Metal 4, 4', 4"",-tetracarboxylic phthalocyanines (MPTC) are prepared by reaction of trimellitic anhydride, a salt or hydroxide of the desired metal (or the metal in powdered form), urea and a catalyst. A purer form of MPTC is prepared than heretofore. These tetracarboxylic acids are then polymerized by heat to sheet polymers which have superior heat and oxidation resistance. The metal is preferably a divalent metal having an atomic radius close to 1.35A

Achar, B. N.

Fohlen, G. M.

Parker, J. A.

English

NASA Technical Reports Server

United States Patent [I91 
Achar et al. 
[54] METAL PHTHALOCYANINE 
INTERMEDIATES FOR THE PREPARATION 
O F  POLYMERS 
[75] Inventors: Bappalige N. Achar, Mysore, India; 
George M. Fohlen, Millbrae; John A. 
Parker, Los Altos, both of Calif. 
[73] Assignee: The United States of America as 
represented by the United States 
National Aeronautics and Space 
Administration, Washington, D.C. 
[21] Appl. No.: 514,117 
[22] Filed: Sep. 15, 1983 
Related U.S. Application Data 
[62] Division of Ser. No. 415,880, Sep. 8, 1982, Pat. No. 
4,456,268. 
[51] Int. CI.3 ............................................ C07D 487/22 
[52] U.S. C1. ............................ 260/245.75; 260/245.9; 
528/327 
[58] Field of Search ......................... 260/245.75, 245.9 
[11] Patent Number: 4,522,755 
[45] Date of Patent: Jun. 11, 1985 
[561 References Cited 
FOREIGN PATENT DOCUMENTS 
57-25361 2/1982 Japan ................................ 260/245.9 
OTHER PUBLICATIONS 
Moser et al., "Phthalocyanine Compounds", (Rein- 
Primary Examiner-Robert T. Bond 
Attorney, Agent, or Firm-Darrell G. Brekke; John R. 
Manning; Robert D. Marchant 
1571 ABSTRACT 
Metal 4, 4', 4", 4"-tetracarboxySic phthalocyanines 
(MPTC) are prepared by reaction of trimellitic anhy- 
dride, a salt o r  hydroxide of the desired metal (or the 
metal in powdered form), urea and a catalyst. A purer 
form of MPTC is prepared than heretofore. These tetra- 
carboxylic acids are then polymerized by heat to sheet 
polymers which have superior heat and oxidation resis- 
tance. The metal is preferablyoa divalent metal having 
an atomic radius close to 1.35A. 
. 
hold), (1963), pp. 104-141. 
5 Claims, 3 Drawing Figures 
https://ntrs.nasa.gov/search.jsp?R=19860009984 2020-03-23T06:53:47+00:00Z
U.S. Patent Jun. 11,  1985 Sheet 1 of 3 4,522,755 
HOOC 
COOH 
\ 
COOH 
us. Patent Jun. 11,  
I 
1985 Sheet 2 of 3 4,522,755 
M=Cu, Co,Ni, ... 
FIG 2 
U.S. Patent Jun. 11, 1985 Sheet 3 of 3 4,522,755 
W 
I 
I- 
s a 
a 
I 
I- 
I 
*L  a w  
(3I 
I-rn 
I I I I I I I I 1 
O O R %  - d - m  O O g e  
SSOl lH913M % 
3 
? 
3 -  
3 
N 
3 
1 
0 0  0 
W o ,  0 
4,522,755 
1 2 
separation and purification, is polymerized by heat in a 
vacuum or in an atmosphere of an inert gas such as 
nitrogen. The MPTC prepared by this method is purer 
than MPTC's prepared heretofore and the polymer 
5 derived from it is free of impurities which detract from 
its 
DESCRIPTION OF THE DRAWINGS 
METAL PHTHALOCYANINE INTERMEDIATES 
FOR THE PREPARATION OF POLYMERS 
ORIGIN OF T H E  INVENTION 
The invention described herein was made in the per- 
formance of work under a NASA contract and is sub- 
ject to the provisions of Section 305 of the National 
Aeronautics and Space Act of 1958, Public Law 85-568 
(72 Stat. 435; 42 U.S.C. 2457). 
This is a division of application Ser. No. 415,880 filed 
Sept. 8, 1982, now U S .  Pat. No. 4,456,268, granted May 
22, 1984. 
Properties. 
FIG. 1 iS a structural formula of the metal 4,4',4",4"'- 
10 tetracarboxy phthalocyanine which is to be polymerized. 
FIG. 2 is a structural formula of the resulting poly- 
FIG. 3 is a graph showing T G A  and DTG curves for 
mer. 
these polymers, including the polymer of FIG. 2. 
1 5  FIELD O F  THE INVENTION _ _  
This invention relates to metal phthalocyanine tetra- 
carboxylic acids, to a novel method of synthesizing the 
same and to polymers of the same. 
DETAILED DESCRIPTIQN OF THE 
INVENTION 
EXAMPLE 1 
tetracarboxylic acid 1 
BACKGROUND OF T H E  INVENTION 20 Preparation of Copper (11) phthalocyanine 
In recent years there has been an increasing demand 
in industry and defense for polymeric substances which 
would either remain intact or continue to serve in a 
more or less degraded state under conditions where 
temperatures far above the ordinary are encountered. In 25 
many cases highly cross-linked organic polymers have 
been found promising. The phthalocyanine structure is 
one of the most thermally stable organic structures 
known. Attractive properties like resistance to chemical 
attack, electrical properties, catalytic activity and mod- 30 
erate cost of manufacture with good coloring properties 
have made phthalocyanines the object of intensive 
world-wide investigations. Many attempts to synthesize 
polymers based on phthalocyanines have failed to pro- 
vide the expected thermal stability. Phthalocyanine 35 
polymers so far produced have shown less thermal 
stability than the phthalocyanine monomer itself be- 
cause of the presence of impurities, weak chemical 
bonds and low degree of polymerization with structural 
inhomogeneity. Impurities have the considerable effect 40 
of decreasing thermal stability of the phthalocyanine 
monomers as well as the polymers produced from them. 
It IS well known that the way in which the repeating 
units are linked is reflected in the properties of the poly- 
mers. If the repeating phthalocyanine mer units are 45 
linked in the way phenyl groups are linked in biphenyl, 
the conjugation extends throughout the macromolecule 
This compound has the formula 
HOOC 
HOOC 
COOH 
wherein is 'OWer (I1). 
It was prepared as follOws: 12.0 g "PIJer ('1 "Ifate 
thereby increasing the extent of delocalization of the 
r-electrons. This is expected to increase the conductiv- 
pentahydrate, 33.8 g trimellitic anhydride, 4.5 g ammo- 
nium and 6o g 0.5 g ammonium 
ity as well as the thermal stability of the phthalocyanine 50 
polymers. 
were ground together and placed in a 500 m1 
three-necked flask containing 25 rnl of nitrobenzene. 
The flask was provided with a thermometer, condenser 
and a mechanical stirrer. The temperature of the flask 
Objects of the invention include methods of prepar- was slowly increased to 180" C. and maintained at 185" 
ing metal phthalocyanine monomers in a pure state and 55 c. for four hours. The color of the reaction mixture 
the preparation from such monomers of thermally sta- gradually deepened and finally a deep colored solid was 
ble sheet polymers which have biphenyl type linkages obtained. The Product Was ground Well and Washed 
between the mer units, high thermal and thermal oxida- with methanol until it was free from nitrobenzene. The 
tive stability and electrical conductivity, also good solid product was added to 500 ml of 1.ON hydrochloric 
flame and fire resistance. 60 acid saturated with sodium chloride, boiled briefly, 
cooled to room temperature and filtered. The resulting 
solid material was treated with 500 ml of 2.ON sodium 
OBJECTS O F  T H E  INVENTION 
OF THE INVENTION 
A metal phthalocyanine tetracarboxylic acid hydroxide containing 200 g sodium chloride and heated 
(MPTC) is prepared in pure form by reaction of trimel- at 90" C. until the evolution of ammonia ceased. The 
litic anhydride with urea and a soluble metal salt in the 65 solution after filtration was treated with 500 ml 2.ON 
presence of a suitable catalyst and in a suitable solvent. hydrochloric acid and the product was separated by 
The metal is that which it is desired to introduce into centrifugation. The residue was redissolved in 0.1N 
the intended metal complex. The resulting MPTC, after sodium hydroxide and filtered to separate the insoluble 
4,522,755 
3 4 
materials. The compound was re-precipitated with 1.ON 
hydrochloric acid and centrifuged to obtain the solid 
material. Dissolution and precipitation steps were re- 
peated twice. Then the compound was washed until 
blue product was dried at 100" in vacuum. 
Compound C36H16NsOgCu. (CuPTC): Calcd: c, 
57.5; H, 2.14; N, 14.9; Cu, 8.45; Eq. wt. 188.0. Found: C, 
chloride free and finally washed with methanol. The 5 HOOC 
II 
0 
(which provides the benzenoid rings), urea and possibly 
57.1; H, 2'3; Nl 15'O; cu7 8'5; Eq' wt. 187'6' IR absorp- 1o also the ammonium chloride. The ammonium &loride 
tion bands (cm-l): 3500-2500 (broad), 1691 (broad), may be used alone as the catalyst but the use of ammo- 
1614m' 1578m' 1508m' 1329m' 1279m' 1246m (broad)' 
774w, 736s. 
nium molybdate as well allows the reaction to proceed 
Nitrobenzene is an advantageous solvent because, 
15 besides being unreactive and being a good solvent for 
the reactants, it has a high boiling point (210" C.). Other 
aprotic solvents such as quinoline and tetralin may be 
used. Yields of 90% or 
may be removed from the molecule as 
20 by dissolving it in concentrated sulfuric acid to produce 
1188m, 1149m, 1 0 8 9 ~  1050~7  9 6 8 ~ 7  9 4 0 ~ 9  8 5 1 ~ 7  8 3 ~ 9  at a lower temperature and increases the yield. 
EXAMPLES 2 A N D  3 
were prepared 
by the same method using in Example 2 cobalt sulfate 
and in Example 3 nickel sulfate. The empirical formulae 
and analytical results obtained were as follows: 
Example 2 (Cobalt) 
Compound C36H16NsOsC0, (CoPTC): Calcd: C, 
57.8; H, 2.15; N, 15.0; Co, 7.88; Eq. wt. 186.9. Found: C, 
57.5; H, 2.2; N, 15.2; Co, 7.90; Eq. wt. 186.7. IR absorp- 
tion bands (cm-I): 3500-2500 (broad), 1696 (broad), 
1613m, 1586m, 1521m, 1330m, 1281m, 1246m, (broad), 
1189m, 1149m, 1090s, 1050w, 9730w, 944w, 848w, 
782w, 773w, 742s. 
Example 3 (Nickel) 
The and Of 
are obtainable. 
The metal 
25 
30 
the hydrogen (protonated) species in which each of the 
two covalent bonds is connected to hydrogen. The 
protonated species may then be treated with an alco- 
holic solution of a metal salt, e.g., copper sulfate, to 
insert the metal, e.g., Cu(I1). In this way one metal may 
be substituted for another. However, it is preferred to 
choose the desired metal initially and to insert it in the 
phthalocyanine molecule in the synthesis of the tetra- 
carboxylic acid. 
EXAMPLE 4 
Compound C36H16NsO~Ni, (NiPTC): Calcd: C, 
57.86; H, 2.15; N, 15.0; Ni, 7.86; Eq. wt. 186.8. Found: 
absorption bands (cm-l) 3500-2500 (broad), 1699 35 acid was finely ground in a small vibrating ball mill and 
848w, 779w, 738s. dense volatile products, stopcocks to connect gas col- 
may be lection tube and IR cell for gaseous analysis. The appa- 
used in place of divalent copper, cobalt and nickel, e.g., 4~ ratus was connected to vacuum system. Reaction tube 
Cu(I), cobalt and nickel in other valence states, Fe(II), was evacuated to 10-5-10-6 torr pressure and 
Fe(III), Zn,Al, lead, tin, palladium, germanium, vana- heated to 4500 The gaseous and products 
dium, and molybdenum in various valence were condensed in separate traps using liquid nitrogen. 
states; monovalent metals such as ~ i ,  Na and K, etc. The reaction was found to be completed after one hour 
Where the metal is monovalent two atoms will be pres- 45 Of heating at 450" c. in 
ent, one atom above and the other atom below the plane EXAMPLE 5 
of the phthalocyanine molecule. With a trivalent metal 
Polymerization of MPTC-Method 2 such as aluminum, one of the valences may be satisfied 
by a ligand such as C1, F, acetate, etc., e.g., the metallic Finely ground metal phthalocyanine tetracarboxylic 
compound can be represented as M' where M' is the 50 acid was taken in a reaction tube fitted with a glass 
metal atom and X is an inorganic atom or radical or an enclosed iron-constantan thermocouple and inlet and 
organic group. outlet tubes. The polymerization tube was carefully 
Preferably the met51 is divalent and has an atomic purged with nitrogen by repeated evacuation and refill- 
radius close to 1.35 A. Metals of substantially larger ing. Then it was gradually heated to 450" C. in a current 
atomic radius may not fit well into the molecule and 55 of nitrogen and maintained temperature of 450"-500" C. 
metals having a substantially smaller atomic radius are in a current of nitrogen for one hour. 
more likely to be extracted by strong acids, e.g., con- Methods 1 and 2 were applied to produce the divalent 
centrated sulfuric acid. Metals having ligands may be copper, cobalt and nickel compounds. Analytical re- 
susceptible to hydrolytic action. sults were the same for products of the two methods 
may be used provided the counter ion is compatible (1) Compound C32H12NsCu: Calcd: C, 67.18; H, 2.1 1; 
with the reactants and the reaction product. For exam- N, 19.58; Cu, 11.2. Found: C, 66.9; H, 2.21; N, 19.8; Cu, 
ple, the metal M may be used in the form of its sulfate, 11.5. IR absorption bands (cm-1): 1610w, 1503w, 
chloride, nitrate, acetate, oxalate, etc. Also, it may be 1407w, 1328m, 1271m, 1164m, 1118w, 1089m, 1065m, 
used in the form of a finely divided metallic powder. 65 898w, 773w, 754w, 738s. 
Preferably the reactants are used in approximately stoi- (2) Compound C32H12NsCo: Calcd: C, 67.73; H, 2.13; 
chiometric proportions. The reactants are trimellitic N, 19.75; Co, 10.39. Found: c ,  67.6; H, 2.3; N, 19.95; Co, 
anhydride 10.46. IR absorptlon bands (cm-1): 1599w, 1502w, 
Polymerization of MPTC-Method 1 
C, 57.91; H, 2.2; N, 15.05; Ni, 7.88; Eq. wt. 186.6. IR 
(broad), 1615m, 1590m, 1530m, 1333m, 1274m, 1238m 
(broad), 1189m, 1150m, 1089s, 105Ow, 976w, 944w, 
About g of metal phthalocyanine tetracarboxylic 
placed in a polymerization tube. The tube was con- 
nected to an apparatus provided with a tube to con- 
Any mono-, di- or higher valency metal 
Any soluble salt or hydroxide of the selected metal 60 and were as follows: 
5 
4,522,755 
6 
1408w, 1329m, 1292m, 1115w, 1090m, 1060w, 940w, These polymers are soluble in concentrated (98%) 
(3) Compound C32H12NsNi: Calcd: C, 67.76; H, 2.13; chlorosulfuric acid and trimethyl sulfonic acid. They 
N, 19.75; Ni, 10.35. Found: C, 67.8; H, 2.18; N, 19.92; have high thermal resistance and have a higher electri- 
Ni, 10.43. IR absorption bands (cm-I): 1602w, 1519w, 5 cal conductivity (as well as a higher thermal oxidative 
1409w, 1334m, 1287m, 1157m, 11 15w, 1086m, 1053w, resistance) than the phthalocyanine monomers. Thresh- 
944w, 914w, 782w, 745w, 743m. old temperatures at which major decomposition occurs 
The polymerization reaction proceeds by way of the are typically higher than 450" C. in air; they have a high 
elimination of carboxyl groups and the formation of a char yield in nitrogen and in nitrogen atmosphere no 
sheet polymer in which the mer units are linked by 10 catastrophic decomposition has been observed up to 
biphenyl linkage. The formula of the polymer may be 1000" C. Char yields at 800" C. in nitrogen and electric 
expressed as follows: conductivities are given in Table I. 
- 902w, 785w, 740w, 741s. sulfuric acid, concentrated (36%) hydrochloric acid, 
M = Cu, Co, Ni, . . . 
4,522,755 
7 8 
sentially of trimellitic anhydride, a source of metal 
selected from finely divided powders and salts of said 
metal, and urea in the presence of a catalyst compris- 
POLYMER PDTmor "C. (800' C.) (0-cm) ing ammonium chloride and ammonium molybdate in 
CuPc-Sheet 760 90.5% 3.2 X 10-lo-3.8 X 5 a nitrobenzene reaction medium, and 
Polymer b. recovering the desired metal 4,4',4'',4"'-tetracarboxy- 
CoPC-Sheet 860 89.0% 1.8 x 10-8-2.3 x lic phthalocyanine from the reaction mixture by, 
b.1. washing the reaction mixture with methanol to Po 1 y m e r NiPc-Sheet 890 93.0% 1.4 X 10-8-3.9 X lop5 
Polymer give a washed product, 
b.2. boiling the washed product in aqueous mineral 
acid to give an acid-wash product, 
b.3. treating the acid wash product with inorganic 
hydroxide at elevated temperature until ammonia 
TABLE 1 
CHAR CONDUCTIVITY 
YIELD (22-300' C.) 
lo 
In FIG. 3 of the drawing the results plotted are for 
Cu, Co and Ni sheet polymers heated in an atmosphere 
of nitrogen. The ordinate scale on the left represents 
percent decomposition and the ordinate scale on the 15 
polymers did not undergo substantial decomposition 
below 750" C. to 800" C. (See curves at top.) The rate of 
decomposition (lower set of curves) did not become 
substantial until about 750" to 900" C. 
It will be apparent that purer metal phthalocyanine 
tetracarboxylic acids are provided, that a new and use- 
ful method of preparing them has been provided and 
that new and useful polymers and methods of producing 
them have been provided. 
and a product 
right represents rate of weight loss. As will be Seen the b.4. precipitating the desired metal 4,4',4"@"-tet- 
racarboxylic phthalocyanine as a solid from the 
soluble product, and 
b.5. isolating and washing the solid metal 4,4',4",4"'- 
tetracarboxylic phthalocyanine with methanol and 
drying. 
2. The method of claim 1 wherein the metal is a diva- 
2o 
lent ?eta1 having an atomic radius of approximately 
1.35 A. 
3. The method of claim 2 wherein the metal is copper 
It is claimed: and the source of metal is a copper salt. 
1. A method of preparing an isolated metal 4. The method of claim 2 wherein the metal is nickel 
4,4',4",4"'-tetracarboxylic phthalocyanine which com- and the source of metal is a nickel salt. 
prises 5. The method of claim 2 wherein the metal is cobalt 
a. heating at about 185" C. for about four hours a reac- 30 and the source of metal is a cobalt salt. 
25 
tion mixture comprising an anhydride consisting es- * * * * *  
35 
40 
45 
50 
55 
60 
65 
UNITED STATES PATENT OFFICE 
CERTIFICATE OF CORRECTION 
1nventor-s) B . N .  Achar,  G.M. Fohlen  and J . A .  P a r k e r  
It i s  certified that  error appears i n  the above-identif ied patent 
and that  s a i d  Letters Patent are hereby corrected as shown below: 
F i r s t  page, l i n e  [ 2 2  I, change "Sep. 15 ,  1983" to 
First page, l i n e  [62], change " P a t .  No. 4,456,268" 
--July 1 5 ,  1983--. 
t o  - - P a t .  No. 4,450,268--. 
Column 1, l i n e  1 2 ,  d e l e t e  "4,456,268" and i n s e r t  
-- 4,450,268--.  
4igned and 5 e a l e d  this 
Firsf Day o f  Ocrober 1985 
[SEAL] 
Attest: 
Attesting Officer 
DONALD 1. QUI= 
Commissioner of Patents a d  
Trademerks-&sigmte 


Metal phthalocyanine intermediates for the preparation of polymers

Abstract

Similar works

Full text

Available Versions

NASA Technical Reports Server