The method of producing perphosphate lithium, perphosphate lithium electrolytes for lithium batteries, lithium secondary batteries

 

(57) Abstract:

The invention relates to a new method of obtaining perphosphate lithium General formula (I), where a = 1, 2, 3, 4, or 5, b = 0 or 1, C = 0, 1, 2 or 3, d = 0, 1, 2 or 3; e = 1, 2, 3, or 4, provided that the sum of a+e = 6, the sum of b+c+d = 3, and b and C are not simultaneously denote 0, provided the ligands (CHbFc(CF3)d) can be different, and monochlor - or fluorine-, dichloro - or debtor, chlortetracycline, hormone, HARDI-, Hartry or chlortetracycline, formano, Ferdi-, fortri or fortetracycline or cryptomonadales subjected to electrochemical fluorination in an inert solvent, the resulting mixture of products if necessary, divide by distillation at various fluorinated products and the fluorinated alkylphosphine, put in an aprotic, polar solvent at from -35 to 60oWith interaction with lithium fluoride. Also disclosed themselves perphosphate lithium General formula (I), electrolytes for lithium-ion batteries and lithium secondary batteries. The invention can be used in electrical engineering to obtain a simple and effective method of secondary lithium batteries, containing stable towards hydrolysis tocope] (I)

The invention relates to new perforatum lithium General formula

Li+[PFa(CHbFc(CF3)d)e]-,

where a = 1, 2, 3, 4, or 5, b = 0 or 1, c = 0, 1, 2 or 3, d = 0, 1, 2 or 3 and e = 1, 2, 3, or 4, provided that the sum of a + e = 6, the sum of b + c + d = 3, and b and C are not simultaneously denote 0, provided that the ligands (CHbFc(CF3)d) can be different,

the method of production of these compounds, to their use in electrolytes, as well as made with the use of these electrolytes in lithium batteries.

The invention relates also to compounds of General formula

[PFa(CHbFc(CF3)d)e], (Ia)

where, as in the formula (I), b = 0 or 1, C = 0, 1, 2 or 3, d = 0, 1, 2 or 3 and e = 1, 2, 3 or 4, however, a = 1, 2, 3 or 4, which are used as intermediates for producing compounds of formula (I).

Performanceperformance as starting materials for the synthesis of various perfectrelations.com compounds cause the keen interest (N. V. Plavenko: "Reaction of tris(perfluoroalkyl)phosphine oxides and tris(perfluoroalkyl)difluorophosphoranes with fluoride ion", Journ. General Chem. UdSSR, volume 59, pages 469-473, 1989).

Typically, in lithium secondary batteries in kachestve, this salt has a relatively low resistance to hydrolysis. In this regard, there have been numerous attempts to find this salt suitable replacement. For example, in international application WO 88/03331 describes salts of cyclic puertoricensis(sulfonyl)imides, in particular their lithium salts that can be used as conductive salts in nonaqueous electrolytes for secondary lithium batteries. However, as shown by the experiments, the receipt of such compounds is possible only at high logistical costs, and upon completion of the synthesis of them is necessary to remove unwanted by-products. In addition, it is required to clean salts, as for use as a component of electrolytes for batteries need to be recovered property.

With regard to the foregoing, the invention was based on the task to get the corresponding conductive salt for electrolytes used in lithium batteries. The invention aims also to develop a method by which a simple and economical way, it was possible to obtain a conductive salt according to the invention.

The task according to the invention of Resv>d)e]-(I)

where a = 1, 2, 3, 4, or 5; b = 0 or 1, C = 0, 1, 2 or 3; d = 0, 1, 2 or 3 and e = 1, 2, 3, or 4, provided that the sum of a + e = 6, the sum of b + c + d = 3, and b and C are not simultaneously denote 0, provided that the ligands (CHbFc(CF3)d) can be different,

which can replace hexaphosphate lithium, commonly used as conductive salts in lithium secondary batteries, and can also be used in mixtures with each other.

The object of the invention in accordance with this are the new proposed salt of the formula (I), and the retrieval method and compounds of General formula (Ia)

[PFa(CHbFc(CF3)d)e], (Ia)

where, as in the formula (I), b = 0 or 1; with = 0, 1, 2 or 3; d = 0, 1, 2 or 3 and e = 1, 2, 3 or 4, however, a = 1, 2, 3, or 4

which are used as intermediates for producing compounds of formula (I).

The object of the invention are hereinafter also referred to as electrolytes containing salts according to the invention, and batteries that are manufactured with the use of these electrolytes. Such galvanic cells can represent both primary and secondary battery containing the lithium compounds of formula (I).

Volume
d)

< / BR>
e)

< / BR>
f)

< / BR>
g)

< / BR>
h)

< / BR>
their use as conductive salts in the electrolytes, the electrolytes containing these salts, and lithium batteries, in which these compounds are present as conductive salts.

To obtain the salts according to the invention in the first stage corresponding monochloro - or fluorine-, dichloro - or debtor, chlortetracycline, hormone, HARDI-, Hartry or chlortetracycline, formano, Ferdi-, fortri or fortetracycline or cryptomonadales dissolved in an inert solvent and by known techniques is subjected to electrochemical fluorination at a temperature in the range from -15 to 20oWith at normal pressure. As the solvent for this reaction is suitable hydrogen fluoride. The fluorination reaction stopped after absorbing 90-150%, primarily 110-130% of theoretical amount of electricity. This is determined by the method of kulonometrii.

Depending on the duration of the reaction will receive a mixture of products, which are fully saturated with fluorine compounds, and compounds, partially fluorinated. For example, when R>
,

e)

,

Actually salt of the formula (I) according to the invention will have due to the fact that obtained in the first stage fluorinated alkylphosphine (II) in the form of a mixture product, preferably after separation by distillation in anhydrous conditions dissolved using the appropriate aprotic, polar solvent, such as diethyl ether, dimethoxyethane or mixtures thereof, and is subjected to interaction with lithium fluoride, depending on the reactivity at a temperature in the range from -35 to +60oC, preferably at room temperature, results in compounds of formula (I).

The electrolytes according to the invention can be used as pure compounds of formula (I), and a mixture obtained by the reaction of fluorination. Preferably through the recoverability of electrolytic properties to use for the preparation of solutions of electrolytes net connection.

Unexpectedly in the course of the experiments it was found that the compounds of formula (I) in an aprotic, polar solvents are at room temperature, resistance to hydrolysis, namely, first of all those of them, the alkyl residues, which are completely saturated with fluoride>Under aprotic, polar solvents such as

the NITRILES include acetonitrile or benzonitrile,

- ethers: diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane or dimethyltetrahydrofuran,

- esters: methyl or ethyl esters of formic acid, acetic acid, propionic acid, and cyclic ethers, such as butyrolactone, and organic carbonates, such as, for example, dimethylcarbonate, diethylcarbamyl, ethylmethylketone, ethylene carbonate resulting or propylene carbonate,

- amides include dimethylformamide, diethylformamide, N-methylpyrrolidine, or

- sulfones: dimethyl sulfone, tetramethylarsonium or other sulfolane.

In addition, the salts according to the invention have an extremely high solubility in these solvents, and low hygroscopicity differ primarily in connection completely saturated with fluorine.

The tests showed that these compounds are extremely stable. When stored in dry conditions in the solid state the perforated joints at temperatures below 100oWith no evidence of any decomposition. And with further increase in temperature they show resistance. Only when temperaturesensitive, even after a few weeks no changes are observed colorations, as well as the formation of decomposition products.

By itself, this factor supports without reservation the applicability of the proposed compounds, especially compounds of formulas III, IV, V, VI and VII, as conductive salts in non-aqueous electrolytes for lithium-ion batteries.

Further, the electrolyte solutions containing these compounds are relatively high chemical and electrochemical stability. Thus, in particular, is not observed oxidation of the conjugated anion prior to the deposition of lithium.

The electrolytes of this type along with organic lithium salts, which are compounds of formula (I) according to the invention, contain one or more non-aqueous organic solvents and do not necessarily other additives. Optionally, the electrolyte as conductive salts, addition compounds according to the invention, it is possible to add other known lithium salt. More detailed explanations about the features of such electrolytes, as well as the layout and functionality of lithium batteries are well known to the expert in Yes is their purpose known lithium compounds and demonstrate exceptionally high resistance. The relevant elements of the battery are of excellent properties regarding the capacity and stability of the voltage, as well as unlimited health for a long period of time, including cycles of charge-discharge and far superior to the average.

The examples below are for a more detailed explanation of the present invention without limiting its scope and the claimed indications.

Example 1

Bis(heptafluoroisopropyl)triftorpentan (IIA) and its derivatives

The reaction Simmons diisopropylfluorophosphate electrochemically foryouth in an electrolyzer containing hydrogen fluoride as a solvent. In this case, use a cylindrical cell with a volume of 310 cm3equipped with Nickel anodes with an effective area S=3.75 DM2and cathodes with the same effective area. In addition, the electrolytic cell equipped with a condenser. The element temperature of the electrolytic cell during electrolysis support level -5oC, and the temperature of the condenser - level -30oC.

57 g of Diisopropylfluorophosphate dissolved in 200 g of hydrofluoric acid, are added in several portions to 235 g pre podbereznyi products after passing through the condenser and PTFE-traps (means PTFE polytetrafluoroethylene) is cooled to -78oC.

The electrolysis is carried out at a voltage of 4.4 to 5.4 and In flux density between 0.30 to 0.53 A/DM2ends after consumption 420 Ah (131% of theory), and the electrolysis collect 220 g of liquid product. After establishing a temperature below -20oWith and separating the lower phase from the phase hydrogen fluoride obtain 18 g of crude product. Method19F-NMR spectroscopy to determine that this product contains 75% of bis(heptafluoroisopropyl)tripterospermum (IIA), 15% heptafluoroisopropyl(1,1,1,3,3,3-hexafluoroisopropyl)tripterospermum (IIb) and 10% bis(1,1,1,3,3,3-hexafluoroisopropyl)tripterospermum (IIC).

Fractional distillation of this mixture can be divided into fractions, each of which contains one of these compounds as the main component. In addition, after the separation from the phase hydrogen fluoride from the cooling traps get 33 g of liquid at low temperatures products. As shown19F-NMR spectroscopic analysis, these products are predominantly heptachlorodibenzofuran (IId), 1,1,1,3,3,3-hexafluoroisopropylidene (IIE) and perftoran. By heating up the 20oWith perftoran you can drive away. The rest can be resultsofconsiderationofurban (IIE) as main components.

The compounds obtained can be characterized by the following indicators.

Bis(heptafluoroisopropyl)triftorpentan (IIA):

< / BR>
19F-NMR, ppm million: (CD3SP-film with CCl3F as standard), -39,72 dtm (3 F1); -70,15 m (12 F3); -171,78 dm (2 F2);

31P-NMR, ppm million: (CD3CN film with 85% H3RHO4as a standard), -26,0 qtm;

Heptafluoroisopropyl (1,1,1,3,3,3-hexafluoroisopropyl)triftorpentan (IIb):

< / BR>
19F-NMR, ppm million: (CD3SP-film with 85% CCL3F as standard), -33,10 dm (3 F1); -59,56 m (6 F4); -70,26 m (6 F3); -171,90 m (1 F2) .

31P-NMR, ppm million: (CD3SP-film with 85% H3RHO4as a standard), -23,2 qdm;

'H-NMR, ppm: (CD3SP-film with TMS as standard), 3,9 dm.

Bis(hexa-1,1,1,3,3,3-hexafluoroisopropyl)triftorpentan (IIc):

< / BR>
19F-NMR, ppm million: (CD3SP-film with CC13F as standard), -25,96 dm (3 F1); -59,51 m (12 F2);

31P-NMR, ppm million: (CD3CN film with 85% H3RHO4as a standard), -20,69 qm;

'H-NMR, ppm: (CD3CN film with TMS as standard), 3,9 dm.

Heptachlorodibenzofuran 0 dm (4 F1); -72,22 m (6 F3); -172,83 dm (F 12);

31P-NMR, ppm million: ((CD3D3film with 85% H3RHO4as standard); -40oS): -55,3 pdsep

1,1,1,3,3,3-Hexafluoroisopropylidene (IIE):

< / BR>
19F-NMR, frequent. /million: ((CD3SP-film with CC13F as standard); -30oS): -40,90 dm (4 F1); -61,8 m (6 F2).

31P-NMR, ppm million: ((CD3D3film with 85% H3RHO4as standard); -40oS): -50,8 pdsep; J2P,N=27,0 Hz.

Example 2

Tris(pentafluoroethyl)diftormetan (VA)

In the same way as described in example 1 of the 69 g tritylthiocyanate(pentafluoroethyl)dipterofauna(Va).Data31P-NMR spectroscopy correspond to those known from the literature (V. J. Semenii and others, Journal of General chemistry of the USSR, 1985, vol 55, 12 p. 2716-2720).

< / BR>
31P-NMR, (CD3D3film with 85% H3RHO4as standard) frequent. /million: -47,55 tsep; J1P,F=1003,0 Hz; J2P,F=122,0 Hz.

Example 3

Bis(heptafluoroisopropyl)TETRAPHOSPHATE lithium (II)

It loaded in made of PTFE reaction vessel to a solution of 0.82 g (0,031 mol) of LiF and 60 ml expose the stirring by the magnetic stirrer 12 g (0,028 mol) bis(heptafluoroisopropyl)tripterospermum (IIa), and temperature by cooling in an ice bath support level at room temperature. Then at the same temperature and continue stirring for one hour, adding a small amount of metallic lithium. Then the reaction mixture for 24 h incubated at room temperature, then filtered, after which it can directly be used as the electrolyte for the battery charge. However, resulting from the reaction of bis(heptafluoroisopropyl)TETRAPHOSPHATE lithium (II) to allocate by removal of the solvent under high vacuum. The selected product is a complex lithium salt (II), Li+[(i-C3F7)2F4]-DMA, tPL126-128oC; temperature resistant up to 130oC.

Analysis: Li

theoretically: 0,93%,

found: 1,15%.

The solvent can be removed by heating the complex salt (II) for several days under high vacuum to a temperature of 80oC.

Example 3A

To obtain lithium salts according to the invention obtained in example 1 forgottenboy mixture can be used directly, without fractional distillation.

16 g Forgottenboy smcac described above, to a solution of 1.0 g LiF and 80 ml of DME. The resulting solution can also after filtering directly be used as the electrolyte. However, Li-salt can be distinguished from solution by crystallization, adding these purposes subjected to preliminary drying hexane to DME-solution. After recrystallization of the resulting product is carried out with a mixture of solvents from dry DME and dibutylamino ether (ratio 1: 2), gain of 13.6 g of bis(heptafluoroisopropyl)TETRAPHOSPHATE lithium (II) together with 6% heptafluoroisopropyl(1,1,1,3,3,3-hexafluoroisopropyl)TETRAPHOSPHATE lithium (III).

The structure of the salt (II) and (III) was determined using the 19F and31P-NMR spectroscopy. NMR spectra were determined in CD3D3-solutions with CCl3F, and in another case - 85% H3RHO4as external standards.

Bis(heptafluoroisopropyl)TETRAPHOSPHATE lithium (II):

19F-NMR, ppm million: -58,14 dm (4 F1); -71,07 pdd (12 F3); -184,40 dpsep (2, R2);

31P-NMR, ppm million: -149,27 ptm; -148,42 ptm (CD3CN-solution);

Heptafluoroisopropyl (1,1,1,3,3,3-hexafluoroisopropyl)TETRAPHOSPHATE lithium (III):

19F-NMR, ppm million: -47,20 dddm (4 F1); -58,01 dpd (6 F4); -70,79 pdd (6 F3); -183 lithium (VIII)

Getattributeinternal lithium (VIII) are obtained, similarly to that described in example 3, the interaction of ferroforma (IId) with LiF in a dry dimethoxyethane. As mentioned above, after filtering the resulting solution can directly be used as the electrolyte solution or the above-mentioned salt can be distinguished by removal of the solvent under high vacuum or by crystallization carried out by adding hexane.

The mixture perfectionof obtained according to example 1, can also be used to prepare solutions of the electrolyte, exposing its interaction with LiF without pre-treatment. The solution of both lithium salts (VIII) and (IX) obtained in this case can also be used as electrolyte for lithium batteries. Both salts can be distinguished in the same way as described above.

Getattributeinternal lithium (VIII):

19F-NMR, frequent. /million: (solvent: CD3D3; standard: CCL3F): -62,62 dddsep (4 F1); -73,13 p (1 F2); -71,49 pdd (6 F4); -183,72 dpsepm (1 F3);

31P-NMR, frequent. /million: (solvent: CD3CN; external standard: 85% N3RHO4) -148,16 pddsep;

1,1,1,3,3,3-UB>3F): -52,95 dddsep (4 F1); -69,04 p (1 F2); -59,40 dp (6 F3);

31P-NMR, frequent. /million: (solvent: CD3SP; external standard: 85% N3RHO4) -145,82 pddsep; J2P,H=29.0 Hz;

Using getattributeinternal lithium (VIII) conducted experiments on cyclicity, the results of which are shown in Fig. 1. These experiments were performed under the following conditions:

the change interval potentials - 0,0-3,0; 3,0-6,0;

the rate of change of 100 mV/s;

the working electrode is Pt, the surface 1,9610-3cm2;

the control electrode - Li;

the electrode - Li;

electrochemical stability up to 5,0 Century

Example 5

Tris(pentafluoroethyl)triphosphate lithium (V)

Tris(pentafluoroethyl)triphosphate lithium (V) are obtained analogously to example 3 by the interaction of the obtained according to example 2 of ferroforma (Va) with LiF in subjected to preliminary drying dimethoxyethane. And in this case obtained in the reaction and after filtering the reaction solution can be directly used as an electrolyte or salt (V) can be distinguished by removal of the solvent under high vacuum or by crystallization can be carried out is: (solvent: CD3COCD3; standard: CCL3F): -87,0 d (2 F1); -43,6 dm (F 12); -115,3 m (4 F3); -115,7 m (2 F5); -79,7 m (3 F6); -81,3 m (6 F4).

31P-NMR, frequent. /million: (solvent: CD3D3; external standard: 85% N3RHO4): -149,8 tdpt

The complex Tris(pentafluoroethyl)triphosphate lithium (V) with DME has tPL116-118oC and has a temperature resistance up to 130oC.

Using 1 ml of Tris(pentafluoroethyl)triphosphate lithium (V) dissolved in DME, and adding 19 ml LP10, conducted experiments on cyclicity. The results of the first and fifth experiments on the cycle shown in Fig. 2. These experiments were performed under the following conditions:

the change interval potentials - 0,0-3,0; 3,0-6,0;

the rate of change of 100 mV/s;

the working electrode is Pt, the surface 1,9610-3cm2;

the control electrode - Li;

the electrode - Li;

electrochemical stability up to 5,0 Century

Example 6

1. Bis(1,1,1,3,3,3-hexafluoroisopropyl)TETRAPHOSPHATE lithium (IV)

< / BR>
The specified connection formula (IV) are obtained in a mixture with compounds of the formula (II) and (III) in accordance with example 3A.

19F-NMR spectrum, ppm (solvent: CD3COD3basic soy is P>31P-NMR spectrum, ppm (solvent: CD3CN, the underlying connection: 85% N3RHO4as external standard): -144,86 quin, m; J1P,F= 914 Hz;

Example 7.

2. Bis(trifluoromethyl)TETRAPHOSPHATE lithium (VI)

< / BR>
The original compound bis(trifluoromethyl)triftorpentan (CF3)2F3synthesized according to the method described in W. Mahler, Neorg. chemistry, 2, (1963), 230.

1.5 g (6,64 mmol) (CF3)2PF3in 15 ml of anhydrous HF is mixed with 0.21 g (8,08 mmol) of powdered lithium fluoride (LiF) in PFA-flask at -35oC. the resulting reaction mixture is stirred at this temperature for 2 hours and then incubated overnight at -21oC. Excessive amount of LiF is separated by decantation.

31P-NMR spectrum of the pure solution confirms the formation of salts of the formula (VI).

31P-NMR spectrum, ppm (solvent: HF, CD3CN, temperature: -40oS): -149,86 quin, sep (the underlying connection was: 85% N3RHO4in the film); -2,45 quin, sep (basic connection: PF6as an internal standard). j1P,F= 929 Hz.

To highlight the salt of formula (VI) is distilled HF. The remaining solid is dissolved in a mixture of ethylene carbonate resulting in: dimethylcarbonate 1:1 (wt.).19F-D3SP-film underlying connection: CCl3F in the film): -68,63 d, quin (2CF3); -76,86 d,m (PF4); j1P,F=896 Hz; J2P,F=147 Hz; J3F,F=14,2 Hz.

Example 8.

3. Triftormetilfullerenov lithium (VII).

< / BR>
Methyldichlorosilane CH3PCl2subjected to electrochemical fluorination as described in example 1. The solution triftormetilfosfinov CF3F4in HF is collected after passing through the PTFE-trap. By treating this solution LiF get lithium salt of the formula (VII) directly in a solution of HF acid.

F-NMR spectrum, ppm (solvent: CD3D3film temperature: -50oWith base connection: PF6-as internal standard): -2,00 d,m (CF3); -2,33 d,m (PF5); J1P,F=817 Hz; j2P,F= 145 Hz;

31P-NMR spectrum, ppm (solvent: HF, CD3D3film temperature: -40oWith base connection: 85% N3RHO4in the film): -149,10 sex.q.

To highlight the salt of formula (VII) is distilled HF and the remaining product is dissolved dimethoxyethane (DME).

1. The method of producing perphosphate lithium General formula

Li+[PFa(CHbFc(CF3)d
provided that the ligands (CHbFc(CF3)d) may be different, wherein (a) monochlor - or fluorine-, dichloro - or debtor, chlortetracycline, hormone, HARDI-, Hartry or chlortetracycline, formano, Ferdi-, fortri or fortetracycline or cryptomonadales subjected to electrochemical fluorination in an inert solvent, b) the mixture of products if necessary, divide by distillation at various fluorinated products, and b) a fluorinated alkylphosphine put in an aprotic, polar solvent at from -35 to +60oWith interaction with lithium fluoride.

2. The method according to p. 1, wherein the fluorination is carried out in the temperature range from -15oWith up to room temperature and under normal pressure.

3. The method according to p. 1, characterized in that the purification of fluorinated products by distillation is carried out in an atmosphere of inert gas.

4. The method according to p. 1, characterized in that the interaction with lithium fluoride is carried out at room temperature.

5. Perphosphate lithium General formula

Li+
e = 1, 2, 3, or 4, provided that the sum of a+e = 6, the sum of b+c+d = 3, and b and C are not simultaneously denote 0,

provided that the ligands (CHbFwith(CF3)d) may be different.

6. Perphosphate lithium under item 5 of formulas II - IX

a)

< / BR>
b)

< / BR>
c)

< / BR>
d)

< / BR>
e)

< / BR>
f)

< / BR>
g)

< / BR>
h)

< / BR>
7. Electrolytes for lithium-ion batteries containing perphosphate lithium General formula (1) PP. 5 and 6.

8. Secondary lithium batteries, containing electrolyte under item 7.

 

Same patents:
The invention relates to the field of electrical engineering, in particular for lead-acid batteries

The invention relates to electrical engineering and can be used in the manufacture of chemical current sources (CCS), namely in the preparation of electrolytes

The invention relates to electrical engineering and can be used in the manufacture and treatment" failed due to sulfate crystallization of lead batteries

The invention relates to organic chemistry, to the class of heterocyclic compounds - drive dihydrofuran with one carbonyl group in the cycle and the phosphorus-containing fragment in the side chain, namely to a new way to obtain previously unknown connections - 5-aryl-2-hydroxy-2-(triphenylphosphonio)methoxycarbonylmethyl-2,3-dihydr-3-formulaHBrwhich can find application in medicine as drugs with antimicrobial action

The invention relates to a new organoboron compound having catalytic activity, of the formula I

[RjM-Xd-MRj]a-bAc+(I)

in which R are, independently of one another, identical and denote C1-C40alkyl; X is, independently from each other, equal or different and denote C1-C40alkyl; M is, independently of one another, identical or different and denote an element of IIIa, IVa, Va group of the Periodic system of elements, provided that one M is boron, a is a cation of an element Ia, IIa and IIIa groups of the Periodic system of elements, carbene-hydronium - or sulfonyl - cation or compound Quaternary ammonium, and a is an integer from 0 to 10, b is an integer from 0 to 10, C is an integer from 0 to 10 and a = C; d is 1; j is an integer from 1 to 3

FIELD: organic chemistry, chemical technology, electrolytes.

SUBSTANCE: invention relates to new fluoroalkyl phosphates that can be used as electrolytes in primary current sources, secondary current sources, capacitors, super capacitors and/or galvanic units. Invention describes fluoroalkyl phosphates of the general formula (I): Mn+[PFx(CyF2y+1-zHz)6-x]n wherein 1 ≤ x ≤ 6, 1 ≤ y ≤ 8, 0 ≤ z ≤ 2y + 1, 1 ≤ n ≤ 5 and Mn+ means a monovalent, bivalent or trivalent cation, in particular: NR1R2R3R4, PR1R2R3R4, P(NR1R2)kR3mR44-k-m (wherein k = 1-4; m = 0-3 and k + m ≤ 4), C(NR1R2)(NR3R4)(NR5R6), C(aryl)3, Rb or tropylium wherein R1-R8 mean hydrogen atom (H), alkyl or (C1-C8)-aryl that can be substituted partially for F, Cl or Br atoms and wherein Mn+ means Li+, Na+, Cs+, K+ and Ag+ are excluded. Except for, invention describes a method for preparing fluoroalkyl phosphates and electrolytes for primary current sources based on fluoroalkyl phosphates. Invention provides preparing new compounds possessing useful properties.

EFFECT: improved preparing method, valuable properties of compounds.

11 cl, 1 dwg, 7 ex

FIELD: chemistry of organophosphorus compounds, chemical technology.

SUBSTANCE: invention relates to fluorinated phosphoric acids of the general formula: [RyPF6-y]-H+ [I] wherein y = 1, 2 or 3; ligands R are similar and R represents perfluorinated (C1-C8)-alkyl or aryl group or partially fluorinated (C1-C8)-alkyl or aryl group wherein some atoms F and H can be replaced for chlorine atom. Also, invention relates to a method for synthesis of above described acids by interaction perfluoroalkylphosphorane with fluorohydrogen in the presence of suitable solvent and/or proton acceptor, to salts comprising cation and anion of above described acid, and to a method for synthesis of salts. Acids of the formula [I] can be easily synthesized and show high proton activity and stable at room temperature in highly concentrated solution.

EFFECT: improved method of synthesis, improved and valuable properties of acids.

18 cl, 33 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method of obtaining organic salts, which contain anions of bis(perfluoroalkyl)phosphinate and can be applied in organic synthesis. Difference of claimed method lies in the fact that it includes carrying out reaction of tris(perfluoroalkyl)phosphinoxide with alcohol and organic base, stronger than alcohol.

EFFECT: elaboration of new method of obtaining organic salts with properties of ionic liquids.

11 cl, 14 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining (S)-2-methoxy-3-{4[2-(5-methyl-2-phenyloxazol-4-yl)ethoxy]benzo[b]thiophen-7-yl}propionic acid of formula (I) or its salts, in which formula (II) compound or its salt is hydrated in the presence of an iridium-including catalyst, in which the catalyst includes iridium and formula (III) compound, in which R1 stands for hydrogen, isopropyl, phenyl or benzyl and in which R2 stands for phenyl, 3,5-dimethylphenyl or 3,5-di-tert-butylphenyl. The invention also relates to the application of a complex of the catalyst, containing iridium and the formula (III) compound for obtaining the formula (I) compound.

EFFECT: obtaining the formula (I) compound with a high degree of conversion and enantiomeric purity.

6 cl, 4 tbl, 21 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method for obtaining compound of formula or its salt by hydration of formula compound or its salt in presence of catalyst, including iridium and compound of formula , where R1 represents alkyl, aryl or arylalkyl and R2 represents aryl. Catalyst represents Ir(L1)(L2)nY, where L1 represents compound of formula (X), L2 represents cyclooctane, 1,5-cyclooctadiene, ethylene, 1,5-hexadiene or norbornadiene, Y represents chloride, iodide, bromide, fluoride, trifluoroacetate, tetrafluoroborate, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tetraphenylborate, hexafluoroantimonate, hexafluorophosphate, triflate, mesylate, perchlorate, perbromate, periodate, nitrate, hydrosulphate or acetylacetonate, and n has values 1 or 2.

EFFECT: obtaining compound of formula (I) with high enatiomeric excess and high output.

7 cl, 4 tbl, 35 ex

FIELD: chemistry.

SUBSTANCE: invention relates to compounds of formula I, production and use thereof to obtain corresponding organophosphinates [Kt]z+ z[(CnHmF2n+1-m)xPCIyF6.x.y]- (I) where [Kt]z+ is an organic cation of formula (1) [NR4]' (1) where R is an optionally phenyl-substituted linear C1-4-alkyl; formula (2) [PR24]+ (2) where R2 is independently C6-14-alkyl; or formula (6) [HetN]z+ (6), where HetNz+ is a heterocyclic cation selected from a group comprising imidazolium, pyrazolium, dihydroimidazolium, pyrrolidinium, triazolium, pyridinium, pyridazinium, pyrimidinium, piperidinium, piperazinium, pyrazinium, R1,-R4, denote H or C1-10-alkyl; n=1-4, m=0 to 2n+1, x=1-4, y=1, z=1-2, under the condition that x+y<5.

EFFECT: novel compounds, a method of producing said compounds and use of said compounds to obtain valuable compounds are disclosed.

12 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel heterocyclic radicals of formulae and , having bactericidal and fungicidal properties, which can be used in veterinary and medicine, as well as labels when investigating metabolic routes of medications in living organisms.

EFFECT: novel, unparalleled bactericidal and fungicidal compounds are disclosed.

1 cl, 1 tbl, 3 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing chlorophosphoranimines of general formula R2(Cl)P=NSiR′3 and can be used in chemical industry. Method of producing chlorophosphoranimines general formula R2(Cl)P=NSiR′3 comprises reacting chlorophosphorane of general formula R2PCl3, where R is a chloro, alkyl, aryl, alkoxy or aryloxy group, with silazane and is characterised by that starting silazane used is hexaalkyl disilazane of general formula HN(SiR′3)2, dissolved in a chlorohydrocarbon, chlorophosphorane is added in crystalline form, synthesis is carried out at a temperature of -60 to 0 °C with a gradual raise, and hexaalkyl disilazane is used in an amount of 1 to 1.33 mol per 1 mol chlorophosphorane.

EFFECT: novel efficient method of producing compounds of general formula R2(Cl)P=NSiR′3.

3 cl, 4 ex

FIELD: chemical current supplies; electrolytes used for lead-acid batteries.

SUBSTANCE: electrolyte is doped with polyacrylamide in the amount of 0.001 to 6.0 mass percent per amount of electrolyte. Polyacrylamide added to electrolyte depends for its action on its coagulating properties and on increase of electrolyte viscosity which holds powdered active masses and products of reaction on electrolyte surface thereby preventing their fall-down, creeping, and wash-out. Polyacrylamide is introduced in the form of its aqueous solution before or after battery is filled with electrolyte to function as its additive.

EFFECT: improved operating characteristics and enhanced service life of batteries.

2 cl

FIELD: electrical engineering; chemical current sources; production of lead-acid cells, additives for sulfuric-acid electrolytes in particular.

SUBSTANCE: proposed additive is made from mixture of sulfate of metal with phosphonocarboxylic acids and aminoalkylphosphonic or hydroxyalkylene diphosphonous acids in diluted sulfuric-acid medium at pH no more than 0.8 and total content of phosphonous acids equal to 0.001-0.015 mass-% and metal sulfate of 10-18 mass-%. Additive may additionally include fluorine-containing surfactants in the amount of 0.01-0.1 mass-%. Proposed additive is used for excluding sulfitation of plates of lead-acid cells and restoration of sulfated storage batteries.

EFFECT: enhanced efficiency.

5 cl, 3 ex

FIELD: electrical engineering; lead battery manufacture.

SUBSTANCE: proposed lead battery has strengthened active material on its positive plate thereby enhancing its utilization efficiency at low internal resistance of battery. Novelty is that only positive plates hold in their voids gel-like sulfuric-acid electrolyte and remaining space of battery is filled with liquid sulfuric acid electrolyte.

EFFECT: enlarged service life of battery.

1 cl, 1 tbl

FIELD: electrical engineering.

SUBSTANCE: proposed method for preparing electrolyte aqueous component for chemical current supply includes magnetization of distilled water for which purpose permanent magnet is immersed in the latter, then water is heated to boiling temperature, and boiling water is doped with animal-origin substrate in the amount of 5 to 8 g per 1 liter of water and boiled for 20 - 30 minutes, whereupon vegetable-origin oil in the amount of 15 - 20 ml per 1 liter of water and vegetable-origin resin in the amount of 20 - 25 ml per 1 liter of water are added thereto, and boiling is continued for 5 - 10 minutes; then solution obtained is cooled down and filtered off.

EFFECT: enhanced power characteristics of battery.

4 cl, 1 tbl

FIELD: electrical engineering.

SUBSTANCE: proposed method is used for reconditioning lead battery cells filled with sulfuric acid based electrolyte using additive based on aqueous solution of hydrogen peroxide, saccharides, and/or aldehydes, or their derivatives. Novelty is that lead battery is alternately or periodically charged and discharged in the course of electrochemical reconditioning of cells upon its treatment with some reconditioning additives based on aqueous solution of hydrogen peroxide and after main charge. Battery is charged to full possible level by current amounting to 1.1-4% of rated value and its discharge is conducted with current of 0.01-5% of rated capacity of cell or battery; as an alternative, battery is charged in two phases by current of constant magnitude. Discharge below admissible value is conducted by current amounting to 1 to 4% of rated capacity followed by charging with current amounting to 3-10% of battery capacity until voltage per cell or per any cell of battery is reduced to 1.6 V. In the process battery acquires 10-15% of its rated capacity; entire procedure is repeated two to five times. Reconditioning additive has 1 to 70 ml of sulfuric acid at density of 1 to 1.32 g·cm-3, 0.1 to 10 g of saccharides in the form of solid material and/or aldehydes, or their derivatives, 0.1 to 10 g of sodium and/or potassium bicarbonate, and/or at least one hydroxide out of group of alkali metals in the form of solid material, and 0.1 to 20 g (better 0.5 to 2 g) of disulfonic acid dinaphthyl methane disodium salt per every liter of hydrogen peroxide aqueous solution. Reconditioning additive can also incorporate 0.1 to 10 g of sodium perborate and/or tetraborate, and/or pyrophosphate in the form of solid material.

EFFECT: enhanced battery capacity exceeding primary rated value.

11 cl, 5 ex

FIELD: electricity.

SUBSTANCE: invention is attributed to lead batteries (AB). In this invention lead AB contains group of plates fitted into accumulator jar and ionogen introduced in it for plate group saturating with ionogen with simultaneous forming processing. Here lead AB is adapted to be used partly charged when charge condition is limited within interval from exceeding 70% to less than 100%. Plate group is formed by package consisting of large number of negative electrode bases including grid bases filled with active material of negative electrodes, of large number of positive electrode bases including grid bases filled with active material of positive electrodes and porous separator located between negative electrode bases and positive electrode bases. Ionogen contains at least one kind of ions selected from group consisting of aluminium ions, selenium ions and titanium ions.

EFFECT: creation of lead battery suitable to be used in partly charged condition.

23 cl, 9 tbl, 71 ex

FIELD: chemistry.

SUBSTANCE: invention relates to compounds of formula I, production and use thereof to obtain corresponding organophosphinates [Kt]z+ z[(CnHmF2n+1-m)xPCIyF6.x.y]- (I) where [Kt]z+ is an organic cation of formula (1) [NR4]' (1) where R is an optionally phenyl-substituted linear C1-4-alkyl; formula (2) [PR24]+ (2) where R2 is independently C6-14-alkyl; or formula (6) [HetN]z+ (6), where HetNz+ is a heterocyclic cation selected from a group comprising imidazolium, pyrazolium, dihydroimidazolium, pyrrolidinium, triazolium, pyridinium, pyridazinium, pyrimidinium, piperidinium, piperazinium, pyrazinium, R1,-R4, denote H or C1-10-alkyl; n=1-4, m=0 to 2n+1, x=1-4, y=1, z=1-2, under the condition that x+y<5.

EFFECT: novel compounds, a method of producing said compounds and use of said compounds to obtain valuable compounds are disclosed.

12 cl, 10 ex

Up!