Method for preparing fluorinated ester

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of fluorinated ester. The process involves the re-esterification step wherein compound of the formula: RAF-COOCF2-RAF and compound of the formula: RA-CH2OH are subjected for the re-esterification reaction in the molar ratio = 1:(1-2) to yield RAF-COOCH2-RA, and the fluorination step wherein the synthesized compound is fluorinated with yielding the reaction product in the amount exceeding the mole amount before the re-esterification reaction and comprising compound of the formula: RAF-COOCF2-RAF wherein RA means a monovalent (C1-C20)-hydrocarbon group, monovalent halogen-containing (C1-C20)-hydroarbon group, monovalent heteroatom-containing (C1-C20)-hydrocarbon group or monovalent (C1-C20)-hydrocarbon group containing halogen atom and heteroatom, and RAF means the same group as RA group or monovalent hydrocarbon group prepared by fluorination of RA group.

EFFECT: improved method of synthesis.

 

The present invention relates to a method for producing a fluorinated ether complex and to a method for producing fluorinated allford and fluorinated vinyl ether using a fluorinated ether complex.

Fluorinated ester is a compound suitable as an intermediate product for the synthesis of, for example, fluorinated allford or fluorinated vinyl ether. In the present application proposes a method of receiving fluoridated of ester and fluorinated allford by combining some of the processes such as the reaction of esterification, the fluorination reaction and the reaction of dissociation of the ether linkages. It also offers continuous method, in which the fluorinated allford obtained in this way, re-use in the esterification reaction (WO 00/56694).

This method is a process that essentially involves three stages, i.e. stage of esterification, the stage fluorination stage and dissociation of essential communications. That is, it represents the way in which the following fluorinated allford (4) and the following compound (2)having a hydroxyl group is subjected to the esterification reaction to obtain the following compound (3), which is an ester, which foryouth to get the next n the same fluorinated ester (1), and the ester linkage fluorinated ether complex (1) is subjected to dissociation to obtain fluorinated allford (4), which is used for the esterification reaction of the above compound (2) to perform the same way (here, the values of the symbols in the following diagram are the same as the values of the symbols listed below).

Next, as a more efficient method of producing fluorinated ether complex (1) in large quantities, the applicants have also proposed a method, where the fluorinated complex fluids with the same group (RAF) at both ends of the molecule, obtained by reaction of esterification, and two essential communication complex diapir subjected to dissociation, receiving twice the molar amount of fluorinated allford.

The present invention is to provide ways through which fluorinated ester (1) and fluorinated allford (4) can now be obtained in large quantities smaller number of stages than in the case of the above-mentioned methods. Another objective of the present invention is to provide method of producing a fluorinated vinyl ether using a fluorinated ether complex (1) and fluorinated allford (4)obtained in this way.

As a result of comprehensive the surveys to achieve the above objectives, the applicants have discovered, what can you accomplish this goal and get the fluorinated ester mass production, combining stage interesterification fluorinated ether complex with stage fluorination. Further, the applicants have found that you can get fluorinated allford or fluorinated vinyl ether, using fluorinated ester obtained in this way.

That is, the present invention provides a method of obtaining the following fluorinated ether complex (1), which includes a step of transesterification, where the following fluorinated ester (1) interacts with the following compound (2) with the formation at the expense of the interesterification reaction following compounds (3), and stage fluorination, where the compound (3) then foryouth to get the following fluorinated ester (1) in excess of the molar quantity to the interesterification:

RAF-COOCF2-RAF(1)
RA-CH2OH(2)
RAF-COOCH2-RA(3)

where RAdenotes a monovalent organic group, and RAFdenotes the same group as RAor a monovalent organic group obtained by ftorirovanie the m R A.

Further, the present invention is the above method of obtaining a fluorinated ether complex (1), where in stage fluorination fluorination of the compound (3) is conducted by introducing gaseous fluorine in a liquid phase.

Further, the present invention is the above method of obtaining a fluorinated ether complex (1)where at the stage of fluorination is used as a compound (3)containing the following fluorinated allford (4) and/or the compound (1)obtained at the stage of interesterification, when it contains fluorinated allford (4) and/or the connection (1):

RAF-COF(4)

where RAFis the same as described above.

Further, the present invention is the above method of obtaining a fluorinated ether complex (1)where the stage of transesterification is carried out in the absence of solvent.

Further, the present invention is the above method of obtaining a fluorinated ether complex (1), where the fluorinated ester (1) at the stage of interesterification is a fluorinated ester (1)obtained at the stage of fluorination.

Further, the present invention is the above method of obtaining a fluorinated ether complex (1), which includes a step for the trail is the future below fluorinated ether complex (1) by fluorination in the liquid phase the following compounds (3), obtained by the reaction of the following fluorinated allford (4) with the following compound (2), and where the fluorinated ester (1), obtained at this stage, is used as a fluorinated ether complex (1) at the stage of interesterification:

RAF-COF(4)
RA-CH2OH(2)
RAF-COOCH2-RA(3)
RAF-COOCF2-RAF(1)

where RAand RAFare as defined above.

Further, the present invention is a method of obtaining a fluorinated allford (4), which involves the dissociation of the ether link below fluorinated ether complex (1)obtained by the above method:

RAF-COOCF2-RAF(1)
RAF-COF(4)

where RAFis the same as defined above.

Further, the present invention is the above method of obtaining a fluorinated ether complex (1), where the fluorinated ester (1) is the following compound (1a), compound (2) is the following compound (2a), connect the out (3) is the following compound (3a) and R AFis an RAF1O-CF(CF3)-:

RAF1O-CF(CF3)-COOCF2-CF(CF3)-ORAF1(1a)
RA1O-CX1(CX2X3X4)-CH2OH(2a)
RAF1O-CF(CF3)-COOCH2-CX1(CX2X3X4)-ORA1(3a)

where RA1represents a monovalent organic group, RAF1represents the same group as specified for RA1or a monovalent organic group obtained by fluorination of the specified RA1and each of X1X2X3and X4that may be the same or different, represents a hydrogen atom or a fluorine atom.

Further, the present invention provides a method of obtaining the following fluorinated vinyl ether (5a), which involves the dissociation of the ether links the following compound (1a)obtained in the above manner, to obtain the following compounds (4a), and the pyrolysis of the compound (4a):

RAF1O-CF(CF3)-COOCF2-CF(CF3)-ORAF1(1a)
RAF1O-CF(CF3)-COF(4a)
RAF1O-CF=CF2 (5a)

where RAF1is the same as defined above.

Further, the present invention provides a method of obtaining the following fluorinated vinyl ether (5a), which includes the following pyrolysis of the compound (1a)obtained in the above manner, at a temperature of at least 250°With:

RAF1O-CF(CF3)-COOCF2-CF(CF3)-ORAF1(1a)
RAF1O-CF=CF2(5a)

where RAF1is the same as defined above.

The BEST MODE of carrying out the INVENTION

Typical interesterification reaction in which at most twice the molar amount of compound (2) interacts with fluorinated ether complex (1), presents the following scheme, where RAand RAFare as defined above.

It is believed that the mechanism of the interesterification reaction is that the first equimolar amount of compound (2) interacts with fluorinated ether complex (1) with education as a result of the interesterification reaction of equimolar amounts of compounds (3) and equimolar amount of fluorinated allford (4) (RAFCOF), and then fluorinated allford (4) Yes is it interacts with the equimolar amount of the compound (2) with the formation of equimolar amounts of the compound (3). That is twice the molar amount of compound (2) interacts with fluorinated ether complex (1) with the formation of the double molar amount of compound (3). Then twice the molar amount of compound (3)obtained by the interesterification reaction, foryouth, receiving twice the molar amount of the fluorinated ether complex (1).

This series of reactions will be shown in the following diagram. That is, the interesterification reaction and then the reaction of fluorination is carried out, using twice the molar amount of compound (2) with respect to fluorinated ether complex (1), whereby theoretically, the molar amount of the fluorinated ether complex (1) will be increased two times (here, RAand RAFin the schema are as described above).

Hereinafter the present invention will be described with reference to the reaction mechanism.

In the compounds of the present invention each RAand RA1represents a monovalent organic group. In the present invention, the "organic group" refers to a group containing at least one carbon atom, and the organic group may have any structure with a linear chain, a branched structure or a cyclic structure.

As RAand RA1preferred is the 1-20monovalent organic group. As the monovalent organic group is preferable monovalent hydrocarbon group, halogenated monovalent hydrocarbon group containing a heteroatom monovalent hydrocarbon group or a halogenated monovalent hydrocarbon group containing a heteroatom. As the monovalent hydrocarbon group among these groups, preferred is a monovalent aliphatic hydrocarbon group. In monovalent aliphatic hydrocarbon group may contain an unsaturated bond. As the monovalent organic group is preferred monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group, a monovalent hydrocarbon group containing an etheric oxygen atom, or a partially halogenated monovalent saturated hydrocarbon group containing an etheric oxygen atom. Here the "rich" group is a group where the carbon-carbon are exclusively single bond, and containing a heteroatom group" means a group containing in its structure heteroatom such as oxygen atom, nitrogen atom or sulfur atom. As the heteroatom predpochtitel the output is, for example, an ethereal oxygen atom (-O-) or =O. Among them, particularly preferred is an etheric oxygen atom.

Monovalent saturated hydrocarbon group may be an alkyl group, cycloalkyl group or cycloalkenyl group. Cycloalkyl group, preferably represents cycloalkyl group containing 3-6-membered ring, or a group having at least one hydrogen atom in such cycloalkyl group, substituted alkyl group. Cycloalkylation group, preferably represents a group in which one hydrogen atom With1-3alkyl group substituted by the above cycloalkyl group.

Halogenated monovalent saturated hydrocarbon group may be a group in which at least one hydrogen atom of the above monovalent saturated hydrocarbon group galogenidov, and it preferably represents an alkyl fluoride or fluorine(partially chlorine substituted alkyl)group. As a monovalent saturated hydrocarbon group containing an etheric oxygen atom, particularly preferred is alkoxyalkyl group or alkoxygroup.

Halogenated monovalent saturated hydrocarbon group containing an etheric oxygen atom, can transform the conduct of a group, in which at least one hydrogen atom of the above halogenated monovalent saturated hydrocarbon group containing ether oxygen, galogenidov, and it preferably represents forelcosure, peralkaline group, chlorethoxyfos, chlorococcalean group, fluorine(partially chlorine substituted alkoxy)group or a fluorine(chlorine substituted partially alkoxyalkyl)group.

From the viewpoint of availability of the compound (2) and economic efficiency of each of RAand RA1preferably represents a monovalent organic group containing no fluorine atom, which can be fluoridate reaction with fluorine in a liquid phase. As such groups are especially preferred is an alkyl group, alkoxygroup, alkoxyalkyl group, partially chlorinated alkyl group, a partially chlorinated alkoxygroup or partially chlorinated alkoxyalkyl group.

In the above compounds, RAFis the same group as RAor a monovalent organic group obtained by fluorination of RAand RAF1is the same group as RA1or a monovalent organic group obtained by fluorination of RA1. In the present invention "fluoridation" is a reaction to the introduction of the atom is the Torah. Fluoridation of the present invention is typically a reaction of substitution of the hydrogen atom linked to a carbon atom, the fluorine atom. However, when there is a carbon-carbon unsaturated double bond (-CH=CH-), will be the reaction of substitution of hydrogen atom, fluorine atom and the reaction of accession. In the case when RAand RA1represent groups which cannot be fluorinated, or they are groups, which may be fluorinated, but are not fluorinated, RAFand RAF1are the same groups as RAand RA1, respectively. For example, in the case when RAand RA1are perhalogenated monovalent hydrocarbon group or perhalogenated monovalent hydrocarbon group containing an etheric oxygen atom, the halogen atoms in these groups will not be replaced, even when they react with fluorine in a liquid phase, and thus, RAFand RAF1will represent the same groups as RAand RA1respectively.

Each group RAFand RAF1preferably is a group that will not change even by a fluorination reaction, after the specified continuous method can be implemented in such a way. As this group is preferable perverseness the Naya monovalent organic group, especially preferred is perforamance monovalent saturated hydrocarbon group, a PERFLUORO(partially chlorinated)monovalent saturated hydrocarbon group, perforamance monovalent saturated hydrocarbon group containing an etheric oxygen atom or a PERFLUORO(partially halogenated)monovalent saturated hydrocarbon group containing an etheric oxygen atom, and particularly preferred is performanceline group, a PERFLUORO(partially chlorinated)alkyl group, performancehttp, PERFLUORO(partially chlorinated)alkoxygroup, performancecriteria group or a PERFLUORO(partially chlorinated)alkoxyalkyl group.

Each of X1-X4in the compound (2A) and the compound (3A) represents a hydrogen atom or a fluorine atom. Taking into account the availability of compounds (2A), preferably all the substituents from the X1to X4represented the hydrogen atoms.

In this description, "halogenated" group refers to a group in which at least one of the hydrogen atoms associated with carbon atom substituted by a halogen atom; "perhalogenated" group refers to a group in which essentially all of the hydrogen atoms associated with carbon atom substituted by halogen atoms, and partially halogenated what the group refers to a group, in which some hydrogen atoms associated with carbon atom substituted by halogen atoms. In the case where the halogen atoms are fluorine atoms, such groups can be represented as "perfluorinated", "partially fluorinated" or similar. Next perhalogenated" group or "partially halogenated" group may contain halogen atoms of one type or two or more different types. "Perhalogenated" group, preferably represents a group in which all hydrogen atoms associated with carbon atom substituted by halogen atoms, but even when still remain unsubstituted hydrogen atoms, provided that the nature as a group, essentially the same as the "perhalogenated" group, that group will be included in the concept of "perhalogenated" group.

As specific examples of the fluorinated ether complex (1) and compounds (1A), you can specify connection the following formulas.

CF3CF2CF2OCF(CF3CF2OCF(CF3CF2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3,

CF3(CF2)kOCF(CF3CF2OCOCF(CF3)O(CF2)kCF3(where k is an integer from 0 to 9).

As specific examples of the compound (2) and the compound (2A), you can specify connection SL is blowing below formulas.

CH3CH2CH2OCH(CH3)CH2OCH(CH3)CH2OH,

CH3(CH2)kOCH(CH3)CH2OH (where k is an integer from 0 to 9).

As specific examples of the compound (3) and the compound (3A) you can specify connection the following formulas.

CH3CH2CH2OCH(CH3)CH2OCH(CH3)CH2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3,

CH3(CH2)kOCH(CH3)CH2OCOCF(CF3)O(CF2)kCF3(where k is an integer from 0 to 9).

As specific examples of fluorinated allford (4) and the compound (4A), you can specify connection the following formulas.

CF3CF2CF2OCF(CF3CF2OCF(CF3)COF,

CF3(CF2)kOCF(CF3)COF (where k is an integer from 0 to 9).

As specific examples of the fluorinated vinyl ether (5A) you can specify connection the following formulas.

CF3CF2CF2OCF(CF3CF2OCF=CF2,

CF3(CF2)kOCF=CF2(where k is an integer from 0 to 9).

Stage interesterification of the present invention is a stage in which the fluorinated ester (1) interacts with the compound (2), producing the interesterification connection (3).

At the stage of interesterification proportional the optional content (molar fraction) of the compound (2), which must interact with fluorinated ether complex (1)is not specifically limited and can be any arbitrary molar fraction. However, if the molar proportion of the compound (2) is more than twice the amount, per mole, the product of the interesterification reaction will remain unreacted compound (2). And, it is likely that the presence of unreacted compound (2) will cause an unwanted reaction at the stage of fluorination. It will therefore be necessary to separate such unreacted compound (2) before the subsequent stage of the fluorination. In addition, even if the connection (2) reacts in excess of twice the molar amount, of the stoichiometric impossible to obtain the compound (3) in excess of more than two times the molar quantity of the fluorinated ether complex (1). Accordingly, the proportion of the compound (2), which is required for the reaction with fluorinated ether complex (1), preferably greater than the molar amount of the fluorinated ether complex (1) at most twice.

On the other hand, if the molar ratio of the compound (2), required for the reaction with fluorinated ether complex (1)is too low, the resulting number of connections (3) will be reduced. In addition, the product will contain fluorinated allford (4) the quality of the ve intermediate reaction product and/or unreacted fluorinated ester (1). Further, if the proportional content of the compound (2) does not exceed one molar proportion, it is impossible to realize the goal of obtaining fluorinated allford (1) mass production. From the preceding it is clear that the proportion of the compound (2), which should react with fluorinated ether complex (1), relative to the fluorinated ether complex (1), preferably, ranges from once to twice per mole, more preferably from 1.5 times to twice per mole, particularly preferred double the mole fraction.

Fluorinated ester (1), connection (2) and the compound (3)used at the stage of transesterification, preferably represent a compound (1A), the compound (2A) and the compound (3A), respectively.

The interesterification reaction of fluorinated ether complex (1) and compounds (2) can be performed under known reaction conditions. The above reaction can be carried out in the presence of a solvent (hereinafter referred to as "solvent 1"). However, it is preferable to conduct the reaction in the absence of solvent 1, because through this, you can use the crude liquid without additional processing at a later stage fluorination. When it is necessary to use a solvent 1, it is preferable that he was a di is Loretan, chloroform, triethylamine or a mixed solvent of triethylamine and tetrahydrofuran. The amount of solvent 1 that is to be used preferably ranges from 50 to 500 wt.% from the total amount of fluorinated ether complex (1) and compounds (2).

In the interaction of fluorinated ether complex (1) with compound (2) can be formed HF. As absorber HF in the reaction system can be entered, for example, a fluoride of an alkali metal (preferred is NaF or KF) or trialkylamine. However, it is preferable that in the absence of such absorber HF, HF was removed from the reaction system by a stream of nitrogen, because this way you can use the crude liquid without additional processing at the next stage fluorination. When you need to use a fluoride of an alkali metal, its molar quantity, preferably exceeds the number of fluorinated ether complex (1) 1-10 times.

The reaction temperature fluorinated ether complex (1) with compound (2), preferably, is at least -50°and, preferably, at most +100°or at most equal to the boiling temperature of the solvent in the usual case. When in the absence of the absorber HF, HF is removed from the reaction system by a stream of nitrogen, the reaction temperature, preferably, the composition is employed, at least +20°and at most +100°or at most equal to the boiling temperature of the solvent. Further, the reaction time, respectively, may vary depending on the feed rate of raw materials and quantities of compounds that must be used for the reaction. The reaction pressure (gauge pressure, the same used in the future), preferably ranges from atmospheric pressure to 2 MPa.

The composition of the compounds contained in the reaction product stage interesterification can arbitrarily be changed depending on the amounts of the compounds used in the interaction, or the reactivity of the compounds. That is the reaction product at the stage of interesterification may contain in addition to the compound (3) unreacted fluorinated ester (1), connection (2) and fluorinated allford (4), which may be present as an intermediate reaction product. Including, if the reaction product contains a compound (2), it is better to remove. On the other hand, the presence in the reaction product of a fluorinated allford (4) will not have an adverse impact on the next stage after the transesterification stage fluorination, and it is preferable not to remove, as it may be in the liquid phase to phase CFT is compete. In this case, when the phase fluorination is carried out in the presence in the reaction system fluorinated allford (4), fluorinated allford (4)may also be present in the reaction product phase fluorination. However, if the above continuous method is carried out in the presence of fluorinated allford (4), the compound (2) and fluorinated allford (4) will respond to the stage of transesterification in the second cycle with the formation of compound (3). Next, when in the crude reaction product at the stage of interesterification is unreacted fluorinated ester (1), it is preferable not to delete such fluorinated ester (1), as it may be in the liquid phase to phase fluorination. That is, when the reaction product at the stage of interesterification, in addition to the compounds (3), contains frorianny allford (4) or fluorinated ester (1), it can be used on stage fluorination without additional processing.

In the present invention, the fluorine content in the compound (3), preferably, is at least 30 wt.%, whereby it is possible to easily carry out the fluorination in the liquid phase, which is the best method of fluorination. If the fluorine content in the compound (3) is less than 30 wt.%, solubility in the liquid phase them is no tendency to be insufficient for the method of fluorination in the liquid phase. The fluorine content in the compound (3) can be adjusted arbitrarily, depending on the type of the liquid phase, but, more preferably, the fluorine content is from 30 to 86 wt.%, even more preferably, from 30 to 76 wt.%.

Moreover, the molecular mass of the compound (3), preferably, ranges from 200 to 1000. If the molecular weight of the compound (3) is less than 200, the boiling point of the compound (3) tends to be low, whereby in the way fluoridation there is a possibility of evaporation of the compound (3), and yield of fluorination has a tendency to decline. Then there is the probability of the reaction of decomposition. On the other hand, if the molecular weight exceeds 1000, there is a possibility that the solubility in the liquid phase will decrease when it is necessary to carry out the method of fluorination in the liquid phase, or purification tends to be difficult.

The compound (3)obtained in the above stage interesterification, is subjected to fluorination at the stage fluorination with obtaining fluorinated ether complex (1). Fluorinated ester (1) can represent a connection using the connection (3) partially fluorinated. However, preferably, the fluorinated ester (1) is a compound with the compound (3) fully fluorinated, since it is difficult kontrolirovat the ü provision for the introduction of fluorine atoms in the reaction of fluorination, and because by means of this method according to the present invention can be implemented in a continuous process, which will be described later. However, when the product phase fluorination contains unreacted compound (3) and partially fluorinated compound (3), a continuous method can be carried out without additional processing, whereby it is possible to increase the proportion of the fluorine introduced into the compound (3).

From the point of view of the efficiency and effectiveness of the reaction the reaction of fluorination on stage fluorination, preferably, carried out in the liquid phase. The fluorination reaction can be performed ECF method, method of cobalt fluoridation or method of fluorination in the gas phase. However, the method of liquid-phase fluorination, where fluoridation is carried out in liquid phase, from the point of view of the reaction product yield and efficiency in the implementation of the reaction, is a very effective method and, thus, preferred.

Method of liquid-phase fluorination preferably carried out by introducing gaseous fluorine in a liquid phase in which the present compound (3). In this case, gaseous fluorine can be used without any additional preparation or you can apply gaseous fluorine diluted with an inert gas. As a preferred inert gas is nitrogen gas or gazoobraznye helium, and for economic reasons, nitrogen gas is particularly preferred. The amount of fluoride in the gaseous nitrogen is not specifically limited, and it preferably is at least 10 vol.% from the point of view of efficiency and, particularly preferably at least 20 vol.%.

Preferably, the liquid phase forms a solvent which essentially contains a C-F bond and contains no C-H bond. As such a solvent (hereinafter referred to as "solvent 2") it is preferable to use a solvent which can dissolve at least 1 wt.% compounds (3), especially a solvent which can dissolve at least 5 wt.%. Next, the solvent is 2, preferably, is a fluorinated ester (1) or fluorinated allford (4) as a product in phase fluorination. When the fluorinated ester (1) is used as a solvent 2, there is a positive aspect, consisting in the fact that the subsequent processing after the reaction is easy. In addition, when the solvent for the reaction is used fluorinated allford (4), and when it is necessary to conduct the above-mentioned stage of pyrolysis, such a stage can be made without separating the fluorinated allford (4) from the product stage of ftoridov the deposits.

When the solvent 2 use a solvent other than a fluorinated ether complex (1) and fluorinated allford (4), he may represent, for example, perftoran, perforator, parfocality, chlorofluorocarbon, hartocollis, perforaciones or inert liquid. The amount of solvent 2, preferably five times by mass, particularly preferably from 10 to 100 times by weight greater than the amount of the compound (3).

As the reaction system for the reaction of fluorination you can specify the periodic system or a continuous system. In a continuous system, you can specify the following continuous system 1 and a continuous system 2. However, from the point of view of the reaction product yield and selectivity, it is preferable reaction system 2. Next, gaseous fluorine diluted with an inert gas such as nitrogen gas, can be used in any case where the fluorination is carried out in a periodic system or a continuous system. The following description of gaseous fluorine may be diluted with gaseous fluorine.

Continuous system 1

The manner in which the compound (3) and the solvent 2 is loaded into the reactor, start stirring and after adjusting the temperature and pressure to the pre-defined reaction the temperature and the reaction pressure for the implementation of the reaction continuously served gaseous fluorine or gaseous fluorine and solvent 2.

Continuous system 2

The manner in which the solvent 2 is loaded into the reactor, start stirring and after adjusting the temperature and pressure to a pre-prescribed reaction temperature and reaction pressure continuously and simultaneously in a predefined molar ratio serves the compound (3) and gaseous fluorine.

When the compound (3) is served in the continuous system 2, it is preferable to apply the compound (3), diluted with solvent 2, whereby it is possible to improve selectivity and reduce the amount of by-products. In addition, when the compound (3) is diluted with solvent in a continuous system 2, the ratio of solvent 2 to the number of connections (3), preferably, is at least 5 by weight, particularly preferably at least 10 mass. This condition is the same also in the case when a continuous system 2 is used as a compound (3A).

Relative amount of fluorine to be used in the fluorination reaction, in any case, when the reaction is carried out in a periodic system or in a continuous system, it is preferable that the gaseous fluorine was always present in excess relative to the hydrogen atoms, which are necessary to fluoridate, and particularly preferably from the viewpoint of selectionist is, to gaseous fluorine was used so that it exceeds at least 1.5 times by equivalent (i.e. at least 1.5 times the moles).

The reaction temperature for the fluorination reaction is usually preferably at least -60°and at most equal to the boiling point of the compound (3), and from the point of view of the reaction product yield, selectivity and applicability in industry, particularly preferably, it ranges from -50°C to +100°S, even more preferably from -20°to +50°C. the Reaction pressure for the fluorination reaction are not specifically limited, and from the point of view of output the reaction product, selectivity and applicability in industry, especially preferred pressure is from atmospheric up to 2 MPa.

Further, in order to enable the fluorination reaction to proceed efficiently, it is preferable in the reaction system to add a compound containing C-H bond, or to irradiate with ultraviolet light at a later stage of the reaction. For example, in the reaction carried out in the periodic system, it is preferable to add a compound containing C-H bond in the reaction system or to carry out ultraviolet irradiation at a later stage of the fluorination reaction. In the reaction carried out in a continuous system, preferably podavat the connection, containing C-H bond, or to irradiate UV light, at the same time continuing to serve gaseous fluorine at the completion of injection of the compound (3). Through this it is possible effectively to fluoridate the compound (3)present in the reaction system, whereby it is possible to significantly increase the reaction rate.

As compounds containing C-H bond, it is preferable aromatic hydrocarbons and, particularly preferred, for example, is benzene or toluene. The number of compounds containing C-H bond, preferably ranges from 0.1 to 10 mol.%, particularly preferably, from 0.1 to 5 mol.%, based on the number of hydrogen atoms in the compound (3).

Compounds containing C-H bond, add in the condition that the reaction system is gaseous fluorine. Next when the add compound containing C-H bond, it is preferable to maintain a high pressure in the reaction system. Created by the pressure preferably ranges from 0.01 to 5 MPa.

In phase fluorination, if the reaction occurs substitution of hydrogen atoms by fluorine atoms, as a by-product can be formed HF. To remove a by-product HF is preferably in the reaction system to enter the absorber HF or make contact absorber HF with withdrawing gases at the exit of the gases from the reactor. As such HF absorber you can use the sinks mentioned above, and preferred is NaF.

When Pets presence of the absorber HF in the reaction system, its amount is preferably equal to 1 to 20 times moles, especially preferably 1-5 times (moth) the total number of hydrogen atoms present in the compound (3). When the HF absorber is placed at the gas outlet of the reactor, it is advisable to establish (a) a cooling device (preferably, to maintain a temperature from about 10°C to room temperature, particularly preferably at about 20°C), (b) a dense layer of NaF pellets and (c) cooling unit (preferably, to maintain the temperature from -78°C to +10°preferably from -30°0° (C) sequentially in the order (a)-(b)-(c). In addition, it may be provided with the recirculation line fluid to return the condensed liquid from the cooling unit (s) in the reactor.

The crude product containing the fluorinated ester (1)obtained at the stage of fluorination can be used without purification, depending on a particular purpose, or it can be clear that he had a high purity. As a cleaning method, you can specify, for example, the method of distillation of the crude product at atmospheric pressure or at Pont the leaders introduce pressure.

In a method of producing fluorinated ether complex (1) of the present invention, through the stage of transesterification and phase fluorination, once using 1 mol fluorinated ether complex (1), you can get a maximum of 2 mole of fluorinated ether complex (1). Next, using the same stage, using as feedstock received 2 mole of fluorinated ether complex (1), you can get a maximum of 4 mole of fluorinated ether complex (1). That is, repeating stage interesterification and phase fluorination of n, the maximum you can get the 2ntime (moth) fluorinated ether complex (1). Thus, repeating the same stages with the use of fluorinated ether complex (1)obtained at the stage of transesterification and stage fluorination until you get the desired amount, it is possible to continuously and efficiently to get the fluorinated ester (1) mass production. This reaction scheme may be represented by the following chemical formula.

In the present invention, the fluorinated ester (1)received only a single stage of transesterification and phase fluorination, it is possible to allocate, or fluorinated ester (1) can be distinguished after multiple stage interesterification and stage ftorirovanie is.

Fluorinated ester (1) can be used without additional processing for a particular purpose, or it can be converted to another connection. For example, the fluorinated ester (1) can be subjected to the reaction of dissociation of the ether link, through which fluorinated allford (4) can be obtained stoichiometric two-fold molar amount relative to the fluorinated ether complex (1).

In accordance with the method of obtaining a fluorinated ether complex of the present invention fluorinated allford (4) can be obtained fewer stages compared with the method described in WO 00/56694. Further advantage is that the temperature on the stage of the transesterification according to the present invention is generally lower than the temperature of the stage interesterification in the traditional way.

In the method according to the present invention, the fluorinated ester (1) as the starting material is a compound having the same group (RAF) on both ends of the molecule. This fluorinated ester (1), preferably produced by a method described, for example, in WO 00/56694.

That is, the fluorinated ester (1), preferably, obtained by fluorination in the liquid phase of the compound (3), which is obtained by the interaction of fluorinated allford (4) with whom EDINENIE (2). The interaction of fluorinated allford (4) with compound (2) can be performed in the presence of a solvent. However, from the point of view of the volumetric efficiency, it is preferable to carry out interaction in the absence of solvent.

In the interaction of the compound (2) with fluorinated allfreedom (4) is formed HF. Accordingly, in the reaction system, you can enter the absorber HF or without the use of HF absorber, it is possible to remove HF from the reaction system by a stream of nitrogen. As HF absorber you can use the same materials as mentioned above. The reaction temperature of the compound (2) with fluorinated allfreedom (4), preferably, is at least -50°and, preferably, at most +100°or at most it is equal to the boiling temperature of the solvent. In addition, the reaction time may appropriately be changed depending on the feeding speed of the original substance and the number of connections that must be used for the reaction. The reaction pressure preferably ranges from atmospheric pressure to 2 MPa.

The crude product containing the compound (3)obtained by the interaction of the compound (2) with fluorinated allfreedom (4), can be cleaned depending on the specific purpose or can be used without additional processing at the next stage, and so what. When the crude product contains unreacted compound (2), it can be removed by cleaning to ensure a smooth reaction of fluorination. As a method of purification of this crude product can be specified, for example, the method of distillation of the crude product without further processing, the processing method of the crude product dilute aqueous alkaline solution, followed by separation of liquids, extraction of the crude product with a suitable organic solvent, followed by distillation, or chromatography on a column of silica gel.

After obtaining thus the connection (3) from compound (2) and fluorinated allford (4) connection (3) foryouth in the liquid phase, to obtain the fluorinated ester (1). As for the reaction conditions of fluorination, in this case, the fluorination can be performed in the same manner as at the stage of fluorination in the above method for obtaining fluorinated ether complex.

Of the fluorinated ether complex (1), obtained by the method according to the present invention, as described above, then you can get fluorinated allford (4) and fluorinated vinyl ether (5A).

As a method of producing fluorinated allford (4) of the fluorinated ether complex (1) you can specify R is an action of dissociation of essential communication, as described in WO 00/56694. The reaction of dissociation of essential communication is a reaction shown the following formula, whereby theoretically from 1 mole of fluorinated ether complex (1) can be obtained 2 mole of fluorinated allford (4).

RAFCOOCF2RAF(1) → 2RAFCOF (4)

When the reaction of dissociation of the ether connection, it is necessary to carry out a liquid-phase method, it can be done in the absence of solvent or in the presence of a solvent (hereinafter referred to as "solvent 3"). As a concrete example 3 the preferred solvent is an inert solvent, such as perftorsilanami or perpendicular, or oligomer of chlorotrifluoroethylene having the highest boiling point among the chlorofluorocarbons. Further, the amount of solvent 3, preferably, is from 10 to 1000 wt.% with respect to fluorinated ether complex (1).

As a method of producing a fluorinated vinyl ether (5A) from the compound (1A), which represents a fluorinated ester (1), you can specify a method of obtaining a fluorinated vinyl ether (5A) from the compound (1A) by means of the following compounds (4A) (hereinafter called "stage pyrolysis-1") or a method of obtaining a fluorinated vinyl ether (5A) directly from compound (1A) (in what he called "stage pyrolysis-2").

As shown in the following diagram, stage pyrolysis-1 is a step for fluorinated vinyl ether (5A) by the stage of dissociation of the essential communications to obtain the compound (4A) dissociation essential communication connection (1A) and the stage of pyrolysis of the compound (4A). Stage pyrolysis-2 is a step for fluorinated vinyl ether (5A) direct pyrolysis of the compound (1A) at a temperature of at least 250°C.

Stage pyrolysis-1 can be performed under the same conditions as the above conditions of pyrolysis essential communication fluorinated ether complex (1), whereby theoretically from 1 mole of fluorinated ether complex (1A) can be obtained 2 mole of compound (4A). Next stage of pyrolysis of the compound (4A) can be used, for example, the gas-phase pyrolysis of the compound (4A) or by pyrolysis of a salt of alkali metal carboxylic acid obtained by the reaction of the compound (4A) with a hydroxide of an alkali metal.

The reaction temperature gas-phase pyrolysis of the compound (4A)preferably ranges from 250 to 400°S, more preferably from 250 to 350°C. the Reaction temperature pyrolysis of the above alkali metal salt of carboxylic acid, preferably ranges from 150 to 350°S, more preferably from 200 to 280°C. Ecoregional temperature gas-phase pyrolysis is less than 250° Or if the reaction temperature pyrolysis alkali metal salt of carboxylic acid is less than 150°With the conversion in the fluorinated vinyl ether (5A) tends to be low. On the other hand, if the reaction temperature gas-phase pyrolysis exceeds 400°or if the reaction temperature pyrolysis of a salt of an alkali metal carboxylic acid exceeds 350°With, will increase the tendency for the formation of other by-products of pyrolysis, non-fluorinated vinyl ether (5A)obtained from the compound (4A).

Preferably the gas-phase pyrolysis of the compound (4A) in a continuous reaction. Continuous reaction is preferably carried out by a method in which the evaporated compound (4A) is passed through the heated reaction tube, to obtain the resulting fluorinated vinyl ether (5A) in the form of a facing strip, and this escaping gas condense and continuously emit. When pyrolysis is carried out gas-phase reaction, it is preferable to use a tubular reactor. In the case when using a tubular reactor, retention time, preferably, is from about 0.1 seconds to 10 minutes at a superficial velocity. The reaction pressure is not specifically limited. In addition, when the compound (4A) is a compound with high temperature instrumentation is tion, it is preferable to conduct the reaction under reduced pressure. When the compound (4A) is a compound with a low boiling point, it is preferable to conduct the reaction at elevated pressure, whereby it is possible to suppress the decomposition of the product and to increase the reaction rate.

When gas-phase pyrolysis is carried out using a tubular reactor, the reaction tube is preferably filled with glass, alkali metal salt or alkaline earth salt of the metal to accelerate the reaction. As such a salt of an alkali metal salt or alkaline earth metal is preferred carbonate or fluoride. As the glass you can specify normal sodium glass, and especially preferred are glass beads, in accordance with which the form of balls increases fluidity. Salt of the alkali metal may be sodium carbonate, sodium fluoride, potassium carbonate or lithium carbonate. Salt of the alkali earth metal may constitute, for example, calcium carbonate, calcium fluoride or magnesium carbonate. Further, when the reaction tube must be filled with glass, the salt of an alkali metal or alkali earth metal salt is particularly preferred to use glass beads or fine powder soda ash, the ima is the overall particle size of from about 100 to 250 μm, whereby it is possible to use the reaction system type fluidized bed.

When gas-phase pyrolysis, it is preferable to carry out the reaction in the presence of inert gas, which will not be directly included in the pyrolysis, in order to accelerate the evaporation of the compound (4A). As such an inert gas, you can specify, for example, nitrogen, carbon dioxide, helium or argon.

The quantity of inert gas, preferably approximately from 0.01 to 50 vol.%, based on the amount of the compound (4A). If the amount of inert gas is too large, the extraction product is likely to be low, thus being undesirable. On the other hand, if the boiling point of the compound (4A) is high, the pyrolysis is possible to carry out a liquid-phase reaction.

Stage pyrolysis-2 can carry out the gas-phase pyrolysis or liquid-phase pyrolysis. In the case where the boiling point of the compound (1A) at atmospheric pressure equal to 50°With up to 350°S, it is preferable to use gas-phase pyrolysis. However, it is required that the temperature of pyrolysis for gas-phase and liquid-phase pyrolysis was at least 250°C, preferably from 250 to 450°C. If the temperature of the pyrolysis exceeds 450°, fluorinated vinyl ether (5A) as a product of pyrolysis is then subjected to pyrolysis is, whereby the yield tends to decrease.

When the stage pyrolysis-2 conduct gas-phase reaction, it is preferable to conduct the reaction by using a tubular reactor in the same way as for the gas-phase pyrolysis of the compound (4A). When the compound (1A) is a compound with a high boiling point, it is preferable to carry out the pyrolysis under reduced pressure. In the case of compounds with a low boiling point, it is preferable to carry out the pyrolysis at high pressure.

The compound (5A), with RAF1O-group associated with viniferins group, has an excellent ability to polymerization and, thus, is a compound useful as a material for the polymer. This compound (5A) can be polimerizuet or the compound (5A) can be copolymerizate capable of polymerization with a monomer, which can cure with the compound (5A), whereby it is possible to obtain a useful polymer.

Capable of polymerization with a compound (5A), the monomer is not specifically limited and may be selected from known able to polymerization of the monomers. As a method for the polymerization reaction can be used a known method for the reaction as it is. For example, in the case where the compound (5A) is a PERFLUORO(Ala vinilovyi ether), capable of polymerization with a compound (5A) monomer, for example, can be veratile, such as CF2=CF2, CF2=CFCl or CF2=CH2forprofile, such as CF2=CFCF3, (perfluoroalkyl)ethylene, where the number of carbon atoms in perforaciones group is from 4 to 12, such as CF3CF2CF2CF2CH=CH2or CF3CF2CF2CF2CF=CH2, vinyl ether, having a group which can be converted into a carboxylic acid group or sulfonic acid group, such as CH3OC(=O)CF2CF2CF2OCF=CF2or FSO2CF2CF2OCF(CF3CF2OCF=CF2or olefin, such as ethylene, propylene or isobutylene. Obtained by the reaction of polymerization, the polymer is useful as a fluoropolymer. The fluoropolymer is a useful functional material having excellent heat resistance and chemical resistance.

EXAMPLES

Now the present invention will be described in detail with reference to examples, but the present invention is in no way limited to these examples. The following gas chromatography will be called GC and gas chromatography with mass spectroscopic analysis will be called GC-MS.

EXAMPLE 1

Example of getting a CH3CH2CH2Och(CH3/sub> )CH2OCOCF(CF3)OCF2CF2CF3(3b) (stage interesterification)

CH3CH2CH2Och(CH3)CH2HE (hereafter referred to as compound (2b), 20,0 g, to 0.17 mol) is placed in a flask and stirred and, at the same time carrying out bubbling gaseous nitrogen. Maintaining an internal temperature of 28 to 35°C for a period of time equal to 30 minutes, added dropwise CF3CF2CF2OCF(CF3CF2OCOCF(CF3)OCF2CF2CF3(hereinafter called compound (1b)of 67.4 g, 0.10 mol). After completion of adding dropwise conduct stirring for 2 hours at a temperature of 50°and add an additional amount of compound (1b) (22,5 g 0,034 mol). When you are finished adding spending stirring at 35°C for 3 hours, getting 90.0 g of the crude liquid.

The crude liquid analyze GC,1H-NMR and19F-NMR confirmed the formation of CH3CH2CH2Och(CH3)CH2OCOCF(CF3)OCF2CF2CF3(hereinafter called compound (3b)). Output connection (2b)calculated1H-NMR equal to 99%.

EXAMPLE 2

Example of getting CF3CF2CF2OCF(CF3CF2OCOCF(CF3)OCF2CF2CF3(1b) (stage fluorination)

Compound (3b) (200,0 g), polucen the e in example 1, dissolve in CF3CF2CF2OCF(CF3)COF (hereinafter called compound (4b), 1000,0 g). On the other hand, in 3000 ml autoclave made of Nickel, is placed a NaF powder (260,5 g) and add the compound (4b) (2000,0 g), followed by stirring and cooling to -10°C. After feeding nitrogen gas for 1 hour serves gaseous fluorine, diluted to 20% nitrogen gas, a flow rate of 22,59 l/h for 1 hour, and maintaining the flow at the same flow rate above the fractionated solution is injected over a period of time equal to 60 hours.

Then, when the supply of fluorine gas diluted to 20% with gaseous nitrogen, at the same time supporting the above flow rate, injected 20 ml of a solution of the compound (4b) in benzene (0.01 g/ml), close the outlet valve of the autoclave and then when the pressure is 0.12 MPa, close the inlet valve of the autoclave, followed by stirring for 1 hour. Hereinafter, this operation is repeated 4 times over a period of time until the temperature rises from -10°C to room temperature, and then 5 times at room temperature. During this period serves benzene in the total number of 1,800 g and enter the compound (4b) in the total number of 281,0, then served gaseous nitrogen for 2 hours and the reaction mixture is removed by decantation. The crude liquid concentrated using an evaporator, and quantitatively analyze the product by using19F-NMR, in accordance with what it contains CF3CF2CF2OCF(CF3CF2OCOCF(CF3)OCF2CF2CF3(compound (1b)) with a yield of 69%. Select the part of the crude liquid and distilled under reduced pressure, obtaining the compound (1b). The boiling point of the compound (1b) is from 46 to 51°/a 5.2 kPa.

EXAMPLE 3

An example of obtaining the compound (1b) in a continuous way

Using the compound (2b) (75,5 g, 0,640 mol) and obtained in example 2, the compound (1b) (213,1 g, 0,321 mol), conducting the reaction in the same manner as in example 1, obtaining the compound (3b) (quantity: 272,4 g, 0,634 mol). Output connections (3b), quantitatively defined1H-NMR, is 99%. Then the compound (3b) is reacted with fluorine in the same manner as in example 2, with the formation of compound (1b) (quantity: 294,0 g, 0.44 mol). Repeat the same operation to ultimately get 3000 g of compound (1b).

EXAMPLE 4

Example of getting CF3CF2CF2OCF(CF3)COF (4b) dissociation of the ether linkages (liquid-phase reaction is the dissociation of the ether bond)

In an autoclave of stainless steel having a volume of 2 l and equipped with a stirrer, was loaded with 1800 g of the crude liquid of the compound (1b)obtained in example 2 and gave the e a KF powder (30 g), prepared by spray drying, and heated to 70°under stirring. When the temperature reaches the prescribed level, the crude liquid of the compound (1b) is continuously fed into the reactor with a speed of 115 g/hour. The resulting gas is continuously divert through a column of stainless steel with a shirt that is installed in the upper part of the reactor, heated to 60°and capture trap containing dry ice. From the mass captured by the trap of the product and data analysis GC found that CF3CF2CF2OCF(CF3)COF (compound (4b)) is formed with a speed of 110 g/hour. The yield of compound (4b) is 99%.

EXAMPLE 5

Example of receipt of the product (4b) dissociation essential communication connection (1b) (gas-phase reaction of dissociation of the ether bond)

The empty reactor was U-shaped, made of Inconel 600 (internal volume: 200 ml), immersed in a salt bath, the temperature of which is supported at 250°C. From the inlet of the reactor serves gaseous nitrogen at a rate of 1 l/h and serves obtained in example 2, the compound (1b) with a speed of 15 g/hour. The retention time of support equal to from 10 to 12 seconds. Remove the crude gas formed in the reaction, using traps dry ice/methanol and traps with liquid nitrogen at the outlet of the reactor. After reaction for 2 hours, the liquid image is C (23 g) are removed from the trap. Method GC-MS confirmed that the main product is the compound (4b). Output according to NMR is equal to 73%.

EXAMPLE 6

Example of getting CF3CF2CF2OCF=CF2(5b) stage gas-phase pyrolysis-2

Column made of stainless steel (inner diameter: 20 mm, length: 1 m) and the reactor was a stainless steel fluidized bed having an inner diameter of 45 mm and a height of 400 mm and filled with 280 g of powder Na2CO3having an average particle size of 160 μm, connected in series and set in a salt bath, and the temperature of the salt bath support at 270°C. In the reactor serves gaseous nitrogen with the speed of 1520 ml/min and the compound (4b)obtained in example 5, is served with rate of 60.2 g/hour for 1.8 hours using a metering pump. The product is removed by the reactor exit trap dry ice/ethanol. The compound (4b) is not defined, and find that CF3CF2CF2OCF=CF2(hereinafter called compound (5b)) is formed with yields of 80%. Peaks19F-NMR (564,6 MHz, solvent: CDCl3standard CFCl3of the product are in accordance with the peaks of the standard product.

EXAMPLE 7

Examples of receipt of CF3CF2CF2OCF=CF2(5b) stage gas-phase pyrolysis-2

390 g of a powder of Na2CO3placed in a reactor with a fluidized bed, sod is Rashi hollow container (inner diameter: 51 mm, length: 400 mm), made of stainless steel and equipped with upper and lower perforated plates (filtering accuracy: 0.5 µm, made of stainless steel). Used Na2CO3has a particle size in the range from 100 to 250 μm. This reactor is installed in a bath of molten salt heated to 260°and from the bottom of the reactor serves gaseous nitrogen at 234 nl/hour for 8 hours to expose Na2CO3the treatment of dehydration. After that, while maintaining the reactor temperature is 260°With the crude liquid of the compound (1b)having a purity of 95%, is diluted with nitrogen gas continuously supplied from the lower part of the reactor, and the gas removed from the upper part of the reactor, szhizhajut and allocate trap with dry ice. Feed speed is adjusted so that the speed of supplying raw liquid of the compound (1b) was equal to 160 g/HR and the feed rate of nitrogen gas would be 205 l/h. Coming out of the reactor gas after 2 hours from the reaction start, analyze GC, in accordance with the conversion of the compound (1b) is 83,2%, and the selectivity for the compound (5b) is 95.2 percent. Further, the selectivity for the compound (4b) is 0.8%. In addition, after 3 hours from the beginning of the reaction converting compound (1b) 96.7%, and the selectivity for connected the Yu (5b) is 95.4%. Further, the selectivity for the compound (4b) is 1.8%.

EXAMPLE 8

An example of obtaining the compound (1b) with the compound (2b) and the compound (4b)

The compound (2b) (620 g) placed in a 2 l autoclave made of Hastelloy C and stirred at the same time barbotine gaseous nitrogen. Maintaining an internal temperature of 25 to 35°during the period of 8 hours, and thereto are added dropwise the compound (4b) (1830). After completion of adding dropwise, then continue bubbling gaseous nitrogen to remove HF and an excess of the compound (4b), getting 2245 g of compound (3b). Using the compound (3b) (1800 g), carry out the fluorination reaction in the same manner as in example 2, obtaining the compound (1b) with a yield of 69%.

APPLICATION IN INDUSTRY.

Fluorinated ester of the present invention can be obtained by a smaller number of reaction stages. Further, the method according to the present invention represents an effective way, in accordance with the yield of the reaction is high and the cost can be reduced. In addition, using fluorinated ester obtained in this way, it is possible to produce significant amounts of useful fluorinated allford and useful fluorinated vinyl ether.

1. A method of obtaining a fluorinated ether complex (1), which includes the t stage interesterification, where the fluorinated ester (1) and the compound (2) enter the interesterification reaction at a molar ratio of 1:1-2 with the formation of compound (3), and stage fluorination, where the compound (3) then foryouth to obtain the fluorinated ester (1) in excess of the molar quantity to the interesterification:

where RArepresents C1-20monovalent hydrocarbon group, C1-20monovalent hydrocarbon group containing halogen, C1-20monovalent hydrocarbon group containing a heteroatom or C1-20monovalent hydrocarbon group containing a halogen and a heteroatom, and RAFdenotes the same group as RAor a monovalent hydrocarbon group obtained by fluorination of RA.

2. A method of obtaining a fluorinated ether complex (1) according to claim 1, where at the stage of transesterification, at most, twice the molar amount of compound (2) interacts with fluorinated ether complex (1).

3. A method of obtaining a fluorinated ether complex (1) according to claim 1 or 2, where the phase fluorination fluorination of the compound (3) is carried out by introduction of fluorine gas in the liquid phase.

4. A method of obtaining a fluorinated ester is (1) according to claim 1 or 2, where on stage fluorination fluorination of the compound (3) is conducted by introducing gaseous fluorine in a liquid phase containing dissolved fluorinated ester (1) or the following fluorinated allford (4):

where RAFis the same as described above.

5. A method of obtaining a fluorinated ether complex (1) according to any one of claims 1 to 4, where the phase fluorination is used as a compound (3)containing fluorinated allford (4) and/or the compound (1)obtained at the stage of interesterification, when it contains fluorinated allford (4) and/or the connection (1):

where RAFis the same as described above.

6. A method of obtaining a fluorinated ether complex (1) according to any one of claims 1 to 5, where stage interesterification is carried out in the absence of solvent.

7. A method of obtaining a fluorinated ether complex (1) according to any one of claims 1 to 6, where the fluorinated ester (1) at the stage of interesterification is a fluorinated ester (1)obtained at the stage of fluorination.

8. A method of obtaining a fluorinated ether complex (1) according to any one of claims 1 to 6, where the fluorinated ester (1)used at the stage of transesterification, is produced by interaction of fluorinated allford (4) with compound (2) and fluoridation receive the tion in the reaction of the compound (3) in the liquid phase:

where RAand RAFare as defined above.

9. A method of obtaining a fluorinated ether complex (1) according to any one of claims 1 to 8, wherein the fluorinated ester (1) is a compound (1A), compound (2) is a compound (2A), the compound (3) is a compound (3A) and RAFis an RAF1O-CF(CF3)-:

where RA1is the same as RA, RAF1represents the same group as the specified RA1or a monovalent hydrocarbon group obtained by fluorination of the specified RA1and each of X1X2X3and X4that may be the same or different, represents a hydrogen atom or a fluorine atom.



 

Same patents:

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of ester perfluorinated derivative by using a chemical reaction. This reaction represents the fluorination reaction of the parent compound as a raw, the reaction of chemical conversion of fragment of ester perfluorinated derivative to yield another ester perfluorinated derivative or the interaction reaction of carboxylic acid with alcohol under condition that at least one or reagent, i. e. carboxylic acid or alcohol, represents a perfluorinated compound wherein indicated perfluorinated derivative of ester represents a compound comprising a fragment of the formula (1):

with a boiling point 400°C, not above. The reaction time for carrying out abovementioned chemical reaction is sufficient to provide the required yield of ester perfluorinated derivative and wherein this yield of ester perfluorinated compound is determined by the gas chromatography method by using a nonpolar column. Also, invention relates to a method for pyrolysis of ester perfluorinated derivative with a boiling point 400°C, not above, to yield the dissociation product wherein this product represents a derivative of acyl fluoride or ketone and wherein pyrolysis time is sufficient to provide the required degree of conversion of ester perfluorinated derivative and wherein the indicated conversion degree of ester perfluorinated derivative is determined by gas chromatography method by using a nonpolar column. Also, invention relates to a method for analysis of ester perfluorinated derivative with a boiling point 400°C, not above, that involves analysis of ester perfluorinated derivative in a sample containing ester perfluorinated derivative by gas chromatography method by using a nonpolar column wherein ester perfluorinated derivative represents compound comprising a fragment of above given formula (1).

EFFECT: improved method of synthesis.

8 cl, 1 dwg, 2 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.

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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.

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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.

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< / BR>
where x= CF2or bond, the sum n + m + C 3 10

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of ester perfluorinated derivative by using a chemical reaction. This reaction represents the fluorination reaction of the parent compound as a raw, the reaction of chemical conversion of fragment of ester perfluorinated derivative to yield another ester perfluorinated derivative or the interaction reaction of carboxylic acid with alcohol under condition that at least one or reagent, i. e. carboxylic acid or alcohol, represents a perfluorinated compound wherein indicated perfluorinated derivative of ester represents a compound comprising a fragment of the formula (1):

with a boiling point 400°C, not above. The reaction time for carrying out abovementioned chemical reaction is sufficient to provide the required yield of ester perfluorinated derivative and wherein this yield of ester perfluorinated compound is determined by the gas chromatography method by using a nonpolar column. Also, invention relates to a method for pyrolysis of ester perfluorinated derivative with a boiling point 400°C, not above, to yield the dissociation product wherein this product represents a derivative of acyl fluoride or ketone and wherein pyrolysis time is sufficient to provide the required degree of conversion of ester perfluorinated derivative and wherein the indicated conversion degree of ester perfluorinated derivative is determined by gas chromatography method by using a nonpolar column. Also, invention relates to a method for analysis of ester perfluorinated derivative with a boiling point 400°C, not above, that involves analysis of ester perfluorinated derivative in a sample containing ester perfluorinated derivative by gas chromatography method by using a nonpolar column wherein ester perfluorinated derivative represents compound comprising a fragment of above given formula (1).

EFFECT: improved method of synthesis.

8 cl, 1 dwg, 2 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: 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

The invention relates to an improved process for the preparation of diethyldichlorosilane starting compounds to obtain the quinoline-2,3-dicarboxylic acid

FIELD: industrial organic synthesis.

SUBSTANCE: invention, in particular, relates to production of fatty acid alkyl esters via catalytic reesterification of triglycerides/fatty acids mixture. During this reaction, ester phase containing fatty acid alkyl esters and glycerol phase containing fatty acids are formed in reaction mixture. Phases are separated from each other. Fatty acids are isolated from glycerol phase in the form of fatty acid phase. The latter is further combined with triglycerides/fatty acids mixture and fatty acids contained in resulting mixture in amount about 10% are esterified with alcohol to produce esterification mixture containing triglycerides and fatty acid alkyl esters. This mixture is then subjected to reesterification with alcohol to produce additional amount of fatty acid alkyl esters. Esterification is effected in presence of acid catalysts and reesterification in presence of alkali catalysts.

EFFECT: improved economic characteristics of process due to recovery of additional amount of desired product.

7 cl

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to improved process of producing compounds of general formula I: (I), which are preferably used as antioxidants. In formula I, R1 and R2 . independently of each other, represent C1-C8-alkyl, cyclopentyl, and cyclohexyl, m is 1, 2, or, 3 (preferably 2), n is integer from 1 to 4, and R3 represents n-valent linear or branched C4-C30-alkyl chain optionally interrupted with oxygen atom. Process consists in reaction of compounds having general formula II: (II), in which R represents C1-C3-alkyl, with compounds depicted by general formula R3(OH)n (III), where R3 and n are such as defined above. Reaction is carried out at substantially neutral pH in presence of at least one, dissolved or suspended in reaction mixture, carboxylic acid alkali metal salt, provided that carboxylic acid in question is at least partially volatile under reaction conditions. Preferred salts are alkali metal formate and alkali metal acetate.

EFFECT: enabled conduction of reaction in absence of carrier and in substantially neutral medium and thus a number of drawbacks of the prior technical level is avoided.

16 cl, 8 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to the improved method for re-esterification of fat and/or oil of biological origin by alcoholysis. Method involves preparing fat and/or oil of biological origin for re-esterification process in suitable capacity followed by alcoholysis by addition of monoatomic alcanol and catalyst to the prepared fat and/or oil. Amino acid or derivative of amino acid metallic salt insoluble in monoatomic alcanols is used as a catalyst. Also, invention relates to fatty acid monoesters preparing by indicated method that are used as diesel fuel. This simple method provides preparing the end product with high yield that is not contaminated with catalytic material impurities.

EFFECT: improved method for re-esterification.

19 cl, 28 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing β-(4-hydroxy-3,5-di-tert.-butylphenyl)propionic acid esters that are used in polymeric industry as stabilizing agents. Method is carried out by the re-esterification reaction of β-(4-hydroxy-3,5-di-tert.-butylphenyl)propionic acid methyl ester with polyhydric alcohols at enhanced temperatures (130-190°C) in the inert gas flow in the presence of catalyst comprising the following components, wt.-%: sodium 4-(β-methylcarboxyethyl)-2,6-di-tert.-butylphenolate, 30.0-45.5, and sodium aluminate, 54.5-70.0. Indicated compounds of alkaline metal are used in the amount 0.7-6.0 mole% of the amount of β-hydroxy-3,5-di-tert.-butylphenol)propionic acid methyl ester. Invention provides enhancing yield and improving color index, reducing cost of the process and reducing amount of by-side products formed.

EFFECT: improved preparing method.

2 cl, 1 tbl, 10 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing β-(4-hydroxy-3,5-di-tert.-butylphenyl)-propionic acid esters that are used in industry of polymers as stabilizing agents. Method involves carrying out the process of the ester interchange reaction of β-(4-hydroxy-3,5-di-tert.-butylphenyl)-propionic acid methyl ester with polyhydric alcohols in inert gas flow at enhanced temperatures (130-190°C in the presence of the following components, wt.-%: 2,6-di-tert.-butylphenolate sodium, 1.5-3.6; 4-(β-methylcaboxyethyl)-2,6-di-tert.-butylphenolate sodium, 4.0-8.6; sodium acrylate, 2.1-6.4; 2,6-di-tert.-butylphenol, the balance. Indicated compounds of alkaline metal are used in the amount 0.4-5.1 wt.-% of the amount of β-(4-hydroxy-3,5-di-tert.-butylphenyl)-propionic acid methyl ester as measure for the sum of 4-(β-methylcarboxyethyl)-2,6-di-tert.-butylphenolate sodium, alkaline metal 2,6-di-tert.-butylphenolate and sodium acrylate. Invention provides increasing yield of the end product and its enhanced quality.

EFFECT: improved preparing method.

2 cl, 1 tbl, 10 ex

The invention relates to an improved method of obtaining pentaerythrol-tetrakis-[3-(3,5-di-tert-butyl-4 oksifenil)-propionate], used as a colorless treatment effective, non-toxic low volatile stabilizer for rubbers, plastics and other polymeric materials
The invention relates to a new composition for skin care containing lipid mixture, where this lipid mixture contains a mixture of linoleic acid anda-linolenic acid, where these acids are in the form selected from the group consisting of acidic form, derived complex monoether derived triglyceride-derived amide and mixtures thereof, and contains about 5% to 40% of the total weight of the lipid mixture, at least one modified coconut oil consisting essentially of a10-C14fatty acids in the form of mono-, di - and triglycerides and having a turbidity less than 5oWith, and specified the lipid mixture is present in an amount effective to improve the physiological state of the skin

The invention relates to a process for the preparation of ester, which comprises carrying out the esterification reaction in the presence of a catalyst which is a reaction product of artefiera or condensed orthoevra titanium or zirconium and alcohol containing at least two hydroxyl group of 2-hydroxycarboxylic acids and bases
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