Ionic liquid, containing phosphonium ion, and method of producing said liquid

FIELD: chemistry.

SUBSTANCE: present invention relates to ionic liquids based on a cation of formula (1): where substituting groups R1-R9 are selected from hydrogen, alkyl; any carbon atom in R1-R9 can be substituted with a -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2- or -SO3- group; X is S, O or C; R8 and R9 exist only when X is carbon; the anion is selected from [RSO3]-, [RfSO3]-, [(RfSO2)2N]-, [(FSO2)3C]-, [RCH2OSO3]-, [RC(O)O]-, [RfC(O)O]-, [CCl3C(O)O]-, [(CN)3C]-, [(CN)2CR]-, [(RO(O)C)2CR]-, [B(OR)4]-, [N(CF3)2]-, [N(CN)2]-, [AlCl4]-, PF6-, BF4-, SO42-, HSO4-, NO3-; where R is hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, Rf is a fluorine-containing substituting group.

EFFECT: obtaining new ionic liquids with improved electrochemical properties.

15 cl, 18 ex, 2 dwg

 

The scope to which the invention relates

The present invention relates to ionic liquid, which is in a liquid state in a wide temperature range from low temperatures, has a low viscosity and excellent electrochemical stability, to its preparation and to its use, including electric storage device, lithium rechargeable battery, a capacitor with a double electric layer, dye sensitized solar cells, fuel cells and reaction solvents.

The level of technology

Up to the present time have been reported many ionic liquids, in which a nitrogen-containing one-cation, such as, typically, the ammonium cation. They are in a liquid state at temperatures above 25°C, but at 25°C or below are just a few of ionic liquids can be stored in a liquid state. In addition, until now, has only been reported about the ionic liquid, which has a high viscosity at a temperature close to the room, and it is difficult to use by itself as an electrolyte or solvent (see patent documents 1 and 2 and non-patent documents 1-3).

Moreover, the number of ionic liquids, which contain a cation having a relatively low viscosity and melting point, such as the cation imidazoline, many of the ionic liquids are difficult to use as the electrolyte for electrical storage devices due to the lack of stability, due to their low resistance to recovery and narrow potential window (see patent document 3 and non-patent documents 4 and 5).

A big stumbling block to the use of ionic liquids in batteries, capacitors electric double layer fuel cells, dye sensitized solar cells, or in the electrolyte, the electrolyte solutions or supplements for electric storage devices is that there is a very small number of ionic liquids, the stable liquid state in a wide temperature range from low temperature, low viscosity and high conductivity with excellent electrochemical stability, and which themselves fit for use.

Patent document 1: international publication number WO 02/076924 pamphlet form

Patent document 2: published patent application of Japan No. 2003-331918

Patent document 3: published patent application of Japan No. 2001-517205

Non-patent document 1: Hajime Matsumoto and Yoshinori Miyazaki, YOYUEN OYOBI KOONKAGAKU, Vol.44, p.7 (2001)

Non-patent document 2: H. Matsumoto, M. Yanagida, K. Tanimoto, M. Nomura, Y. Kitagawa and Y.Miyazaki, Chem. Lett, Vol.8, p.922 (2000)

Non-patent document 3: D.R. MacFarlane, J. Sun, J. Golding, P. Meakin and M. Forsyth, Electrochemica Acta, Vol.45, p.1271 (2000)

Non-patent document 4: Rika Hagiwara, Electrochemistry, Vol.70, No.2, p.130 (2002)

Not atentry document 5: Y. Katayama, S. Dan, T. Miura and T. Kishi, Journal of The Electrochemical Society, Vol.148 (2), C102-C105 (2001).

Description of the invention

Problems that must be solved by the invention of

The purpose of the present invention is to offer an ionic liquid having a low viscosity, adequate electrical conductivity and excellent electrochemical stability, and method of producing the ionic liquid. Moreover, the purpose of the present invention is to offer an ionic liquid, which can be used for the above-described solutions of electrolytes in lithium batteries, capacitors electric double layer, dye sensitized solar cells, fuel cells, reaction solvent and the like, in particular, the proposal by the ionic liquid, which is stable in the liquid state at a temperature close to the room, in particular, the ionic liquid containing the new cation of phosphonium.

Resolving problems

The authors of the present invention have synthesized a number of salts consisting of a cationic component and an anionic component, and conducted intensive studies of ionic liquids to achieve the above objectives. As a result, the authors of the present invention have found that the ionic liquid containing the cationic component one kind renesola varieties of components, selected from the group consisting of organic cations represented by the following General formula (1)has a low viscosity, adequate electrical conductivity and excellent electrochemical stability.

[Chemical 1]

where the substituting group R1-R9can be independently the same or different from each other; each of the substituting groups R1-R9represents a hydrogen atom, alkyl group with straight or branched chain, containing from 1 to 30 carbon atoms, alkenylphenol group with a straight or branched chain, containing from 2 to 30 carbon atoms, with one or more double bonds, alkylamino group with a straight or branched chain, containing from 2 to 30 carbon atoms, with one or more triple bonds, saturated or partially or fully unsaturated cycloalkyl group, aryl group or heterocyclic group; any hydrogen atoms contained in one substituting group or many alternative groups

R1-R9may be partly or completely replaced by halogen atom, or partially replaced by a CN group or NO2group; any one of the alternative groups of R1-R9may form a cyclic structure together with each other; any carbon atom content is present in the replacement group, R 1-R9may be replaced by atoms and/or atomic group selected from the group consisting of-O-, -C(O)-, -C(O)O-,

-S-, -S(O)-, -SO2-, -SO3-, -N=, -N=N-, -NH-, -NR'-, -N(R')2-, -PR'-, -P(O)R'-, -P(O)R'-O-, -O-P(O)R'-O - and-P(R')2=N-, where R' is an alkyl group with straight or branched chain, containing from 1 to 10 carbon atoms, the alkyl group is partially or fully substituted by fluorine atom, saturated or partially or fully unsaturated cycloalkyl group, unsubstituted or substituted phenyl group, or unsubstituted or substituted heterocyclic group; X represents a sulfur atom, an oxygen atom or a carbon atom; R8and R9exist only when X is a carbon atom; when X represents a carbon atom, X, R1, R8and R9may form a saturated or partially or fully unsaturated cyclic structure together with each other; and the dotted line represents the mating structure.

Namely, the above objectives of the present invention have been achieved by the proposal "ionic liquid comprising an organic substance represented by the General formula (1)as a cationic component and an ionic liquid including a cationic component and an anionic component and the cationic component is a one kind or the number of varieties, selected from the group consisting of cationic components represented by the General formula (1)".

Brief description of drawings

Figure 1 is a graph showing current-voltage characteristics of bis-triftormetilfullerenov three(dimethylamino)butoxypropan in example 3.

Figure 2 is a graph showing current-voltage characteristics of bis-triftormetilfullerenov three(dimethylamino)butylphosphine in example 4.

The best option of carrying out the invention

As the cation component represented by the General formula (1), each of the substituting groups R1-R9in the General formula (1) represents a C1-30alkyl group with straight or branched chain, saturated or partially or fully unsaturated cycloalkyl group, aryl group or heterocyclic group. Any hydrogen atoms (H)contained in one species or many species replacement data groups R1-R9partially or completely replaced by halogen atom, or partially replaced by a CN group or NO2. In addition, any carbon atom contained in the replacement group, R1-R9preferably replaced by atoms and/or atomic group selected from the group consisting of-O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -NR' -, and-N(R')2-, where R' represents a C 1-10alkyl group with straight or branched chain alkyl group, partly or completely replaced by fluorine atom, saturated or partially or fully unsaturated cycloalkyl group, unsubstituted or substituted phenyl group, or unsubstituted or substituted heterocyclic group. More preferably, each group of R1-R9in the General formula (1) represents a C1-20alkyl group, or alkoxygroup straight or branched chain (R1R9may be the same or different from each other).

Moreover, X in the General formula (1) represents a sulfur atom, an oxygen atom or a carbon atom.

Anionic component used in the present invention, is one or more kinds selected from the group consisting of [RSO3]-, [RfSO3]-, [(RfSO2)2N]-, [(RfSO2)3C]-, [(FSO2)3C]-, [RCH2OSO3]-, [RC(O)O]-, [RfC(O)O]-,

[CCl3C(O)O]-, [(CN)3C]-, [(CN)2CR]-, [(RO(O)C)2CR]-, [R2P(O)O]-, [RP(O)O2]2-, [(RO)2P(O)O]-, [(RO)P(O)O2]2-, [(RO)(R)P(O)O]-, [Rf2P(O)O]-, [RfP(O)O2]2-, [B(OR)4]-, [N(CF3)2] , [N(CN)2]-, [AlCl4]-PF6-BF4-, SO42-, HSO4-, NO3-, F-, Cl-, Br-and I-where each replacement group R represents a hydrogen atom, a halogen atom, a C1-10alkyl group with straight or branched chain, C2-10alkenylphenol group with a straight or branched chain having one or more double bonds, With2-10alkylamino group with a straight or branched chain having one or more triple links, or saturated or partially or fully unsaturated cycloalkyl group; any hydrogen atoms contained in the data replacing the R groups may be partly or completely replaced by halogen atom, or partially replaced by a CN group or NO2group; any carbon atom contained in the data R may be replaced by atoms and/or atomic group selected from the group consisting of-O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N=, -N=N-, -NR'-, -N(R')2-, -PR'-, -P(O)R'-, -P(O)R'-O-, -O-P(O)R'-O - and-P(R')2=N-, where R' represents a C1-10alkyl group with straight or branched chain alkyl group, partly or completely replaced by fluorine atom, saturated or partially or fully unsaturated cycloalkyl group, unsubstituted or substituted phenyl group, or n is substituted or substituted heterocyclic group; and Rfrepresents a fluorine-containing replacement group. Data anionic components are combined with the above cationic components and provide an ionic liquid having a low viscosity, adequate electrical conductivity and excellent electrochemical stability.

Anionic component is used as the counterion of the cationic component represented by the General formula (1)preferably represents one or more kinds selected from the group consisting of [RSO3]-, [RfSO3]-, [(RfSO2)2N]-, CF3SO3-, CF3COO-PF6-BF4-, [N(CN)2]-, [AlCl4]-, SO42-, HSO4-, NO3-, F-, Cl-, Br-and I-and, more preferably, one or more kinds selected from the group consisting of [RSO3]-, [RfSO3]-, [(RfSO2)2N]-, CF3SO3-, CF3COO-, [N(CN)2]-, [AlCl4]-, SO42-, HSO4-and NO3-.

Combinations of the above cationic components and data preferred anionic component capable of providing ionic liquid with even more before actualname properties namely, the stable liquid state in a wide temperature range from low temperature, low viscosity, adequate electrical conductivity and excellent electrochemical stability.

In a particularly preferred ionic liquid anionic component which is a cationic counterion component represented by the General formula (1)represents one or more kinds selected from the group consisting of [RSO3]-, [RfSO3]-, [(RfSO2)2N]-, CF3SO3-, CF3COO-PF6-BF4-, [N(CN)2]-, [AlCl4]-, SO42-, HSO4-, NO3-, F-, Cl-, Br-and I-; and each of the groups R1-R9in the General formula (1) represents a C1-10alkyl group, or alkoxygroup straight or branched chain (R1-R9may be the same or different from each other).

In a more preferred case, X in the cation component represented by the General formula (1)is a sulfur atom or an oxygen atom. The ionic liquid, substituted these atoms has a low melting temperature. Even more preferred is an ionic liquid having an oxygen atom as X.

When preparing the ionic fluid is here, at the same time, focusing on the importance of low viscosity, it is required to select a specific cationic component so that R2-R7in the General formula (1) represents a C1-4alkyl group with a straight chain; R8and R9represent hydrogen atoms; R1represents a C1-10alkyl group, or alkoxygroup straight or branched chain; X preferably represents a sulfur atom or an oxygen atom; and particularly preferably, X represents an oxygen atom, and as the anionic component which is the counterion of the cationic component, you want to choose specific anionic compound, preferably, from (CF3SO2)2N-PF6-or BF4-and, particularly preferably, (CF3SO2)2N-. When these combinations can be obtained ionic liquid, which shows a stable liquid state in a wide temperature range from low temperature, low viscosity, adequate electrical conductivity and excellent electrochemical stability.

The ionic liquid according to the present invention shows excellent electrical conductivity, and has a low viscosity and excellent electrochemical stability. Due to superior operational data character is stick the ionic liquid of the present invention is used as a material for the electrolyte, solutions of electrolytes, additives, etc. for electrical storage devices; lithium batteries; capacitors electric double layer; fuel cells and dye sensitized solar cells and use as a reaction solvent for various reactions. Note that up to now this ionic liquid, which has a low viscosity, and electrochemical stability, was not achievable. The ionic liquid of the present invention accurately satisfies both of these properties.

In the present description cation component represented by the General formula (1)shows the cation of phosphonium, with a positive charge on the phosphorus atom for convenience of writing, but the positive charge can be delocalized over the molecule depending on the type of heteroatom represented by X.

A typical method for the synthesis of ionic liquid, which contains a cation component represented by the General formula (1)will be listed below.

[Chemical 2]

The source of organic matter represented by the General formula (2), added dropwise alkylating agent (R1W) and the reaction is carried out at a predefined temperature for a predefined time. After react the mixture was washed with diethyl ether or the like, it is dried under vacuum. Alkylating agent (R1W) may include diallylsulfide, diallylsulfide, dialkylamino, trialkylphosphates, alkylanthraquinones, alkylpolyglycoside, peralkaline, alkylarylsulfonate, alkylaminocarbonyl, alkylpolyglucosides, alkylphenolethoxylate, alkylated, allylbromide, alkylchloride, sulfuric acid, nitric acid and hydrochloric acid.

In addition, for example, the ionic liquid having different views of the anion can be obtained by anionic exchange, as shown below.

[Chemical 3]

Here, ion binding AQ connection may include, for example,

LiN(CF3SO2)2, NaN(CF3SO2)2, KN(CF3SO2)2, CF3SO3Li, CF3SO3Na, CF3SO3K, CF3CH2SO3Li, CF3CH2SO3Na, CF3CH2SO3K, CF3COOLi, CF3COONa, CF3COOK, LiPF6, NaPF6, KPF6,

LiBF4, NaBF4, KBF4, LiSbF6, NaSbF6, KSbF6, NaN(CN)2, AgN(CN)2, Na2SO4, K2SO4, NaNO3and KNO3but it is not limited to these compounds.

In the General formula (3) replacement of the group R1-R9can be independently the same or different on the other. Each of the substituting groups R1-R9represents a hydrogen atom, a halogen atom, a C1-30alkyl group with straight or branched chain, C2-30alkenylphenol group with a straight or branched chain, containing one or more double bonds, C2-30alkylamino group with a straight or branched chain, containing one or more triple relations, saturated or partially or fully unsaturated cycloalkyl group, aryl group or heterocyclic group. Any hydrogen atoms contained in one or many data replacement groups R1-R9may be partly or completely replaced by halogen atom, or can be partially replaced by a CN group or NO2group. Any substitute group, R1-R9may form a cyclic structure together with each other. Any carbon atom contained in the replacement group, R1-R9may be replaced by atoms and/or atomic group selected from the group consisting of-O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N=, -N=N-, -NH-, -NR'-, -N(R')2-, -PR'-, -P(O)R'-, -P(O)R'-O-, -O-P(O)R'-O - and-P(R')2=N-, where R' represents a C1-10alkyl group with straight or branched chain alkyl group, partly or completely replaced by fluorine atom, saturated or partially or fully unsaturated, cyclea kilou group, unsubstituted or substituted phenyl group, or unsubstituted or substituted heterocyclic group. X represents a sulfur atom, an oxygen atom or a carbon atom. R8and R9exist only when X is a carbon atom. When X represents a carbon atom, X, R1, R8and R9may form a saturated or partially or fully unsaturated cyclic structure together with each other.

The above-described halogen atom may include F, Cl, Br and I.

The above cycloalkyl group may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cycloneii and cyclodecyl. Cycloalkyl group may include a group that has an unsaturated bond, for example, cycloalkenyl group and cycloalkenyl group. Cycloalkyl group may be partially or completely replaced by halogen atom, or partially replaced by a CN group or NO2group.

The above-described heterocyclic group may include pyridinyl, Pasolini, imidazolidinyl, imidazolyl, pyrazolidine, personal, piperidyl, piperazinyl, morpholinyl or thienyl. In addition, these heterocyclic groups can contain one or more substituents selected from alkyl groups, alkoxygroup, hydroxy-group, carboxyhb is s, amino group, alkylamino, dialkylamino, Tilney group and alkylthiol group, and halogen atom.

The above aryl group may include phenyl, cumenyl, mesityl, tolyl, xylyl or other Data aryl group may contain one or more substituents selected from alkyl groups, alkoxygroup, hydroxy-group, carboxypropyl, acyl group, formyl group, amino group, alkylamino, dialkylamino, Tilney group, alkylthiol group and halogen atom.

In addition, the replacement group, R1-R9may include alkoxyalkyl group, such as methoxymethyl, methoxyethyl, ethoxymethyl and ethoxyethyl etc.

Moreover, as a heteroatom, represented by X in the formula, you can specify a sulfur atom, an oxygen atom or a carbon atom. Particularly preferably, here you can specify a sulfur atom or an oxygen atom. Through displacement of a given atom can be obtained ionic liquid having a lower melting temperature. As the anionic component Q, which can interact with the compound represented by General formula (3), and is used in combination, it is possible to transfer the above-mentioned anionic compounds.

EXAMPLES

The present invention will be further described in detail with reference to the following examples, but should understand the ü, that the present invention is in no way limited to these examples.

Example 1

(a) Obtaining three methyl sulfate(dimethylamino)methoxypropane

In dvuhgolosy flask in the form of eggplant, equipped with irrigation condenser, addition funnel and magnetic stirrer, 2.0 g in (11.2 mmol) hexametaphosphate triamide at room temperature under nitrogen atmosphere was added dropwise 1.4 g in (11.2 mmol) of dimethylsulfate. After 15 hours stirring at room temperature was obtained a white solid salt. Salt was washed with sufficient amount of ether and dried under vacuum at 50°C for 5 h, receiving three methyl sulfate(dimethylamino)methoxypropane with yield 74%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: acetone-d6, standard: tetramethylsilane was): δ 4,06 (d, 3H); 3,47 (s, 3H); 2,90 (d, 18H).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 4]

(b) Obtaining bis-triftormetilfullerenov three(dimethylamino)methoxypropane

3,05 g (10.0 mmol) of methyl sulfate three(dimethylamino)methoxypropane obtained in (a), the solution is whether in 100 ml of pure water. After the admixture was extracted with CH2Cl2to the resulting aqueous solution under stirring was added an aqueous solution 2,87 g (10.0 mmol) of bis-triftormetilfullerenov lithium in 100 ml of pure water. After 60 minutes of continuous stirring the resulting hydrophobic white solid was washed with water two or three times, was extracted with dichloromethane and purified on a column of aluminum oxide. The extract was concentrated and then dried under vacuum at 80°C for 10 h, receiving 4,50 g (yield: 95%) of product, which was a white solid at room temperature and a colorless transparent liquid at 130°C.

The connection is identified by a nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). The connection is identified as the desired compound, which represents a bis-triftormetilfullerenov three(dimethylamino)methoxypropane. Spectral data is shown below.

1H-NMR (300 MHz, solvent: acetone-d6, standard: tetramethylsilane was): δ 4,06 (d, 3H); 2,90 (d, 18H).

19F-NMR (282 MHz, solvent: acetone-d6, standard: CF3Cl): δ

-79,93 (s, 6F).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical 5]

The fact is the melting temperature value measured by differential scanning calorimeter (DSC8230, supplied by Shimadzu Corp.). The melting temperature was 127°C.

Example 2

(C) Obtaining ethyl sulfate three(dimethylamino)ethoxypropane

In dvuhgolosy flask in the form of eggplant, equipped with irrigation condenser, addition funnel and magnetic stirrer, 2.0 g in (11.2 mmol) of hexamethylphosphoramide at room temperature under nitrogen atmosphere was added dropwise 2.1 g (a 13.4 mmol) diethylsulfate. After 5 days of stirring at 20°C was obtained a white solid salt. Salt was washed with sufficient amount of ether and dried under vacuum at 50°C for 5 h, getting ethyl sulfate three(dimethylamino)ethoxypropane with the release of 87%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: acetone-d6, standard: tetramethylsilane was): δ 4,47 of 4.38 (m, 2H); 3,86 (q, 2H); 2,90 (d, 18H); a 1.45 (t, 3H); of 1.13 (t, 3H).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 6]

(d) Obtaining bis-triftormetilfullerenov three(dimethylamino)ethoxypropane

3,23 g (9.7 mmol) of ethyl sulfate three(dimethylamino)ethoxypropane obtained in (c), was dissolved in 100 ml of pure water. After impurities were extracted

CH2Cl2to the resulting aqueous solution under stirring was added an aqueous solution of 2.8 g (9.7 mmol) of bis-triftormetilfullerenov lithium in 100 ml of pure water. After 60 minutes of continuous stirring the resulting hydrophobic white solid was washed with water two or three times, was extracted with dichloromethane and purified on a column of aluminum oxide. The extract was concentrated and then dried under vacuum at 80°C for 10 h, receiving 4.35 g (yield: 92%) of product, which was a white solid at room temperature and a colorless transparent liquid at 90°C.

The connection is identified by a nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). The connection is identified as the desired compound, which represents a bis-triftormetilfullerenov three(dimethylamino)ethoxypropane. Spectral data is shown below.

1H-NMR (300 MHz, solvent: acetone-d6, standard: tetramethylsilane was): δ 4,46 4,37 (m, 2H), 2,90 (d, N), a 1.45 (t, 3H).

19F-NMR (282 MHz, solvent: acetone-d6, standard: CF3Cl): δ -79,91 (s, 6F).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 7]

The melting temperature measuring and scanning differential calorimeter (DSC8230, supplied by Shimadzu Corp.). The melting temperature was 88°C.

Example 3

(e) Receiving butylsulfide three(dimethylamino)butoxypropan

In dvuhgolosy flask in the form of eggplant, equipped with irrigation condenser, addition funnel and magnetic stir bar, 50.0 g (279 mmol) of hexamethylphosphoramide at room temperature under nitrogen atmosphere was added dropwise of 70.4 g (335 mmol) dibutylaniline. After 7 days of stirring at 30°C was obtained a white solid salt. Salt was washed with sufficient amount of ether and dried under vacuum at 50°C for 5 h, getting butylsulfide three(dimethylamino)butoxypropan with the release of 93%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: acetone-d6, standard: tetramethylsilane was): δ of 4.38 (q, 2H); 3,82 (t, 2H); 2,90 (d, 18H); 1,80-of 1.73 (m, 2H); 1,55-of 1.30 (m, 6H); to 0.96 (t, 3H); from 0.90 (t, 3H).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 8]

(d) Obtaining bis-triftormetilfullerenov three(dimethylamino)butoxypropan

58,4 g (150 mmol) of butylsulfide three(dimethylamino)butoxypropan obtained in (e), was dissolved in 20 ml of pure water. To the resulting aqueous solution under stirring was added an aqueous solution of 43.1 g (150 mmol) of bis-triftormetilfullerenov lithium in 150 ml of pure water. After 2 hours of continuous stirring the resulting hydrophobic transparent liquid was washed with water five times and was extracted with dichloromethane. The extract was concentrated and then dried under vacuum at 80°C for 20 h, receiving 76.9 g (yield: 99%) of product, which was a colorless transparent liquid at room temperature.

The connection is identified by a nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). The connection is identified as the desired compound, which represents a bis-triftormetilfullerenov three(dimethylamino)butoxypropan. Spectral data is shown below.

1H-NMR (300 MHz, solvent: acetone-d6, standard: tetramethylsilane was): δ 4,36 (q, 2H); 2,90 (d, 18H); of 1.84 and 1.75 (m, 2H); 1,55-of 1.42 (m, 2H); to 0.96 (t, 3H).

19F-NMR (282 MHz, solvent: acetone-d6, standard: CF3Cl): δ -79,92 (s, 6F).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 9]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). Temperature p is Alenia was -7,5°C, and the temperature of crystallization was -67°C. the Temperature of thermal decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Corp.). The initial temperature of the mass loss measured at a rate of temperature increase of 10°C/min, was 200°C. these results show that the salt of this example supports a stable liquid state in a wide temperature range from -7,5°C to 200°C.

The viscosity, measured using a vibration type viscometer (supplied by A&D Co., Ltd)was 45 MPa·s at 25°C.

The conductivity, measured by the method of impedance AC current (Electrochemical Measurement System HZ-3000 set Hokuto Denko Corp.), was 0.3 Cm·m-1at 25°C.

In addition, cyclic voltammogram measured Electrochemical Measurement System HZ-3000 set Hokuto Denko Corp., using a Pt working electrode, Pt counter-electrode and Li reference electrode, showed that the window of potential ranged from minus 0.1 V to 4.9 In relation to the potential of Li/Li+. Volt-ampere characteristic of bis-triftormetilfullerenov three(dimethylamino)butoxypropan shown in figure 1.

Example 4

(g) Receiving butylsulfide three(dimethylamino)butylphosphine

In dvuhgolosy flask in the form of eggplant, equipped with irrigation condenser, addition funnel and magnetic stirrer, 24.2 g (149 mmol) of Tria the IDA of hexamethylphosphoric at room temperature under nitrogen atmosphere was added dropwise with 37.4 g (178 mmol) of diethylsulfate. After 3 days of stirring at room temperature was obtained a white solid salt. Salt was washed with sufficient amount of ether and dried under vacuum at 50°C for 5 h, getting butylsulfide three(dimethylamino)butylphosphine with the release of 94%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: acetone-d6, standard: tetramethylsilane was): δ a 3.83 (t, 2H); 2,85 (d, 18H); 2,73-2,63 (m, 2H); 1.70 to to 1.33 (m, 8H); to 0.97 (t, 3H); from 0.90 (t, 3H).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 10]

(h) Obtaining bis-triftormetilfullerenov three(dimethylamino)butylphosphine

with 37.4 g (100 mmol) of butylsulfide three(dimethylamino)butylphosphine obtained in (g), was dissolved in 200 ml of pure water. To the resulting aqueous solution under stirring was added an aqueous solution of 28.7 g (100 mmol) of bis-triftormetilfullerenov lithium in 150 ml of pure water. After 2 hours of continuous stirring the resulting hydrophobic transparent liquid was washed with pure water five times and was extracted with dichloromethane. The extract was concentrated and then dried under vacuum at 80°C is for 20 h, getting to 46.7 g (yield: 93%) of product, which was a colorless transparent liquid at room temperature.

The connection is identified by a nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). The connection is identified as the desired compound, which represents a bis-triftormetilfullerenov three(dimethylamino)butylphosphine. Spectral data is shown below.

1H-NMR (300 MHz, solvent: acetone-d6, standard: tetramethylsilane was): δ 2,85 (d, 18H); 2,66-of 2.56 (m, 2H); 1,75-to 1.63 (m, 2H); 1.57 in-a 1.45 (m, 2H); to 0.97 (t, 3H).

19F-NMR (282 MHz, solvent: acetone-d6, standard: CF3Cl): δ -79,87 (s, 6F).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 11]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). The melting temperature was 20.8°C, and the crystallization temperature was minus 0.6°C. the Temperature of thermal decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Corp.). The initial temperature of the mass loss measured at a rate of temperature increase of 10°C/min, 320°C. these results show that the salt of this example supports a stable liquid state in a wide temperature range from 20,8°C to 320°C.

The viscosity, measured using a vibration type viscometer (supplied by A&D Co., Ltd), was 53 MPa·s at 40°C.

The conductivity, measured by the method of impedance AC current (Electrochemical Measurement System HZ-3000 set Hokuto Denko Corp.), was 0.3 Cm·m-1at 40°C.

In addition, cyclic voltammogram measured Electrochemical Measurement System HZ-3000 set Hokuto Denko Corp., using a Pt working electrode, Pt counter-electrode and Li reference electrode, showed that the window of potential ranged from 0 to 4.9 In relation to the potential of Li/Li+. Volt-ampere characteristic of bis-triftormetilfullerenov three(dimethylamino)butylphosphine shown in figure 2.

Example 5

(i) Obtaining Tris(methylbutylamine)phosphine

In a 1000 ml three-neck flask equipped with a dropping funnel and a magnetic stirrer, at room temperature and under nitrogen atmosphere was added 8.7 ml (0.10 mol) of trichloride phosphorus and 1000 ml of anhydrous diethyl ether. After cooling the mixture in an ice bath gradually dropwise with stirring was added 70 ml of 0.60 mol) of methylbutylamine. After the reaction mixture was stirred for 1 h while cooling in an ice bath. The reaction mixture was filtered under pressure in a nitrogen atmosphere, and the resulting crystals three times washed with anhydrous diethyl ether. Crystals is ciali by distillation at a temperature of from 105°C to 118°C under reduced pressure of 0.2 kPa, getting 21,28 g of Tris(methylbutylamine)phosphine, which was a transparent liquid. The yield was 74%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): δ was 2.76 (m, 6H); 2,43 (d, 9H); to 1.45 (m, 6H); of 1.27 (m, 6H); of 0.91 (t, 9H).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): δ 120,88 (s, 1P).

The structural formula is shown below.

[Chemical product 12]

(h) Obtaining methyl sulfate Tris(methylbutylamine)methylphosphine

In 50 ml of dvuhgolosy flask equipped with a magnetic stirrer, at room temperature under nitrogen atmosphere was added a cooled on an ice bath of 4.00 g (0,0138 mol) of Tris(methylbutylamine)phosphine obtained in (i), and then was added dropwise 1.6 ml (of 0.017 mol) dimethylsulfate. After 12 hours stirring at room temperature the reaction mixture was three times washed with diethyl ether and then dried under vacuum at room temperature, receiving 4,18 g of methyl sulfate Tris(methylbutylamine)methylphosphine, which was a transparent liquid at room temperature. The yield was 73%.

The resulting connection ID which was tificially spectrometer nuclear magnetic resonance (BRUKER Ultra Shield 300 NMR spectrometer, supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): δ 3,71 (s, 3H); 2,96 (m, 6H); was 2.76 (d, 9H); 2,09 (d, 3H); 1.57 in (m, 6H); of 1.33 (m, 6H); to 0.96 (t, 9H).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): 58,79 (m, 1P).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 13]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). The glass transition temperature was -70,4°C. the Temperature of thermal decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Corp.). The temperature of 5% weight loss measured at a rate of temperature increase of 10°C/min, was 263,5°C.

Example 6

Obtaining bis-triftormetilfullerenov Tris(methylbutylamine)methylphosphine

In a 100 ml flask in the form of eggplant, equipped with a magnetic stirrer, was added to 1.00 g (0,0024 mol) of methyl sulfate Tris(methylbutylamine)methylphosphine obtained in (j), and 10 ml of ultrapure water, and then with stirring, was added an aqueous solution of 0.8 g (0,0026 mol) bis-triftormetilfullerenov lithium in 10 ml of ultrapure water. The reaction mixture was stirred at room temperature for 62 hours Obtained in achiev is Tata salt was extracted with 20 ml of CH 2Cl2and the aqueous layer was additionally extracted with 20 ml of CH2Cl2. Then the organic layer was three times washed with 20 ml of ultrapure water, the extract was concentrated on a rotary evaporator, three times washed with diethyl ether and then dried under vacuum at 80°C, receiving of 0.91 g of bis-triftormetilfullerenov Tris(methylbutylamine)methylphosphine, which was a transparent liquid at room temperature. The yield was 65%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): δ 2.91 in (m, 6H); a 2.71 (d, 9H); of 1.92 (d, 3H); and 1.56 (m, 6H); 1.32 to (m, 6H); to 0.96 (t, 9H).

19F-NMR (282 MHz, solvent: CDCl3reference: CF3Cl): δ -78,82 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): δ 57,98 (m, 1P).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 14]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). The melting point was -5,5°C. the crystallization Temperature was -484°C. The glass transition temperature was -82,9°C. the Temperature of thermal decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Corp.). The temperature of 5% weight loss measured at a rate of temperature increase of 10°C/min, was 377,6°C.

Example 7

(1) Obtaining tetrafluoroborate Tris(methylbutylamine)methylphosphine

In a 100 ml flask in the form of eggplant, equipped with a magnetic stirrer, was added to 1.00 g (0,0024 mol) of methyl sulfate Tris(methylbutylamine)methylphosphine obtained in (j), and 10 ml of ultrapure water, and then with stirring, was added an aqueous solution of 0.3 g (0,0026 mol) of tetrafluoroborate of ammonia in 10 ml of ultrapure water. The reaction mixture was stirred at room temperature for 62 hours the resulting salt was extracted with 20 ml of CH2CL2and the aqueous layer was additionally extracted with 20 ml of CH2CL2. Then the organic layer was three times washed with 20 ml of ultrapure water, the extract was concentrated on a rotary evaporator, three times washed with diethyl ether and then dried under vacuum at 80°C, receiving 0,60 g tetrafluoroborate Tris(methylbutylamine)methylphosphine, which was a white solid at room temperature. The yield was 64%.

The resulting compound was identified spectrometer nuclear magnetic resonance is (BRUKER Ultra Shield 300 NMR spectrometer, supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): δ 2,96 (m, 6H); 2,73 (d, 9H); 1,99 (d, 3H); of 1.55 (m, 6H); of 1.33 (m, 6H); of 0.95 (t, 9H).

19F-NMR (282 MHz, solvent: CDCl3reference: CF3Cl): δ -152,69 (d, 4F).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): δ 58,72 (m, 1P).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 15]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). The melting point was 116,5°C. the Temperature of thermal decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Corp.). The temperature of 5% weight loss measured at a rate of temperature increase of 10°C/min, was 404,6°C.

Example 8

(m) Receiving hexaphosphate Tris(methylbutylamine)methylphosphine

In a 100 ml flask in the form of eggplant, equipped with a magnetic stirrer, was added to 1.00 g (0,0024 mol) of methyl sulfate Tris(methylbutylamine)methylphosphine obtained in (j), and 10 ml of ultrapure water, and then with stirring, was added an aqueous solution of 0.4 g (0,0026 mol) of hexaflurophosphate lithium in 10 ml of ultrapure water. The reaction mixture was stirred at room is the temperature within 86 hours The resulting salt was extracted with 20 ml of CH2Cl2and the aqueous layer was additionally extracted with 20 ml of CH2Cl2. Then the organic layer was three times washed with 20 ml of ultrapure water, the extract was concentrated on a rotary evaporator, three times washed with diethyl ether and then dried under vacuum at 80°C, receiving 0,48 g hexaphosphate Tris(methylbutylamine)methylphosphine, which was a white solid at room temperature. The yield was 44%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): δ 2,92 (m, 6H); 2,72 (d, 9H); of 1.92 (d, 3H); and 1.56 (m, 6H); 1.32 to (m, 6H); to 0.96 (t, 9H).

19F-NMR (282 MHz, solvent: CDCl3reference: CF3Cl): δ -72,84 (d, 6F).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): 58,32 (m, 1P); -144,25 (hept, 1P).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 16]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). There was no peak corresponding tempera is ur melting. The temperature of thermal decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Corp.). The temperature of 5% weight loss measured at a rate of temperature increase of 10°C/min, was 393,2°C.

Example 9

(n) Obtaining ethyl sulfate Tris(methylbutylamine)ethylphosphonic

In 50 ml of dvuhgolosy flask equipped with a magnetic stirrer, at room temperature under nitrogen atmosphere was added a cooled on an ice bath of 4.00 g (0,0138 mol) of Tris(methylbutylamine)phosphine obtained in (i), and then was added dropwise 2.2 ml (of 0.017 mol) diethylsulfate. After 37 hours of stirring at 30°C the reaction mixture was three times washed with diethyl ether and dried under vacuum at room temperature, receiving 3,41 g of ethyl sulfate Tris(methylbutylamine)ethylphosphonic, which was a transparent liquid at room temperature. The yield was 57%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): δ 4.09 to (m, 2H); 2,96 (m, 6H); 2,78 (d, 9H); 2,60 (m, 2H); to 1.59 (m, 6H); 1,40-of 1.24 (m, 12H); to 0.96 (t, 9H).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): δ 61,87 (m, 1P).

The structural formula shown in the e (dotted line in the formula represents a paired structure).

[Chemical product 17]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). There was no peak corresponding to the melting point. The temperature of thermal decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Corp.). The temperature of 5% weight loss measured at a rate of temperature increase of 10°C/min, was 250,5°C.

Example 10

(o) Obtaining bis-triftormetilfullerenov Tris(methylbutylamine)ethylphosphonic

In a 100 ml flask in the form of eggplant, equipped with a magnetic stirrer, was added to 1.00 g (0,0023 mol) of ethyl sulfate Tris(methylbutylamine)ethylphosphonic obtained in (n), and 10 ml of ultrapure water, and then with stirring, was added an aqueous solution of 0.8 g (0,0026 mol) bis-triftormetilfullerenov lithium in 10 ml of ultrapure water. The reaction mixture was stirred at room temperature for 62 hours the resulting salt was extracted with 20 ml of CH2Cl2and the aqueous layer was additionally extracted with 20 ml of CH2Cl2. Then the organic layer was three times washed with 20 ml of ultrapure water, the extract was concentrated on a rotary evaporator, three times washed with diethyl ether and then dried under vacuum at 80°C, receiving 0.73 g of bis-triftormetilfullerenov the Tris(methylbutylamine)ethylphosphonic, which was a transparent liquid at room temperature. The yield was 53%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: Dl3standard: tetramethylsilane was): δ 2,92 (m, 6N); 2,72 (d, N); is 2.37 (m, 2H); was 1.58 (m, 6N); 1,39-1,20 (m, N); 0,97 (t, N).

19F-NMR (282 MHz, solvent: Dl3reference: CF3CL): δ - 78,83 (s, 6F).

31P-NMR (121 MHz, solvent: Dl3reference: triphenylphosphine): δ 61,02 (m, 1P).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 18]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). The melting point was -20,6°C. the glass transition Temperature was -84,6°C. the Temperature of thermal decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Corp.). The temperature of 5% weight loss measured at a rate of temperature increase of 10°C/min, was 362,8°C.

The conductivity, measured by the method of impedance AC current (Electrochemical Measurement System HZ-3000 set Hokuto Denko Corp.), status the Vila of 0.085 Cm·m -1at 25°C.

Example 11

(p) Obtaining tetrafluoroborate Tris(methylbutylamine)ethylphosphonic

In a 100 ml flask in the form of eggplant, equipped with a magnetic stir bar, was added 0,86 g (0,0019 mol) of ethyl sulfate Tris(methylbutylamine)ethylphosphonic obtained in (n), and 10 ml of ultrapure water, and then with stirring, was added an aqueous solution of 0.3 g (0,0026 mol) of tetrafluoroborate of ammonia in 10 ml of ultrapure water. The reaction mixture was stirred at room temperature for 14 hours the resulting salt was extracted with 20 ml of CH2Cl2and the aqueous layer was additionally extracted with 20 ml of CH2Cl2. Then the organic layer was three times washed with 20 ml of ultrapure water, the extract was concentrated on a rotary evaporator, three times washed with diethyl ether and then dried under vacuum at 80°C, receiving 0.65 g of tetrafluoroborate Tris(methylbutylamine)ethylphosphonic, which was a transparent liquid at room temperature. The yield was 84%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): δ 2,95 (m, 6H); 2,75 (d, 9H); of 2.45 (m, 2H); was 1.58 (m, 6H); 1,37-1,22 (m, 9H); to 0.96 (t, 9H).

19F-NMR (282 MHz, rest ritel: CDCl 3reference: CF3Cl): δ -153,27 (d, 4F).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): δ 61,41 (m, 1P).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 19]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). The melting temperature was 1.0°C. the crystallization Temperature was -32,7°C. the glass transition Temperature was -75,5°C. the Temperature of thermal decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Corp.). The temperature of 5% weight loss measured at a rate of temperature increase of 10°C/min, was 389,1°C.

Example 12

(q) Receiving hexaphosphate Tris(methylbutylamine)ethylphosphonic

In a 100 ml flask in the form of eggplant, equipped with a magnetic stirrer, was added to 1.00 g (0,0023 mol) of ethyl sulfate Tris(methylbutylamine)ethylphosphonic obtained in (n), and 10 ml of ultrapure water, and then with stirring, was added an aqueous solution of 0.7 g (0,0046 mol) of hexaflurophosphate lithium in 10 ml of ultrapure water. The reaction mixture was stirred at room temperature for 14 hours the resulting salt was extracted with 20 ml of CH2Cl2and the aqueous layer was additionally extracted with 20 ml of C 2Cl2. Then the organic layer was three times washed with 20 ml of ultrapure water, the extract was concentrated on a rotary evaporator, three times washed with diethyl ether and then dried under vacuum at 80°C, receiving 0.65 g of hexaflurophosphate Tris(methylbutylamine)ethylphosphonic, which was a transparent liquid at room temperature. The yield was 44%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): δ of 2.93 (m, 6H); 2,73 (d, 9H); 2,47 (m, 2H); was 1.58 (m, 6H); 1,37 is 1.20 (m, 9H); of 0.95 (t, 9H).

19F-NMR (282 MHz, solvent: CDCl3reference: CF3Cl): -73,15 (d, 6F).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): 61,00 (m, 1P); -144,29 (hept, 1P).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 20]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). There was no peak corresponding to the melting point. The temperature of thermal decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Cop.). The temperature of 5% weight loss measured at a rate of temperature increase of 10°C/min, was 319,5°C.

Example 13

(r) Receiving n-butylsulfide Tris(methylethylamine)n-butylphosphine

In 50 ml of dvuhgolosy flask equipped with a magnetic stirrer, at room temperature under nitrogen atmosphere was added 2,33 g (0,0114 mol) of Tris(methylethylamine)phosphine obtained as in (i). After cooling in an ice bath was added dropwise to 2.7 ml (0,0136 mol) of di-n-butylsulfide. The reaction mixture was stirred for 87 hours at room temperature and then for 72 hours at 30°C. Then the reaction mixture was three times washed with diethyl ether and dried under vacuum at room temperature, receiving a 3.83 g of n-butylsulfide Tris(methylethylamine)n-butylphosphine, which was a transparent liquid at room temperature. The yield was 94%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): Android 4.04 (t, 2H); 3,11 (m, 6H); 2,77 (d, 9H); 2,48 (m, 2H); 1,67 to 1.37 (m, 8H); to 1.24 (t, 9H); 0,99-to 0.88 (m, 6H).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): 59,52 (m, 1P).

The structural formula shown below (the dotted line in the formula p is ecstasy mating structure).

[Chemical product 21]

Example 14

(s) Receiving bis-triftormetilfullerenov Tris(methylethylamine)n-butylphosphine

In a 100 ml flask in the form of eggplant, equipped with a magnetic stirrer, was added to 1.00 g (0,0024 mol) of n-butylsulfide Tris(methylethylamine)n-butylphosphine obtained in (r), and 10 ml of ultrapure water, and then with stirring, was added an aqueous solution of 0.9 g (0,0029 mol) bis-triftormetilfullerenov lithium in 10 ml of ultrapure water. The reaction mixture was stirred at room temperature for 14 hours the resulting salt was extracted with 20 ml of CH2Cl2and the aqueous layer was additionally extracted with 20 ml of CH2Cl2. Then the organic layer was three times washed with 20 ml of ultrapure water, the extract was concentrated on a rotary evaporator, three times washed with diethyl ether and then dried under vacuum at 80°C receives 0.74 g of bis-triftormetilfullerenov Tris(methylethylamine)n-butylphosphine, which was a transparent liquid at room temperature. The yield was 57%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: Dl3reference: tetr methylsilane): δ 3,05 (m, 6N); 2,72 (d, N); 2,28 (m, 2H); is 1.51 (m, 4H); of 1.23 (t, N); to 0.97 (t, 3H).

19F-NMR (282 MHz, solvent: CDCl3reference: CF3CL): δ - 78,84 (s, 6F).

31P-NMR (121 MHz, solvent: Dl3reference: triphenylphosphine): δ 59,02 (m, 1P).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 22]

[Chemical product 22]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). The melting point was -18,7°C. the crystallization Temperature was -47,9°C. the Temperature of thermal decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Corp.). The temperature of 5% weight loss measured at a rate of temperature increase of 10°C/min, was 393,0°C.

Example 15

(t) Receive tetrafluoroborate Tris(methylethylamine)n-butylphosphine

In a 100 ml flask in the form of eggplant, equipped with a magnetic stirrer, was added to 1.00 g (0,0024 mol) of n-butylsulfide Tris(methylethylamine)n-butylphosphine obtained in (r), and 10 ml of ultrapure water, and then with stirring, was added an aqueous solution of 0.4 g (0,0029 mol) of tetrafluoroborate of ammonia in 10 ml of ultrapure water. The reaction mixture was stirred at room the temperature for 14 hours The resulting salt was extracted with 20 ml of CH2Cl2and the aqueous layer was additionally extracted with 20 ml of CH2Cl2. Then the organic layer was three times washed with 20 ml of ultrapure water, the extract was concentrated on a rotary evaporator, three times washed with diethyl ether and then dried under vacuum at 80°C, receiving 0.87 g of tetrafluoroborate Tris(methylethylamine)n-butylphosphine, which was a white solid at room temperature. The yield was 99%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): δ is 3.08 (m, 6H); 2,75 (d, 9H); of 2.38 (m, 2H); 1,53 (m, 4H); of 1.23 (t, 9H); to 0.97 (t, 3H).

19F-NMR (282 MHz, solvent: CDCl3reference: CF3Cl): δ -153,07 (d, 4F).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): δ 59,40 (m, 1P).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 23]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). There was no peak corresponding to the temperature of plaul the deposits. The temperature of thermal decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Corp.). The temperature of 5% weight loss measured at a rate of temperature increase of 10°C/min, was 333,0°C.

Example 16

(u) Receiving hexaphosphate Tris(methylethylamine)n-butylphosphine

In a 100 ml flask in the form of eggplant, equipped with a magnetic stirrer, was added to 1.00 g (0,0024 mol) of n-butylsulfide Tris(methylethylamine)n-butylphosphine obtained in (r), and 10 ml of ultrapure water, and then with stirring, was added an aqueous solution of 0.5 g (0,0029 mol) of hexaflurophosphate lithium in 10 ml of ultrapure water. The reaction mixture was stirred at room temperature for 14 hours the resulting salt was extracted with 20 ml of CH2Cl2and the aqueous layer was additionally extracted with 20 ml of CH2Cl2. Then the organic layer was three times washed with 20 ml of ultrapure water, the extract was concentrated on a rotary evaporator, three times washed with diethyl ether and then dried under vacuum at 80°C, receiving 0.95 g of hexaflurophosphate Tris(methylethylamine)n-butylphosphine, which was a white solid at room temperature. The yield was 97%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer, set aemy BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): δ of 3.06 (m, 6H); 2,72 (d, 9H); 2,39 (m, 2H); of 1.52 (m, 4H); 1,22 (t, 9H); to 0.97 (t, 3H).

19F-NMR (282 MHz, solvent: CDCl3reference: CF3Cl): δ -73,08 (d, 6F).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): δ 59,08 (m, 1P); -144,27 (hept, 1P).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 24]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). He observed no peak corresponding to the melting point. The temperature of thermal decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Corp.). The temperature of 5% weight loss measured at a rate of temperature increase of 10°C/min, was 369,2°C.

Example 17

(v) Obtaining oxide Tris(methylbutylamine)phosphine

In a 200 ml three-neck flask equipped with a dropping funnel and a magnetic stirrer, at room temperature and under nitrogen atmosphere was added 1.8 ml (at 0.020 mol) of phosphorylchloride and 100 ml of anhydrous dibutylamino ether. After cooling the mixture in an ice bath gradually dropwise with stirring was added 21 ml (0,180 mol) mailbu is Ilumina. Next, the reaction mixture was stirred at 120°C for 36 h, and then the reaction mixture was filtered under pressure in a nitrogen atmosphere. The resulting crystals three times washed with anhydrous debutalbum ether and purified by distillation under reduced pressure of 0.2 kPa and a temperature of from 119 to 124°C, receiving 5,54 g of Tris(methylbutylamine)oksolina, which was a transparent liquid. The yield was 74%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): δ equal to 2.94 (m, 6H); 2,66 (d, 9H); is 1.51 (m, 6H); of 1.30 (m, 6H); of 0.93 (t, 9H).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): δ 25,26 (m, 1P).

The structural formula is shown below.

[Chemical product 25]

(w) to Obtain ethyl sulfate Tris(methylbutylamine)ethylphosphonic

In 50 ml of dvuhgolosy flask equipped with a magnetic stirrer, at room temperature under nitrogen atmosphere was added and 2.26 g (0,0074 mol) of Tris(methylbutylamine)oksolina obtained in (v), and then was added dropwise 1.2 ml (0,0089 mol) diethylsulfate. The mixture was stirred at 30°C for 69 h, and then three times washed with diethyl ether and dried under Vacu the IOM at room temperature, getting 0.65 g of ethyl sulfate Tris(methylbutylamine)ethoxypropane, which was a transparent liquid at room temperature. The yield was 19%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): δ 4,36 (m, 2H); 4,10 (square, 2H); to 3.02 (m, 6H); 2,84 (d, 9H); was 1.58 (m, 6H); a 1.45 (t, 3H); 1,40-of 1.26 (m, 9H); to 0.96 (t, 9H).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): δ 35,87 (m, 1P).

The structural formula shown below (the dotted line in the formula represents a paired structure).

[Chemical product 26]

Example 18

(x) Receiving bis-triftormetilfullerenov Tris(methylbutylamine)ethoxypropane

In a 50 ml flask in the form of eggplant, equipped with a magnetic stir bar, was added 0.65 g (0,0014 mol) of ethyl sulfate Tris(methylbutylamine)ethoxypropane obtained in (w), and 10 ml of ultrapure water, and then with stirring, was added an aqueous solution of 0.5 g (0,0015 mol) bis-triftormetilfullerenov lithium in 10 ml of ultrapure water. The reaction mixture was stirred at 30°C for 62 h the resulting salt was extracted with 20 ml of CH2Cl2and the water layer will complement the flax was extracted with 20 ml of CH 2Cl2. Then the organic layer three times washed with 40 ml of ultrapure water, the extract was concentrated on a rotary evaporator, three times washed with diethyl ether and then dried under vacuum at 80°C, obtaining 0.8 g of bis-triftormetilfullerenov Tris(methylbutylamine)ethoxypropane, which was a transparent liquid at room temperature. The yield was 93%.

The resulting compound was identified by nuclear magnetic resonator (BRUKER Ultra Shield 300 NMR spectrometer supplied by BRUKER Corp.). Spectral data is shown below.

1H-NMR (300 MHz, solvent: CDCl3standard: tetramethylsilane was): δ to 4.23 (m, 2H); 2,98 (m, 6H); 2,77 (d, 9H); was 1.58 (m, 6H); 1,46-of 1.27 (m, 9H); to 0.96 (t, 9H).

19F-NMR (282 MHz, solvent: CDCl3reference: CF3Cl): δ -78,83 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3reference: triphenylphosphine): δ 35,83 (m, 1P).

The structural formula shown below (the dotted line in the formula represents a paired structure)

[Chemical product 27]

The melting temperature was measured by differential scanning calorimeter (DSC8230 supplied by Shimadzu Corp.). The melting point was -19,9°C. the crystallization Temperature was -55,8°C. the glass transition Temperature was -85,9°C. the Temperature of the baths is ical decomposition was measured by thermogravimetric analyzer (TG8120, supplied by Rigaku Corp.). The temperature of 5% weight loss measured at a rate of temperature increase of 10°C/min, was 208,6°C.

Industrial applicability

The present invention provides an ionic liquid, which shows a stable liquid state in a wide temperature range from low temperatures and has a low viscosity, adequate electrical conductivity and excellent electrochemical stability.

The ionic liquid of the present invention can be used in such applications as lithium batteries, capacitors, electric double layer, fuel cells, dye sensitized solar cells, electrolytes, electrolyte solutions or additives for electrical storage devices of the reaction solvents, etc.

1. The ionic liquid including a cationic component and an anionic component and the cationic component is a one kind or more kinds selected from the group consisting of a cation component represented by the following formula (I)

where the substituting group R1-R9can be independently the same or different from each other; each of the substituting groups R1-R9represents a hydrogen atom or alkyl group with p the pit or branched chain, containing from 1 to 30 carbon atoms; any carbon atom contained in the replacement group, R1-R9may be replaced by atoms and/or atomic group selected from the group consisting of-O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-;
X represents a sulfur atom, an oxygen atom or a carbon atom; R8and R9exist only when X is a carbon atom and the dotted line represents the mating structure;
anionic component is one or more kinds selected from the group consisting of [RSO3]-, [RfSO3]-, [(RfSO2)2N]-, [(FSO2)3C]-, [RCH2OSO3]-, [RC(O)O]-, [RfC(O)O]-, [CCl3C(O)O]-, [(CN)3C]-, [(CN)2CR]-, [(RO(O)C)2CR]-, [B(OR)4]-, [N(CF3)2]-, [N(CN)2]-, [AlCl4]-PF6-BF4-, SO42-, HSO4-, NO3-; where each replacement group R represents a hydrogen atom, halogen atom, alkyl group with straight or branched chain, containing from 1 to 10 carbon atoms, alkenylphenol group with a straight or branched chain, containing from 2 to 10 carbon atoms, with one or more double bonds, alkylamino group is straight or branched chain, containing from 2 to 10 carbon atoms, with one or more triple bonds, saturated or partially or fully unsaturated cycloalkyl group; any hydrogen atoms contained in the replacement of the R groups may be partly or completely replaced by halogen atom; any carbon atom contained in the replacement of the R groups may be replaced by atoms and/or atomic group selected from the group consisting of-O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2- and-SO3-; and Rfrepresents a fluorine-containing replacement group.

2. The ionic liquid according to claim 1 where the anionic component is one or more kinds selected from the group consisting of [RfSO3]-, [(RfSO2)2N]-, CF3SO3-, CF3Soo-PF6-BF4-, SO42-, HSO4-, NO3-.

3. The ionic liquid according to claim 1 where the anionic component is one or more kinds selected from the group consisting of [RfSO3]-, [(RfSO2)2N]-, CF3SO3-, CF3Soo-, SO42-, HSO4-and NO3-.

4. The ionic liquid according to any one of claims 1 to 3, where the substituting group, R1-R9can be independently the same or different is engaged from each other; each of the substituting groups R1-R9represents a hydrogen atom or alkyl group with straight or branched chain, containing from 1 to 30 carbon atoms; any carbon atom contained in the replacement group, R1-R9may be replaced by atoms and/or atomic group selected from the group consisting of-O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-.

5. The ionic liquid according to any one of claims 1 to 3, where each of the substituting groups R1-R9in the General formula (1) represents an alkyl group with straight or branched chain, containing from 1 to 20 carbon atoms, and they may be the same or different from each other.

6. The ionic liquid according to any one of claims 1 to 3, where X in the General formula (1) represents a sulfur atom or an oxygen atom.

7. The ionic liquid according to any one of claims 1 to 3, where X in the General formula (1) represents the oxygen atom.

8. The ionic liquid according to claim 1 where the anionic component is one or more kinds selected from the group consisting of [RfSO3]-, [(RfSO2)2N]-, CF3SO3-, CF3Soo-, SO42-, HSO4-and NO3-in the General formula (1) each of R1-R9represents an alkyl group with straight or branched chain, containing from 1 to 10 atoms of plastics technology : turning & the Yes, and they may be the same or different from each other.

9. The ionic liquid according to claim 1 where the anionic component is one or more kinds selected from the group consisting of [RfSO3]-, [(RfSO2)2N]-, CF3SO3-, CF3Soo-, SO42-, HSO4-and NO3-; and in General formula (1) each of R1-R9represents an alkyl group with straight or branched chain, containing from 1 to 10 carbon atoms, and they may be the same or different from each other; and X represents a sulfur atom or an oxygen atom.

10. The ionic liquid according to claim 1 where the anionic component is one or more kinds selected from the group consisting of [RfSO3]-, [(RfSO2)2N]-, CF3SO3-, CF3Soo-, SO42-, HSO4-and NO3-; and in General formula (1) each of R1-R9represents an alkyl group with straight or branched chain, containing from 1 to 10 carbon atoms, and they may be the same or different from each other; and X represents an oxygen atom.

11. The ionic liquid according to claim 1, where in the General formula (1) each of R2-R7is sobieskiego group with a straight chain, containing from 1 to 4 carbon atoms; each of R8and R9represents a hydrogen atom; and R1represents an alkyl group with straight or branched chain, containing from 1 to 10 carbon atoms; and the anionic component is a (CF3SO2)2N-, F6-or BF4-.

12. The ionic liquid according to claim 1, where in the General formula (1) each of R2-R7represents an alkyl group with a straight chain containing from 1 to 4 carbon atoms; each of R8and R9represents a hydrogen atom; R1represents an alkyl group with straight or branched chain, containing from 1 to 10 carbon atoms; X represents a sulfur atom or an oxygen atom; and the anionic component is a (CF3SO2)2N-PF6-or BF4-.

13. The ionic liquid according to claim 1, where in the General formula (1) each of R2-R7represents an alkyl group with a straight chain containing from 1 to 4 carbon atoms; each of R8and R9represents a hydrogen atom; R1represents an alkyl group with straight or branched chain, containing from 1 to 10 carbon atoms, X represents an oxygen atom; and the anionic component is a (CF3SO2)2N-,F 6-or BF4-.

14. The ionic liquid according to claim 1, where in the General formula (1) each of R2-R7represents an alkyl group with a straight chain containing from 1 to 4 carbon atoms; each of R8and R9represents a hydrogen atom; R1represents an alkyl group with straight or branched chain, containing from 1 to 10 carbon atoms; and the anionic component is a (CF3SO2)2N-.

15. The ionic liquid according to claim 1, where in the General formula (1) each of R2-R7represents an alkyl group with a straight chain containing from 1 to 4 carbon atoms; each of R8and R9represents a hydrogen atom; R1represents an alkyl group with straight or branched chain, containing from 1 to 10 carbon atoms; X represents a sulfur atom or an oxygen atom; and the anionic component is a (CF3SO2)2N-.



 

Same patents:

FIELD: metallurgy.

SUBSTANCE: invention relates to a method of obtaining glass-to-metal and metal-ceramic compounds and metal-metal compounds used in solid oxide fuel cells. According to the invention, the compounds are obtained by using a mixture of powders of base glass and metal oxide. Adding some components to the glass used in the composite joints, for instance MgO, that influence on its viscosity and wetting ability ensures a local change in the glass properties near the interface with the metal and at the same time making glass bulk properties including increased coefficient of thermal expansion closer to the properties of the other components of the joint.

EFFECT: high performance, durability and operating safety of the fuel cells.

16 cl, 9 dwg, 2 tbl, 14 ex

Fuel element // 2361328

FIELD: physics.

SUBSTANCE: invention relates to a fuel element with a separator. According to the invention, the fuel element (100) has a junction area, in which a first conducting separator (1), electrolyte strengthening substrate (3) and a second conducting separator (8) are successively joined by hard solders (11) and (12). The electrolyte strengthening substrate (3) is such that, it is bigger than the junction of the first conducting separator (1) and the junction of the second conducting separator (8) at the junction area. The electrolyte strengthening substrate (3) has insulating property at least in the same area where the electrolyte strengthening substrate (3) is in contact with hard solders (11) and (12).

EFFECT: prevention of electrical locking.

6 cl, 7 dwg

FIELD: instrument making.

SUBSTANCE: invention relates to units incorporating solid-oxide fuel elements. In compliance with this invention, the unit incorporating the solid-oxide fuel element comprises the main load-bearing branch pipe containing one or more transforming catalysts, fuel element plate, current collector with current corrector plate and, at least, one fuel element. The proposed unit differs from known designs in that, at least, its one fuel element and current collector plate can move in direction parallel to the lengthwise axis of, at least, one fuel element.

EFFECT: reduction or elimination of temperature loads that are likely to cause premature fault of solid-state fuel elements.

25 cl, 22 dwg

FIELD: instrument-making.

SUBSTANCE: invention relates to fuel cell and fuel cell separator construction. According to the invention the fuel cell contains a junction of the electrolyte and the separator, having one side as the side which forms the tract of the flow of gas, with the flow of gas formed on it to make it possible for the flow of reactive gas, and the other side which is opposite the first side, as the side which forms the tract for the flow of the coolant, with the tract for the flow of the coolant formed on it to make it possible for the flow of the coolant. The side forming the tract for the flow of gas of the separator has a lot of linear tracts for the flow of gas, which are located parallel to each other, and an interconnecting tract for the flow of gas, which divides many linear tracts for the flow of gas into many groups of linear tracts for the flow of gas and joins at least part of the many groups of linear tracts for the flow of gas sequentially. The side which forms the tract for the flow of the coolant, has a lot of linear tracts for the flow of the coolant, which are formed like inverted (reverse) construction of many tracts for the flow of gas to the side forming the tracts for the flow of gas, and an interconnecting tract for the flow of the coolant, which is formed as an inverted construction interconnecting the tract for the flow of gas to the side, which forms the tract for the flow of gas, in order to join many linear tracts for the flow of the coolant in parallel.

EFFECT: an increase in electrical and thermal conductivity.

29 cl, 28 dwg

FIELD: electrics.

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19 cl, 21 dwg

FIELD: electricity.

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EFFECT: improved technical properties of the material.

25 cl, 4 dwg, 3 tbl, 3 ex

FIELD: electricity.

SUBSTANCE: invention deals with bipolar plates designed to provide for dispensation of reactants with fuel cell batteries and electrical commutation between the battery fuel cells. Method proposed envisages fabrication of fuel cell bipolar plates of suitable sheet material prepared by way of shaping and application of carbon coating. Its specificity consists in the sheet material being manufactured of thermally expanded graphite through graphite particles consolidation, rolling and intermediate annealing, cylinder rolled or pressed into shape and applied carbon material coating on through pulse pyrolytic saturation at temperature of 600-1000°C, the weight increment as a result of the coating application as compared to the sheet material pre-product amounting to 2÷10%. The fuel cell bipolar plate thus fabricated is composed of conductive shaped sheet and a carbon coating; its density is equal to 1÷1.2 g/cm3 with specific resistivity in the direction perpendicular to the bipolar plate plane amounting to 0.03÷0.05 Ohm·cm.

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2 cl, 1 ex

FIELD: heating; electricity.

SUBSTANCE: in bipolar plate of fuel element, which contains plate that has certain area and thickness; inlet and outlet buffer channels, which are formed accordingly on both sides of plate with certain area and depth; multiple channels for connection of inlet buffer channel and outlet buffer channel; multiple buffer bulges formed in inlet and outlet buffer channels with certain height; inlet path formed on one lateral side of plate that is connected with inlet buffer channel; and outlet path formed on the other lateral side of plate connected with outlet buffer channel, there is a possibility to make distribution of flows uniform and to reduce the resistance to flow of fuel and air that are accordingly supplied to fuel electrode and air electrode of fuel element.

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12 cl, 19 dwg

FIELD: physics.

SUBSTANCE: invention refers to bipolar plates (BP) designed for reagent distribution in fuel cell (FC) battery and electric switching of FC in the battery. According to invention, BP for FC contains metal base and carbon layers. The base layer is coated with intermediate layer made of mixed powder of low-density graphite and polytetrafluorethylene (PTFE) of 0.5-2.0 mass % and sheet extracted from nonporous powder mix e.g. natural graphite and PTFE of 10÷20 mass %. Base is made of steel, aluminium, its alloys, copper and its alloys. Method of BP production includes manufacturing base layer coated with carbon layers and layer package assembly. The base layer is covered with intermediate layer of mixed powder of low-density graphite and polytetrafluorethylene (PTFE) of 0.5÷2.0 mass %, coated with sheet extracted from nonporous powder mix, e.g. natural graphite and PTFE of 10÷20 mass %. Package is heated to temperature of 120÷170°C at pressure of 200÷300 kg/cm2.

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4 cl, 1 ex

FIELD: engines and pumps.

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30 cl, 4 dwg

FIELD: electrical engineering.

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8 cl, 1 dwg, 1 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: present invention concerns the salts containing bis(trifluoromethyl)imide anions and saturated, partially or completely unsaturated heterocyclic cations, method of production and application thereof as ionic liquids.

EFFECT: production of new salts to be used as ionic liquids.

19 cl, 5 ex

FIELD: electricity.

SUBSTANCE: invention is attributed to the field of electric engineering, specifically to cathodes of lithium chemical current sources (LCCS). According to the invention LCCS contains sealed body, cover with sealed current taps and filler nozzle, electrode group consisting of anode and cathode plates and separators laid successively, electrolytic solution deposited in sealed body and filling the interelectrode space at that electrode group is placed into polypropylene isolator, cover is provided with recession where filler nozzle and sealed current taps are located. Sealed current taps have outer ring, central metal rod and glass isolator. Sealed current taps can have central metal rod and composite insulator made of fluoroplastic and rubber. To central rods of current taps bridges are welded, cathode bridge is made of titan, anode bridge is made of nickel at that cross-section of titan bridge is twice as large as nickel bridge cross-section.

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11 cl, 5 dwg

FIELD: electricity.

SUBSTANCE: invention is attributed to the field of electric engineering, specifically to cathodes of lithium chemical current sources (LCCS). According to the invention LCCS cathode contains titan current tap, two electrodes with active mass on the basis of fluorinated hydrocarbon applied onto opposite sides of current tap, and multilayer separator the inner layer of which is made of nonwoven polypropylene at that current tap is made of perforated titan foil 0.03÷0.06 mm in thickness with perforation total area of 0.4÷0.6 of electrode area, the separator additionally contains porous polypropylene film covered from both sides with porous polyethlene film, and glass fabric layer adjoining the inner layer of nonwoven polypropylene separator. Before applying the electrodes current tap surface can be treated by chemical etching or by chemical etching with applying the coatings of colloidal graphite solution or of compound on the basis of glycan or of titan carbide and/or nitride. Active electrode mass is applied on current tap via dry thermal pressing technique at temperature of 150 to 170 °C, pressure of 80÷480 kg/cm2 and time of 25÷60 s. Active electrode mass contains (wt %): fluorocarbon - 80÷90%, fluoroplastic emulsion as binding substance - 2÷5% and carbon black and/or colloidal-graphite preparation as electroconductive additive - the rest.

EFFECT: obtaining of lithium chemical current sources cathodes with improved technical characteristics.

4 cl, 3 dwg, 1 ex

FIELD: electrical engineering.

SUBSTANCE: invention relates to lithium secondary storage battery with electrolyte containing ammonium compounds. In compliance with the invention, the lithium storage battery incorporates a cathode of transfer metal lithium-containing oxide, an anode with graphitised carbon and a nonaqueous solution ammonium admixture producing ammonium ions.

EFFECT: improved performances of storage battery at higher temperature thanks to adding ammonium compounds into electrolyte.

9 cl, 1 tbl, 7 ex

FIELD: chemical power supplies using organic electrolytes.

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EFFECT: reduced low value of battery operating temperature range.

6 cl, 1 dwg, 1 tbl

FIELD: electrical engineering; manganese dioxide-lithium current supplies.

SUBSTANCE: novelty is that proposed manganese dioxide-lithium current supply has sealed case accommodating at least one positive and at least one negative plates with separator in-between, electrolyte filling plate-to-plate space, and at least one porous heat-sensing component. The latter is made in the form of low-melting inert material layer, minimum 0.13 mm thick, applied directly to entire surface of positive plate facing negative one.

EFFECT: enhanced safety in operation and stability of power characteristics of chemical current supply.

1 cl, 2 dwg

FIELD: chemistry of organometallic compounds, chemical technology.

SUBSTANCE: invention relates to new methods for preparing bis-(trifluoromethyl)-imido-salts of the general formula (I): [Ma+][(N(CF3)2-]a wherein if a = 1 then Ma+ represents copper or silver cation; or if a = 1 then Ma+ means cation of the general formula (III): [([R1b R2c R3d R4e]Ax)yKt]+ wherein Kt means N, P, As, Sb, S, Se; A means N, P, P(O), O, S, -S(O), As, -As(O), Sb, -Sb(O); R1, R2, R3 and R4 are similar or different and mean hydrogen atom (H), halogen atom, unsubstituted alkyl of the formula CnH2n+1, unsubstituted (C1-C18)-alkenyl with one or some doubles bonds, unsubstituted (C1-C18)-alkynyl with one or some triple bonds, unsubstituted cycloalkyl of the formula CmH2m-1, unsubstituted phenyl wherein n = 1-18; m = 3-7; x = 0 or 1; y = 1-4, y = 1 for x = 0 wherein in each case b, c, d and e mean 0 or 1, and b + c + d + e ≠ 0; A can be incorporated into different positions of R1, R2, R3 and/or R4; groups bound with Kt can be similar or different; or at a = 2 the index Ma+ represents mercury, copper, zinc or cadmium cation wherein there is at least one group of trifluoromethanesulfonate of the general formula (II): (Ma+)[(OSO2CF3)-]a wherein Ma+ has the abovementioned values. Method involves interaction of above proposed compounds with bis-(trifluoromethyl)-imido-rubidium in organic solvent medium and the prepared by such method bis-(trifluoromethyl)-imido-salt of the general formula (I) can be purified and/or isolated by the conventional methods. Also, invention relates to new compounds of the formula (I) wherein Ma+ means Cd2+, Zn2+ or Cu+, to electrolytes comprising at least one compound of the formula (I) and to electrochemical elements comprising the indicated electrolyte.

EFFECT: improved preparing method.

11 cl, 3 dwg, 6 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention proposes a method for preparing vinylene carbonate mixture. Method involves interaction of monohaloethylene carbonate of the formula (II): wherein X means halogen atom with a dehydrohalogenating agent at temperature in the range 40-80°C but preferably at 60°C in organic solvent medium wherein ethylene carbonate is used as an organic solvent. As a dehydrohalogenating agent method involves using amine, in particular, trialkylamine but preferably triethylamine, and monochloroethylene carbonate is used as monohaloethylene carbonate preferably. Interaction is carried out in inert gas atmosphere preferably. Invention provides preparing vinylene carbonate mixture by a simple and economy method with the high content of vinylene carbonate in the end product. Method provides easily isolation of vinylene carbonate from the prepared mixture by distillation off, for example, under vacuum in the film evaporator. Also, invention relates to a crude vinylene carbonate mixture prepared by above described method that is designated as an additive for lithium-ionic batteries as a component of surface coating material as a monomer for preparing polyvinylene carbonate.

EFFECT: improved preparing method.

7 cl, 3 ex

FIELD: electrical engineering.

SUBSTANCE: proposed secondary lithium battery electrode incorporates aliphatic nitrile composition. The latter is applied to electrode surface or introduced into active electrode materials.

EFFECT: enhanced battery safety without impairing its working characteristics.

10 cl, 16 dwg, 2 tbl, 17 ex

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