CS257546B1 - Double cobalt-calcium cyclo-tetraphosphates - Google Patents

Abstract

"j, v p · p <.; ■ i n · ■ i / k 1111 i1t ra l <i :; fot ecnany koi ) l fir.li '.. ·, υ.ίι, η. iíi ,,) 1 ν / υυ'ΐ '<-' t'o2-x (-ayJ, 4 ^ 1 2 ') 1 ■ ”i ■; ■ nu: ■ i rt. (Values approaching . · 11 ij;.: '5' ho.Ondy one. A rat is prepared , m i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i n i i n i i m i m i m i m i m i m i m i m i m i m i m ■ Nude 890 ° C, including! kutionty kobaltnaH for calcium in a mole ratio to each other ! '() / C.i corresponding to (2-xj / x and further obmuhu.jeeí fostoric acid anions in quantities corresponding to? (? 4-Cu) equal to 0.98 u? 1.05, i i m i u t i u l i 1 i - s i n can be np l .i t-.n i t v »· t <) · o o r <cuhic 'leehno logii and vzhieilčfri the product also in the product orskeiu priim '/ :; l u pi i d u d i n d i n d i o n d i n corrosion, iodine, ceramic, ceramic [joiinyi u pi iptevinugi cyan colors a in the chemist at the drinker / drinker buo i i ''.

Description

This is also the case in the case of cobalt condensed phosphates, where there is both dicobaltic cyclo-tetraphosphate (c-Co ^ P ^ O ^> ^t ) and higher linear cobasic phosphates (Co _n / 2 ^H 2 ^P n ° 3n + 1 * ^V). the case of calcium compounds, however, reported the existence of particular higher linear phosphates (Ca ^ Y 2 ^H 2 ^P n ° 3 nM ^'ZAT-mco product having cyclic tctraíos] n ečnanovými anions (c-C ^ P ^ Q ^ i ίθ ^Í ^ ° chemical individuum little.

Therefore, double cyclo-tetraphosphates containing calcium catalyzed Lonty, in addition to other divalent metal cations, are gaining in importance. These products have not been known so far and, if the existence of condensed phosphates with pairs of these cations was considered, only as higher linear phosphates. However, these higher linear divalent metal phosphates, whether single or double cations, have some properties that are less suitable for use. They are substances of amorphous, non-crystalline, vitreous ohatuctet, which are fragile. They are also relatively readily soluble and some even have unions I; . Their thermal stability is limited by temperatures i ecryst and 1 acacc (400 to Ί ^1.0 ° C).

Due to the existence of simple higher linear orthophosphates (with one catirutend and simple cyclotetrophosphates with the corresponding kut ion and, in particular, of other properties thereof), it is expected that double compounds of the cyclotetaphosphate type, one of the cations being calcium It can be assumed that the lobes will be more suitable than higher linear phosphates for all contemplated uses of condensed phosphates - both as special inorganic pigments and also as mih i. efficiency.

The invention consists in that it provides double cycloalkyl Loi et: .rafos íorečnany koballnil 'upenaté as novel compounds of formula ^C-CO 2 _X ^(~' x ^{and E} '4 ⁰ i2' and ^X '' ^{in one of ZMP 1J} ' The lower limit for x results from the fact that values of zero cannot be p-ui ti, since they would no longer be a double product, but a pure, simple cycle. c-Co ^ P ^ O ^ · upper limit of the molar calcium content - value one - can be reached but cannot be exceeded because the double products of the cyclo-orthophosphate type with a calcium content higher than the formula c-CoCaP ^ 0 _{19 can} already be prepared.

The cobalt-calcium double cyclotetaphosphates are intensely blue-violet substances with densities ranging from Co / Ca in the range of 3.002 to 3. They have a crystal structure in a monoclinic system with a spatial group C 2 / c. According to the Co / Ca ratio, the lattice parameters range from 1.1796 to 1.2102 nm for a, 0.8298 to 0.8525 nm for b, 0.9898 to 1.0069 nm for c, 118.69 to 118.78 ° for the beta angle and the volume of the elemental cell is in the range 0.8492 to 0.918 nm.

Cobalt-calcium double cyclo-tetraphosphates are chemically and thermally very stable substances. They are insoluble in water, organic solvents and dilute mineral acids; they slowly dissolve in solutions of lye. It melts at high temperatures according to the Co / Ca ratio in the range of 885 to 1060 [deg.] C., with latent melts in the range of 65 to 74.5 kJ / mol. In a completely dry atmosphere or in vacuum, they melt congruently, in an atmosphere containing at least traces of water vapor they melt non-congruently.

The present invention further provides that cobalt calcium calcium cyclotetaphosphates are prepared in such a way that the melt at a temperature above 890 ° C, preferably above 1060 ° C, containing cobalt and calcium cations in a Co / Ca molar ratio corresponding to (2). -x) / xa and further comprising phosphate anions in an amount corresponding to a molar ratio of P 2 O 4 / Co + Ca 1 equal to 1. . i, 'i. discharge equal to 1 to 1, ÍHI5, not ρυΐητ HJ · / {· -o, i dry jLmoufíýfr or vacuum

·.ιη'π ni ·. Advantageously, the speed of immunity is no. / 10 to produce a microcrystalline shape. li jloilii tnvcniny jo tiob.i voted me bodoin lani, rozp. tuhnut ι. n (a), which has a Co / Ca dip in the range of 1 ° C to 1 ° C.

The ratio of the cobalt to the hardened and the calcium phathions is selected according to the requirement for their content in the product, and the amount of calcium bituminous may range from values close to zero up to the value of planes. Jui kob.i 1 t per body, kut ion; this value, however, must not be a rate of change, as otherwise, in addition to the double-cyclo-tetruphosphates, by-products in the form of condensed phosphates would also be formed. Calcium orates.

The content of anions in tosíorečnanovýoh tavunínč Baby Ipovídut the molar ratio Γ ₂ 0,. / (Co + Ia) lovnému one (or values differing little from one ion) as it corresponds to the empirical models Product ^Co ~ ^c> - _{^χ ι} ^{, ι} χ ^Ρ i ° ij ^{? Ί ΗΙ, ,: ι l} 'Y by- products originated in the form of other types of condensed phosphates, and the proportion of the main product would be significantly decreased.

Crystallization of the product by solidification from the cooling melt should be conducted in a completely dry atmosphere (or under vacuum), and the presence of even trace amounts of water vapor would again lead to condensed fairies from other anions rather than cyclotetaphosphate anions. In this case, it is advantageous to deposit the melt and melt at a rate of less than 10 [deg.] C./min, since the possibility of other undesirable condensation products is reduced. Alternatively, the products according to the invention can be further purified by leaching with hydrochloric, sulfuric, nitric or phosphoric acid, since the double cyclo-tetraphosphates resist this leaching, while the other by-products which may be formed pass into solution. The preferred concentration of acids for leaching is 0.1 to 10% by weight, where by-product separation is sufficiently effective, while the risk of attacking the main product is negligible.

The advantages of the invention are that it indicates the existence of new compounds which have not been known so far. These compounds accumulate advantageous physicochemical and application properties which have simple dicyclic cyclo-tetraphosphates. The anticorrosive effects are emphasized, which is important for their pigmentary use in anticorrosive paints, and their long-term solubility is significantly influenced, which in turn is important for their agrochemical use. The distinctive colourfulness of the products in blue-violet with a reduced cobalt content (compared to pure C-CO2P4O12) makes it possible to reduce the raw material requirements for this color compound.

Example 1

The melt prepared by melting 100 g of higher linear cobalt phosphates and 91.3 g of higher linear calcium phosphates at 1080 ° C was cooled in a dry atmosphere at a rate of 8 ° C / min. 191 g of a microcrystalline product was obtained which contained 98.9 wt. · Blue-violet microcrystals are in a monoclinic system, spatial group C 2 / c, whose lattice parameters are a = 1.2192 nm, b = 0.8525 nm, c = 1.0069 nm, beta = 118.73 [deg.] And a unit cell volume of 0.918 nm. Their density is 3.002 g / cm &lt; 3 &gt; and a melting point of 74.5 kJ / mol.

Example 2

The melt prepared by melting 150 g of higher linear cobalt phosphates and 45.65 g of higher linear calcium phosphates at 1070 ° C was cooled under vacuum at a rate of 30 ° C / min. 195.5 g of a microcrystalline product were obtained, containing 99.2 wt. % Double cyclo-tetraphosphate cobalt-calcium of the formula ^C-Co-Ca 5 Q 5 ^P 4 ° i2 ^'Strength ^ ^vn ^ violet microcrystals are monoclinic, space group C2 / c, the lattice parameters and - 1.1948 nm , b = 0.8376 nm, c = 0.9977 nm, beta = 118.7 ° and an elemental cell volume of 0.8759 nm. Their density is 3.218 g / cm 2, the melting point is 900 ° C and the heat of fusion is 66, 5 kJ / mol.

Claims (1)

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