CA2007549C - Preparation of imidomethyl phthalocyanine derivatives - Google Patents
Preparation of imidomethyl phthalocyanine derivatives Download PDFInfo
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- CA2007549C CA2007549C CA002007549A CA2007549A CA2007549C CA 2007549 C CA2007549 C CA 2007549C CA 002007549 A CA002007549 A CA 002007549A CA 2007549 A CA2007549 A CA 2007549A CA 2007549 C CA2007549 C CA 2007549C
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- phthalocyanine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/12—Obtaining compounds having alkyl radicals, or alkyl radicals substituted by hetero atoms, bound to the phthalocyanine skeleton
- C09B47/16—Obtaining compounds having alkyl radicals, or alkyl radicals substituted by hetero atoms, bound to the phthalocyanine skeleton having alkyl radicals substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
- C09B67/0035—Mixtures of phthalocyanines
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- Nitrogen Condensed Heterocyclic Rings (AREA)
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Abstract
A process for the production of an imidomethyl phthalocyanine derivative having the formla I
(see Fig I) wherein Pc represents a phthalocyanine residue optionally substituted by chlorine or bromine; M is hydrogen, or any metal capable of forming a metal phthalocyanine; m is a number within the range of from 0 to 1.0; n is a number within the range of from 0.1 to 4 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 aminomethyl phthalocyanine having the formula II
(SO3H)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
wherein X has its previous significance.
The compounds of formula I are useful as additives for surface coatings and as thermal stabilisers for pigments used in engineering plastics.
(see Fig I) wherein Pc represents a phthalocyanine residue optionally substituted by chlorine or bromine; M is hydrogen, or any metal capable of forming a metal phthalocyanine; m is a number within the range of from 0 to 1.0; n is a number within the range of from 0.1 to 4 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 aminomethyl phthalocyanine having the formula II
(SO3H)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
wherein X has its previous significance.
The compounds of formula I are useful as additives for surface coatings and as thermal stabilisers for pigments used in engineering plastics.
Description
;~oo~s~9 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:
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:
PC + X ~ HOCH~N R --~ Pc(CH2N R)X
O O
wherein Pc, R and x have their previous significance.
X20 o y 4~
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:
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:
PC + X ~ HOCH~N R --~ Pc(CH2N R)X
O O
wherein Pc, R and x have their previous significance.
X20 o y 4~
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 (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
o x I~
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.
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 (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
o x I~
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.
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 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 ° o x fan U U M
f1n N U
N M
x N _ U N z x N
0 0 o z o .. ., "' / ~ \
\ ~ \ / ~ \ /
,... ..
U '-' U
x O ~ O
O O
O
O O
O
N f~ h7 x w b U O
fr O
z >~
Q ~ H ~ ~.
N M ~t W
_g_ O
o O o x 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
~~JO'~~4~
o n x c M
o ~ O
x M U
V
M
cV V M, N
~M x U
z v o o z 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 w ~~t~'r54~
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 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~
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.
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 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 ° o x fan U U M
f1n N U
N M
x N _ U N z x N
0 0 o z o .. ., "' / ~ \
\ ~ \ / ~ \ /
,... ..
U '-' U
x O ~ O
O O
O
O O
O
N f~ h7 x w b U O
fr O
z >~
Q ~ H ~ ~.
N M ~t W
_g_ O
o O o x 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
~~JO'~~4~
o n x c M
o ~ O
x M U
V
M
cV V M, N
~M x U
z v o o z 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
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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 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~
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.
Claims (9)
1. A process for the production of an imidomethyl phthalocyanine derivative having the formula I
wherein Pc represents a phthalocyanine residue optionally substituted by chlorine or bromine; M is hydrogen, or any metal capable of forming a metal phthalocyanine; 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 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 aminomethyl phthalocyanine having the formula II
(SO3H)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
wherein X has its previous significance, and wherein the process is performed at a temperature within the range of from 100 to 300°C in a solvent which dissolves one or both of the reactants while being chemically inert to the reactants and to the imidomethyl phthalocyanine products.
wherein Pc represents a phthalocyanine residue optionally substituted by chlorine or bromine; M is hydrogen, or any metal capable of forming a metal phthalocyanine; 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 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 aminomethyl phthalocyanine having the formula II
(SO3H)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
wherein X has its previous significance, and wherein the process is performed at a temperature within the range of from 100 to 300°C in a solvent which dissolves one or both of the reactants while being chemically inert to the reactants and to the imidomethyl phthalocyanine products.
2. A process according to claim 1, wherein M is magnesium, aluminum, cobalt, nickel, copper, iron, zinc lead or tin.
3. A process according to claim 1, wherein M is copper or aluminum.
4. A process according to claim 1, wherein n is a number within the range of from 1.0 to 3Ø
5. A process according to claim 1, wherein the compound of formula II is sulphonated aminomethyl copper phthalocyanine.
6. A process according to claim 1, wherein the compound of formula III is succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, 3,6-endoxo-1,2,3,6-tetrahydrophthalic anhydride, 1,2- or 2,3-naphthalic anhydride or quinolinic anhydride (pyridine-2,3-dicarboxylic anhydride) each unsubstituted or substituted by one or more halogen atoms, C1-C20alkyl groups, C3-C20alkenyl groups, nitro group or carboxy groups.
7. A process according to any one of claims 1 to 6 wherein the solvent is an aprotic solvent.
8. A process according to claim 7 wherein the aprotic solvent is dimethylformamide.
9. The method of using an imidomethyl phthalocyanine derivative of formula I as defined in any one of claims 1 to 4, as a thermal stabiliser for a pigment colourant in an engineering plastics material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB898900762A GB8900762D0 (en) | 1989-01-13 | 1989-01-13 | Process |
| GB8900762.9 | 1989-01-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2007549A1 CA2007549A1 (en) | 1990-07-13 |
| CA2007549C true CA2007549C (en) | 2000-06-13 |
Family
ID=10649995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002007549A Expired - Fee Related CA2007549C (en) | 1989-01-13 | 1990-01-11 | Preparation of imidomethyl phthalocyanine derivatives |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0378509B1 (en) |
| JP (1) | JP3144677B2 (en) |
| KR (1) | KR0135518B1 (en) |
| CA (1) | CA2007549C (en) |
| DE (1) | DE59006801D1 (en) |
| DK (1) | DK0378509T3 (en) |
| ES (1) | ES2058867T3 (en) |
| GB (1) | GB8900762D0 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210332280A1 (en) * | 2018-11-07 | 2021-10-28 | Dow Global Technologies Llc | Thermally conductive composition and methods and devices in which said composition is used |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9110260D0 (en) * | 1991-05-11 | 1991-07-03 | Ciba Geigy Ag | Pigment compositions |
| EP1026207B1 (en) * | 1999-02-02 | 2006-02-22 | Ciba SC Holding AG | Pigment particle growth and/or crystal phase directors |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE852588C (en) * | 1950-11-16 | 1952-10-16 | Bayer Ag | Process for the production of new phthalocyanine dyes |
| US2761868A (en) * | 1953-05-13 | 1956-09-04 | American Cyanamid Co | Sulfonated and unsulfonated imidomethyl, carboxyamidomethyl and aminomethyl phthalocyanines |
| JPS5792036A (en) * | 1980-11-28 | 1982-06-08 | Toyo Ink Mfg Co Ltd | Prevention of heat deterioration of polyolefin |
-
1989
- 1989-01-13 GB GB898900762A patent/GB8900762D0/en active Pending
-
1990
- 1990-01-04 ES ES90810003T patent/ES2058867T3/en not_active Expired - Lifetime
- 1990-01-04 DK DK90810003.5T patent/DK0378509T3/en active
- 1990-01-04 EP EP90810003A patent/EP0378509B1/en not_active Expired - Lifetime
- 1990-01-04 DE DE59006801T patent/DE59006801D1/en not_active Expired - Lifetime
- 1990-01-11 KR KR1019900000281A patent/KR0135518B1/en not_active IP Right Cessation
- 1990-01-11 CA CA002007549A patent/CA2007549C/en not_active Expired - Fee Related
- 1990-01-12 JP JP00366790A patent/JP3144677B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210332280A1 (en) * | 2018-11-07 | 2021-10-28 | Dow Global Technologies Llc | Thermally conductive composition and methods and devices in which said composition is used |
| US11851603B2 (en) * | 2018-11-07 | 2023-12-26 | Dow Silicones Corporation | Thermally conductive composition and methods and devices in which said composition is used |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59006801D1 (en) | 1994-09-22 |
| DK0378509T3 (en) | 1994-09-12 |
| EP0378509A3 (en) | 1992-01-02 |
| GB8900762D0 (en) | 1989-03-08 |
| EP0378509A2 (en) | 1990-07-18 |
| JP3144677B2 (en) | 2001-03-12 |
| JPH02233685A (en) | 1990-09-17 |
| ES2058867T3 (en) | 1994-11-01 |
| EP0378509B1 (en) | 1994-08-17 |
| KR900011730A (en) | 1990-08-02 |
| CA2007549A1 (en) | 1990-07-13 |
| KR0135518B1 (en) | 1998-04-23 |
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