Polymer compositions

Thermosetting, thermoplastic or elastomeric polymer compositions having and exhibiting conductive properties comprising from about 0.00005 to 20% by weight of a crystalline compound selected from substituted or unsubstituted aquocyanophthalocyaninatocobalt cyanide and aquocyanophthalocyaninatoiron(III).

The present invention relates to thermosetting, thermoplastic or 
elastomeric polymer compositions, comprising certain organic additives, 
which can impart electrical conductivity to the polymers or which can be 
applied as pigments or as nucleating agents. 
Polymer compositions that are electrically conductive can be produced by 
incorporating conductive organic metallomacrocyclic compounds into the 
polymer matrix. Known metallomacrocyclic conductors can be divided into 
two main groups: compounds that have enhanced conductivity because of 
doping with halogen atoms, such as iodine and compounds that are 
intrinsically conductive without doping. In the literature, conductors of 
the latter group are consistently referred to as being polymers by nature, 
they comprise a series of macrocycle structures, for example 
phthalocyanine structures, in substantially parallel arrangement. It is 
believed that delocalization of pi-electrons along the polymer axis, via 
suitable bridging ligands such as cyano groups, would impart adequate 
conductivity levels as a result of which there is no need for subsequent 
doping. 
The present invention is based upon the finding of certain novel 
metallomacrocyclic compounds which are intrinsically conductive and which 
are non-polymeric by nature. These compounds can be produced in 
microcrystalline form and they can easily be incorporated into polymer 
matrices by conventional techniques such as dry powder blending or by 
dispersing the microcrystalline particles into a liquid matrix such as a 
liquid curable epoxy resin component. In lower concentrations, the novel 
compounds can be applied as nucleating agents or pigments. 
The polymer compositions of this invention comprise thermosetting, 
thermoplastic or elastomeric polymers and from 0.00005 to 20% by weight 
and preferably from 0.005 to 5% by weight of a crystalline compound 
selected from substituted and unsubstituted 
aquocyanophthalocyaninatocobalt(III) and 
aquocyanophthalocyaninatoiron(III). The preferred compounds are those 
available as flat microcrystallites measuring from 30.times.30 to 
200.times.200 nm and having a thickness of from 5 to 30, preferably from 
10 to 25 nm. 
The novel compositions of this invention can be further processed using 
known art techniques such as fiber spinning, compression molding, 
injection molding, extrusion, co-extrusion laminating, blow-molding, solid 
phase pressure forming, vacuum forming, deep drawing, powder coating, 
solution coating, casting, prepregging and the like. The final articles of 
manufacture include fibers, monofilaments, yarns, coatings, pipes, tubes, 
tires, films, sheetings, non-woven fabrics, various moldings, castings and 
laminates. Antistatic or static control film made from thermoplastic 
polymers or antistatic or static control floorings or coatings produced 
from thermosetting polymer matrices are also very attractive. 
The polymers suitable for the practice of this invention include random and 
block copolymers of styrene and various dienes, homopolymers such as 
polybutadiene, polyisoprene, neoprene, polyisobutene, polybutene-1, 
polyethylene, polypropylene, polyesters, such as PET or PBT, epoxy resins, 
polyurethane resin, (both thermosetting and elastomeric), 
polyvinylchloride, polyacrylate, polycarbonate, polysulfone, 
polyphenyleneoxide, polyester, polyaramide, cellulosetriacetate, 
polyamides, polyvinyl alcohol, copolymers of ethylene and carbon monoxide, 
terpolymers of ethylene, propylene and carbon monoxide, polystyrene, 
expanded polystyrene, polymethacrylate and polyvinylacetate. Preferred 
polymers are polypropylene, polyethylene, polyaramides, ethylene/CO 
copolymers, ethylene/propylene block copolymers, ethylene/propylene random 
copolymers, expandable polystyrene, epoxy resins, and thermoplastic 
elastomers selected from styrene/butadiene copolymers, whether or not 
hydrogenated and whether or not functionalized. 
The crystalline compounds that are employed in the compositions of this 
invention are novel compounds. Proof of the novelty of these compounds can 
be illustrated by a proper determination of their crystal structures and 
by analyzing various interatomic distances which lead to the interatomic 
distances between the successive parallel stacked macrocyclic structures 
being significantly more than twice the largest distance possible in sigma 
bonds or coordinate bonds. Hence the cyano group does not function as a 
bridging ligand positioned in between and linking successive cobalt atoms 
and consequently, the crystalline compounds are not polymeric by nature. 
The dimensions of the unit cell are given in terms of a, b, and c, which 
represent the angles of the cells. Techniques and/or methods for measuring 
these angles are kown in the art, particularly in the existing inorganic 
chemistry references. 
The dimensions of the unit cell of compounds that are preferred in this 
invention are a=0.73 nm.+-.0.03, b=2.5 nm.+-.0.1, c=0.72 nm.+-.0.03 and 
angle beta is 103.degree..+-.2; angles alpha and gamma each being 
90.degree..+-.2.degree. . The interatomic distances (in nm) that are 
preferred in this invention range from 0.19+0.06 to 0.19-0.06 for Co-C 
(from CN) and for Fe-C (from CN) and from 0.23+0.05 to 0.23-0.05 for Co-O 
(from OH.sub.2) and for Fe-O (from OH.sub.2), the cyanide group being 
structurally positioned in between two parallel macrocyclic structures. 
Similarly, the water molecule (OH.sub.2) is positioned in between two 
parallel macrocyclic structures. 
Further detailed information on the crystalline structures as well as the 
methods of analysis are disclosed in the examples herein. 
In so far as the novel crystalline compounds of this invention are cobalt 
compounds they can be prepared by prolonged heating in boiling water of an 
alkali metal salt comprising hydroxy or alkoxy phthalocyaninato cobalt 
cyanide (PcCoCN.X) as monovalent anion, provided the heating is effected 
under exclusion of oxygen or air, e.g. under nitrogen blanket and provided 
the alkali metal salt, subjected to heating, is of at least 95% purity. 
The latter proviso means that when the alkali metal salt is produced by 
converting a precursor, such conversion should be continued to at least 
85% conversion. In said compound PcCoCN.X the ligand X stands for a 
hydroxy or alkoxy group. 
A suitable illustration of such conversion is a two-step process of which 
the first step comprises the reaction of alpha or beta phthalocyanine 
cobalt with sodium cyanide in ethanol/water mixture while bubbling through 
oxygen to produce an intermediate compound (most probably the sodium salt 
of phthalocyaninato cobalt in which the cobalt atom is linked to two cyano 
ligands ([PcCoCN.sub.2 ].sup.- Na.sup.+) and the second step comprises 
CN.rarw..fwdarw. OH and/or CN.rarw..fwdarw. OEt ligand exchange by 
prolonged washing of the intermediate product with a mixture of ethanol 
and water. The two steps together should then be effected to obtain at 
least 85% conversion. The ratio of --OH to --OEt ligands in the compound 
PcCoCN.X is substantially governed by the molar ratio of water to ethanol 
in the washing liquid. 
Similarly, obtaining the novel aquocyanophthalocyaninatoiron(III) 
crystalline compound is very much a matter of emphasizing the maintenance 
of very high standards in excluding impurities during their synthesis. 
Suitably, in a first reaction step phthalocyaninato iron(III) chloride is 
converted into the sodium or potassium salt of phthalocyaninato iron(III) 
in which the iron atom is linked to a cyano ligand by refluxing in a 
mixture of ethanol and sodium or potassium cyanide for about 30 minutes. 
It is essential that this reaction step proceed under complete exclusion 
of air or oxygen, otherwise the envisaged iron(III) compounds cannot be 
obtained in a high yield but instead thereof one obtains a mixture of a 
minor amount of iron(III) and a major amount of iron(II) compounds. 
Subsequent washing of the reaction product with water, filtration and 
further storage of the compound must likewise be done under rigorous 
exclusion of oxygen or air. The invention is however not restricted to 
compounds that are essentially iron(III) compounds, iron(II) compounds of 
up to 50 wt. % may also be present in the envisaged conductive compounds. 
The resulting iron(III) compound is converted into the conductive 
crystalline compound by suspending in deoxygenated, demineralized water 
and heating at 80 .degree. C. under complete exclusion of oxygen or air 
for 5 to 20 hours. Once again, subsequent filtration and storage of the 
resulting crystalline compound should be done under rigorous exclusion of 
oxygen or air. 
While the invention has been primarily described by reference to 
unsubstituted phthalocyanine compounds, substituted derivatives may also 
be employed. Suitable substituents on the phenyl rings in the macrocyclic 
structure are halogen, lower alkyl, such as methyl, ethyl, isopropyl, 
n-butyl or isopentyl groups, amine, amide, nitro,sulfonic acid, cyano, 
alkoxy, phenoxy, hydroxyl or carboxyl groups. With large substituents 
there will be a marked increase in the b dimension of the unit cell but 
the distance between the parallel macrocyclic structures will hardly be 
affected. Preferred substituents are small atoms or ligands which do not 
substantially affect the essential features of the crystalline structure.

The invention is further illustrated by the following non-limiting 
examples. 
EXAMPLE 1 
242 g beta phthalocyanine cobalt, 2510 g ethanol, 125.2 g NaCN and 175 g 
demineralized water w.RTM.re introduced into a 3 litre glass reactor 
vessel. The mixture was heated in air at 70.degree. to 72.degree. C. for 
72 hours. After cooling, solid reaction product was isolated by filtration 
and the product was washed with a mixture of 1351 g demineralized water 
and 151.3 g ethanol. After drying the reaction product in vacuum for 24 
hours it was found that the product was [PcCO(CN)(OH)].sup.-Na.sup.+. 
Conversion was 98%. In the wet product some of the --OH ligands will have 
been replaced by --OEt (ethoxy) ligands. 
EXAMPLE 2 
347 g of the wet product produced in Example 1 were suspended in a 3L 
deoxygenated, demineralized water in a 5L glass reactor. The stirred 
suspension was heated under nitrogen blanket for 72 hours at 98.degree. C. 
Upon filtration and washing with water and drying (under nitrogen), 276.8 
g of intrinsically conductive compound was obtained (conversion more than 
95%). The product was dried for three days in vacuum at 80.degree. C. The 
powder conductivity of the compound was 1.3.10-3 sigma.sup.-1.cm.sup.-1 
(two steel electrodes, 5 t pressure). 
EXAMPLE 3 
Upon thermal analysis (heating to 1000.degree. C.) it was found that the 
compound contained 1 mol water per mol. Elemental analysis of the compound 
corresponds with the formula PcCo(OH.sub.2)(CN). 
From the XRD pattern (Daresbury synchrotron, wavelength 0.10474 nm) one 
finds via peak finding, and TREOR autoindexing (J. of Applied 
Crystallography (1988) 21, p.305-310) the dimensions of the unit cell. The 
density of 1.6.times.10.sup.3 g/l measured with a pycnometer, and the 
molecular weight unit were used as input for the autoindexing program to 
eliminate solutions with a calculated specific weight not equal to 
1.6+/-0.2.times.10.sup.3 g/l (one unit cell may contain n [n=1,2,3 . . .} 
formula units). The unit cell dimensions found are (in nm): a=0.73; 
b=2.49; c=0.72, all +/-0.02; angles alpha, gamma: 90 degree; beta: 102.6 
degree +/-0.2 degree. From these dimensions and from the density data it 
follows that the unit cell holds two molecules of PcCo(OH.sub.2)(CN). 
FT-IR: mCN=2156 cm.sup.-1. Electron microscopy shows the presence of 
square, flat ("book-shaped") crystallites measuring 50.times.50.times.15 
nm on average. 
Table I lists the most important values of the observed XRD reflections, 
the diffractogram is shown in FIG. I. 
TABLE I 
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2-theta 
d (nm) 
______________________________________ 
1 4.852 1.237 
2 8.825 0.681 
3 9.714 0.619 
4 10.601 0.567 
5 11.301 0.531 
6 11.665 0.515 
7 14.593 0.412 
8 17.189 0.350 
9 17.362 0.347 
10 19.137 0.315 
11 19.907 0.303 
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FIG. III gives further details of the configuration, the marked interatomic 
distances are given in nm. The latter are determined by crystallographic 
modelling using CERIUS Software and subsequent Rietveld refinement. The 
structure of the phthalocyanine plate was taken from the literature and 
handled as a rigid plate during this procedure. A selection of possible 
monoclinic space-groups was made based on the systematic absence of lines 
in the diffraction pattern. A further reduction of the number of 
space-groups was realised by crystallographic modelling with the criterion 
that a space-filling structure should result. From the remaining 
space-groups, P21 was selected as the space-group by crystallographic 
modelling and comparison of the simultaneously calculated diffraction 
pattern with the measured pattern. After determination of the space-group 
a global position of the phthalocyanic plate was found by shifting this 
plate in the cell until a close fit was found between the measured 
diffraction intensities and the simulated ones. This position was used as 
a starting point for Rietveld refinement using the combined XRD and 
neutron diffraction analysis (NDA), with wavelengths 0.104074 (XRD) and 
0.257167 nm (NDA). The positions of O and CN were found in the difference 
Fourier map during the refinement procedure. Sometimes, soft constrained 
distance values of from Co-O 0.234 nm to Co-C (from CN) 0.196 nm were 
employed. In FIG. III the drawn horizontal lines mark the positions of the 
parallel, flat phthalocyanine ring structures. The positions of the CN 
group and of the water molecule are marked as well together with all 
relevant interatomic distances. It follows that the CN group is not a 
bridging ligand linking two successive cobalt atoms of the macrocycles. 
Thus, the novel intrinsic conductor of this invention is not a polymer but 
a non-ionic compound. The short Co-O and Co-C (from CN) distances found 
are in agreement with the presence of a chemical bond, there is no bond 
linking N (from CN) to O or H (from OH.sub.2). 
The arrangement of molecules to form a "layered" crystalline lattice is 
shown in the schematic drawings of FIG. II, which represent a crystallite 
with the lateral faces seen in directions A and B. In FIG. IIA the 
horizontal drawn lines mark the positions of the parallel stacked 
phthalocyanine macrocycles, the downwardly extending dotted lines are the 
hypothetical "axis" passing through the sequence of Co-atoms. The 
positions of the CN-groups and the water molecules are not shown, but 
those will be clear from FIG. III. In the layer shown in FIG. IIA, there 
are series of alternating, parallel "axis" which are arranged such that 
the macrocycles in one series are positioned halfway between the positions 
of the macrocycles in the other series. These staggered positions each 
show a significant overlap such that phenylene nuclei of the successive 
phthalocyanine structures are aligned: one is stacked above another, and 
so on. FIG. IIA shows the layer of the crystal lattice forming the lateral 
face seen in direction A. The structure of the subsequent parallel layers 
positioned behind the first layer appears schematically from FIG. IIB (the 
lateral face semi-direction "B") which also marks the angles formed 
between the downwardly extending "axis" and the planes of the macrocyclic 
structures. As shown in FIG. IIB these angles alternate in the series of 
layers, they are either positive or negative in respect of the "axis". 
Unlike the overlapping of the staggered macrocyclic adjacent structures 
within the first layer as shown in FIG. A, there is no such overlap 
between the first and second layer, nor between the second and third 
layer, etc. as shown in FIG. IIB. This is due to the very dense packing in 
all layers that run parallel to the first layer shown in FIG. IIA, this 
dense packing leaves no room for overlapping of phthalocyanine macrocycles 
other than within each layer. For the rest, the arrangement of the 
structures in the second layer is analogous to that in the first layer. 
The third layer is a blueprint copy of the first layer and so continues 
the series of layers in an alternating manner. 
EXAMPLE 4 
10 g phthalocyaninato iron(III) chloride was reacted with 4 g sodium 
cyanide in 500 ml ethanol in a 2L glass reactor under nitrogen blanket at 
a temperature of 72.degree. C. for 30 minutes. Upon filtration, washing 
under nitrogen with deoxygenated, demineralized water and drying in vacuum 
for 24 hours a compound represented by the formula [PcFe(CN)(OH)].sup.- 
NA.sup.+ FT-IR mCN=2119 cm.sup.-1 was obtained. 
EXAMPLE 5 
The iron compound from Example 4 (6.14 g) was dissolved in 750 ml 
deoxygenated, demineralized water and under strict maintenance of a 
nitrogen blanket. The mixture was heated to 80.degree. C. for 20 hours. 
The solution was then cooled to room temperature to deposit a crystalline 
solid (yield 57% of theoretical, leaving close to 43% of product in 
solution). Analysis of the intrinsically conducting novel compound 
produced the following data: 
FT-IR: mCN=2131 cm.sup.-1 ; 
microcrystallites: "platelets" 50.times.50.times.20 nm (on average); 
powder conductivity: 2.10-3 sigma.sup.-1.cm.sup.-1 ; (two steel electrodes, 
5t pressure) 
XRD diffractogram: FIG. IV; 
XRD reflections: Table II; 
chemical analysis: PcFe(OH.sub.2)(CN) (1 mol of water per mol of product); 
unit cell: a=0.7308, b=2.489, c=0.715 (all in nm.+-.0.001); 
angle alpha,gamma: 90.degree. ; angle beta: 102.6.degree.+0.2.degree.; 
symmetry: P2.sub.1 ; 
crystalline structure: FIG. II; 
interatomic distances: FIG. III (substituting Fe-atoms for Co-atoms). 
TABLE II 
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2-theta [.degree.] 
d (nm) 
______________________________________ 
1 7.99 1.245 
2 14.53 0.686 
3 16.02 0.622 
4 17.68 0.564 
5 18.69 0.534 
6 19.43 0.514 
7 24.12 0.415 
8 28.69 0.358 
9 28.97 0.347 
10 29.82 0.337 
11 31.76 0.317 
12 33.10 0.304 
______________________________________ 
EXAMPLE 6 
Different samples of polypropylene and PcCo(OH.sub.2) (CN) illustrated in 
the preceding examples were prepared by powder blending the polymer with 
respectively 1,2 and 4% by weight of PcCo(OH.sub.2) (CN) and further 
processing the mixture on a roller bank. Test samples were prepared by 
compression molding. Conductivity testing (ASTM D-991) showed for all 
samples a conductivity level of between 10.sup.-6 and 10.sup.-7 
Scm.sup.-1. 
EXAMPLE 7 
A 5% by weight powder blend of PcCo(OH.sub.2)(CN) in polypropylene was made 
on a roller bank. This masterbatch was dispersed in neat polypropylene. 
Part of the diluted powder mixtures were extruded at 220.degree. C. The Tc 
(crystallization temperature) of these extruded samples as well as of the 
powder blends were determined using DSC (25.degree.-200.degree.-25.degree. 
C.; 10.degree. C. min.sup.-1). The results are given below: 
______________________________________ 
% wt Tc (.degree.C.) extrudate 
Tc (.degree.C.) powder 
______________________________________ 
blank 113.7 112.7 
0.001 119.8 117.9 
0.01 123.5 120.9 
0.1 128.3 121.7 
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EXAMPLE 8 
In 2 gram glycerol monostearate, 0.1 gram PcCo(OH.sub.2)(CN) is dispersed 
at a temperature of 100.degree. C. (Solution A). 0.2 ml of solution A is 
coated on 10 gram expandable EPS. The product is further processed using 
conventional methods. The expanded particles have antistatic properties. 
While this invention has been described in detail for the purpose of 
illustration, it is not to be construed as limited thereby but is intended 
to cover all changes and modifications within the spirit and scope 
thereof.