Note: Descriptions are shown in the official language in which they were submitted.
;~oo~s~9
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P-17414/+/MA 1953
Preparation of imidomethyl phthalocyanine derivatives
The present invention relates to a new process for the production of
imidomethyl phthalo-
cyanine derivatives which are useful e.g. as non-flocculating, non-
crystallising additives
for surface coatings and, especially, as thermal stabilisers for pigments used
in
engineering plastics.
It is known, e.g. from GB 695523, to produce imidomethyl phthalocyanines by
reacting a
phthalocyanine with a source of formaldehyde and with a cyclic imide, under
dehydrating
conditions, provided e.g. by using a medium of sulphuric acid and/or oleum,
according to
the reaction scheme:
0 0
PC + X~HCHO + X ' ~ R ---~ Pc(CH2N R)X
O O
wherein Pc is an optionally metallised phthalocyanine, R is a divalent
aliphatic or
aromatic residue, such as an alkylene or ortho-phenylene residue and x is a
number
ranging from 0.1 to 4, being the average number of imidomethyl groups on the
phthalocyanine.
In a modification of this known route, as described e.g. in US 2891964, the
formaldehyde
and imide are first reacted to form a hydroxymethylimide which is then reacted
with the
phthalocyanine, under dehydrating conditions, according to the reaction
scheme:
0 0
PC + X ~ HOCH~N R --~ Pc(CH2N R)X
O O
wherein Pc, R and x have their previous significance.
X20 o y 4~
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In a still further known process, described e.g. in Japanese patent
specification 80 66584,
imidomethyl phthalocyanine derivatives are produced by reacting
chloromethylated
phthalocyanine with a metal salt of an imide according to the scheme:
o ~ o
Pc (CH2C1)x + x ~HN R ~ Pc(CHZN R)x + X~HCl
O O
wherein Pc, R and x have their previous significance.
These known methods all rely on the use of imides as an essential reactant.
The use of
imide reactants is disadvantageous in that the range of commercially-available
imides is
quite narrow, thereby limiting the scope of the imidomethyl phthalocyanine
derivatives
which can be obtained by these known methods.
We have now found that, by using an entirely different reaction involving
cyclic acid
anhydride reactants, a very wide range of imidomethyl phthalocyanine
derivatives can be
produces.
Accordingly, the present invention provides a process for the production of an
imidomethyl phthalocyanine derivative having the formula
O
(S03H) -MPc(CH2N X)
m ~ n
O
wherein Pc represents a phthalocyanine residue optionally substituted by
chlorine or
bromine; M is hydrogen, or any metal capable of forming a metal phthalocyanine
e.g.
magnesium, aluminium, cobalt, nickel, copper, iron, zinc, lead or tin,
preferably copper or
aluminium; m is a number within the range of from 0.07 to 0.71, n is a number
within the
range of from 0.1 to 4 preferably from 1.0 to 3.U; and X is a residue such
that, in
combination with the group -C(=O)-N-C(=O)- , it forms a 5-, 6- or 7-membered
cyclic
anhydride,
which process comprises reacting an anunomethyl phthalocyanine having the
formula II
2~0 ~ i49
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(SOgH)m MPc(CH2NH2)n II
wherein Pc, M, m and n have their previous significance, with a 5-, 6- or 7-
membered
cyclic acid anhydride having the formula III
0
o x I~
0
wherein X has its previous significance.
The reactants of formula II are known compounds, having been described, e.g.
in US
2761868 and GB 717137, and may be prepared by subjecting the corresponding
phthalimidomethyl phthalocyanine to alkaline hydrolysis, followed by acid
hydrolysis, or
by subjecting phthalimidomethyl phthalocyanine to hydrazinolysis. The
compounds of
formula II are preferably used as the free base in the process of the present
invention.
Likewise, the starting materials of formula III are known materials and
include:
a) 5-membered cyclic anhydrides
succinic anhydride,
malefic anhydride,
itaconic anhydride,
tetrahydrophthalic anhydride,
tetrachlorophthalic anhydride,
cis-5-norbornene-endo-2,3-dicarboxylic anhydride,
3,6-endoxo-1,2,3,6-tetrahydrophthalic anhydride,
phthalic anhydride,
1,2- or 2,3-naphthalic anhydride, or quinolinic anhydride (pyridine-2,3-
dicarboxylic
anhydride),
each unsubstituted or substituted with one or more halogen atoms, preferably
chlorine or
bromine atoms; C1-C2oalkyl groups; C3-C2oalkenyl groups; nitro groups or
carboxy
groups.
200549
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b) 6-membered cyclic anhydrides
glutaric anhydride,
3,3-tetramethylene glutaric anhydride,
1,8-naphthalic anhydride,
perylene-1,12-dicarboxylic anhydride,
isatoic anhydride,
each unsubstituted or substituted with one or more halogen atoms, preferably
chlorine or
bromine atoms; Ct-C2oalkyl groups; C3-CZOalkenyl groups; nitro groups or
carboxy
groups.
c) 7-membered c cl~hydrides
adipic anhydride,
diphenic anhydride,
each unsubstituted or substituted with one or more halogen atoms, preferably
chlorine or
bromine atoms; Ct-C2oalkyl groups; C3-C2oalkenyl groups; nitro groups or
carboxy
groups.
The 5-membered cyclic anhydrides are preferred.
Optionally Ct-C2nalkyl substituents in the anhydrides may be methyl, ethyl,
isopropyl,
n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-
octadecyl or eicosyl
groups. Optional C3-C2oalkenyl substituents include, e.g. propenyl, butenyl,
pentenyl,
hexenyl, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl
or eicosenyl
groups.
The process according to the present invention is conveniently performed at an
elevated
temperature at a temperature within the range of from 100 to 300 and most
preferably within the range of 130 and 200°C.
Depending upon the reaction temperature, the reaction may be continued for a
period
ranging from 30 minutes to 12 hours, preferably from 3 to 8 hours.
The reaction is carried out in a solvent which dissolves one or both of the
reactants, while
being chemically inert to the reactants and to the imidomethyl phthalocyanine
products.
Suitable solvents include aromatic solvents having a boiling point above
100°C; protic
solvents, e.g. alcohol or acids, which have a boiling point about 100°C
and which do not
2~0 i~49
-s-
react with the anhydride reactant of formula III; and, especially aprotic
solvents having a
boiling point above 100°C.
Examples of preferred aprotic solvents are dimethylsulphoxide, N-
methylpyrrolidone,
tetramethylurea, ethylene glycol, dimethyl ether, dioxan, hexamethylphosphoric
triamide,
pyridine, sulpholane, propylene carbonate and 1-formylpiperidine and,
especially,
dimethylformamide.
Reactions of the aminomethyl phthalocyanines of formula II with the cyclic
acid
anhydrides of formula III probably do not go fully to completion. Unreacted
material may
therefore be present in the reaction product. Such unreacted material,
however, has no
detrimental effect on the pigment.
The present invention is illustrated by the following Examples. Percentages
are by weight.
Example 1:
A. Preparation of Sulphonated aminomethyl copper phthalocyanine
34 g 100 % sulphonated phthalimidomethyl copper phthalocyanine (containing
about
2.3 phthalimidomethyl groups and 0.07 sulphonic acid groups per copper
phthalocyanine
molecule) as filtercake are slurried in 100 ml water at 90°C. When a
smooth lump-free
paste is obtained, is g 98-100 % hydrazine hydrate is added and the mixture
refluxed with
stirnng in an oil bath maintained at 130°C for 8 hours. Heating is
removed, the mixture
diluted with water and the pH adjusted to 8.0 with 0.880 SG ammonia solution.
The
product is filtered and washed well with 1 % aqueous ammonia and all hard
lumps broken
down.
The slurry is filtered and washed with warm water and used as presscake at 22
% solids
content. Analysis of a dried sample showed an aminomethyl content of 2.3
groups and a
sulphonic acid content of 0.07 groups.
B. Preparation of sulphonated tetrachlorophthalimidomethyl copper
phthalocyanine
100 g of sulphonated aminomethyl copper phthalocyanine, obtained as a 22 %
solids
presscake in step A) and having the formula:
(S03H)p.o~CuPc(CH2NH2)2.3~
are slurried in 2s0 g of dimethylformamide and heated, with good stirring to
1s0°C, using
an oiI bath. The dimethylformamide/water mixture so produced is collected by
distillation
~:~n~'/~~9
-6-
over 2 hours, then 22.9 g of tetrachlorophthalic anhydride are added. The
mixture so
obtained is heated at 150°C for 6 hours; cooled to 100°C; and
then poured into 1500 ml of
cold water, while stirring. The solid product obtained is filtered off, washed
with water
and dried giving 40 g of sulphonated tetrachlorophthalimidomethyl copper
phthalocyanine.
Examples 2 to 12: Using the procedure described in Example 1 (B), sulphonated
amino-
methyl copper phthalocyanine, as obtained in Example 1 (A), is reacted with
the
anhydrides indicated in column 2 of the following Table, thereby producing the
product
designated in column 4 of the following Table.
~~JO'~549
0
0
0
0 0
° o x
0
fan U U M
f1n N U
N M
x N _ U N z x N
0 0 o z o
0 0
0 0
.. .,
"' / ~ \
\ ~ \ / ~ \ /
,... ..
U '-'
U
x
O ~ O
O O
O
O O
O
N f~ h7
0
x
0
w
b
U O
fr
O
z
>~
Q ~ H ~ ~.
N M ~t
W
2UU X549
_g_
0
O
o O o
x
0 0 ~'
0
U
a a
G~a~ U c~n U cn U cn
U M N fV (V
N N N N
N x
x z z z
U
O O O O O O
O =__~~ O
U U V U U
U
.b
O
O O O
O O O O O O
O
O =_~ O
V x x U U
U U
O
w
b
...U., U
c~
~,;b O '~
O
b
U ~ ~
Q ~ ~ ~1
a~
W
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-9-
o n
0 0
x c
M
o ~ O
x
M U
L4
V
M
cV V M,
N
~M x
U
z
v o o z
0 0
O ====~~ O N
U
'r' U
M
x _
V U / U
''-' V
U
O
b
O
O O
O O
O O
N
O U
U
x
U / U
U
U
O
w
'
b
~
O U
U
U U
a ~ o v
0
w
~~t~'r54~
- 10-
Example 13:
A. Preparation of sulphonated aminometh~pper phthaloc a
Sulphonated phthalimidomethyl copper phthalocyanine, containing about 1.4
phthal-
imidomethyl and 0.71 sulphonic acid groups per copper phthalocyanine molecule,
is
treated as for Example lA to give sulphonated aminomethyl copper
phthalocyanine of
formula (S03H)o.~iCuPc(CH2NH2)i.4~
B. Preparation of sulphonated phthalimidometh~l copper phthalocyanine
85 g of the material obtained in Example 13A are slurned, as a presscake
containing 9.5 %
solids, in 250 g of dimethylformamide and the mixture is heated, with
efficient stirring, to
150°C. The dimethylformamide/water mixture so produced is collected by
distillation
over 2 hours, then 4.12 g of phthalic anhydride are added. The mixture is
heated at 150°C
for 6 hours, cooled to 100°C, and then poured into 1000 ml of cold,
well-stirred water. The
product obtained is filtered off, washed well with water and dried giving 9.2
g of the title
compound containing 0.71 sulphonic acid, and 1.4 phthalimidomethyl groups per
copper
phthalocyanine molecule.
Example 14:
A. Preparation of sulphonated aminomethyl aluminium phthaloc~ranine
Sulphonated aminomethyl aluminium phthalocyanine containing about 2.5
aminomethyl
groups and 0.7 sulphonic acid per aluminium phthalocyanine molecule, is
prepared in a
similar manner to the derivative of Example lA.
B. Preparation of sulphonated tetrachlorophthalimidomethyl aluminium phthaloc
a
100 g of sulphonated aminomethyl aluminium phthalocyanine, obtained as a 18 %
solids
presscake in step A, are slurned in 250 g of dimethylformamide. The stirred
mixture is
heated to 150°C and the dimethylformamide/water distillate is
collected. 24.3 g of
tetrachlorophthalic anhydride are added and the mixture obtained is heated at
150°C for
6 hours then poured into 1000 ml of cold, well-stirred water. The product is
filtered off,
washed with water and dried giving 27.5 g of sulphonated
tetrachlorophthalimidomethyl
aluminium phthalocyanine.
Example 15: Preparation of sulphonated diphenicimidomethyl
copper~hthaloc~anine
49 g of sulphonated aminomethyl copper phthalocyanine, obtained as a 20.4 %
solids
presscake by the procedure of Example lA, are slurried in 250 g of
dimethylsulphoxide
~oo~a4s
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and heated, with good stirring, until all the water is removed. The mixture is
cooled to
80°C and 8.5 g of diphenic anhydride are added portionwise to the
stirred slurry. The
temperature is then raised to 160°C and stirring is continued for a
further 6 hours. The
mixture is then cooled to 100°C, poured into 1000 ml of well-stirred
cold water, and the
suspension filtered to give sulphonated diphenicimidomethyl copper
phthalocyanine
containing about 0.07 sulphonic acid groups and 2.3 diphenicimidomethyl groups
per
copper phthalocyanine molecule.
Example 16: Copper phthalocyanine (29.3 g), anhydrous calcium chloride (55.0
g) and
sodium acetate crystals (5 g) are ball-milled in a vibration mill with 12 mm
steel balls for
12 hours then slurried into isopropanol/water (83:17, 280 g) containing gum
rosin solution
(10 g of an alkaline solution of 16.6 % rosin). The mixture is refluxed with
agitation for 1
hour, then hot water (160 ml) is added. The isopropanol is removed as an
azeotrope and
cold water (68 ml) is added to the residue.
The product from Example 1B (1.6 g at 100 %) is slurried in water and added to
the
copper phthalocyanine slurry. After 30 minutes stirnng, 36 % hydrochloric acid
(16.6 parts) is added and the mixture is stirred for 1 hour at 50-60°C.
The pigment is
filtered off, washed with cold water until the filtrate is chloride free, then
dried at 60°C,
and sieved through a 150 micron screen.
Into a two-roll mill, with the rollers set at 150°C and 110°C
and the nip gap at 0.3 mm, is
introduced high density polyethylene (HDPE), 100 g. The polymer is milled for
one
minute to ensure uniformity, then the pigment, as prepared above (0.1 g) is
sprinkled, over
30 seconds, into the polymer. After milling for 8 minutes, the nip is adjusted
to
1.5 mm and the hide sheeted off and chipped.
The chipped material is fed to an injection moulding machine with the barrel
set at 200°C.
Once the feed is running uniformly through the machine, a HDPE moulding is
obtained
which has a strong blue shade. The procedure is repeated several times with
the barrel
temperature being increased in steps of 20°C to 320°C.
The strong blue shade is maintained to a significantly higher temperature than
if the
pigment used is prepared without the incorporation of the sulphonated
tetrachloro-
phthalimidomethyl copper phthalocyanine.
~~~ ~~4r~
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Example 17: Preparation of sulphonated phthalimidomethyl copper
phthaloc'ranine
Using the procedure described in Example 13B), 22 g (dry weight) sulphonated
aminomethyl copper phthalocyanine, as obtained in Example lA), is reacted with
22.9 g
of phthalic anhydride in dimethylformamide to give the title compound. The
reaction is
carried out at 100°C for 8 hours.
Example 18: Preparation of sulphonatedphthalimidomethyl copper phthaloc, ay
nine
Using the procedure described in Example 13B), 22 g (dry weight) sulphonated
amino-
methyl copper phthalocyanine, as obtained in Example lA), is reacted with 11.9
g of
phthalic anhydride in N-methylpyrrolidone to give the title compound. The
reaction is
carried out at 200°C for 3 hours.
