Schiff base metal complex compounds, and organometallic ultrathin film composed thereof and oxygen separation films composed thereof

A Schiff base metal complex compound represented by formula (I) ##STR1## wherein rings A and B each denote an o-phenylene or o-naphthylene group having at least one long-chain hydrocarbon group represented by formula --X--C.sub.n H.sub.m (14.ltoreq.n.ltoreq.22, 21.ltoreq.m.ltoreq.45) in which X denotes a binding group between --C.sub.n H.sub.m and the ring A or B, such as --O--, --COO--, --NHCO-- or --S--, PA1 R.sub.0 denotes a hydrocarbon group having not more than 6 carbon atoms, whose adjacent carbon atoms or adjacent carbon atoms via one carbon atom are bound to bonds a and b, and PA1 M denotes a metal selected from the group consisting of Fe, Co, Cu, Ni, Mn, Cr and Zn, an organometallic ultrathin film composed mainly of said compound, an oxygen separation film having a layer composed mainly of said compound and a process for producing the same.

FIELD OF THE INVENTION 
This invention relates to a novel Schiff base metal complex compound, an 
organometallic ultrathin film composed of said compound and a oxygen 
separation film composed of said compound. More specifically, it relates 
to a novel process for producing an organometallic ultrathin film. 
DESCRIPTION OF THE PRIOR ART 
An attempt has been hitherto made to synthesize compounds having an ability 
to absorb and desorb oxygen, similar to oxygen carriers in organisms that 
reversibly absorb and desorb oxygen molecules, such as hemoglobin and 
myoglobin. Porphyrin metal complexes, Co(Salen) complexes, etc. are 
examined as models for oxygen carriers of materials of separating oxygen 
from air. 
However, these conventional metal complexes have defects that (1) 
irreversible oxidative degradation via dimerization tends to occur about 
room temperature, (2) oxidative degradation tends to occur in the presence 
of a small amount of water, and (3) an oxygen absorption efficiency at 
about room temperature is poor. The defects are great problems in 
utilizing these complexes. To remedy the problems, J. P. Collman et al. J. 
Am. Chem. Soc. 1975, vol. 97, p. 1427 discloses a method wherein 
dimerization is prevented by introducing a bulky substituent into a 
compound itself as in Picket-fence porphyrin, but this is still 
unsatisfactory and its concrete usage is not yet examined. 
Meanwhile, as an attempt to utilize these metal complexes as oxygen 
carriers, a method whrein liposomes are formed by ultrasonic treatment 
using mixtures of phospholipids and haems to disperse the haemis in lipid 
films of the liposomes and develop oxygen absorbability in the aqueous 
solution is disclosed in E. Tsuchida: Biochem. Biophys. Res. Commun. vol. 
104, p. 793 (1982) and vol. 105, p. 1416 (1982). However, this method also 
inevitably causes degradation by dimerization of haems before formation of 
the liposomes; strict treatment in an oxygen-free atmosphere is needed and 
prevention of the degradation is not enough. 
In the circumstances, it has been long demanded to develop materials having 
better ability to absorb and desorb oxygen and free from degradation, and 
to produce ultrathin films that find concrete use in gas separation films 
and artificial lungs, etc. 
SUMMARY OF THE INVENTION 
A first object of this invention is to provide a material having excellent 
ability to absorb and desorb oxygen and free from degradation. 
A second object of this invention is to provide an excellent oxygen 
separation film. 
A third object of this invention is to provide an organometallic ultrathin 
film having excellent ability to absorb and desorb oxygen and free from 
degradation. 
In accordance with this invention, the first object can be achieved b a 
Schiff base metal complex compound represented by formula (I) 
##STR2## 
wherein rings A and B each denote an o-phenylene or o-naphthylene group 
having at least one long-chain hydrocarbon group represented by formula 
--X--C.sub.n H.sub.m (14.ltoreq.n.ltoreq.22, 21.ltoreq.m.ltoreq.45) in 
which X denotes a binding group between --C.sub.n H.sub.m and the ring A 
or B, such as --O--, --COO--, --NHCO-- or --S--, 
R.sub.0 denotes a hydrocarbon group having not more than 6 carbon atoms, 
whose adjacent carbon atoms or adjacent carbon atoms via one carbon atom 
are bound to bonds a and b, and 
M denotes a metal selected from the group consisting of Fe, Co, Cu, Ni, Mn, 
Cr and Zn. 
The second object can be achieved by an oxygen separation film having at 
least one layer composed mainly of said Schiff base metal complex compound 
or Schiff base metal complex units. 
The third object can be achieved by using a process which comprises 
spreading an acyclic multidentate compound represented by formula (II) 
##STR3## 
wherein rings A and B each denote an o-phenylene or o-naphthylene group 
having at least one long-chain hydrocarbon group represented by formula 
--X--C.sub.n H.sub.m (14.ltoreq.n.ltoreq.22, 21.ltoreq.m.ltoreq.45) in 
which X denotes a binding group between --C.sub.n H.sub.m and the ring A 
or B, such as --O--, --COO--, --NHCO-- or --S--, and 
R.sub.0 denotes a hydrocarbon group having not more than 6 carbon atoms, 
whose adjacent carbon atoms or adjacent carbon atoms via one carbon atom 
are bound to bonds a and b, 
on the surface of an aqueous phase; and either after or before compression, 
supplying a metallic ion from the aqueous phase to form a chelete ring 
with the metallic ion. 
The Schiff base metal complex compound of this invention is a complex of a 
central metal in low valence and a ligand of a Schiff base compound. 
The central metal of the Schiff base metal complex compound in this 
invention is a transition metal of low valence selected from the group 
consisting of iron, cobalt, copper, nickel, manganese, chromium and zinc. 
Iron and cobalt are most preferable. 
Rings A and B in formula (1) are each an o-phenylene or o-naphthylene group 
having at least one long-chain hydrocarbon group represented by formula 
--X--C.sub.n H.sub.m (14.ltoreq.n.ltoreq.22, 21.ltoreq.m.ltoreq.45) in 
which X denotes a binding group between --C.sub.n H.sub.m and the ring A 
or B, such as --O--, --COO--, --NHCO-- or --S--. --C.sub.n H.sub.m is an 
alkyl, alkenyl or alkynyl group having 14 to 22 carbon atoms. Concrete 
examples thereof are alkyl groups such as tetradecyl, pentadecyl, 
hexadecyl, heptadecyl, octadecyl, docosyl, etc., branched alkyls such as 
isostearyl, et al., and linear unsaturated hydrocarbon groups such as 
cis-9-hexadecenyl, cis-9-cis-12-octadecadienyl, octadeca-10,12-diyl, etc. 
However, these are not limitative. Preferable of these are hexadecyl, 
octadecyl, eicosyl, docosyl, trans-2-octadecenyl, cis-9-ocadecenyl, 
pentadeca-2,4-diyl, heptadeca-2,4-diyl and tricosa-10,12-diyl. 
R.sub.0 denotes a hydrocarbon group having not more than 6 carbon atoms, 
whose adjacent carbon atoms or adjacent carbon atoms via one carbon atom 
are bound to bonds a and b. Preferable is a hydrocarbon group whose carbon 
atoms are directly adjacent each other. 
Concrete examples of Ro are --CH.sub.2 CH.sub.2 --, --CH.sub.2 --CH.sub.2 
--CH.sub.2 --, --CH(CH.sub.3)CH.sub.2 --, --CH.sub.2 C(CH.sub.3).sub.2 --, 
--CH(CH.sub.3)--CH(CH.sub.3)--, --C(CH.sub.3).sub.2 C(CH.sub.3).sub.2, 
--CH(C.sub.2 H.sub.5)CH.sub.2 --, --CH(C.sub.2 H.sub.5)CH(C.sup.2 H .sub.5 
--, --CH.sub.2 C(C.sub.2 H.sub.5).sub.2 
##STR4## 
Preferable are --CH.sub.2 CH.sub.2 --, --CH.sub.2 C(CH.sub.3).sub.2 --, 
##STR5## 
The Schiff base metal complexes in this invention can be obtained by, for 
example, reacting salicylaldehyde derivatives with diamines to form Schiff 
bases and introducing metals of low valence into said Schiff bases. 
When use as an oxygen absorbent, said Schiff base metal complexes may be 
employed in powder form as such or in particulte or pellet form or in 
solution. 
The Schiff base metal complex bonding units in the oxygen separation film 
of this invention mean recurring units of a polymer resulting from a 
polymerization reaction of the Schiff the metal complex compound 
represented by formula (1). 
The oxygen separation film in this invention has at least one layer 
composed mainly of the Schiff base metal complex compound or the Schiff 
base metal complex binding units. Such layer may be formed from the Schiff 
base metal complex compound or the polymer having the Schiff base metal 
complex binding units directly by a casting method, a spin coating method, 
or a method for making a monomolecular film (e.g. a LB method). As will be 
later described, it may also be produced by making the thin film and then 
coordinating the metal or conducting the polymerization reaction. 
In this invention, other compounds than the complex compound or the complex 
binding units, which may be present to aid in layer (film) formation, are 
e.g. carboxylic acids having a long-chain alkyl, alkenyl or alkynyl group 
having 14 to B 24 carbon atoms, esters, amines, amides, ureas and 
alcohols. 
Concrete examples thereof are myristic acid, palmitic acid, stearic acid, 
arachic acid, behenic acid, petroselinic acid, oleic acid, etc., and their 
esters and amide derivatives; tetradecylamine, stearylamine, etc. and 
their amide and urea derivatives; tetradecanol, octadecanol, eicosanol, 
docosanol, etc. and their ester derivatives, and so forth. 
The proportion of these compounds is not more than 20%, preferably not more 
than 10%. 
In order to stabilize the complexes and improve the ability to absorb and 
desorb oxygen in this invention, compounds capable of coordinating with 
the complex may be added to the complex. Examples of such compounds are 
pyridine, 4-methylpyridine, 4-aminopyridine, 4-t-butylpyridine, 
4-cyanopyridine, 3,4-lutidine, quinoline, imidazole, benzimidazole, 
N-methylimidazole, dimethylformamide, dimethylsulfoxide, oxazole, thiazole 
and pyrrole. 
The complexes to which these compounds have been added may be used directly 
s an oxygen absorbent or as an oxygen separation film in layer (film) 
form. 
Particularly in the oxygen separation film of this invention, another film 
can be laminated on a film (layer) composed of said complex for 
stabilizing the complex and improving the ability to absorb and desorb 
oxygen. Such film is made of a film-forming compound capable of 
coordinating with the complex. Examples of said compound are 
4-octadecylpyridine, N-dodecylimidazole, 4-palmitoylaminopyridine, 
4-octadeclquinoline, 2- octadecylimidazole, 2-eicosyloxazole and 
2-docosylthiazole. 
A most preferable process for producing an organometallic ultrathin film or 
an oxygen separation film in this invention comprises spreading an acyclic 
multidentate compound represented by formula (II) 
##STR6## 
wherein rings A and B each denote an o-phenylene or o-naphthylene group 
having at least one long-chain hydrocarbon group represented by formula 
--X--C.sub.n H.sub.m (14.ltoreq.n.ltoreq.22, 21.ltoreq.m.ltoreq.45) in 
which X denotes a binding group between --C.sub.n H.sub.m and the ring A 
or B, such as --O--, --COO--, --NHCO-- or --S--, and 
R.sub.0 denotes a hydrocarbon group having not more than 6 carbon atoms, 
whose adjacent carbon atoms or adjacent carbon atoms via one carbon atom 
are bound to bonds a and b, on the surface of an aqueous phase, and either 
after or before compression, supplying a metallic ion from the aqueous 
phase to form a chelete ring with the metallic ion. 
Said acyclic multidentate compound is such that two or more coordination 
sites exist and a line obtained by joining the sites does not form a loop. 
A method of forming a thin film of an organic compound on the surface of 
the aqueous phase is generally known and performed by spreading a suitable 
amount of a solution of an organic compound dissolved in a volatile 
solvent substantially immiscible with the aqueous phase on the surface of 
the aqueous phase and volatilizing the solvent. In the process of this 
invention, a suitable amount of a solution of the amphiphilic acyclic 
multi-dentate compound in a volatile solvent immiscible with an aqueous 
phase is spread on the surface of the aqueous phase, and the solvent is 
then volatilized. It is at times advantageous to use a mixture of some 
organic solvents. In case the most suitable solvent for a specific acyclic 
multidentate compound is water-miscible, it can commonly be used in 
admixture with another water-immiscible solvent. 
A metallic ion may be charged in the aqueous phase either before or after 
spreading the solution of the acyclic multidentate compound, or either 
before or after compression. By supplying the metallic ion, the acyclic 
multidentate compound forms a chelate ring by a chelate reaction with the 
metallic ion to provide a rigid film. 
Examples of the metallic ion are those described as chelete-forming metals 
in e.g. "Chemistry of the Metal Chelate Compounds" b A. E. Martell and M. 
Carbin. Most preferable metallic ions are Cu, Ni, Co, Zn, Fe, Mn and Cr. 
These metallic ions can be added to the aqueous phase in varying salt 
forms. Examples of the salts are acetates, hydrochlorides, sulfates and 
phosphates. 
According to the process of this invention, a monomolecular layer of the 
chelate compound with molecules oriented substantially uniformly is formed 
on the surface of the aqueous phase. When compressed before chelating, a 
monomolecular layer of the acyclic multidentate compound is commonly 
degraded. However, the monomolecular layer made by this invention becomes 
a rigid condensed film via compression, providing a LB film. 
Since in such film-forming process the chelated compounds are aligned on 
the surface of the aqueous phase as monomolecular layers, the chelete 
surfaces are not opposite to each other, making it possible to achieve a 
great secondary effect that degradation by dimerization is preventable. 
Moreover, as the chelate compounds formed from the acyclic multidentate 
compounds have hydrophobic groups and are thus hard to crystallize, 
purification thereof is difficult. Even if said compounds can be purified, 
they are close to each other, therefore easy to dimerize and prone to 
degradation. Nevertheless, in this invention, purification may be 
conducted before chelating and is easy, and degradation does not occur 
because there is no step which easily allows dimerization as noted above. 
The organometallic ultrathin film of this invention may also be obtained by 
forming a thin film of a precursor of the Schiff base metal complex 
bonding units and then conducting polymerization. It can be achieved by 
using long-chain linear unsaturated hydrocarbon groups such as 
cis-9-hexadecenyl, cis-9-cis-12-octadecadienyl and octadeca-10,12-diyl and 
exposing to energy rays such as electron rays and ultraviolet rays. 
In the oxygen separation film of this invention, a support can be used to 
make up for lack of a self-supporting property of the Schiff base metal 
complex thin film. Examples of such support are porous supports made of 
metals, glasses, ceramics, and synthetic and natural polymers. The form 
thereof can be optionally selected from a sheet, a plate, a spiral mode, a 
tube and hollow fibers depending on the purpose. Most preferable are 
polymer porous materials such as a polyethylene porous film, a 
polypropylene porous film, a cellulose ultrafilter, a polycarbonate porous 
film, a polysulfone ultrafilter and a polyvinylidene fluoride porous film. 
Moreover, for improvement of adhesion and surface smoothness, the surfaces 
of these supports may be modified too. 
When the Schiff base metal complex afforded in this invention is contacted 
with oxygen as a powdery solid or in a solution or suspension containing 
an inert solvent such as benzene, toluene, chloroform or methylene 
chloride or a coordination solvent such as dimethylformamide, 
dimethylsulfoxide, pyridine or imidazole, it absorbs oxygen rapidly at 
room temperature and an atmospheric pressure. Oxygen absorbed can easily 
be desorbed by placing an oxygen absorbent that has absorbed oxygen under 
reduced pressure or heating it. Said complex is thus available as an 
oxygen absorbent. 
The oxygen separation film in this invention lends itself to condensation 
of oxygen from air in particular.

The following Examples illustrate this invention. However, this invention 
is not limited to said Examples. 
Example 1: Synthesis of bis(2-hydroxy-4-octadecyl-oxybenzal) 
ethylenediimine, (H.sub.2 (SO-Salen)) 
1.95 L g of 2-hydroxy-4-octadecyl-oxybenzaldehyde was dissolved in 30 ml of 
pyridine, and a solution of 0.15 g ethylenediamine in 10 ml pyridine was 
added thereto dropwise. With stirring, the mixture was heated to 
60.degree. C. and the reaction was run for 1 hour. After the mixture was 
left to cool, a precipitate was filtered, and the filtrate was washed with 
ethanol and then vacuum dried to obtain a pale yellow needle crystal. 
NMR and IR spectra of H.sub.2 (SO--Salen) are: 
______________________________________ 
NMR 0.88 ppm CH.sub.3 
1.25, 1.76, 3.83, 3.94 
CH.sub.2 
6.36, 6.40, 7.05 benzene ring 
8.18 CH 
13.61 OH 
IR 2919.sup.cm- 1 .nu..sub.C--H, as 
2850 .nu..sub.C--H, s 
1629 .nu..sub.C.dbd.N 
______________________________________ 
In MS spectrum, a molecular ion peak of M/e=804 was observed and formation 
of H.sub.2 (SO-Salen) was thus ascertained. 
Example 2: Synthesis of bis(2-hydroxy-4-octadecyl-oxybenzal)ethylenediimine 
cobalt (Co(SO-Salen)) 1.00 g of H.sub.2 (SO-Salen) was dissolved in 50 ml 
of pyridine, and a solution of 0.309 g Co(CH.sub.3 COO).sub.2.4H.sub.2 O 
in 25 ml of pyridine was added thereto dropwise. With stirring, the 
mixture was reacted for 3 hours under reflux. After pyridine was distilled 
off and the residue was evaporated to dryness, the product was dissolved 
again in chloroform and washed with water to remove an unreacted material 
and by-products. Chloroform was distilled off to afford a reddish black 
solid. 
IR spectrum and elemental analysis of the solid are: 
______________________________________ 
IR 2921.sup.cm- 1 
.nu..sub.C--H' as 
2851 .nu..sub.C--H, s 
1606 .nu..sub.C.dbd.N 
Elemental 
analysis: Co(SO-salen) 
Calc.; H:C:N:Co = 10.1:72.4:3.3:6.8 
Obs.; H:C:N:Co = 10.0:71.4:3.2:7.0 
______________________________________ 
Formation of Co(SO-Salen) was thus ascertained. 
Example 3: Synthesis of 
1,2-bis(2-hydroxy-4-octadecyloxy-benzal)phenylenediimine H.sub.2 
(SO-Salphn)) 
1.95 g of 2-hydroxy-4-octadecyl-oxybenzaldehyde was dissolved in 30 ml of 
pyridine, and a solution of 0.27 g o-phenylenediamine in 10 ml of pyridine 
was added thereto dropwise. With stirring, the mixture was heated to 
60.degree. C. and reacted for 1 hour. Pyridine was distilled off and the 
residue was evaporated to dryness. Recrystallization from ethanol gave a 
yellow branch-like crystal. 
NMR and IR spectra of the product are: 
______________________________________ 
NMR 0.87 ppm CH.sub.3 
1.25, 1.78, 3.97 CH.sub.2 
6.41, 6.51, 7.19-7.28 
benzene ring 
8.53 CH 
13.57 OH 
IR 2920.sup.cm- 1 .nu..sub.C--H, as 
2851 .nu..sub.C--H, s 
1614 .nu..sub.C.dbd.N 
______________________________________ 
Formation of H.sub.2 (SO-Salphn) was thus ascertained. 
Example 4: Synthesis of 
1,2-bis(2-hydroxy-4-octadecyloxy-benzal)phenylenediimine cobalt 
(Co(SO-Salphn)) 
The procedure in Example 2 was repeated in the same way as in Example 2 
except that 0.91 g of H.sub.2 (SO-Salphn) was used instead of 1.00 g of 
H.sub.2 (SO-Salen) and the amount of Co(CH.sub.3 COO)HD 2.4H.sub.2 O was 
changed from 0.309 g to 0.25 g. There resulted a reddish black solid of 
Co(SO-Salphn). 
Example 5: Use of Co(So-Salen) as an oxygen absorbent 
0.580 g of Co(SO-Salen) obtained in Example 2 was dissolved in 50 ml of 
pyridine, and the solution was freezed and degassed. The solution was put 
on a gas burette in a constant temperature box of 30.degree. C. and 
contacted with oxygen of an atmospheric pressure. As a result, it absorbed 
11.6 l (STP)/mol as shown in FIG. 1 attached hereto. After pyridine was 
distilled off, the residue was dissolved again in DMF, and absorption and 
desorption of oxygen were repeated. Thus, reversibility was evaluated as 
shown in FIG. 2 attached hereto. From FIG. 2, it became apparent that 
Co(SO-Salen) had excellent reversibility to absorb and desorb oxygen. 
Example 6 
0.597 g of Co(SO-Salphn) obtained in Example 4 was evacuated in solid state 
as such, and put on a gas burette in a constant temperature box of 30+ C. 
and contacted with oxygen of an atmospheric pressure. It absorbed 6.7 l 
(STP)/mol of oxygen. Subsequently, the sample was dissolved in 50 ml of 
pyridine, and oxygen absorbability was evaluated as in Example 5. As a 
result, an amount of oxygen absorbed was 3.8 l (STP)/mol. 
Example 7 
A trough fitted with a stationary barrier, a movable barrier moved by a 
drive device was filled with a cobalt acetate aqueous solution 
(5.times.10.sup.-5 mol/l) as an aqueous phase. 4.4 mg of 
bis(2-hydroxy-4-octadecyl-oxybenzal)ethylenediimine was dissolvd in 10 ml 
of chloroform, and 200 microliters of the solution was spread on the 
surface of the aqueous phase. The molecules remaining on the aqueous phase 
after evaporation of the solvent were left to stand for 30 minutes. Then 
the movable barrier was moved at a rate of 0.2 mm/S. While the 
monomolecular film was compressed, change in surface pressure to an area 
surrounded by the stationary barrier, the movable barrier and both ends of 
the trough was measured. A rising portion of a pressure shows a 
compression ratio 
##EQU1## 
and it revealed formation of a condensed film. Moreover, the film could be 
placed on a glass plate by vertically moving the glass plate across the 
film plate while maintaining the pressure at 25 mN/m. 
Comparative Example 
Area-pressure change was examined in the same way as in Example 7 except 
using pure water as an aqueous phase. 
Though the pressure once started to rise, it lowered again and degradation 
of the film occurred. This film could not be moved onto a glass substrate 
in complete form. 
Example 8 
A trough fitted with a stationary barrier, a movable barrier moved by a 
drive device and a pressure sensor to measure a surface pressure was 
filled with a cobalt acetate aqueous solution (5.times.10.sup.-5 mol/l) as 
an aqueous phase. 
4.6 mg of 1,2-bis(2-hydroxy-4-octadecyl-oxybenzal)phenylenediimine was 
dissolved in 10 ml of chloroform, and 200 microliters of the solution was 
spread on the surface of the aqueous phase. After it was left to stand for 
30 minutes, the movable barrier was moved at a rate of 0.2 mm/S. While the 
monomolecular film was compressed, change in surface pressure to an area 
surrounded by the stationary barrier, the movable barrier and both ends of 
the trough was measured. A rising portion of a pressure shows a 
compression ratio 
##EQU2## 
and it revealed formation of a condensed film. Moreover, the film could be 
placed on a glass plate by vertically moving the glass plate across the 
film while maintaining the pressure at 25 mN/m. 
Example 9 
A thin coating layer of a silicon polymer was formed on a polypropylene 
porous film ( .circle.R Celgard 2400) to afford a modified support having 
an oxygen permebility of 1.04.times.10.sup.-4 cm.sup.3 /cm.sup.2.S.CmHg, 
##EQU3## 
On this support was laminated a monomolecular film made from H.sub.2 
(SO-Salen) obtained in Example 1. 
That is, a trough fitted with a stationary barrier, a movable barrier moved 
by a drive device and a pressure sensor to measure a surface pressure was 
filled with a cobalt acetate aqueous solution (5.times.10.sup.-5 mol/l) as 
an aqueous phase. 200 micoliters of a solution of 4.4 mg H.sub.2 
(SO-Salen) in 10 ml chloroform was spread on the surface of the aqueous 
phase held at 15.degree. C. The molecules remaining on the aqueous phase 
after evaporation of the solvent were left to stand for 30 minutes. Then 
it was compressed to 25 mN/m by the movable barrier. Twenty layers of such 
film were laminated by a horizontal lifting method while keeping a 
constant pressure (25 mN/m). 
Subsequently, a thin overcoat layer of a silicon polymer was formed, and a 
gas selectivity and a gas permeability of the resulting composite film 
were evaluated. As a result, a nitrogen permeability was 
2.69.times.10.sup.-7 cm.sup.3 /cm.sup.2.S.CmHg, an oxygen permeability 
9.29.times.10.sup.-7 cm.sup.3 /cm.sup.2.S.CmHG, and a selectivity 3.5, 
respectively. 
Example 10 
11.1 g of 2,4-dihydroxybenzaldehyde was dissolved in 200 ml of isopropanol, 
and a solution of 2.4 g ethylenediamine in 200 ml of isopropanol was added 
thereto dropwise. With stirring, the mixture was reacted for 2.5 hours 
under reflux. After the reaction mixture was left to cool, 4.5 g of 
potassium hydroxide dissolved in 80 ml of methanol was added. 
Subsequently, a solution of 10 g cobalt acetate tetrahydrate in 45 ml 
water was added, and the mixture was reacted for 2.5 hours under reflux. 
After the reaction mixture was left to cool overight, the resulting 
precipitate was filtered off to obtain a blackish red needle crystal 
(Schiff base complex (I)). 
In IR spectrum of the product, absorption of C.dbd.N was observed in the 
vicinity of 1530 cm.sup.-1. Formation of Schiff base complex was thus 
ascertained. Elemental analysis of the product revealed the composition 
ratio, 
EQU C:H:N:Co=50.2:4.0:7.2:15.2 (%) 
which well corresponded to a calculated value, 
EQU C.sub.16 H.sub.14 N.sub.2 O.sub.4 Co . . . O.sub.2, 
EQU C:H:N:Co=49.4:3.6:7.2:15.1 (%). 
On the other hand, 12.0 g of 2-octadecenoyl chloride was dissolved in 100 
ml of benzene, and a solution obtained by dispersing 7.1 g of the above 
Schiff base complex in 100 ml of pyridine was added thereto dropwise. With 
stirring, the mixture was reacted for 3 hours under reflux. The reaction 
liquid was, after left to cool, washed with water, condensed and 
evaporated to dryness. In IR spectrum of the product, absorption of 
.nu.C.dbd.O was observed in the vicinity of 1735 cm.sup.-1 and absorption 
of .nu.C.dbd.C in the vicinity of 1650 cm.sup.-1. It was thus confirmed 
that an alkenyl group was introduced via an ester linkage. 
0.352 g of the thus obtained Schiff base metal complex was dissolved in 50 
ml of dimethylformamide, and the solution was freezed and degassed. The 
solution was put on a gas burette in a constant temperature box of 
30.degree. C. and contacted with oxygen of an atmospheric presure. It 
absorbed 6.2 ml of oxygen. 
Example 11 
27.6 g of 2,4-dihydroxybenzaldehyde was dissolved in 100 ml of 
dimethylformamide (DMF), and 6.0 g of ethylenediamine was added thereto 
dropwise. With stirring, the reaction was run at 120.degree. for 5 hours. 
After DMF was then distilled off at 50.degree. C. under reduced pressure, 
and unreacted substance and DMF were washed with ether and dried to obtain 
a bright yellow powder (Schiff base (I)). Elemental analysis of the 
product revealed the composition ratio, 
EQU C:H:N=63.41:5.29:9.50 (%) 
which well corresponded to a calculated value, 
EQU C.sub.16 H.sub.16 N.sub.2 O.sub.4, C:H:N:=63.98:5.38:9.33 (%). 
10.4 g of the resulting Schiff base (I) was dissolved in 
100 ml of pyridine, and a solution of 20.8 g 2-octade-cenoyl chloride in 50 
ml benzene was added dropwise with ice cooling. After the addition was 
over, stirring further continued at room temperature for 2 hours. 250 ml 
of ether was added to the reaction liquid, and washing with a Na.sub.2 
CO.sub.3 aqueous solution and water was repeated. The ether layer was 
evaporated to dryness. The resulting product was subjected to liquid 
chromatography to obtain a long-chain Schiff base ligand (II). In IR 
spectrum of the product, absorption of .sup..nu. C.dbd.O was observed in 
the vicinity of 1750 cm.sup.-1 and absorption of .sup..nu.C.dbd.C in the 
vicinity of 1660 cm.sup.-1 respectively. It was thus confirmed that an 
alkenyl group was introduced through an ester linkage. 
Example 12 
A thin coating layer of silicon polymer was formed on a polypropylene 
porous film ( .circle.R Celgard 2400) to afford a modified support having 
an oxygen permeability of 1.04.times.10.sup.-4 cm.sup.3 /cm.sup.2.S.cmHg 
##EQU4## 
On the support was laminated a monomolecular film made from the long-chain 
Schiff base ligand (II) obtained in Example 11. 
That is, a trough fitted with a stationary barrier, a movable barrier moved 
by a drive device and a pressure sensor to measure a surface pressure was 
filled with a cobalt acetate aqueous solution (4.59.times.10.sup.-1 mol/l) 
as an aqueous phase. 200 microliters of a solution of 4.6 mg long-chain 
Schiff base ligand (II) in 10 ml of chloroform was spread on the surface 
of the aqueous phase kept at 10.degree. C. The molecules remaining on the 
aqueous phase after evaporation of the solvent were left to stand for 30 
minutes. Then a film was compressed to 25 mN/m by the movable barrier, and 
20 layers of such film were laminated b a horizontal lifting method while 
keeping a constant pressure (25 mN/m. 
A gas selectivity and a gas permeabilty of the resulting composite film 
were evaluated. Consequently, a nigrogen permeability was 
2.58.times.10.sup.-6 cm.sup.3 /cm.sup.2.S.cmHg, an oxygen permeability 
9.44.times.10.sup.-6 cm.sup.3 /cm.sup.2.S.cmHg, and a selectivity 3.7 
respectively. 
Example 13 
A monomolecular film made from the long-chain Schiff base ligand (II) 
obtained in Example 11 and a monomolecular film made of 
4-octadecylpyridine were alternately laminated on the modified support 
used in Example 12. 
That is, a cobalt acetate aqueous solution (4.59.times.10.sup.-3 mol/l) was 
filled as an aqueous phase. 200 microliters of a solution of 4.6 mg 
long-chain Schiff base ligand (II) in 10 ml chloroform was spread on the 
surface of the aqueous solution held at 10.degree. C. The molecules 
remaining on the aqueous phase after evaporation of the solvent were left 
to stand for 30 minutes. Then a film was compressed to 25 mN/m. While 
maintaining a constant predsure (25 mN/m), the modified support was 
vertically dipped to penetrate the Schiff base metal complex monomolecular 
film formed on the surface of the aqueous phase. Subsequently, while the 
modified support was dipped, the film left on the surface of the aqueous 
phase was removed, and 200 microliters of a solution of 1.8 mg 
4-octadecylpyridine in 10 ml chloroform was then spread. A film was 
compressed to 20 mN/m by the compression barrier, and drawn while keeping 
a constant pressue (20 mN/m). In like manner, dipping and drawing were 
repeated, and 20 Layers of the Schiff base metal complex monomolecular 
film were alternately laminated with 20 layers of the 4-octadecylpyridine 
monomolecular film. 
A gas selectivity and a as permeability of the resulting composite film 
were evaluated. As a result, a nitrogen permeability was 
3.7.times.10.sup.-6 cm.sup.3 /cm.sup.2.S.cmHg, an oxygen permeability 
1.37.times.10.sup.-5 cm.sup.3 /cm.sup.2.S.cmHg, and a selectivity 3.7 
respectively. 
Example 14 
A trough fitted with a stationary barrier, a movable barrier moved by a 
drive device and a pressure sensor to measure a surface pressure was 
charged with a cobalt acetate aqueous soluton (4.59.times.10.sup.-3 mol/l) 
as an aqueous phase. 200 .mu.l of a solution of 4.6 mg 
bis(4-(2-octadecenoyl)sallicylaldehyde) ethylenediimine in 10 ml of 
chloroform was spread on the surface of the aqueous phase. The molecules 
remaining on the aqueous phase after evaporation of the solvent were left 
to stand for 30 minutes. Then the movable barrier was moved at a rate of 
0.2 mm/S, and while the film was compressed, change in surface pressure to 
an area surrounded by the stationary barrier, the movable barrier and both 
ends of the trough was measured. A rising portion of a pressure shows a 
compression ratio 
##EQU5## 
and it revealed formation of a condensed film. Moreover, the film could be 
placed on a glass plate by vertically moving the glass plate across the 
film while maintaining the pressure at 25 mN/m. 
When pure water was used as the aqueous phase, the pressure once started to 
rise but lowered again, causing degradation of the film. This film could 
not be moved onto the glass substrate in complete form.