NOVEL CRYSTALLINE COMPOUNDS, THEIR USE, AND POLYMER COMPOSITIONS COMPRISING THE SAME

Abstract: The present invention relates to novel crystalline compounds, their use and polymer compositions comprising the same. In particular, the invention relates to thermosetting, thermoplastic or elastomeric polymer compositions, comprising from 0.00005 to 20 % by weight of a crystalline compound selected from substituted or unsubstituted aquocyanophthalocyaninatocobalt(III) and aquocyanophthalocyaninatoiron(III).

Description: NOVEL CRYSTALLINE COMPOUNDS, THEIR USE, AND POLYMER COMPOSITIONS COMPRISING THE SAME The present invention relates to novel crystalline compounds, their use and polymer compositions comprising the same. In particu¬ lar, the invention relates to thermosetting, thermoplastic or elastomeric polyme: compositions, comprising certain organic additives, which can impart electrical conductivity to the polymers or which can be applied as > Igments 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 conduc- tors can be divi _d into two main groups: compounds that have enhanced conductivity becau of doping with i.a. halogen atoms, such as iodine ε i compounds that are intrinsically conductive without doping, Λ the literature (cf. Hanack et al, in the Text¬ book: "Conductive Polymers", Marcel Dekker publishers, 1986) conductors of the latter group are consistently referred to as being polymeric by nature. Metalloma ocyclic compounds based on phthalocyanine struc¬ tures may be divided into 3 groups: planar polymerized metallo- phthalocyanines such as poly(copper phthalocyanine) ; stacked metallomacrocycles with metal-metal bonding; or polymeric metallo- macrocycles with bridging ligands. Examples of the latter category are the conductive phthalocyanine polymers of the general formula (PcM.X) wherein Pc is phthalocyaninato, M is a metal such as Fe, Ru, Co, Mn, Cr or Rh a G is a bridging ligand such as CN or SCN. They have been studied ι_ x described amongst others by prof. Hanack's group in Tubingen (cf. J.E. Metz, thesis, University Tubingen, 1983; J.E. Me id M. Hanack, J.Am.Chem.Soc. , 105, 828 (1983); 0. Schneider ar Hanack, Z. Naturforsch. 39b, 265 (1984); and S. Deger, thesis, University Tubingen, 1986). The polymers developed by Prof. Hanack 1 s group are believed to be conductive by delocalization of pi-electrons along the polymer axis. Thus, the bridging ligands impart adequate conductivity levels as a result of which there is no need for subsequent doping. These polymers and their applications have also been subject of patent applications, such as DE-A-3,245,750 (claiming the poly¬ mers), EP-A-168,620 (claiming electrically conductive polymers or polymer blends), and EP-A-261,733 (claiming a process for preparing an electrically conductive polymer composition which comprises preparing a blend of a solution of an intrinsically conductive polymer and a further polymer) . Prof. T. Marks' group at the Northwestern University in the USA has studied doped polymeric phthalocyanine compounds of the general formula (PcML) + Y * (J. Am. Chem. , 108, 7595-7608 (1986)). They are of entirely different structure. Orihashi et al (Chem. Lett., 1617 (1985); Synthetic Metals, 19, 751 (1987)) have also prepared conductive phthalocyanine compounds, although it is uncertain whether this conductivity is derived by doping. The present invention is based upon the finding of certain novel metallomacrocyclic compounds which are intrinsically conduc¬ tive in powder form and which are non-polymeric by nature. The compounds can be produced in microcrystalline form and they can thus easily be incorporated into non-conductive materials such as 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. Other suitable uses are in waxes, sprays and for instance in preparing conductive paper. The novel crystalline compounds can also advanta¬ geously be applied as nucleating agents, pigments, and/or explosion prohibiting agents. The polymer compositions of this invention comprise thermo¬ setting, thermoplastic or elastomeric polymers and from 0.00005 to 20% by weight (%wt) and preferably from 0.0005 to 5 %wt of a crystalline compound selected from substituted and unsubstituted aquocyanophthalocyaninatocobalt(III) and aquocyanophthalo- cyaninatoiron(III) . The preferred compounds have an average crys¬ tallite size of less than 500 nm. More preferred compounds are those available as flat microcrystallites measuring on average from 30 x 30 to 200 x 200 nm and having an average thickness of from 5 to 30, preferably from 10 to 25 nm. The novel compositions of this invention are intended for further processing by any of the techniques known per se. The latter include technology such as fibre spinning, compression moulding, injection moulding, extrusion, co-extrusion, laminating, blow-moulding, solid phase pressure forming, vacuum forming, deep drawing, powder coating, solution coating, casting, prepregging and the like. The envisaged final articles of manufacture can be selected from fibres, monofilaments, yarns, coatings, pipes, tubes, tyres, films, sheetings, non-woven fabrics, various mouldings, 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. A very suitable process for preparing the novel compositions is by preparing a master batch comprising a highly concentrated composition of the thermosetting, thermoplastic or elastomeric polymer and the crystalline compound, the latter for instance up to 60 %wt, and blending this with the polymer up to the desired concentration. Surprisingly, it was found that this improves the volume conductivity of the composition. Suitable elastomeric, thermoplastic or thermosetting polymers may be chosen from any one or more of random and block copolymers of styrene and various dienes, homopolymers such as polybutadiene, pol isoprene, neoprene, polyisobutene, poly(l-butene) , polyethene, polypropene, polyesters, such as PET or PBT, epoxy resins, poly- urethane resins, polyvinylchloride, poly(meth)acrylates, poly¬ carbonates, polysulfones, polyphenyleneoxide, polyaramide, cellu- losetriacetate, polyamides, polyvinyl alcohol, copolymers of ethene and carbon monoxide, terpolymers of ethene, propene and carbon monoxide, (expanded) polystyrene, and polyvinylacetates. Preferred polymers are polypropene, polyethene, polyaramides, ethene/CO copolymers, ethene/propene block copolymers, ethene/propene random copolymers, expandable polystyrene, epoxy resins, and thermoplastic elastomers selected from styrene/butadiene copolymers, whether or not hydrogenated and whether or not functionalized. Surprisingly, it has been found beneficial to include a surface active agent in the compositions according to the inven¬ tion. Preferably, such surface active agent has a surface tension lower than that of the matrix (as determined by any suitable test, such as the spinning drop method or the Du Nouy Ring method; J.J. Elmendorp, Pol. Ing. and Sci., 2__\ > 15 (1987) and "Measurement of interfacial tension and surface", GIT Fachzeitschrift fur das Laboratorium, 24, 642-648 (1980)). For instance, in anti-static floor casting made from epoxy resins and the novel conductive crystalline compounds, conductivity was improved by including small amounts of a fluorinated surface active agent. Anti-static floor castings so prepared compare favourably with common floor castings that require substantial amounts of carbon black powders. The crystalline compounds that are employed in the composi- tions of this invention differ from their polymeric homologues wherein the cyano group ligand functions as a bridging ligand positioned in between and linking successive metal atoms. They are novel compounds and the invention also bears on this important aspect. Proof of the claimed identity follows from microscopic inspection of the crystals, XRD and neutron diffraction analysis, and from analysing various interatomic distances. The latter analysis revealed that the interatomic distances between the nitrogen atom of the ligand and the metal atom of the successive parallel stacked macrocyclic structure as found in the novel crystalline compounds are significantly greater than found in covalent or coordinate bonds (about twice the largest distance possible) . The dimensions of the unit cell of compounds that are pre¬ ferred 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" ± 2; angles alpha and gamma each being 90° ± 2°. The interatomic distances (in nm) M-C (from Co,Fe-CN), respectively M-0 (from Co.Fe—0H_) that are preferred in this invention range from 0.19 + 0.06 to 0.19 - 0.06, and from 0.23 + 0.05 to 0.23-0.05, the cyanide group and the water molecule (0H_) being structurally positioned in between succesive parallel stacked phthalocyanine structures. For the polymeric compound (PcCoCN) (S. Deger, thesis, page 122 (1986)), the dimensions of the (monoclinic) unit cell are: a - 1.321 nm, b - 1.3272 nm, c - 1.537 nm and the angle beta is 126.3". The dimensions of the unit cell the "PcCoCN" prepared by Orihashi et al are again different from either of the above two sets. Further detailed information on the crystalline structures as well as the methods of analysis are included in the working exam- pies 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 (cf. EP-A-261,733) , provided the heating is effected under rigorous exclusion of oxygen or air, e.g. under nitrogen blanket and provid¬ ed the alkali metal salt, subjected to heating, is of at least 85% purity. It is believed that the presence of impurities and oxygen affect the conversion, and the crystal structure and the form thereof. In particular, inorganic cobalt cyanide having an IR absorption of 2254 cm (iCN) has been identified as detrimental to the formation of the novel crystalline compounds, and should therefore be avoided or removed. In said compound PcCoCN.X the ligand X stands for a hydroxy or alkoxy group. A suitable illustration of such conversion is the two-step process of which the first step comprises the reaction of alpha or beta phthalocyanine cobalt with sodiumcyanide in ethanol/water mixture whilst 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„] Na ) and the second step comprises CN < > OH and/or CN < > OEt ligand exchange by prolonged washing of the intermediate product with a mixture of ethanol and water. To obtain optimal yield in the first step, the ethanol/water mixture should be heated to temperatures less than the reflux temperature. The two steps together should than 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. 10 Similarly, the obtaining of the envisaged novel aquocyano- phthalocyaninatoiron(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 phthalocyaninatoiron(III) chloride is converted into 15 the sodium or potassium salt of phthalocyaninatoiron(III) in which the iron atom is linked to at least one cyano ligand. This is done by refluxing the PcFe(III) Cl in a mixture of ethanol and sodium or potassium cyanide during 30 min. It is essential that this reaction step proceeds under complete exclusion of air or oxygen, otherwise 20 the envisaged iron(III) compounds cannot be obtained in a high yield but instead thereof one obtains a mixture of a minor amount of the desired compound and a major amount of oxidised by-products, and -surprisingly- iron(II) compounds (PcFe-0-O-FePc and similar compounds). Subsequent washing of the reaction product with water, ^5 filtration and further storage of the compound must likewise be done under rigorous exclusion of oxygen or air. Thus, although oxygen is beneficial in the oxidation of the Co(II) precursor into the Co(III) intermediate, in the present case it may act in addi¬ tion as an activator for unwanted side-reactions. Nonetheless, 0 minor amounts of iron(II) compounds may also be present in the envisaged conductive compounds, however, not in a proportion of more than 20 %wt. The resulting iron(III) compound is converted into the conduc¬ tive crystalline compound by suspending in deoxygenated, deminera- ^5 lized water and heating at 80 "C under complete exclusion of oxygen or air during 5 to 2C tours. Once again, rubsequent filtration and storage of the resulting crystalline comp> and should be done under rigorous exclusion of oxygen or air. Whilst up to now the invention has been mainly described by reference to unsubstituted phthalocyaninatc ompounds, substituted derivatives may be employed as well. Suitable substituents on the phenyl rings in the macrocyclic structure are halogen, lower alkyl, such as methyl, ethyl, isopropyl, n-butyl or isopentyl groups, a ine, 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 crystal- line structure. EXAMPLES 1. 242 g beta phthalocyanine cobalt, 2510 g ethanol, 125.2 g NaCN and 175 g demineralized water were introduced into a 3 1 glass reactor vessel. The mixture was heated whilst oxygen was passed through at about 70 β 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)] * Na . Conversion was 98%. In the wet product some of the -OH ligands will have been replaced by -OEt (ethoxy) 1igands. 2. 347 g of the aforesaid wet product were suspended in 3 1 deoxygenated, demineralized water in a 5 1 glass reactor. The stirred suspension was heated under nitrogen blanket for 72 hours at 98 β C. Upon filtration and washing with water and drying (under nitrogen) 276.8 - of intrinsically conductive compound was obtained (conversion mc .han 95%) . The product was dried for three days in vacuum at 80 β C. The powder volume conductivity (in Siemens/cm, or -3 S/cm) of the compound was 1.3x10 S/cm (two steel electrodes, the powder compressed at 5 t pressure) . Although this may be less than the powder volume conductivity of the polymeric compound, which is .9 2x10 S/cm (S. Geber, thesis (1986), page 20), or that of the conductive "PcCoCN" of Orihashi et al (5.7x10 S/cm for a single crystal) it is more than that of the monoclinic lead phthalocyanine -4 having a conductivity of 10 S/cm (S. Geber, thesis (1986), page 9), which was believed to be the single non-polymeric, non-doped, semi-conductive phthalocyanine metal. 3. A process similar to that of examples 1 and 2 was followed. Thus, 75 g of beta phthalocyanine cobalt, 400 g of ethanol, 25.5 g NaCN and 25.5 g water were introduced in a 1 1 glass reactor vessel. The mixture was stirred, heated to about 70 β C whilst oxygen was passed through for 48 hours. The ethanol distilled off and 850 of demi-water was added. In this intermediate product a signal was detected at 2254 cm , identified as belonging to an inorganic CoCN complex. Part of the intermediate product was treated for removal of the inorganic CoCN complex by washing with water or water/ethanol (5:1). The CoCN complex was thereafter only detectable in the washing effluent. Both treated and untreated sample were heated under nitrogen at 98 β C under stirring for 72 hours. The reaction product was filtered off. The reaction product of the treated sample had a powder volume conductivity comparable to that of the sample of example 2, .3 1.3x10 S/cm. The reaction product of the untreated sample was substantially less, (no reliable value could be determined). From this experiment it clearly follows that the CoCN complex, if present, must be removed. 4. Upon thermal analysis (PCME, pyrolysis combustion mass spec- trometry elemental analysis, conducted at 1000 °C) it was found that the compound contained per mol 1 mol water and 1 mol CN ligand. Combined with further elemental analysis we found that the formula of the compound corresponds with the formula PcCo(CN)(0H_) . From the XRD pattern (Daresbury synchrotron, wavelength 0.104074 nm) one finds via peak finding, and TREOR autoindexing (J. of Applied Crystallography (1988) 21, p. 305-310) the dimen- sions of the unit cell. The density of 1.6 x 10 g/1, measured with a pyqnometer, and the molecular weight unit were used as input for the autoindexing program to eliminate solutions with a calculated 3 specific weight not equal to 1.6 ± 0.2 x 10 g/1 (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 degr; beta: 102.6 degr ± 0.2 degr. From these dimensions and from the density data it follows that the unit cell holds two molecules of PcCo(CN)(OH.) . -1 FT-IR: iCN - 2153 cm . Electron microscopy shows the presence of square, flat ("book-shaped") crystallites measuring 100 x 100 x 15 nm on average. The known polymeric (PcCoCN) has a FT-IR: vCN - -1 -1 n 2158 cm . The difference of 5 cm is well outside that of system¬ atic error. Electron microscopy of the polymeric compound shows the presence of large (40 micrometer) needle-like crystallites ("plate- lets"). The "PcCoCN" by Orihashi et al has a jCN - 2132 cm " , i.e., far below that of the present compositions. Table I marks the most important ones of the observed XRD reflections, the diffractogram is shown in fig. la. The neutron diffractogram is shown in fig. lb. Fig. Ill gives further details of the configuration, the marked interatomic distances d.. to d, are listed in Table 3. 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 mono¬ clinic 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, P2- 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 phthalo- cyanine 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 diffrac¬ tion analysis (NDA) , with wavelengths 0.104074 (XRD) and 0.257167 nm (NDA) . The positions of 0 and CN were found in the difference Fourier map during the refinement procedure. In figure 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. 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-0 and Co-C (from CN) distances found are in agreement with the presence of a coordination respectively chemical bond. The H-N distance (from 0H„ and CN) indicates the presence of a hydrogen bond. This was confirmed with Deutero NMR experiments on PcCo(CN)- (0D 2 ). The arrangement of molecules to form a "layered" crystalline lattice is shown in the schematic drawings of figure II, which represent a crystallite with the lateral faces seen in directions A and B. In fig. A 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. A, 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 macro¬ cycles 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 anoth¬ er, and so on. Fig. A 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. B (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. B 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. B. This is due to the very dense packing in all layers that run parallel to the first layer shown in fig. A, 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 blue-print copy of the first layer and so continues the series of layers in an alternative manner. 5. 10 g phthalocyaninato iron(III) chloride was reacted with 4 g sodium cyanide in 500 ml ethanol in a 2 1 glass reactor under argon blanket at a temperature of 72 β C during 30 min. Upon filtration, washing under nitrogen with deoxygenated, demineralized water and drying in vacuum for 24 hours one obtained the compound [PcFe(CN)(OH)] " Na + , having an FT-IR absorption (ιCN) of 2119 cm . 6. Under strirf- maintenance of an argon blanket, the said iron compound so prepared (6.14 g) was dissolved in 750 ml deoxygenated, demineralized water and the mixture was heated to 80 β 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: thermal (PCME) analysis: PcFe(CN)(0H~) (1 mol of water, and 1 mol CN per mol of product) ; microcrystallites: "platelets" 50 x 50 x 20 nm (on average); XRD diffractogram: fig. IV; XRD reflections: Table II; unit cell: a - 0.7308, b - 2.489, c - 0.715 (all in nm, ± 0.001); angle alpha,gamma: 90°; angle beta: 102.6° + 0.2°; symmetry: P2 1 ; crystalline structure: fig. II; interatomic distances: fig. Ill; Table III; and -3 powder volume conductivity: 2.10 S/cm; (two steel elec- trodes, 5t pressure). TABLE II 2-theta [ β ] d (nm) 1 7 .99 1.244 2 14.54 0.685 3 16.04 0.622 4 17.70 0.563 5 18.46 0.540 6 19.45 0.513 7 24.15 0.414 8 28.44 0. 353 9 28.97 0.347 10 29.83 0.337 11 31.78 0.317 12 33.10 0.304 7. Different samples of polypropene and PcCo(CN)(0H-) illustrated in the preceding examples were prepared by powder blending the polymer with respectively 1, 2 and 4 %wt of PcCo(CN)(0H ? ) and processing the mixture further on a two roll mill. Test samples were prepared by compression moulding. Conductivity testing (ASTM D-991) showed for all samples a conductivity level between 10 and .9 10 S/cm. In a comparative example, similar samples were prepared with PcCo and PcFeCl. Processing of these powder blends was not possible due to degradation reactions. 8. A 5 %wt powder blend of PcCo(CN)(0H„) in polypropene was made on a roller bank. This powder blend was dispersed in neat poly¬ propene powder. Part of the diluted powder mixtures were extruded at 220 °C. The Tc (crystallization temperature) of these extruded samples, of similarly extruded samples with a common nucleating agent, atomized sodium benzoate, as well as of the powder blends were determined using DSC (25-200-25 β C; 10 °C min " ). The results are given below. From these results it may be concluded that the present crystalline compounds have an unexpected beneficial nucle¬ ating effect. Tc ( β C) Tc ( β C) powder comparative extrudate 112.7 113.7 117.9 113.7 120.9 113.7 n.d. n.d. n.d. 119.1 121.7 121.5 9. A master batch was prepared by blending 30 %wt of PcCo(CN)- (0H_) in linear low density polyethene matrix (M.I. 20-25). The conductivity of this masterbatch was measured on a moulded plate .9 (ASTM D-991; 10 S/cm). This master batch was used to prepare static control LLDPE containing 1.0 %wt of PcCo(CN)(0H-) having a -11 surprisingly high conductivity of 10 S/cm. Also the conductivity of the LLDPE matrix itself was measured on a similar prepared moulded plate, and found to be considerably less, < 10 S/cm. 10. In 2 g glycerol monostearate 0.1 g PcCo(CN)(0H_) is dispersed at a temperature of 100 C (Solution A). 0.2 ml of solution A is coated on 10 g expandable EPS. The product is processed further according to standard methods. The expanded particles have anti¬ static properties. Expanded particles made in a similar fashion but without PcCo(CN)(0H„) showed no antistatic properties. 11. A conductive epoxy casting was made by dispersing in a colloid mill 3.2 %wt of PcCo(CN)(0H 2 ) in an epoxy resin ("Epikote" 235, a diglycidyl ether of a blend of bisphenol-A and bisphenol-F; Epikote is a trademark) , and curing the same with isophorondiamine at 100 β C in 1 hour. Likewise a sample containing 0.8 %wt of the surface active compound FC 430 (tm, an ester of a fluorinated carboxylic acid) and a comparative sample without PcCo(CN)(0H„) were prepared. The volume conductivity for all three samples was determined with a four point measurement (ASTM D-991). At the low concentration of PcCo(CN) (0H_) only a value for the conductivity of the sample -10 containing FC 430 could be measured, being 8x10 S/cm. 12. Conductive epoxy castings for self-leveling floorings were made from a concentrated masterbatch (20 %wt) of PcCo(CN)(0H„) in Epikote 240 (trademark, a blend of the diglycidylether of bisphenol-A and bisphenol-F) containing as main component the curing agent isophorondiamine (Epikure F205, a trademark). This masterbatch was made using a Dispermat and Z-blade. Of this master¬ batch 26.1 parts by weight (pbw) were added to 50 pbw Epikote 240. To this mixture also 97.7 pbw of quartz sand (SM 10), 2.5 pbw of pigment paste, 1.5 pbw of antifoaming agent, 1.5 pbw of methyl- isobutyl carbinole, 9.131 pbw of Epikure F205 and 1.7 pbw of FC430 was added. The mixture was cured for 7 days at ambient temperature. Also a comparative sample without FC430 and PcCo(CN) (0H„) was made. The sample containing PcCo(CN) (OH.) has a volume conductivity of -10 -13 8x10 S/cm, that without smaller or equal to 3x10 S/cm. 13. The use of the novel crystalline compounds as dust explosion prohibiting agent in powders, was tested by measuring the powder volume conductivity of LLDPE comprising 5 %wt of the PcCo(CN)(0H-) . This fine powder was selected as powder to model materials that are eligible for dust explosions. The powder volume conductivity (at a 5 t pressure) measured respectively 6x10 S/cm and, 10 S/cm for the powder with and without PcCo(CN) (0H ? ) . 14. A masterbatch of 5 %wt of PcCo(CN) (0H„) and polypropene (KY 6100) was made usirs- a double screw extruder designed for powder mixing at 235 β C. - s of this masterbatch (2 %wt) were mixed with titanium dioxyde (i %wt) and polypropene nibs (KY 6100, 97 %wt) . The mixture was extruded and injection moulded into test plates of 2 8x4 cm . These test plates were compared with similar test plates containing commercial phthalocyanine master batches (BN-AE and CEXA 45, trademarks of Hoechst) . The colour of these test plates were measured using standard techniques. The intensity of the colour of the three test plates was similar, the PcCo(CN)(OH.) test plate being somewhat more opaque.

Claims: C L A I M S 1. A thermosetting, thermoplastic or elastomeric polymer composi¬ tion comprising from 0.00005 to 20% by weight of a crystalline compound selected from substituted or unsubstituted aquocyano- phthalocyaninatocobalt(III) and aquocyanophthalocyaninatoiron(III) . 2. A composition as claimed in claim 1, wherein the compound has an average crystallite size of less than 500 nm. 3. A composition as claimed in claim 1, wherein the compound has an average crystallite size of from 30 x 30 to 200 x 200 nm, the average thickness of the crystallites being from 5 to 30 nm. 4. A composition as claimed in any one of claims 1 to 4, in which the composition comprises a surface active compound. 5. A composition as claimed in any one of claims 1 to 4, in which the thermosetting polymer is an epoxy resin. 6. A composition as claimed in any one of claims 1 to 4, in which the thermoplastic polymer is a polyolefin. 7. A composition as claimed in any one of claims 1 to 4, in which the thermoplastic polymer is a polyaramide or an expanded poly¬ styrene. 9. A process for preparing a thermosetting, thermoplastic or elastomeric polymer composition comprising from 0.00005 to 20% by weight of a crystalline compound selected from substituted or unsubstituted aquocyanophthalocyaninatocobalt(III) and aquocyano- phthalocyaninatoiron (III), by first preparing a master batch comprising a highly concentrated composition of the thermosetting, thermoplastic or elastomeric polymer and the crystalline compound, the latter for instance up to 60 %wt, and blending this with the polymer up to the desired concentration. 10. Novel crystalline compounds selected from substituted or unsubstituted aquocyanophthalocyaninatocobalt(III) and aquocyano- phthalocyaninatoiron(III) . 11. The compounds as claimed in claim 10, having an average crystallite size of less than 500 nm. 12. The compounds as claimed in claim 10 or 11, wherein the dimensions of the unit cell are: a equals 0.73 nm ± 0.03, b equals 2.5 nm ± 0.1 and c equals 0.72 nm ± 0.03, angles and each being 90° ± 2°, angle β being 103° ± 2°. 13. The compounds as claimed in any one of claims 10 to 12, wherein the interatomic distances (in nm) M-C (from Co,Fe-CN) range from 0.19 + 0.06 to 0.19 - 0.O6 and M-0 (from Co.Fe—0H-) range from 0.23 + 0.05 to 0.23 - 0.05, the CN and H 2 0-groups being structurally positioned in between successive parallel stacked phthalocyanine structures. 14. A process for preparing novel crystalline compounds selected from substituted or unsubstituted aquocyanophthalocyaninatoco- balt(III) and aquocyanophthalocyaninatoiron(III) , by converting essentially pure alkali metal salt of hydroxy or alkoxy phthalo- cyaninatometal cyanide under rigorous exclusion of air or oxygen. 15. The process of claim 14, wherein the alkali metal salt of hydroxy or alkoxy phthalocyaninatocobalt cyanide is in situ pre- pared in at least a yield of 85% and inorganic cobalt cyanide detectable by IR, having a i/Cl. of 2254 cm , if present, is re¬ moved. 16. Use of novel crystalline compounds selected from substituted or unsubstituted aquocyanophthalocyaninatocobalt(III) and aquo- cyanophthalocyaninatoiron(III) , as nucleating agent, as pigment, and/or as explosion prohibiting agent.

Inventors: BROKKEN-ZIJP JOSEPHINA CORNELI, DATEMA KLAAS PIETER, DE BRUIJN DIRK PIETER, EMEIS CORNELIS ANTONIUS, KRAMER ARRIS HERMAN, MERUMA AREND-JAN, VAN MECHELEN JOANNES BAPTISTA, BROKKEN-ZIJP, JOSEPHINA, CORNELIA, MARIA, DATEMA, KLAAS, PIETER, DE BRUIJN, DIRK, PIETER, EMEIS, CORNELIS, ANTONIUS, KRAMER, ARRIS, HERMAN, MERUMA, AREND-JAN, VAN MECHELEN, JOANNES, BAPTISTA
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1993
Main classification: C08K5
IPC codes: C07D487, C07F15, C08K5, C08L101, C09B47