Additives and/or additions to industrial oils

FIELD: chemistry.

SUBSTANCE: invention relates to field of organic chemistry, namely to additives and/or additions to industrial oils, which are mixtures of fluorine-containing esters of compositions [RFC(O)OCH2C(CH2OH)3:(RFC(O)OCH2)2C(CH2OH)2:(RFC(O)OCH2)3CCH2OH :(RF C(O)OCH2)4C] (at RF= C6F13 component ratio equals 5 : 11 : 15 : 69, at RF=ClC8F16 component ratio equals 4 : 10 : 14 : 72, at RF=C3F7OCF(CF3)CF2OCF(CF3) component ratio equals 2 : 8 : 16 : 74 ); [RFC(O)OCH2C(CH2OH)2C2H5 :(RFC(O)OCH2)2C(CH2OH)C2H5 :(RFC(O)OCH2)3CC2H5] (at RF= C3F7 component ratio equals 3 : 8 : 89, at RF= C4F9 component ratio equals 5 : 10 : 85, at RF= C6F13 component ratio equals 4:10:86, at RF = ClC6F12 ratio equals 6 : 12 : 82, at RF= C8F17 component ratio 4 : 9 : 87, at RF = CIC8F16 component ratio equals 3 : 11 : 86, at R = C3F7OCF(CF3)CF2OCF(CF3) component ratio equals 4 : 12 : 84); [RFC(O)OCH2C(CH2OH)(CH3)2 : (RFC(O)OCH2)2C(CH3)2] (where RF = C3F7 component ratio equals 4 : 96, at R = C4F9 component ratio equals 5 : 95, at RF= C6P13 component ratio equals 3 : 97, at R = CIC6F12 ratio equals 2 : 98, at RF = C8F17 component ratio equals 2 : 98).

EFFECT: simplification of industrial oils with additives and/or additions producing, as well as improvement of those antifriction and antiwear properties.

1 cl, 55 ex, 3 tbl

 

The invention relates to the field of organic chemistry, namely to the production of lubricating compositions with improved tribological characteristics based on the traditional widely used oils and blends of fluorinated ethers, used as anti-friction anti-wear additives-additives.

It is known that lubricating oils obtained by refining, often do not meet the requirements for operational requirements. The improved performance of lubricating oils by improving methods for their production is limited. A significant contribution to the improvement of tribological properties of lubricating oils contribute additives and additives introduced into the base oil in amounts of 0.01-0.5 and more than 0.5 wt.% respectively.

Range of additives and additives is significant, their diverse nature, and properties that they report lubricating oils, allow the use of modified oils in many important areas of production.

In the literature there are many examples of fluorine-containing compounds as additives to improve the antifriction and antiwear properties of lubricating oils. For example, in the patent [Patent No. 2079545 RF, MPK6SM 161/00, SM 147/04, SM 129/02, C10N 30/06. Antifriction Pris the dka to lubricating oils / Melnikov VG, Friedburg I.Z., Savinkov VK - Appl. 27.01.1995; publ. 20.05.1997] the possibility of improving the anti-friction properties of oils by introducing them (up to 0.2 wt.%) composite additive consisting of organofluorine compounds (10-90 wt.%) and organic additives (90-10 wt.%):

Ra-XYOrganofluorine
where Ra=RF'-RFor (RF'-RF-C6H4-S)3;connection
RF'=CF3O-, C2F5O-, C3F7O - etc.;
RF=-(CF(CF3CF2O)nCF(CF3)- etc.;
X=CO, SO2C6H4SO2etc.;
Y=OM (M=H, Li, Cu (I, II), Fe and other metals)
ZRZ',Organic additive
where Z=CH3-, CH3C(O)-, R NR'r”(CH2)m- etc.;
Z=(O)C-C6H2-(C(CH3)3)2(OH) and other

The organic additive used in this patent, not only reports additional properties of lubricating oils (e.g., antioxidant), but also helps better emulsification of organofluorine compounds in the base environment.

A similar decision by way of introduction organofluorine additives in the engine oil is used in the patent [Patent No. 2061020 RF, MPK6SM 141/10, SM 129/08, C10M 129/16, C10M 147/04, C10N 30/06. Antiwear additive for lubricating oils. / Ryabinin N.A., Mungalov V.E., Iris E.V., A. Ryabinin - Appl. 04.02.1994; publ. 27.05.1996]. Antiwear additive, representing amides or esters performanceaccelerating acid, introduced into the oil by emulsification using polyhydric alcohols or their ethers (ethylene glycol, diethylene glycol, monoglyme, diglyme, trislim etc). The ratio of the organofluorine compound : organic additive is 1-7:9-3.

More complex additive proposed in patent [Patent No. 2194742 RF, MPK7C10M 141/08, SW 33/44, C10M 177/00, C10M 131/14, C10M 129/10, C10M 129/72, C10M 133/12, C10M 135/12, C10N 30/06. Anti-wear, anti-friction additive with a friction modifier, a lubricant and a method of producing friction modifier. / Aptekman A.G., Beklemishev VI, Bolgov V.Y., Makhonin I.I. - Appl. 16.03.2001; publ. 20.12.2002]. It consists of chloroparaffin (92.0-93.0 wt.%), anti is xydata (0.8-1.2 wt.%), complex ester of dicarboxylic acid (6.0-7.0 wt.%) and friction modifier (0.002-0.2 wt.%). The friction modifier is organobentonite obtained from bentonite (inorganic compounds) and fluorine-containing surfactants of the formula RFSO2A (where RF=C3F7(CF2CF(CF3))n, n=1-3, A=[NH(CH2)3N(CH3)2X]+Hal-X=Cl, F, Hal=Cl, I). Presents additive is introduced into the lubricating oil in the amount of 1-8 wt.%.

The use of chlorinated paraffin (0.3-1.7 wt.%), copper or tin salt polyalkylphenol or polyalkylacrylate C10-C14(3.0-7.0 wt.%) and antioxidants amine or phenolic type (1.5-3.0 wt.%) allowed the authors of the invention [Patent No. 2223302 RF, MPK7C10M 141/08, SM 127/06, C10M 131/14, C10M 135/10, C10N 10/02, C10N 10/08, C10N 30/06. Anti-friction, anti-wear additive to lubricants. / Aptekman A.G., Beklemishev VI, Bolgov V.Y., Makhonin I.I. - Appl. 26.07.2002; publ. 10.02.2004] patented additive that improves the tribological characteristics of engine oils. To obtain stable emulsions additives in the oil used polyalkylbenzene and polyalkylene.

All of the above additives and supplements are multi-component compositions, and their uniform distribution in oils makes necessary the use the use of additional solvents as emulsifying means. In addition, for obtaining patents components of additives organofluorine nature requires non-standard raw materials (often toxic) and multistage laboratory processes.

The simplest composition is additive, described in the patent [Patent No. 2206605 RF, MPK7C10M 135/10, C10L 1/24, C10N 30/06. Antiwear additive for lubricants and fuels. / Aleev A.F., Ermakova YOU, Healthy Y.P., Karasev A.V., Polyakov V.S., S.A. Frolov, S. Khokhlov - Appl. 18.03.2002; publ. 20.06.2003]. Excellent anti-wear properties of oils reported vortensity formula [RFC(O)CH2SO2O]nM (where RF=CF3CF2O(CF2CF2O)mCF2or CF3CF2CF2[CF(CF3CF2O]mCF(CF3), m=1-3, n=1-3, M=Li, Na, Zn, Cu, Al, and others). To reduce wear of friction pairs until the full effect of bezsennosc and extend the service life of machines and mechanisms in 2 and more times requires only 0.001-0.5 wt.% these additives. The proposed additives are neutral substances, moderately soluble in polar organic solvents, stable, not flammable, not toxic, does not cause corrosion of metals.

The authors describe the synthesis of pertension as the interaction between a 10%solution of 1,1-dihydropyrrol-4,7-dioxane-2-sulfonic acids in diethyl (sulfur) ether and 10%-the first solution of lithium methylate in methanol (example 1). Next, the solvents evaporated and receive 1,1-dihydropyrrol-4,7-dioxane-2-sulfonate lithium in the form of a thick amorphous mass. Methods other pertension similar.

However, these additives have a number of disadvantages.

1. Source polytonality used in the synthesis of pertension, are not commercial products. These reagents are toxic and available only in small-scale laboratory conditions.

2. It follows that the methods of obtaining pertension are multi-stage.

3. Methods of obtaining pertension involve the use of flammable liquids (ether and methanol), also related to toxic compounds.

4. The authors argue that produced vortensity selectively adsorbed on the metal surface from a solution in lubricating environment. The authors did not describe the method of preparation of solutions. According to our data, long polytetrafluroethylene radical (RF), which is present in fortissimo, creates serious obstacles to create a sustainable solution pertension in the lubricating oils of hydrocarbon nature. The analysis of the above work shows that a similar Fluorochemical demand for emulsification in oil use additional reagents emulsifiers.

Previously, we have obtained full the e esters based on PERFLUORO-, ω-Harberger-, performoperation acids (or their halides) and polyols [Gorbunov TI, Sorokina S.M., Zapevalov YA, shootin VI thermal-Oxidative stability polyporaceae full esters of polyatomic alcohols. Comparison with non-fluorinated analogues. // Journal of General chemistry. 2006. T. VIP. S-1884]. Experimental the aim of this research is to involve the reaction of esterification of polyols percarbonate acids all hydroxyl groups of polyhydric alcohols and receive individual full esters.

Received individual fully fluorinated esters are characterized by high thermal-oxidative stability and insolubility in hydrocarbons. Use them as additives-additives for lubricating oils without additional reagent-emulsifier impossible.

The present invention is an improved anti-friction and anti-wear properties of lubricating oils by introducing new mixtures of fluorine-containing esters, obtained by the interaction percarbonic acids and polyols. The proposed new mixture of fluorine-containing esters are products of one-stage process, they are derived from the available chemical materials, easily emulsified in the lubricating oil without additional reagents-emulsifiers, which then leads to simplification of the production of lubricating oils with additives-additives.

It is known that individual fluorine-containing esters have low surface energy, chemical inertness, high thermal stability, resistance to fire, good lubricating properties [Mamedyarov M.A. Chemistry of synthetic oils. M.: Chemistry, 1989. 239 S.; Klamann D. Lubricants and related products. M.: Chemistry, 1988, 487 S.].

The main method for the synthesis of fluorine-containing ester is the reaction of esterification of alcohols, carboxylic acids or their halides. While you may receive three types of esters according to the scheme 1.

Scheme 1.

where X=OH or halogen; type I: R1- fluorine-containing fragment, R2is a hydrocarbon fragment; type II: R1is a hydrocarbon fragment, R2- fluorine-containing fragment; type III: R1and R2- fluorine-containing fragments.

The present invention relates to new compounds of fluorine-containing ester type I composition [RFC(O)OCH2C(CH2OH)3:(RFC(O)OCH2)2C(CH2OH)2:(RFC(O)OCH2)3CCH2OH:(RFC(O)OCH2)4C] or [RFC(O)OCH2C(CH2OH)2C2H5:(RFC(O)OCH2)2C(CH2OH)C2H5:(RFC(O)OCH2)3CC2H5], or [RFC(O)OCH2C(CH2OH)(CH3)2:(Rsup> FC(O)OCH2)2C(CH3)2] (where RF= perfluoroalkyl C3-C8or ω-harperperennial C6-C8or perftoralkil C3F7OCF(CF3CF2OCF(CF3)) and to their use as additives-additives for lubricating oils.

It is known that esters in the molecule of which is Quaternary carbon atom in β-position relative to the carboxyl group, are thermally more stable than esters without the Quaternary carbon atom [Synthetic lubricants and fluids. Ed. Raspundere and Awhat. M.: Chemistry, 1965. 385 C.]. These requirements to the structure of esters are compounds based on the available polyols: pentaerythritol (PET), trimethylolpropane (TMP) and 2,2-dimethyl-1,3-propane diol (neopentyl glycol, NPG not).

Fluorinated esters PET, TDM and scientific synthesized by us esterification of the above polyols politikanalyse acids or their halides in the presence of catalytic amounts of sulfuric acid. It was found that the reaction of esterification of polyols constitute an equilibrium mixture of all possible reactions of esters (scheme 2).

Scheme 2.

For pentaerythritol (PET):

For trimethylolpropane (TMP):

For neopentyl glycol (NPG not):

where X=OH or halogen, RF= PERFLUORO - or ω-harperperennial fragment.

Note that in contrast to the methodology of the fluorine-containing esters of the same polyols presented in the article [Gorbunov TI, Sorokina S.M., Zapevalov YA, shootin VI thermal-Oxidative stability polyporaceae full esters of polyatomic alcohols. Comparison with non-fluorinated analogues. // Journal of General chemistry. 2006. T. VIP. S-1884], the synthesis of equilibrium mixtures of fluorinated esters in this application for the invention is carried out at a reduced contact time polyol and performalite (or gelegenheid): article - 2 hours in the case of acid and 1 hour in the case of gelegenheid; in this application is 1.5 and 0.5 hours, respectively (see Example 1). Note that the goal of the authors is to get the individual fluorine-containing esters, and not a mixture. The desire of the authors of this application is the synthesis of the equilibrium mixtures of fluorinated esters with the obligatory presence of products with free BUT-groups.

A longer reaction time of the esterification leads to a deeper tarifitsirovana polyols by performalite or halides, in result, the share is not fully esterified products determined the I residual quantity BUT groups of alcohols, will be less significant than in the case of shorter contact of reagents. Less long process of esterification contributes to obtaining products of such mixtures in which the proportion negoatiation products with free BUT groups is more significant.

Therefore, any change made in the conditions of this reaction will generate different composition of equilibrium mixtures of fluorinated esters. Each such mixture will have its own individual physico-chemical characteristics different from those of the mixtures that have the same quality, but other quantitative compositions.

The proof of this statement can serve the following parameters: boiling point, essential numbers, indicators of oxidative stability and other boiling point and broadcasting number of equilibrium mixtures of fluorine-containing esters described in the present application (see table 1)are different from the corresponding parameters of the full esters of the article [Gorbunov TI, Sorokina S.M., Zapevalov YA, shootin VI thermal-Oxidative stability polyporaceae full esters of polyatomic alcohols. Comparison with non-fluorinated analogues. // Journal of General chemistry. 2006. T. VIP. S-1884] (see table 1, str). The same conclusion can be drawn regarding pokazatel the oxidative stability (table 2 in the application table 3 str article).

Thus, the claimed equilibrium mixture of fluorinated esters synthesized for the first time and have indicators that are characteristic only for the above mentioned formulas:

- certain components shown in table 1;

- these mixes define and affect other physico-chemical properties (boiling point, essential numbers temocillin stability and others).

Our invention has the following advantages:

as additives and additives used a mixture of fluorine-containing esters synthesized by the reaction of esterification (in one phase) of the available domestic chemicals. At the same time as the alcohol component using PET, TDM and scientific (the products of large-scale production), and as tarifitsiruemih agents - PERFLUORO - ω-chlorphentermine acids or their halides of the formula YRFCOX (where Y=F, Cl; X=OH, Cl, F; RF= perfluoroalkyl C3C4C6C8C3F7OCF(CF3CF2OCF(CF3)) (available on an industrial scale). The result of the esterification reaction are a mixture of all possible esters;

- the presence in the structures of the obtained mixtures of esters of fluorine-containing hydrocarbon fragment and without β-hydrogen atoms with respect to boxilai group reports esters high thermal and oxidation stability, what is important for operating lubricant. Data on the oxidative stability of some mixtures of esters are shown in table 2;

- a combination of two fragments of different nature (PERFLUORO-, ω-chlorphentermine and hydrocarbon together BUT with a hydroxyl-groups) allows a conventional mechanical stirring to prepare stable emulsions of mixtures of fluorinated esters in oils hydrocarbon nature. In this case, if RF= perfluoroalkyl C3and C4then the mixture of esters freely emulsified (or dissolved) in the industrial oils (such as 40) and can be used as additives (up to 0.5 wt.% from base oils, and as additives (more than 0.5 wt.% from basic oil). If RF= perfluoroalkyl C6C8and C3F7OCF(CF3CF2OCF(CF3), this group of compounds may be used in the role of additives after mechanical mixing with oils, and the use of ultrasonic agitation and as additives.

Studies of tribological characteristics of the compositions of lubricating oils with additives or additives indicated in table 1 mixtures of fluorinated esters show that, compared with the basic materials oil with additives or supplements have str is chlennymi antifriction and antiwear properties.

The test procedure. Studies of the magnitude of the coefficient of friction (µ) and wear rate (Ihconducted at room temperature according to the scheme "finger plate" in conditions of sliding friction when the reciprocating movement of the finger on the plate treated with the prepared compositions industrial oils with additives (up to 0.5 wt.%) or supplements (0.5-5 wt.%) on the basis of mixtures of fluorinated esters PET, TDM and scientific.

The finger and the plate are parallelepipeds made from the same steel. The size of the finger 7×7×20 mm, wafer - 60×40×10 mm Sliding face of the finger - 7×7 mm, the sliding surface of the plate - 60×40 mm sliding Speed of the finger on the plate - 0.07 m/s, the total path of the finger on the plate 80 m (~1000 double strokes of the finger).

Working surfaces of the fingers and plates mechanically polished, roughness class - 8. Before testing the fingers and the plate thoroughly degreased. Before starting the movement of the finger on the plate pipette caused a drop volume of 100 µl of the prepared emulsion of the mixture of fluorinated esters in industrial oil.

Coefficient of friction (µ) is defined as the ratio of the friction force (F) normal load (N) by the formula:

µ=F/N

The friction force (F) measured by means of an elastic element (steel rings) with a fixed strain gauge sensors p is the punishment of which is recorded on the tape electronic potentiometer PSC-4. Normal load (N) when the finger plate is made of steel grade SH-15, is 1666 N, in other cases - 294 N.

The wear rate (Ih) fingers calculated by the formula:

Ih=ΔQ/ρ·L·S

where ΔQ is the weight loss of the sample-finger, g; ρ is the density of the sample material, g/cm3; L - way friction, cm; S - geometric contact area, cm2.

Weight loss (ΔQ) is determined by weighing fatless after testing samples of the fingers on an analytical balance with an accuracy of 0.0001 g

The results are given in table 3.

Data analysis table 3 shows that when a pair of "finger plate" made of steel grade SH-15, introduced in the lubricating oil of a mixture of fluorine-containing esters, mainly improve the wear resistant properties of the rubbing surfaces (up to 2 times). In some cases there is also a slight reduction of the friction coefficient.

Far more influential is the impact of mixtures of fluorinated esters to improve the tribological behavior of metal surfaces made of austenitic steels (grade 12H18N9, GA and SA). In the case of steel 12H18N9 increasing the wear resistance of 1-2 orders of magnitude, reducing the coefficient of friction in 2 and more times, if the mixture of esters is used is as an additive, and in 2-8 times, if the mixture of esters is used as an additive.

Similar trends can be traced on samples of steel grades GA and SA.

Thus, the presented data suggest the benefits of using lubricating oils put into them additives-additives which are the reaction products of the esterification PET, TDM and scientific PERFLUORO - ω-chlorphentermine (or halides). Thus, the decrease of the coefficient of friction and increase wear resistance of the friction pairs from the same steel, separated cooked lubricating compositions.

Below are examples of synthesis of additives-additives and the preparation of lubricants based lubricants.

The IR spectra of compounds 1-17 (non mixtures of esters correspond to the numbers of column №№ p/p table 1) registered on the spectrophotometer Perkin-Elmer Spectrum One" with the Fourier-transformation: in a thin layer for mixtures 1, 3-17, using the method of diffuse reflection (DRA) for mixture 2. Derivatographic thermogravimetric analysis performed on the unit Director-IOM programming temperature increase of 5°C/min, a suspension of 100 mg, the measurement error of 0.5%. The composition of the mixtures 1-17 control on gas-liquid chromatograph Shimadzu GC-17A with data processing system "Chromatopac C-RGA" with a flame-ionization is tectorum (silica capillary column MDH-5S (SE-54) with a length of 30 m with an inner diameter of 0.2 mm, the carrier gas is nitrogen). Enter 10%solutions in chloroform synthesized mixtures is carried out at an initial column temperature of 40°C, followed by exposure (5 min) and programming of raising the temperature up to 300°C (10°C/min), the evaporator temperature is 300°C, detector at 320°C.

EXAMPLE 1. A typical method for the synthesis of mixtures of esters 1-17

a) of the polyol and percarbonates acid: to a mixture of 6.7 g of TMP and 32.1 g performancenow acid, heated to the melting temperature, pin 1 ml of sulfuric acid. After continued heating for 1.5 hours the Reaction mass is washed with water, soda solution, water, dried l2and distilled in vacuum oil pump, obtain 30.1 g of a mixture of esters 4, TKIP-155°C/ 5 mm Hg;

b) of the polyol and gelegenheid percarbonates acid: 13.6 g PE are added dropwise 219.6 g foramerica performancewas acid with such a speed that the temperature of the reaction mixture did not rise above 55°C. After the introduction, the number of foramerica the reaction mass is heated at 140°C for 0.5 h Distilled off excess foramerica, the residue is distilled in a vacuum oil pump, get 78.3 g of a mixture of esters of 1, BP. 278-283°C (60 mm Hg).

EXAMPLE 2. A typical method of preparing a lubricant based industrial oils and mixtures of esters 1-17

a) the industrial oil is with an additive (0.5 wt.%): into the flask contribute 100.0 g butter-20 and 0.5 g of a mixture of 4, close the tube and vigorously shaken, achieving a homogeneous solution (emulsion).

Similarly prepare lubricants on the basis of I-40 and other industrial oils and mixtures of fluorinated esters 1-17.

Instead of shaking may use mechanical agitators;

b) industrial oil additive (5 wt.%): into the flask contribute 100.0 g butter-20 and 5.3 g of a mixture of 4, close the tube and vigorously shaken, achieving a homogeneous solution (emulsion).

Similarly prepare lubricants on the basis of I-40 and other industrial oils and mixtures of fluorinated esters 5.11 and 12;

in industrial oil additive (5 wt.%): in the glass making 100.0 g butter-20 and 5.3 g of a mixture of 1, placed in an ultrasonic disperser, stirred for 2 min at intensity 9 units and synchronization 0. After stirring receive homogeneous opaque solution (emulsion). Similarly prepare lubricants on the basis of I-40 and other industrial oils and mixtures of fluorine-containing esters of 2, 3, 6-10, 13-17.

Additives and/or additives for industrial oils, which are blends of torso is containing a series of esters of compounds [R FC(O)OCH2C(CH2OH)3:(RFC(O)OCH2)2C(CH2OH)2:(RFC(O)OCH2)3CCH2OH:(RFC(O)och2)4S] (when RF=C6F13the mixing ratio is 5:11:15:69, RF=ClC8F16the mixing ratio is 4:10:14:72, when RF=C3F7OCF(CF3CF2OCF(CF3) the ratio of the components is 2:8:16:74); [RFC(O)OCH2C(CH2OH)2C2H5:(RFC(O)OCH2)2C(CH2OH)C2H5:(RFC(O)OCH2)3CC2H5] (when RF=C3F7the mixing ratio is 3:8:89, when RF=C4F9the mixing ratio is 5:10:85, when RF=C6F13the mixing ratio is 4:10:86, when RF=ClC6F12the ratio is 6:12:82, when RF=C8F17the mixing ratio 4:9:87, RF=ClC8F16the mixing ratio is 3:11:86, when RF=C3F7OCF(CF3CF2OCF(CF3) the ratio of the components is 4:12:84);
[RFC(O)OCH2C(CH2OH)(CH3)2:(RFC(O)OCH2)2C(CH3)2] (where RF=C3F7the mixing ratio is 4:96, when RF=C4F9the mixing ratio is 5:95, with RF=C6F13the ratio of the components is avno 3:97, when RF=ClC6F12the ratio is 2:98, when RF=C8F17the ratio of the components is equal to 2:98).



 

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9 cl, 8 ex

FIELD: organic chemistry, in particular polymers.

SUBSTANCE: invention relates to new method for production of vic-dichlorofluoroanhydride useful as intermediate of starting monomer for fluorinated polymers with good yield from available raw material. Claimed method includes fluorination of starting material (I): (RH1-EH1-)CRH2RH3CH2-0CORHB in liquid phase to form compound of formula (II): (CF2ClCFCl-EF1-)CRF2RF3CF2-OCORFB; ester bond splitting of formula (II) in gaseous phase under solvent absence to form compound of formula (III): (CF2ClCFCl-EF1-)CRF2RF3COF or compound of formula (III) and compound of formula (IV): FCORFB, wherein RH1 is CX1X2ClCX3Cl- or CClX4=CCl, wherein each X1-X4 independently is hydrogen; RH2 and RH3 independently are hydrogen or linear or branched alkyl, optionally substituted with one or more oxygen; EH1 is alkylene, optionally substituted with one or more oxygen; EF1 = EH1 wherein perfluoroalkylene group is optionally substituted with one or more oxygen; RHB = RFB and are linear or branched perfluoroalkyl group, optionally substituted with chlorine one or more oxygen; RF2 is fluorinated RH2; RF3 is fluorinated RH3; with the proviso, that RF2 is fluorinated RH2; RF3 is fluorinated RH3, i.e. RF2 and RF3 represent RH2 or RH3 with at least one fluorinated hydrogen. Also disclosed are new compounds, represented in claims of invention.

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides improved process for production of a fluorine-containing compound useful as starting material for manufacture of a variety of fluoropolymers with high output when performing short process and using inexpensive and easily accessible chemicals. Process comprises: (i) interaction of indicated below compound 1 with indicated below compound 2 to form indicated below desired compound 3, which is a compound, wherein content of fluorine is at least 30 wt % and which has hydrogen atom or multiple bond capable of being fluorinated; and (ii) liquid-phase fluorination of compound 3 to give indicated below compound 4 followed by (iii) cleaving group EF in compound 4 to produce compound 5 and compound 6: E1-RA-E1 (1), E2-RB (2), RB-E-RA-E-RB (3),

RBF-EF-RAF-EF-RBF (4), EF1-RAF-EF1 (5),

and RBF-EF2 (6), where RAF represents fluorine-containing bivalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether oxygen atoms; RA represents group, which is the same as group RAF or bivalent organic group capable of being converted into group RAF using fluorination reaction; RBF represents fluorine-containing polyvalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether or carbonyl oxygen atoms; RB represents group, which is the same as group RBF or polyvalent organic group capable of being converted into group RBF using fluorination reaction; E1 and E2 are such that, when group E1 is -CH2OH or Q1-CH2OH group, then group E2 is -COX or -SO2X group and, when group E2 is -CH2OH or -Q2-CH2OH group, then group E1 is -COX or -SO2X group, where X is halogen atom and Q1 and Q2 may be identical or different and represent -CH(CH3)- or -CH2CH2- group; E represents group -CH2OCO-, -CH2OSO2-, -Q1-CH2OCO-, -Q2-CH2OCO-, -Q1-CH2OSO2-, or -Q2-CH2OSO2-; EF represents group, which is the same as group E or group obtained by fluorination if group E on conditions that at least one group RAF, RBF, or EF is a group formed by fluorination reaction and groups EF1 and EF2 are groups formed by cleaving group EF. Invention also relates to novel fluorine-containing compounds of formulas 3-12, 3-13, 3-14, 3-15, 3-16, 4-12, 4-13, 4-14, 4-15, 4-16, 5-16, which are indicated in description.

EFFECT: increased resource of raw materials for production of fluoropolymers.

8 cl, 23 ex

The invention relates to the production of fluorine-containing compounds, such as industrial useful derived foramerica acid
The invention relates to a method for allocation of fluorinated carboxylic acids, allowing you to get them with a high degree of purity

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides improved process for production of a fluorine-containing compound useful as starting material for manufacture of a variety of fluoropolymers with high output when performing short process and using inexpensive and easily accessible chemicals. Process comprises: (i) interaction of indicated below compound 1 with indicated below compound 2 to form indicated below desired compound 3, which is a compound, wherein content of fluorine is at least 30 wt % and which has hydrogen atom or multiple bond capable of being fluorinated; and (ii) liquid-phase fluorination of compound 3 to give indicated below compound 4 followed by (iii) cleaving group EF in compound 4 to produce compound 5 and compound 6: E1-RA-E1 (1), E2-RB (2), RB-E-RA-E-RB (3),

RBF-EF-RAF-EF-RBF (4), EF1-RAF-EF1 (5),

and RBF-EF2 (6), where RAF represents fluorine-containing bivalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether oxygen atoms; RA represents group, which is the same as group RAF or bivalent organic group capable of being converted into group RAF using fluorination reaction; RBF represents fluorine-containing polyvalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether or carbonyl oxygen atoms; RB represents group, which is the same as group RBF or polyvalent organic group capable of being converted into group RBF using fluorination reaction; E1 and E2 are such that, when group E1 is -CH2OH or Q1-CH2OH group, then group E2 is -COX or -SO2X group and, when group E2 is -CH2OH or -Q2-CH2OH group, then group E1 is -COX or -SO2X group, where X is halogen atom and Q1 and Q2 may be identical or different and represent -CH(CH3)- or -CH2CH2- group; E represents group -CH2OCO-, -CH2OSO2-, -Q1-CH2OCO-, -Q2-CH2OCO-, -Q1-CH2OSO2-, or -Q2-CH2OSO2-; EF represents group, which is the same as group E or group obtained by fluorination if group E on conditions that at least one group RAF, RBF, or EF is a group formed by fluorination reaction and groups EF1 and EF2 are groups formed by cleaving group EF. Invention also relates to novel fluorine-containing compounds of formulas 3-12, 3-13, 3-14, 3-15, 3-16, 4-12, 4-13, 4-14, 4-15, 4-16, 5-16, which are indicated in description.

EFFECT: increased resource of raw materials for production of fluoropolymers.

8 cl, 23 ex

FIELD: organic chemistry, in particular polymers.

SUBSTANCE: invention relates to new method for production of vic-dichlorofluoroanhydride useful as intermediate of starting monomer for fluorinated polymers with good yield from available raw material. Claimed method includes fluorination of starting material (I): (RH1-EH1-)CRH2RH3CH2-0CORHB in liquid phase to form compound of formula (II): (CF2ClCFCl-EF1-)CRF2RF3CF2-OCORFB; ester bond splitting of formula (II) in gaseous phase under solvent absence to form compound of formula (III): (CF2ClCFCl-EF1-)CRF2RF3COF or compound of formula (III) and compound of formula (IV): FCORFB, wherein RH1 is CX1X2ClCX3Cl- or CClX4=CCl, wherein each X1-X4 independently is hydrogen; RH2 and RH3 independently are hydrogen or linear or branched alkyl, optionally substituted with one or more oxygen; EH1 is alkylene, optionally substituted with one or more oxygen; EF1 = EH1 wherein perfluoroalkylene group is optionally substituted with one or more oxygen; RHB = RFB and are linear or branched perfluoroalkyl group, optionally substituted with chlorine one or more oxygen; RF2 is fluorinated RH2; RF3 is fluorinated RH3; with the proviso, that RF2 is fluorinated RH2; RF3 is fluorinated RH3, i.e. RF2 and RF3 represent RH2 or RH3 with at least one fluorinated hydrogen. Also disclosed are new compounds, represented in claims of invention.

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to industrially useful fluorine-containing compounds such as fluorinated ester compounds and acyl fluoride compounds. Invention, in particular, provides ester compound wherein all C-H groups are fluorinated and which is depicted by general formula RAFCFR1FOCORBF (4), where RAF, CFR1, and RBF are specified elsewhere. Preparation of the ester compound comprises fluorination of ester (4), which has hydroxyl group(s), acyl fluoride group(s) and which has a structure allowing compound to be fluorinated in liquid phase, fluorination being effected in mixture of ester compound and compound having acyl fluoride group(s). Method does not involve environmentally unfriendly solvent such as, for instance, R-113.

EFFECT: enabled fluorination requiring no specific solvent for each reaction and which can be carried out without separation of solvent before next stage.

9 cl, 8 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to a method for preparation of multivalent carbonyl compounds and to a novel polyvalent carbonyl compound, which may be useful, for example, as intermediate in production of various fluorinated compounds. Polyvalent carbonyl compound is prepared through economically advantageous way from inexpensive substances and with no need of using any complex synthesis stage. In particular, polyvalent alcohol, including alcohols with at least two structures selected from primary, secondary, and tertiary structures, is brought into reaction with acid halide to form polyvalent ester, which is then fluorinated in liquid phase to form perfluorinated polyvalent ester, in which ester bonds, provided by reaction with primary and secondary alcohols, are further cleaved.

EFFECT: expanded synthetic possibilities in organofluoric compound area.

8 cl, 3 dwg, 2 ex

FIELD: chemical industry; method of production of the fluorine-containing compounds.

SUBSTANCE: the invention is pertaining to the chemical industry, in particular, to the improved method of production of fluorine-containing compounds from the halogen-containing, compounds, preferably, from chlorine-containing compounds due to an exchange of halogen for fluorine at presence of the HF-additional compound of the mono- or bicyclic amine with at least two atoms of nitrogen. At that at least one atom of nitrogen is built in the cyclic system as the fluorating agent; or at presence of anhydrous hydrogen fluoride - as the fluorating agent and the indicated HF-additional compound of the mono- or bicyclic amine as the catalyst. At usage of the applicable solvents the reaction mixtures can be divided into two phases and thus to simplify the reprocessing of the products. The invention also is pertaining to the HF-additional compounds of 1.5-diazabicyclo[4.3.0]non-5-en and N,N-dialkylaminopiridin, where alkyl represents C1-C4alkyl and where the molar ratio of HF to amine makes 1:1, and to HF- additional compounds 1.8- diazabicyclo[5.4.0]undecyl-7-ene, where the molar ratio of HF to amine compounds more than 1:1.

EFFECT: the invention ensures at usage of the applicable solvents to divide the reaction mixture into two phases and thus to simplify reprocessing of the products.

17 cl, 13 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to chemistry of adamantane derivatives, namely, to a novel method for synthesis of 3-halogen-1-(ethoxycarbonyl)-alkyladamantanes of the general formula: wherein Hal means bromine atom (Br); R means hydrogen atom (H), -CH3, -C2H5, -C3H7; Hal means Br; R means -CH3; R1 means -CH3; Hal means chlorine atom (Cl); R means Cl; R1 means Cl that can be used as intermediate compounds used for synthesis of some biologically active substances. Method involves interaction of 1,3-dehydroadamantane with α-halogenalkane carboxylic acids ethyl esters chosen from the following group: ethyl-2-bromoacetate, ethyl-2-bromopropionate, ethyl-2-bromobutyrate, ethyl-2-bromovalerate, ethyl-2-bromo-2-methylpropionate and ethyl-2,2,2-trichloroacetate taken in the mole ratio = 1:(3-5), respectively, in the parent α-halogenalkane carboxylic acid ethyl esters medium, at temperature 50-60°C for 4-6 h. Invention provides expanding assortment of chemical compounds, in particular, synthesis of novel 3-halogen-1-(ethoxycarbonyl)-alkyladamantanes with the high yield.

EFFECT: improved method of synthesis.

6 ex

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