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Патент USA US2410301

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2,410,301
Patented Oct. 29, 1946 ‘
UNITED.’ ,f-srA-TTEs
orifice
MANUFACTURE: ‘OF COPPER PHTHALO
.
M
'
'
CYAZ‘TINE
Q-YESTUFFS‘
_
.
Grady M. O’NeaI,‘ Chicago, Ill., assignor to The
Sherwin-Williams Company, Cleveland, Ohio,
a corporation of Ohio
_‘
J V
,_
No Drawing. Application September’ 15, 1943,
Serial No. 502,506
> 24 Claims. ‘ (o1. zoo-$124.5)‘
2
The present invention relates to the manufac- .
like, are reacted ‘;With a metallic reagent, In gen
eral, along with other objections, the tempera
tures‘ne‘cessary to effect ‘dyestuff formation are
ture
Phthalocyanine
of copper phthalocyanine
isa generic .term
dyestuffs.
for a , class of
blue to green dyestuffs and the following, formula
has been proposed, forv the metal-free phthalo
cyanine parent ‘substancez.
.
N
poor.
,
"
,l
4
It has further been proposed in Fr. Patent No.
826,017 to react a phthalic acid derivative, di
cyandiamide, and a metal-bearing reagent under
special conditions to give the'metallic phthalo
10 cyanine. However, the yields of dyestu? by this
0
Mt, in.
high and the quality of the obtained dyestuffs is
, ‘
\
>
N
CII=N HN——C/
H l\N,L l
process are extremely poor; the operating tem
peratures are high, giving poor quality dyestuffs;
and still worse, the reaction of dicyandiamide
with phthalic acid derivatives is a highly exoe
15 thermic one, often times proceeding with extreme
violence.
'
,
Still other processes, as exempli?ed in U. S.
Patents Nos. 2,197,458, 2,197,459,, and 2,214,477,
have been proposed; using urea with which cer
20
7 It may be systematically designated as either
tain dehydration, and ,deamidation, products, of
diammonium phthalate, ,for instance, phthalic
tetrabenzoporphyrazine or as tetra-benzo-tetra
anhydride, phthalimide, phthaldiamide and, the
like, and a metallic reagent are suitably reacted.
aza-porphin.
Because of the economics
, ‘ and'the
l
dif?culties
' rl‘his proposed process possesses high merit, but
connected with securing. the intermediates used 25 it has the disadvantage that the process is ac
in preparing the parent and derivative sub
companied by undesirable foaming and frothing
stances, for example, o-cyanobenzamide ‘or
of the‘ reaction melt, Due‘ to the nature and
phthalonitrile, it has been proposed to employ
volume of ‘these foams, the reaction mass cannot
other simpler and more readily available initial
be kept .at the necessary temperature of reaction.
starting materials. Processes have been offered 30 Consequently,‘ processes making use of the “urea
in which a carbocyclic anhydride, imide, or di
method". of synthesis commonly yield a relatively
amide is reacted with ammonia and metallic sub
lowamount of the desired dyestu?; processing
stances, thereby, under appropriate conditions,
equipment is unduly large with respect to the
resulting in metallic phthalocyanine color forma
actual quantity of material processed; and a cer
tion. Processes making use of this method of 35 tain. amount'of danger to the operating personnel
synthesis, in general, are subject to these serious
is always present.
‘
>
A
,
,
objections: poor yields are almost invariably ob
Hoyer
et
al.
in
U,
S.
Alien
Property
Custodian,
tained; great operational difficulties are present;
Serial No. 463,866 have proposedthat the ,disad
and the resultant dyestuff is of poor quality due
vantages inherent ‘with the. “urea process” for
at least in part to the necessary high operating 40 phthalocyanine dyestui‘f formation could be over
temperatures needed to effect color formation.
come by effecting the “urea process” in the pres
Other processes, notably those covered in U. S.
ence of auxiliary agents such as aromatic car
Patents Nos. 2,216,761, 2,216,867, and. 2,216,868,
boxylic acids or sulfonic acids or the amides
and likewise directed towards a simpli?cation of
thereof, these agents not'being capable of con
the process for phthalocyanine dyestuff manu 45 version into phthalocyanines. This proposal has
facture, have been proposed, using aminosul
phonic acid type compounds, with which ;cer
tain dehydration and deamidation products of
, numerous disadvantages‘ among which are: it is
economically wastful due to the excessive
amounts of auxiliary agent required; and it is
diammonium phthalate, for instance, phthalic
anhydride, phthalimide, phthaldiamide, ‘an‘d'the
50
speci?c only to phthalocyanine-forming starting
materials that contain sulfonic acid groups or
2,410,301‘
3
4
may possess the substituents enumerated herein}
carboxyl groups in addition to the carboxyl acid
groups that take part in the phthalocyanine
color-forming reaction.
It is therefore seen that the present state of
the art is such that no existing phthalocyam'ne
dyestuff process successifully combines the de
sired optimum of economy of starting materials,
above.
In effecting the objects of the present inven
tion, the chemical mechanism of the process is
not entirely understood. Apparently, on the basis
of present work, the aromatic compound ?rst re
acts with the biuret to form an addition product.
This addition product, as a result of heat, then
simplicity and ease of operation, safety, and I
quality. The availability of such a'process would
undergoesv a vdehydration, de'amihatioflfand de
?ll a long-felt need‘ and, because‘of numerous
and a copper-yielding compound to give the de
sired dyestuff formation. This may not be, how
composition; in the presence of the auxiliary agent
dependent factors, make the copper phthalocye
anine dyestuffs available for wider and more gen- '
ever, the correct or entire explanation.
eral employment, as well as for entirely new
usages.
My present invention relates to such a ‘
process, heretofore much desired, but not avail
able.
‘
Biuret, also known as allophanarnide, may be
15 considered as a urea derivative or a deammona
_
The present invention aims to provide a simple,
practical, economic, and novel process for manu
tion product of urea. It is well known that urea
is a substantially neutral, if not slightly alkaline,
: substance, while biuret possesses acid properties.
See “The Nitrogen System Of Compounds”-—
facturing copper phthalocyanines ‘which maybe,’
practiced upon a variety of substituted and un 20 Franklin, pp. 114 and 118 v(1935). While biuret
may be obtained from urea by a mere heating, its
substituted benzene ortho-dicarboxylic acid
preparation is best performed by conducting the
compounds or certain of their dehydrated and
urea transformation under special conditions,
deamidated products.
cf., U. S. Patent No. 2,145,392 or'Vanino’s “Pra
A particular object of the invention is the for
parative Chemie-—Organischer Teil,” p. 221
mation of ‘copper phthalocyanine dyestuffs by re 25
(1937).
acting the said substituted and unsubstituted
This is done because the amount of
biuret formed from'heat transformation of urea
at atmospheric pressure is very smallidue to the
fact, that as the temperature is raised or the heat
compound. - ing prolonged in order to convert more of the
_ A further object of the invention is to accom 30
urea, formation of an increasing amount of by
plish the reaction of the said substituted and un
products,
such as ammelide and cyanuric acid,
substituted benzene ortho-dicarboxylic acid com
occurs and the yield of biuret remains quite low.
pounds, or their said derivatives, with biuret and
To illustrate: heating of urea at 147-152” C. for
a copper-yielding compound in the presence of
nine hours gives a yield of biuret (anhydrous
35
an auxiliary agent.
basis) of only 12.0%; and heating at 147—152° C.
A still further object of the invention is to effect
for 43 hours gives a yield of only 13.1%. Like
formation of the copper phthalocyanine dyestuffs
wise, biuret, when heated slightly above its melt
without the excessive foaming and frothing pe
ing point, say at 200° C. for one hour, is com
culiar to other processes of the prior art.
- Various other ancillary objects and advantages 40 pletely decomposed, giving water-insoluble and
gaseous products and a small quantity of mate
will appear from the following detailed descrip
rial melting at 103-106° C.
tion and explanation of the invention.
It is well known that phthalic anhydride and
These objects may be accomplished by reacting
urea react together to give the monoureide at
an ortho aromatic compound of the generic for
118-124° 0., cf. Piutti, “Liebig’s Annalen der
mula:
Chemie,” 1882, 214, pp. 17-30. Further, the inter
o 0 ONH4
action of phthalic anhydride and urea to give
benzene ortho-dicarboxylic acid compounds, or
their said derivatives, with biuret and a copper
R
phthalimide according to the equation:
COONH;
minus cal-I20, minus y NHs, with biuret and a 50
copper-yielding compound. An auxiliary agent
is also present. R is a benzene nucleus and may
by heating at 130-150" C. is well known and is a
contain various substituents such as halogen,
standard method for preparing phthalimide.
Other urea derivatives, notably formamide.
nitro, amino, aryl, alkyl, aryloxy, alkoxy, sulfo,
carboxyl, sulfonyl, benzoyl, and the like. These lv. Ul
substituents may appear more than once and they
may be in combination. a: is an integer which
may vary from 0 through 3; y is an integer which
dicyandiamide, ammonium carbonate, ammoni
um carbamate, guanylurea, guanidine, thiourea,
carbonyl urea, monosodium urea, methylol urea,
ammelin, ammelide, cyanuric acid, and cyana
mide, have been reacted with phthalic anhydride
may vary from 0 through 2, but the sum of a: and
60 in accordance with the procedure of the present
3/ does not exceed 3.
invention. These urea derivatives either give no
The copper phthalocyanine dyestuffs that may
dyestuff formation, or a product that is worth
be prepared according to this invention may be
expressed by this generic formula:
less.
-
In perfecting the present invention, it has been
65 found that the interaction of the described sub
stituted or unsubstituted benzene ortho-dicar
boxylic acid compounds or their derivatives, with
biuret and the copper-yielding compound pro
ceeds with poor yields of dyestuff, even when the
70 operating temperatures are either low, as at
185-200° C., or high, as at around‘ 250-275° C. It
is only through the use of various auxiliary ma
terials that dyestuff formation proceeds at com
paratively low temperatures in high yields and
These auxiliary agents are
wherein R consists of a benzene nucleus which 75 with good quality.
9,410,301
5
6
Specific in nature and only a few seem effectively
to assist in the dyestuff formation. Their exact
the scope of the invention. In the examples that
follow, all parts are given by weight.
role is unknown. .Of some value are those agents
containing the elements: antimony, tungsten, se
lenium, and boron; and of particular value are
- those agents containing the elements: molybden~
EXAMPLE 1
‘ >,
36.0 parts of biuret (M. P. 189.-19.0° C.) ,re
heated‘in a suitable vessel ?tted withan agita
tor. When the ; internal temperature is at
135-14,0° C., 30.0 parts of phthalic anhydride are
added over a 25 minute period with the agitated
fectiveness and variations of various elements in
favoring copper phthalocyanine dyestu? forma 10 mass being held within the 135-1400 C. range.
tion may be viewed in the light of subsequent
Then 0.06 part of ammonium molybdate, . ’
um, arsenic, and vanadium. These elements are
The ei
. all characterized by having acid oxides.
Table I, The auxiliary agents functioning in the
process of the present invention include salts, ox
.ides, acids, and inorganic and organic complexes.
and 7.5 parts of anhydrous cupric chloride are
The reaction
Two or more elements may exist in a compound 15 added over a 10 minute period.
mass at this point is a thick paste.
functioning as an auxiliary agent, for example,
, I
With continued agitation throughout the en
suing reaction period, the reaction temperature
The quantity of auxiliary agent present in the
is raised during 1% hours until an internal, tem
reaction mass may vary, indicating its function
ing in the nature of a catalyst. Small quantities 20 perature of 185-190° C. is reached. During this
temperature rise, 0.5 part portions of biuret are
in terms of the total reaction mass have a very
added at approximately 2.7 minute intervals until
marked and pronounced effect. Even with as
a vanado-molybdic acid.
'
a total of 14.0 parts has been added. The tem
perature rise and biuret additions are so adjusted
that the mass is at all times a fairly viscous paste.
During the temperature rise from 135-1400 C.
the reaction mass becomes greener and darker.
At 160-170° C. a coppery bronze appears and
low as 0.08% in terms of the Weight of the reac
tion mass, favorable action in lowering the for
mative color reaction temperature is observed, as
well as an increased yield of the resulting copper
phthalocyanine dyestu?. When thev quantity of
auxiliary agent is increased much beyond ‘2%,
shortly thereafter, a dark reddish-blue colora
very little added bene?t obtains. Therefore, in
the appended claims the auxiliary agent is re 30 tion.
The mass is then held at 185—190° C. for two
ferred to as a “catalyst.”
hours, and then cooled, and ground to a powder.
By the process of the present invention, color
The resulting powder is then extracted with 1,000
formation has been observed at temperatures as
parts of a dilute aqueous solution of caustic soda,
‘low as 135-140" C. It is generally preferred, how
ever, for optimum results to carry out the reace 35 preferably a 2.5% solution by weight, by heating
at the boiling temperature for 10 minutes. A
tion in the neighborhood of 175-195“ C. The pre
?ltration and washing with .water to neutrality is
ferred range is 160-200° C. The reaction may be
then performed. A second extraction, this time
conducted at temperatures in excess of 200° C.,
with 1,000 parts of a 5% aqueous hydrochloric
and as high as 300° C., but with increased tem
peratures of reaction over about-.1200o C. the qual 40 acid solution, is now performed in the manner
of the caustic soda treatment. This is similarly
ity and yield of the formed dyestuff suffers, in
followed by a ?ltration and water washing to
neutrality of the ?lter cake. The neutral ?lter
cake is then dried, giving a yield of 23.6 parts
part at least due to loss of biuret by decomposi
> tion.
Although the reagents for the reaction mass
may be associated in a variety of Ways, it is pre
ferred that they be associated in stages, thus uti
lizing progressive synthesis.
This
45 of a copper phthalocyanine. This corresponds
to a yield of 76.2%‘of theory, based on the
preference '
phthalic anhydride and considering the product
as a monochlorinated copper phthalocyanine.
gives a method of reacting to'secure the desired
The said copper phthalocyanine crude may
features of economy, quality, and ease of manip
50 then be conditioned for useas a pigment in one
ulation.
of many known ways, preferably that of my 00
The quantity of biuret employed in the present
pending application, Serial No. 381,396, ?led
process‘ may vary, as described hereinaftenuand
(March 1, 1941. The conditioned pigment has
the preferred range is between 1.5-2.0,moles.
excellent quality and high tinctorial value.v
The copper phthalocyanines-of the present in
vention are preferably made by reaction under 55..
EXAMPLE ,2
exposure to the atmosphere. But they may also
In a preparation similar to that of Example '1,
be'prepared by heating the aromatic'compound
a molecular equivalent of anhydrous cupric
with the biuret, auxiliary agent, and copper
bromide is employed as the copper-yielding ma
yielding compound in'a closed vessel under pres
terial. The obtained copper. phthalocyanine re
sure, often times with particularly advantageous 60 sembles the copper phthalocyanine of ‘Example-1,
results.
‘
in properties, and is thought to contain a bromi
As copper-yielding compounds‘it is preferred
nated form. -It is obtained‘in the amount of
to use copper salts. Among those that have been
24.5 parts and possesses pigmentary properties
‘ '
. ,
,used to advantage are the chlorides, bromides, 65 of a high order.
Generally, these copper
EXAMPLE 3
_
,
‘
salts are most advantageously employed in the
51.4 parts of a commercialbiuret having by
anhydrous state. The copper compounds may
analysis a composition given as follows: ..'Z0e.'?5%
be any‘ of those known in the art for making cop
biuret, 15-20 % cyanuric, acid, and. 10 % .ammelide,
per phthalocyanine dyestuif.
u
70 are ground and mixedwith 30.0 parts of phthalic
My invention may best be illustrated by refer
anhydride, 0.06 part of ammonium molybdate
ence-to the ‘following speci?c examples of its ap
and 7.5 parts of anhydrous cupric chloride. The
plication to actual practice, although it is to be
resulting powdery mass‘is placed .into a-suitable
’ acetates, and sulfates.
“understood that theyare; given merely as illus
rt atigns .andz.are_=.noi to lb? construed .aslimitins
vessel and," with agitation, the temperature is
raised over a % hour period until :an-einternal
2,410,301
8
temperature of 185—190‘’ C. is attained. A two
Parts yield
hour reaction period at this temperature is main
tained with stirring throughout the period. At
Ex-1 gmpllloyedéirtho-dicaré Elxgglgsilg?iggp' of phthalo
am
the end of this time the reaction mass is worked '
p
e
up in the'manner of Example 1 to give 18.0 parts
of copper phthalocyanine.
During the reaction period the mass is a heavy
paste and no frothing or foaming occurs. This
example illustrates a somewhat different pro
10
cedural method, as well as a variation in the com
position of the active biuret ingredient.
oxy ‘c aci
compoun
’
.
-
-
cyamne
material
dyesm?
Phthalic acid.-."
Gupric sulfate...
Phthalimide. _
___.
16. 0
__
Phthaldiamide ____ __
_.__do__._
Diammonium phthala
Cupric chloride _
17. 4
20.8
1
12. 1
It has been mentioned hereinabove that the
choice and nature of the auxiliary agent has
considerable bearing on the ease with which the
benzene ortho-dicarboxylic acid compound, the
EXAMPLE 4
biuret, and copper-yielding compound, effect dye
36.0 parts of biuret (M. P. 189—190° C.) are
stu? formation. In Table I which follows, the
placed into a suitable reaction vessel fitted with
procedure employed for the results was exactly
an agitator. Agitation is carried on throughout
like that of Example 4 except that the reaction
the reaction period. The temperature of the
temperature was in the range of 185—200° 0., the
biuret is raised to 160-165° C., then 30.0 parts of
period of ?nal reaction was two hours, and the
phthalic anhydride are added over a 30-40 min 20 copper-yielding material was a chemical equiv
alent of anhydrous cupric chloride in terms of
ute period within the 160~165° C. range. Then
copper.
0.06 part of ammonium molybdate and 8.9 parts
Table I
Item
Nature of auxiliary
Chemical formula of
agent
auxiliary agent
-
Parts ob
auxiliary
affgge
agent in
elemengi;
employed
reaction
agent
,
Per cent
Parts of
auxiliary
terms of
mass
tained of
eriodic
p on
gr
. _ . _ _ _. _ . _ _
ocyanine
1.47
2.0
VI
21.7
._
___
3.68
5.0
VI
21.6
Sodium molybdate ______ __
___
1. 47
2. 0
VI
21. 6
Molybdic acid (anhyd.)-__ M003 _________________ __
1. 47
2. 0
VI
21. 9
Silico-molybdic acid _____ _.
H4SiMoaO4o.XHzO_ ._._
1. 47
2. 0
VI
21. 2
Ammonium metavana-
NH4VO3 ______________ __
1. 47
2. 0
V
15. 0
1. 47
2. 0
V
11.8
7. 0
a e.
,
Arsenous oxide ___________ ._
Antimony trioxide-
1. 47
2. 0
V
Boric acid _______________ __
Zinc oxide _______________ .-
1. 47
1. 47
2. 0
2. 0
III
II
7.0
1. 2
Mecuric oxide
Aluminum oxide
Sodium carbonate
1. 47
1.47
1. 47
2. 0
2. 0
2. 0
II
III
IV
2. 6
3. 4
I. 1
Lead oxide-__. .
1. 47
2.0
IV
1.0
Sodium stanna
1. 47
2. 0
IV
1. 2
Lead titanate. _ -
1.47
2. 0
IV
2. 4
l. 47
2. 0
V
2. 2
0.48
0. 65
V
3. 4
Bismuth trioxide ________ ._
B1203
Diammonium phosphate__
Ammonium persulfate- _ .- (
-
__
1. 2
20. 6
___
..-___do ____________ _.
_ . . __do ____ __
copper
phthal
p
None___: __________________________________________________________________________________ __
Ammonium molybdate
(N H4) BM07024.4H2O . _ _ _
0. 06
0. 08
VI
-__-_d0__
extracted
1. 47
2. 0
VI
0. 8
Tungstic acid ______ . _
1. 47
2. 0
VI
4. 9
Ammonium chromate
l. 47
2. 0
VI
3. 1
1. 47
2. 0
VI
Potassium iodate ________ __
Selenium oxide _____ __
.
1. 47
2. 0
VII
0.7
_ Potassium permanganate__
1. 47
2. 0
VII
2. 9
1. 47
2. 0
VIII
1. 5
Ferric oxide _____________ __
-
5.0
It is seen, therefore, from the data of Table I
of anhydrous cupric sulfate are added over a
that the interaction of biuret, phthalic anhydride
20 minute period. The reaction mass, at this
point a fairly liquid paste, is heated and the 55 and the copper-yielding material, without the
auxiliary agent, is of little value for all practical
reaction temperature raised over a 30 minute"
purposes. On the other hand, when certain spe
period until an internal temperature of ISO-185°
ci?c auxiliary agents are employed, useful yields
C. is reached. Three hours heating follows at
of copper phthalocyanine result.
this temperature. The resulting color mass is
then processed, as in Example 1, giving 18.6 parts 60 It has been mentioned hereinabove that the
aromatic compound may have other substituents
of copper phthalocyanine. The obtained dye
present in the benzene nucleus besides the hydro
stuif possesses excellent pigmentary properties
,gen illustrated in the preceding examples. Typ
and is redder in shade than the copper phthalo
ical substituted benzene ortho-dicarboxylic acid
cyanine of Example 1.
'
compounds that may be employed in the process
65
EXAMPLE. 5
of the present invention are: 3,4-dimethyl
phthalic acid, 4-chloro-phthalic acid, 4-nitro
By substituting a molecular equivalent of an
hydrous cuprie acetate for the cupric sulphate
of Example 4, copper phthalocyanine can be ob
phthalic acid, 4-ethoxy-phthalic acid, 3-phenoxy
phthalic acid, 4-acetamino phthalic acid, 4
' phenyl-phthalic acid, N-benzenesulfonyl-‘i-ami
- 1 '
vFurther examples and results are shown in the 70 no-phthalic acid,v and others. Likewise, these
tained in likewise good yield.
following table._ In these the phthalic anhydride
is replaced by a chemical equivalent of benzene
ortho-dicarboxylic acid or a derivative of it, and
likewise the copper salt is an anhydrous equiva
lent where di?erent.
I
various substituted benzene ortho-dicarboxylic
acids may be employed in the form of their an
hydrides, imides, diamides,' and the like. A typi
cal example illustrating-the use of'a substituted
75 derivative of benzene ortho-dicarboxylic' acid‘ in
9.1
2,410,301
1‘0
preparing copper phthalocyanine dyestuffs in ac
cordance with the present invention follows:
De?ciency or excess of biuret does not affect the
character of the reaction, but only the yield of
product. The present invention contemplates
using relative quantities adjusted to the method
of carrying out the reaction, consistently with
economic results in comparing yield, time, raw
EXAMPLE 10
The procedure of Example 1 is repeated, ex
cept that the 30.0 parts of phthalic anhydride
are replaced by 39.0 parts of ll-nitro-phthalimide
(M. P. 197.5—198° 0.). The yield of dry copper
materials and other factors.
‘
In the foregoing examples a novel and unique
tetra-nitro-phtha1ocyanine, after the extractions
process for manufacturing copper phthalocy
and washings, amounted to 34.5 parts or 89.9% 10 anine dyestu?s has been disclosed and illustrated
of theory. It is a blue-green dyestuff.
in a variety of ways. In this process, when the
It has been indicated earlier that the initial
features of the speci?city of the auxiliary agent,
starting inter-mediates that are suitable for em
the improved manipulative features prevailing
ployment in my new and novel process are all
during the dyestuff formation, the availability of
related and may be regarded, for purposes of 15 the starting materials, and the uniqueness of
biuret as a phthalocyanine dyestu?-forming in
classi?cation, as transformation products of
a substituted or unsubstituted diammonium
gredient when contrasted with the non-phthalo
phthalate compound. In the foregoing examples,
cyanine dyestuff-forming properties of other urea
the use of phthalic anhydride, phthalic acid,
derivatives, are considered, it is seen, that a
phthalimide, phthaldiamide, and diammonium 20 notable advance and contribution has been made
in the phthalocyanine dyestuff art.
phthalate have been illustrated. Each of these
color-forming compounds may be regarded as a
It is intended to cover in the claims which fol
transformation product of diammonium phthal
low all such extensions and variations as would
ate in terms of integer mole units of NH3 and
naturally occur from‘ the foregoing, to one skilled
H20; for example, the entire class of transforma 25 in the art.
I claim:
tion products possible from diammonium phthal
‘ate and applicable in the present invention may
1. The method of making a copper phthalo
be expressed as follows:
cyanine dyestu? which comprises reacting to
gether at a temperature in the range from 1'35°.to
Phthalic acid=diammonium phthalate minus 30 300° C. and in proportions suincient to produce
; 2NH3 and OHzO
copper phthalocyanine, biuret, an ortho com
Phthalic anhydride=diammonium phthalate mi
pound
having the formula: R<COONH4)2, minus
nus ZNH: andlHzO
:rI-IzO, minus Z/NHs, and a copper-yielding com
pound, in the presence of a catalyst for the reac
tion, said formula being such that a: is an integer
Monoammonium o-carbamyl-benzoate=diam
varying from 0 through 3, y is an integer vary
monium phthalate minus ONI-Is and 11120
ing fromio through 2, both while x-l-y is not more
Phthalic acid monoamide=diammonium phthal
than 3, and R is a benzene nucleus selected from
ate minus lNHs and lHzO
Phthaldiamide:diammonium phthalate minus 40 the group consisting of the unsubstituted benzene
nucleus and substituted benzene nuclei.
ONI-Is and 2I-I2O
2. The method of making a copper phthalocy
Phthalimide=diammonium phthalate minus
anine dyestuif which comprises reacting together
1NH3 and 21-120
at a temperature in the range from 135° to 300°
- o-Cyano-benzoic acid=diaminonium phthalate
C., and in proportions sufficient to produce cop
minus 1NH3 ‘and 2H2O
per phthalocyanine, biuret, an ortho compound
Monoarnmonium o-cyano-benzoate=diammoni
having the formula: R(COONI—I4)2, minus x1120,
um phthalate minus ONHa and 2H2O
Monoammonium
phthalate=d i a m m o n i u m
phthalate minus 1NH3 and OHzO
phthalate
minus yNI-Iz, and a copper-yielding compound,
Phthalimimide=diammonium phthalate minus
in the presence of a catalyst for the reaction,
which catalyst is present in quantity from 0.08%
o - Cyano - benzamide=diammonium
minus ONH3 and 3H2O
to 2% by weight of the reaction mass, said for
ONH3 and 3H2O
mula being such that :1: is an integer varying from
0 through 3, y is an integer varying from 0
through 2, both while :c+y is not more than 3,
and R. is a benzene nucleus selected from the
Some of these compounds cannot be obtained
directly from diammonium phthalate, but their
relationship is clear from the above explanation,
and the value of typical representatives of the '
group in copper-phthalocyanine-formation has
been illustrated. In addition, eleven similar
transformation compounds are possible for each >
/
group consisting of the unsubstituted benzene
nucleus and substituted benzene nuclei.
3. The method of making a copper phthalocy
anine dyestuff which comprises reacting together
derivative form wherein a substituent is, or sub
at a temperature in the range from 135° to 300°
stituents are, present on the benzene nucleus of 60 C., and in proportions suf?cient to produce cop
the diammonium phthalate.
per phthalocyanine, biuret, an ortho compound
By examining the formulas above for the
having the formula: C6H4(COONH4)2, minus
phthalocyanines, it is seen that theory calls for
.rHzO, minus yNHa, and a copper-yielding com
4 benzene rings and 8 nitrogen atoms. Biuret
pound, in the presence of a catalyst for the re
contains 3 nitrogen atoms in one ‘mole. Theo 65 action, said formula being such that x is an in
retically, then 2 moles of biuret are required for
teger varying from 0 through 3, y is an, integer
3 moles of phthalic anhydride, for example.
varying from 0 through 2, both while x+y is not
Thus, 0.66 mole of biuret is the minimum reac
more than 3.
tive quantity, in theory, for 1 mole of phthalic
4. The method of making a copper phthalocy
anhydride, or its equivalent. In Example 1, 2
anine dyestuff which comprises reacting together
moles of biuret, and in Examples 3 and 4, ap
at a temperature in the range from 135° to 300°
proximately 1.5 moles of biuret are employed per
C., and in proportions suf?cient to produce cop
mole of benzene nucleus. There is loss of am
per phthalocyanine, biuret, a phthalic anhydride,
monia in the reaction, in part from the reaction,
and a copper-yielding compound, in the presence
and in part from thermal decompositions. 75 of a catalyst for the reaction.
2,410,801
11
5. The method of making a copper phthalocy
anine dyestuff which comprises reacting together
at a temperature in the range from 135° to 300°
C., and in proportions sufficient to produce cop
per phthalocyanine, biuret, an ortho compound
having the formula: R(COONH4)2, minus :cHzO,
minus yNI-Is, and a copper-yielding compound, in
the presence of a catalyst for the reaction, which
12
by weight of the reaction mass, said formula being
such that x is an integer varying from 0 through
3, y is an integer varying from 0 through 2, both
while .r+y is not more than 3, and R is a benzene
nucleus selected from the group consisting of the
unsubstituted benzene nucleus and substituted
benzene nuclei.
, 11. The method of making a copper phthalo
catalyst contains molybdenum; said formula-be
cyanine dyestuff which comprises reacting to
through 3, y is an integer varying from 0 through
2, both while :c-l-y is not more than 3, and R is
200° 0., and in proportions su?icient to produce
copper phthalocyanine, biuret, an ortho compound
having the formula: CsH4(COONI-I4)2, minus
ing such that as is an integer varying from 0 10 gether at a temperature in the range from 160
a benzene nucleus selected from the group con
171-120, minus yNI-Iz, and a copper-yielding com
sisting of the unsubstituted benzene nucleus and
pound, in the presence of a catalyst for the reac
15
substituted benzene nuclei.
tion, said formula ‘being such that r is an integer
6. The method of making a copper phthalo
varying from 0 through 3, y is an integer varying
cyanine dyestuff which comprises reacting to
from 0 through 2, both while :r-l-y is not more
gether at a temperature in the range from 135°
than 3.
to 300° C., and in proportions sufficient to produce
12. The method of making a copper phthalo
copper phtha1ocyanine,biuret, an ortho compound
cyanine dyestuff which comprises reacting to
having the formula: R(COONH4)2, minus .rHzO,
gether at a temperature in the range from 160
minus yNH3, and a copper-yielding compound, in
200° C., and in proportions suf?cient to produce
the presence of a catalyst for the reaction, which
copper phthalocyanine, biuret, phthalic anhy
catalyst contains vanadium; said formula being
such that at is an integer varying from 0 through 25 dride, and a copper-yielding compound, in the
presence of a catalyst for the reaction.
3, y is an integer varying from 0 through 2,'both
13. The method of making a copper phthalo
while r-i-y is not more than 3, and R is a benzene
’
cyanine
dyestuif which comprises reacting to
nucleus selected from the group consisting of the
gether at a temperature in the range from
unsubstituted benzene nucleus and substituted
30 160-200” C., and in proportions su?icient to pro
benzene nuclei.
duce copper phthalocyanine, biuret, an ortho
'7. The method of making a copper phthalo
compound having the formula: R(COONH4) 2,
cyanine dyestu? which comprises reacting to
minus rI-IZO, minus yNI-Is, and a copper-yielding
vgether at a temperature in the range from 135°
compound, in the presence of a catalyst for the
to 300° ,C., and in proportions sufficient to produce
copper phthalocyanine, biuret, an ortho compound 35 reaction, which catalyst contains molybdenum;
said formula being such that a: is an integer vary
having the formula: R(COONH4)2, minus uni-I20,
ing from 0 through 3, y is an integer varying from
minus yNHa, and a copper-yielding compound, in
0 through 2, both while :t-l-y is not more than 3,
the presence of a catalyst for the reaction, which
and R is a benzene nucleus selected from the
catalyst contains arsenic; said formula beingsuch
that :c is an integer varying from 0 through 3, 40 group consisting of the unsubstituted benzene
nucleus and substituted benzene nuclei.
y is an integer Varying from 0 through 2, both
14. The method of making a copper phthalo
while .r-l-y is not more than 3, and R is a benzene
cyanine dyestu?" which comprises reacting to
nucleus selected from the group consisting of the
gether at a temperature in the range from
unsubstituted benzene nucleus and substituted
160-200° C., and in proportions sufficient to pro
benzene nuclei.
7
duce copper phthalocyanine, biuret, an ortho
8. The method of making a copper phthalo
compound having the formula: R(COONH4)2,
cyanine dyestu? which comprises reacting to
minus xHzO, minus yNHs, and a copper-yielding
gether at a temperature in the range from 135°
compound, in the presence of a catalyst for the
to 300° C., and in proportions sufficient to produce
copper phthalocyanine, biuret, phthalimide, and 50 reaction, which catalyst contains vanadium; said
formula being such that :1: is an integer varying
‘a copper-yielding compound, in the presence of
from
0 through 3, y is an integer varying from 0
a catalyst for the reaction.
through 2, both while m+y is not more than 3,
9. The method of making a copper phthalo
and R is a benzene nucleus selected from the
cyanine dyestuff which comprises reacting to
group consisting of the unsubstituted benzene
gether at a temperature in the range from 160
nucleus and substituted benzene nuclei.
200° C., and in proportions su?icient to produce
15. The method of making a copper phthalo
copper phthalocyanine, biuret, an ortho compound
cyanine dyestuff which comprises reacting to
having the formula: R(COONH4)2, minus :BHzO‘,
gether at a temperature in the range from
minus yNHz, and a copper-yielding compound, in
the presence of a catalyst for the reaction, said 60 160~200° C., and in proportions su?icient to pro
duce copper phthalocyanine, biuret, an ortho
formula being such that a: is an integer varying
from 0 through 3, y is an integer varying from
0 through 2, both while zc+y is not more than 3,
and R is a benzene nucleus selected from the
group consisting of the unsubstituted benzene 65
nucleus and substituted benzene nuclei.
10. The method of making a copper phthalo
cyanine dyestuff which comprises reacting to
gether at a temperature in the range from 160
compound having the formula: R(COONH4)2,
minus xHzO, minus yNI-Is, and a copper-yielding
compound, in the presence of a catalyst for the
reaction, which catalyst contains arsenic; said
' formula being such that a: is in integer varying
from 0 through 3, y is an integer varying from 0
through 2, both while x+y is not more than 3,
and R is a benzene nucleus selected from the
200° C., and in proportions su?icient to produce 70 group consisting of the unsubstituted benzene
' nucleus and substituted benzene nuclei.
copper phthalocyanine, biuret, an ortho compound
16. The method of making a copper phthalo~
having the formula: R(COONH4)2, minus xHzO,
cyanine dyestu?‘ which comprises reacting to
minus yNHs, and a copper-yielding compound, in
gether at a temperature in the range from
the presence of a catalyst for the reaction, which
160—200° (2., and in proportions su?icient to pro
catalyst is present in quantity from 0.08% to 2%
13
2,410,301
duce copper phthalocyanine, biuret, phthalimide,
and a copper-yielding compound, in the presence
of a catalyst for the reaction.
17. The method as de?ned in claim 1 in which
said biuret is present in the proportion of at least
0.66 mole per mole of said ortho compound.
18. The method as de?ned in claim 2 in which
said biuret is present in the proportion of at least
0.66 mole per mole of said ortho compound.
19. The method as de?ned in claim 3 in which
said biuret is present in the proportion of at least
0.66 mole per mole of said ortho compound,
20. The method as de?ned in claim 12 in which
said biuret is present in the proportion varying
from 0.66 mole to 2 moles per mole of phthalic 15
anhydride.
'
21. The method as de?ned in claim 13 in which
14
' said biuret is present in the proportion varying
from 0.66 mole to 2 moles per mole of said ortho
compound.
22. The method as de?ned in claim 14 in which
said biuret is present in the proportion varying
from 0.66 mole to 2 moles per mole of said ortho
compound,
23. The method as de?ned in claim 15 in which
said biuret is present in the proportion varying
from 0.66 mole to 2 moles per mole of said ortho
compound.
24. The method as de?ned in claim 16 in which
said biuret is present in the proportion varying
from 0.66 mole to 2 moles per mole of phthalim
ide.
GRADY M. O’NEAL.
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