959
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