JP4655176B2 - Novel vic-dichloro acid fluoride compound - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel vic-dichloro acid fluoride compound having a vic-dichloro structure, which is useful as an intermediate for producing a fluororesin raw material monomer.
[0002]
[Prior art]
Vic-dichloro acid having a vic-dichloro structure (a structure in which one chlorine atom is bonded to each of carbon and carbon adjacent to the carbon) at the end of the perfluoroalkyl chain and also having a fluorocarbonyl group (-COF) A fluoride compound is a useful compound as an intermediate for producing a fluororesin raw material monomer. For example, CF ₂ A compound having a ClCFCl- moiety is reacted with zinc and then dechlorinated to produce a perfluorovinyl group (CF ₂ = CF-). The perfluorovinyl group of the compound is a polymerizable group, and various fluororesins can be produced by polymerizing the group. A fluororesin is a useful resin excellent in heat resistance and chemical resistance.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide an acid fluoride compound having a novel vic-dichloro structure useful as a raw material for a fluororesin.
[0004]
[Means for Solving the Problems]
The present invention provides a compound represented by the following formula (1).
[0005]
CF ₂ ClCFClCF (OR ^f ) COF (1)
[0006]
However, R ^f Represents a perfluoroalkyl group.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the present specification, a compound represented by the formula (1) is described as a compound (1). The same applies to compounds represented by other formulas.
[0008]
R in formula (1) ^f Represents a perfluoroalkyl group. A perfluoroalkyl group refers to a group in which all of the hydrogen atoms in the alkyl group have been fluorinated. R ^f The number of carbon atoms is preferably from 1 to 10, particularly preferably from 1 to 6, especially _Three Is preferred.
[0009]
Specific examples of the compound (1) include the following compounds. However, n shows the integer of 1-9. R of these ^f -CF _Three The compound represented by the following formula (1A) is preferred.
[0010]
CF ₂ ClCFClCF (OCF _Three ) COF (1A)
CF ₂ ClCFClCF (O (CF ₂ ) _n CF _Three COF
[0011]
The compound (1) of the present invention is preferably produced by the following method 1 or method 2.
[0012]
Method 1:
The compound represented by the following formula (A) is esterified with the compound represented by the following formula (B) to obtain a compound represented by the following formula (C). A method for producing a compound represented by the following formula (D) by fluorination and decomposing an ester bond of the compound represented by the formula (D).
[0013]
CH ₂ ClCHClCH (OR) CH ₂ OH (A)
R ^f2 COX (B)
CH ₂ ClCHClCH (OR) CH ₂ OCOR ^f2 ... (C)
CF ₂ ClCFClCF (OR ^f CF ₂ OCOR ^f2 ... (D)
[0014]
However, R is fluorinated and R ^f Represents the group R ^f Means the same as above, R ^f2 Represents a perfluoro monovalent saturated organic group. X represents a halogen atom.
[0015]
Method 2:
The following formula (A ¹ ) Is represented by the following formula (B ¹ ) And a compound represented by the following formula (C ¹ And a compound represented by the formula (C ¹ The compound represented by the following formula (C ² And a compound represented by the formula (C ² ) Is fluorinated to obtain a compound represented by the following formula (D), and the ester bond of the compound represented by the formula (D) is decomposed.
[0016]
CH ₂ = CHCH (OR) CH ₂ OH ... (A ¹ )
R ^f20 COX (B ¹ )
CH ₂ = CHCH (OR) CH ₂ OCOR ^f20 ... (C ¹ )
CH ₂ ClCHClCH (OR) CH ₂ OCOR ^f20 ... (C ² )
CF ₂ ClCFClCF (OR ^f CF ₂ OCOR ^f2 ... (D)
[0017]
However, R, R ^f , X each have the same meaning as described above. R ^f20 Is R ^f2 Perfluoro monovalent saturated organic group or CF ₂ = CFCF (OR ^f CF ₂ -(However, R ^f Indicates the same meaning as above. ).
[0018]
R is the target R ^f A group in which one or more fluorine atoms are substituted with hydrogen atoms, a group in which at least one carbon-carbon bond of the substituted group is an unsaturated bond, R ^f And groups in which one or more carbon-carbon bonds of the group are substituted with unsaturated bonds. The unsaturated bond may be a double bond or a triple bond.
[0019]
Specific examples of R include CH _Three -, H (CH ₂ ) _n CH _Three -(Wherein n represents an integer of 1 to 9), CH _Three -Is preferred.
[0020]
R ^f Examples of these are the same as the above examples.
[0021]
R ^f2 Are preferably a perfluoroalkyl group, a perfluoro (etheric oxygen atom-containing alkyl) group, a perfluoro (partial chloroalkyl) group, or a perfluoro (partial chloro (etheric oxygen atom-containing alkyl)) group, and more particularly perfluoro (partial chloro (ether) Oxygen group-containing alkyl)) group is preferred, CF ₂ ClCFClCF (OR ^f CF ₂ -Is particularly preferred.
[0022]
R ^f2 Specific examples of include the following groups. However, n shows the same meaning as the above, m and p show an integer greater than or equal to 0, the integer of 0-10 is preferable, k shows the integer of 1 or more, and the integer of 1-10 is preferable.
[0023]
CF _Three −,
CF _Three (CF ₂ ) _n −,
CF _Three (CF ₂ ) _m O (CF ₂ ) _k −,
CF _Three (CF ₂ ) _m OCF (CF _Three ) −
CF ₂ ClCFCl (CF ₂ ) _p −
CF ₂ ClCFClCF (OCF _Three CF ₂ −,
CF ₂ ClCFClCF (O (CF ₂ ) _n CF _Three CF ₂ -.
[0024]
In addition, R ^f2 As CF ₂ ClCFClCF (OR ^f )-Is preferred.
[0025]
R ^f20 Is R ^f2 As an example that is the same as R ^f2 The same example is given. R ^f20 Is CF ₂ = CFCF (OR ^f CF ₂ In the case of-, the following groups can be exemplified. However, n has the same meaning as described above.
[0026]
CFCl = CClCF (OCF _Three CF ₂ −,
CFCl = CClCF (O (CF ₂ ) _n CF _Three CF ₂ -.
[0027]
X is specifically a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom, a chlorine atom, or a bromine atom, and particularly preferably a fluorine atom.
[0028]
In the above methods 1 and 2, the esterification reaction can be carried out under the conditions of a normal esterification reaction. The reaction may be carried out using a solvent (hereinafter referred to as an esterification solvent), but it is preferable not to use an esterification solvent from the viewpoint of volume efficiency.
[0029]
In the esterification reaction, HX is by-produced. When an esterification reaction is carried out using a compound in which X is a fluorine atom, HF is generated. Therefore, alkali metal fluorides (for example, NaF, KF, etc.), trialkylamines, pyridines are used as HF scavengers. Etc. may be present in the reaction system. When using an HF scavenger, the amount of compound (B) or compound (B ¹ ) To 1 to 10 times mol. When an HF scavenger is not used, it is preferable to carry out the reaction at a reaction temperature at which HF can be vaporized, and to discharge HF out of the reaction system with a nitrogen stream.
[0030]
In general, the lower limit temperature of the esterification reaction is preferably −50 ° C. or higher, and the upper limit is preferably a lower temperature of + 100 ° C. or the boiling point of the esterification solvent. The reaction time can be appropriately changed according to the feed rate of the raw material and the amount of compound used for the reaction. The reaction pressure (gauge pressure, hereinafter the same) is preferably 0 to 2 MPa.
[0031]
Compound (C) produced by esterification reaction in Method 2 ¹ ) Is chlorinated and compound (C ² ). The chlorination reaction can be carried out using a chlorinating agent under ordinary chlorination reaction operations and reaction conditions. As a chlorinating agent, chlorine (Cl ₂ ) Is preferred. When chlorine is used, the amount of compound (C ¹ ) To 1 to 10 moles, and particularly preferably 1 to 5 moles. Compound (C ¹ ) And a chlorinating agent may be carried out using a solvent (hereinafter referred to as a chlorinated solvent), but it is preferable not to use a chlorinated solvent from the viewpoint of volume efficiency. When a chlorinated solvent is used, it is preferable to use a halogenated hydrocarbon solvent. Examples of the halogenated hydrocarbon solvent include dichloromethane and chloroform. The amount of chlorinated solvent used is the compound (C ¹ ) Is preferably 0.5 to 5 times the mass. The temperature of the chlorination reaction is preferably −78 ° C. to + 200 ° C.
[0032]
Compound (C) of Method 1 and Compound (C) of Method 2 ² Next, a fluorination reaction is carried out. Hereinafter, compound (C) and compound (C ² ) Are collectively referred to as fluorinated substrates. The fluorination reaction can be carried out by an electrochemical fluorination method (ECF method), a method of fluorination using cobalt fluoride, or a method of reacting with a fluorine gas in a gas phase. High yields can be obtained by the liquid phase fluorination method by reacting with fluorine in the liquid phase due to problems such as extremely low product yield, special equipment required, and difficult operation. This is preferable from the viewpoint of ease of operation. Hereinafter, the liquid phase fluorination method will be described.
[0033]
The fluorine content in the fluorinated substrate is preferably changed as appropriate according to the type of liquid phase used in the fluorination reaction. Usually, the lower limit of the fluorine content (the ratio of the total amount of fluorine atoms to the molecular weight of the fluorinated substrate) is 10 It is preferably at least 30% by mass, particularly preferably at least 30% by mass. Further, the upper limit is preferably 86% by mass or less, and particularly preferably 80% by mass or less.
[0034]
Further, each R is adjusted so that the molecular weight of the fluorinated substrate is 300 to 1000. ^f2 And R ^f20 It is preferable to adjust the structure. When the molecular weight is in the above range, it is preferable in that the fluorination reaction in the liquid phase can be carried out smoothly. If the molecular weight is too small, the fluorinated substrate is likely to vaporize, so that a decomposition reaction may occur in the gas phase during the fluorination reaction in the liquid phase. On the other hand, if the molecular weight is too large, it may be difficult to purify the fluorinated substrate.
[0035]
Compound (C) and compound (C) which are fluorinated substrates ² The following examples are given as examples of However, m in the following formula has the same meaning as described above.
[0036]
CH ₂ ClCHClCH (OCH _Three ) CH ₂ OCOCF (CF _Three ) O (CF ₂ ) _m CF _Three ,
CH ₂ ClCHClCH (OCH _Three ) CH ₂ OCOCF ₂ CF (OCF _Three CFClCF ₂ Cl,
CH ₂ = CHCH (OR) CH ₂ OCOCF (CF _Three ) O (CF ₂ ) _m CF _Three ,
CH ₂ = CHCH (OR) CH ₂ OCOCF ₂ CF (OCF _Three CFClCF ₂ Cl.
[0037]
Liquid phase fluorination is preferably carried out by introducing fluorine in a solvent that forms a liquid phase and reacting with the compound. Fluorine may be 100% fluorine gas or fluorine gas diluted with an inert gas. As the inert gas, nitrogen gas and helium gas are preferable, and nitrogen gas is particularly preferable. The amount of fluorine gas in the mixed gas of inert gas and fluorine gas is preferably 5% by volume or more from the viewpoint of efficiency, and in particular, 5-30% by volume prevents chlorine extraction or chlorine migration. Particularly preferred in terms.
[0038]
As the solvent (hereinafter referred to as a fluorinated solvent), a solvent which does not contain a C—H bond and essentially requires a C—F bond is preferable. Furthermore, perfluoroalkanes or organic solvents obtained by perfluorinating a known organic solvent having at least one atom selected from a chlorine atom, a nitrogen atom and an oxygen atom in the structure are preferred. Further, as the fluorinated solvent, it is preferable to use a solvent having high solubility in the fluorinated substrate. In particular, the solvent in which the fluorinated substrate is dissolved by 1% by mass or more with respect to the total amount of the solvent and the fluorinated substrate, particularly It is preferable to use a solvent that dissolves 5% by mass or more.
[0039]
Examples of the fluorinated solvent include compound (D), compound (1), compound (B), perfluoroalkanes (trade name: FC-72, etc.), perfluoroethers (trade name), which are products of the fluorination reaction. : FC-75, FC-77, etc.), perfluoropolyethers (trade names: Krytox, Fomblin, Galden, demnam, etc.), chlorofluorocarbons (trade name: CFC), chlorofluoropolyethers, perfluoroalkylamine (For example, perfluorotrialkylamine etc.), inert fluid (trade name: Florinato) and the like. Among these, as a fluorinated solvent, a compound (D) is preferable. In particular, when the compound (D) is used, there is an advantage that post-treatment after the reaction becomes easy. The amount of the fluorinated solvent is preferably 5 times or more, more preferably 10 to 100 times the mass of the fluorinated substrate.
[0040]
The reaction mode of the liquid phase fluorination reaction is preferably a batch method or a continuous method, and particularly a continuous method is preferable from the viewpoint of reaction yield and selectivity. In addition, the fluorine gas diluted with an inert gas such as nitrogen gas may be used in the batch method or the continuous method. Examples of the continuous fluorination reaction method include the following examples.
[0041]
[Fluorination reaction 1]
A reactor is charged with a fluorinated substrate and a fluorinated solvent, and stirring is started. Next, the reaction is carried out while continuously supplying fluorine gas into the fluorinated solvent under a predetermined reaction temperature and reaction pressure.
[0042]
[Fluorination reaction 2]
Charge the reactor with fluorinated solvent and stir. Next, the fluorinated substrate and the fluorine gas are continuously and simultaneously supplied into the fluorinated solvent at a predetermined molar ratio under a predetermined reaction temperature and pressure.
[0043]
When supplying the fluorinated substrate in the fluorination reaction 2, it may or may not be diluted with a fluorinated solvent. In the case of dilution, the amount of the fluorinated solvent with respect to the mass of the fluorinated substrate is preferably 5 times or more, particularly preferably 10 times or more.
[0044]
In the liquid phase fluorination reaction, in order for the fluorination reaction to proceed efficiently, the amount of fluorine is always in excess equivalent to the hydrogen atoms present in the fluorinated substrate at the latter stage of the reaction. It is preferable to charge fluorine gas, and it is particularly preferable from the viewpoint of selectivity that fluorine gas is charged so as to be 1.5 times equivalent or more (that is, 1.5 times mole or more).
[0045]
The reaction temperature of the liquid phase fluorination reaction is preferably −60 ° C. or higher and not higher than the boiling point of the fluorinated substrate, and is particularly preferably −50 ° C. to + 100 ° C. from the viewpoint of reaction yield, selectivity, and ease of industrial implementation. A temperature of −20 ° C. to + 50 ° C. is particularly preferable in terms of preventing chlorine extraction and chlorine migration. The reaction pressure of the fluorination reaction is not particularly limited, and it is particularly preferably from normal pressure to 2 MPa from the viewpoint of reaction yield, selectivity, and ease of industrial implementation.
[0046]
Further, in the liquid phase fluorination, it is preferable that a C—H bond-containing compound is present in the reaction system or ultraviolet irradiation is performed. For example, it is preferable to add a C—H bond-containing compound to the reaction system in the latter stage of the fluorination reaction or to perform ultraviolet irradiation. Thereby, it is possible to efficiently fluorinate hydrogen atoms that are hardly fluorinated in the fluorinated substrate, and to dramatically improve the reaction rate. The ultraviolet irradiation time is preferably 0.1 to 3 hours.
[0047]
The C—H bond-containing compound is an organic compound other than the fluorinated substrate, and aromatic hydrocarbons are particularly preferable, and benzene, toluene and the like are particularly preferable. The amount of the C—H bond-containing compound added is preferably from 0.1 to 10 mol%, particularly preferably from 0.1 to 5 mol%, based on the hydrogen atoms in the fluorinated substrate.
[0048]
The C—H bond-containing compound is preferably added in a state where fluorine is present in the reaction system. Furthermore, when a C—H bond-containing compound is added, it is preferable to pressurize the reaction system. The pressure at the time of pressurization is preferably 0.01 to 5 MPa.
[0049]
The liquid phase fluorination reaction is performed until the hydrogen atom of the fluorinated substrate is perfluorinated. In the liquid phase fluorination reaction, when a hydrogen atom is substituted with a fluorine atom and an unsaturated bond is present, the fluorine atom is added to the unsaturated bond portion.
[0050]
In the fluorination reaction in the liquid phase, HF is by-produced. In order to remove by-produced HF, it is preferable to allow a HF scavenger to coexist in the reaction system, or to contact the HF scavenger and the outlet gas at the reactor gas outlet. The HF scavenger is preferably a base such as an alkali metal fluoride (for example, NaF, KF, etc.), and the base may be present in the reaction system. As the HF scavenger, NaF is particularly preferable.
[0051]
When the HF scavenger is allowed to coexist in the reaction system, the amount is preferably 1 to 20 times by mole and more preferably 1 to 5 times by mole with respect to the total amount of hydrogen atoms present in the fluorinated substrate. When the HF scavenger is placed at the reactor gas outlet, (a) a cooler (preferably kept at 10 ° C. to room temperature, particularly preferably about 20 ° C.), (b) NaF pellets And (c) a cooler (preferably held at −78 ° C. to + 10 ° C., preferably held at −30 ° C. to 0 ° C.) (a)-(b )-(C) in order. In addition, you may install the liquid return line for returning the condensed liquid to the reactor from the cooler of (c).
[0052]
Next, the target compound (1) is obtained by decomposing | disassembling the ester bond of a compound (D).
[0053]
The decomposition reaction is -CF ₂ This is a reaction in which OCO- is cleaved to form two -COF groups. The reaction is preferably carried out by a thermal decomposition reaction or a decomposition reaction performed in the presence of a nucleophile or an electrophile.
[0054]
The thermal decomposition reaction can be carried out by heating the compound (D). The reaction mode of the thermal decomposition reaction is preferably selected depending on the boiling point of the compound (D) and its stability.
[0055]
For example, the thermal decomposition reaction in the case where the compound (D) is a compound that is easily vaporized is a gas phase heat in which the outlet gas containing the obtained compound (1) is condensed and recovered by continuously decomposing in the gas phase. A decomposition method can be employed. The reaction temperature in the gas phase pyrolysis method is preferably 50 to 350 ° C, particularly preferably 50 to 300 ° C, and particularly preferably 150 to 250 ° C. Further, an inert gas that does not directly participate in the reaction may coexist in the reaction system. Examples of the inert gas include nitrogen gas and carbon dioxide gas. The inert gas is preferably added in an amount of about 0.01 to 50% by volume based on the compound (D). When the addition amount of the inert gas is large, the product recovery amount may be reduced.
[0056]
On the other hand, it is preferable to employ a liquid phase pyrolysis method in which the compound (D) is a compound that is difficult to vaporize, and is heated in a liquid state in the reactor. The reaction pressure in this case is not limited. In general, since the ester decomposition product has a lower boiling point, the reaction is preferably carried out while continuously extracting the low boiling product using a reactor equipped with a distillation column. Moreover, the method of extracting a product collectively from the inside of a reactor after completion | finish of a heating may be sufficient. The reaction temperature in this liquid phase pyrolysis method is preferably 50 to 300 ° C, particularly preferably 100 to 250 ° C.
[0057]
When thermal decomposition is performed by a liquid phase thermal decomposition method, it is preferably performed without a solvent. The reaction may be performed in the presence of a solvent (hereinafter referred to as a decomposition reaction solvent). When a decomposition reaction solvent is used, it is not particularly limited as long as it is a solvent that does not react with compound (D) but is compatible with compound (D) and does not react with compound (1). In addition, it is preferable to select a decomposition reaction solvent that can be easily separated during purification of the product.
[0058]
Specific examples of the decomposition reaction solvent include inert solvents such as perfluorotrialkylamine and perfluoronaphthalene, and chlorotrifluoroethylene oligomers having a high boiling point among chlorofluorocarbons (for example, Asahi Glass Co., Ltd. trade name: CFC). preferable. The amount of the decomposition reaction solvent is preferably 10 to 1000% by mass with respect to the compound (D).
[0059]
Further, the ester bond may be decomposed by reacting the compound (D) with a nucleophile or an electrophile in a liquid phase. In this case, the reaction may be performed without a solvent or in the presence of a decomposition reaction solvent. Nucleophiles include fluorine ions (F ^- ), And fluorine ions derived from alkali metal fluorides are particularly preferred. Alkali metal fluorides include NaF and NaHF ₂ , KF and CsF are preferable, and NaF is particularly preferable. By carrying out the thermal decomposition reaction in the presence of NaF, the thermal decomposition reaction can be carried out at a low temperature and the decomposition reaction of the compound can be prevented.
[0060]
The nucleophile used at the start of the reaction is preferably a catalytic amount, but may be used in excess. The amount of the nucleophilic agent is preferably from 1 to 500 mol%, particularly preferably from 10 to 100 mol%, particularly preferably from 5 to 50 mol%, based on the compound (D). The lower limit of the reaction temperature is preferably −30 ° C. or higher, and the upper limit of the boiling point of the solvent or compound (D) is preferably lower, and usually −20 ° C. to 250 ° C. is particularly preferable.
The ester decomposition reaction is preferably carried out using a reactor equipped with a distillation column.
[0061]
In the ester bond decomposition reaction, compound (B) is produced together with compound (1).
[0062]
R ^f2 But CF ₂ ClCFClCF (OR ^f CF ₂ In the case of-, since the compound (B) is the same compound as the compound (1), it is not necessary to separate the product. But R ^f2 Is CF ₂ ClCFClCF (OR ^f CF ₂ When it is a group other than-, it is preferable to separate the compound (B) in the product. And this compound (B) is used as a compound (B) or a compound (B ¹ ) Is preferably reused.
[0063]
The compound (1) provided by the present invention is a novel compound useful as an intermediate for monomers for producing various fluororesins. For example, compound (1) is reacted with perfluoropropylene oxide to give compound (10), which is thermally decomposed to give compound (11), and this compound (11) is reacted in the presence of zinc to obtain a fluororesin. It leads to the compound (12) useful as a raw material. The fluororesin obtained by polymerizing the compound (12) is a useful fluororesin that is transparent and has a high Tg value (Tg: glass transition temperature).
[0064]
CF ₂ ClCFClCF (OCF _Three CF ₂ OCF (CF _Three ) COF (10)
CF ₂ ClCFClCF (OCF _Three CF ₂ OCF = CF ₂ (11)
CF ₂ = CFCF (OCF _Three CF ₂ OCF = CF ₂ (12)
[0065]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In the following, gas chromatography is denoted by GC, nuclear magnetic resonance spectrum analysis by NMR, gas chromatography mass spectrometry by GC-MS, tetramethylsilane by TMS, dichloropentafluoropropane by AK-225, and liter by L. Moreover, GC purity means the purity calculated | required from the peak area ratio by a gas chromatography.
[0066]
[Example 1] CH by esterification reaction ₂ = CHCH (OCH _Three ) CH ₂ OCOCF (CF _Three OCF ₂ CF ₂ CF _Three Example of manufacturing
CH ₂ = CHCH (OCH _Three ) CH ₂ OH (270 g) was charged into a 2 L pressure-resistant reactor having a refluxer in which a 20 ° C. refrigerant was circulated together with NaF (334 g), and stirred at −10 ° C.
[0067]
By bubbling nitrogen gas into the reactor, HF generated as a by-product by the reaction is discharged out of the system from the upper reflux, while FCOCF (CF _Three OCF ₂ CF ₂ CF _Three (1055 g) was added dropwise over 1.5 hours. At this time, the temperature was adjusted so that the internal temperature of the reactor was 0 ° C. or lower. After completion of the dropping, the reaction was terminated by stirring at 30 ° C. for 18 hours.
[0068]
The crude product (981 g) was obtained by filtering off NaF contained in the crude liquid after completion of the reaction (yield 86.4%). As a result of analysis by NMR, the production of the title compound was confirmed.
[0069]
¹ H-NMR (300.4 MHz, solvent: CDCl _Three Standard: TMS) δ (ppm): 3.29 (s, 3H), 3.85 to 3.90 (m, 1H), 4.24 to 4.45 (m, 2H), 5.34 (s , 1H), 5.39 (d, J = 8.4 Hz, 1H), 5.59-5.71 (m, 1H).
[0070]
¹⁹ F-NMR (282.7 MHz, solvent: CDCl _Three Standard: CFCl _Three ) Δ (ppm): −81.8 (3F), −82.6 (3F), −79.9 to −87.5 (2F), −130.2 (2F), −132.3 (1F) .
[0071]
[Example 2] CH by chlorination reaction ₂ ClCHClCH (OCH _Three ) CH ₂ OCOCF (CF _Three OCF ₂ CF ₂ CF _Three Example of manufacturing
CH obtained in Example 1 ₂ = CHCH (OCH _Three ) CH ₂ OCOCF (CF _Three OCF ₂ CF ₂ CF _Three (981 g) was charged into a 2 L three-necked flask equipped with a Dimroth cooled to 0 ° C., and a reaction was carried out by introducing chlorine gas at a rate of 0.8 g / min while stirring at −10 to 0 ° C. . When 170 g of chlorine gas was introduced, the reaction was terminated to obtain 1084 g of a crude liquid.
[0072]
The obtained crude liquid was purified by distillation under reduced pressure of 6 to 7 mmHg to obtain 744 g of a product. As a result of analysis by NMR and gas chromatography, it was confirmed that the title compound was produced as a mixture of three diastereomers with a GC purity of 98%.
[0073]
¹ H-NMR (300.4 MHz, solvent: CDCl _Three , Standard: TMS) δ (ppm): 3.45 (d, J = 1.5 Hz) and 3.47 (s) and 3.55 (d J = 0.6 Hz) total 3H, 3.56-3. 80 (m, 2H), 3.82 to 4.12 (m, 2H), 4.43 to 4.57 (m, 1H), 4.65 (dd, J = 6.3 Hz, 11.4 Hz) and 4.89 (ddd, J = 42.4 Hz, 12.0 Hz, 3.0 Hz) and 5.49 (q, J = 5.1 Hz) total 1H.
[0074]
¹⁹ F-NMR (376.0 MHz, solvent: CDCl _Three Standard: CFCl _Three ) Δ (ppm): −79.93 to −80.65 (1F), −81.72 to −81.80 (3F), −82.47 to −82.56 (3F), −86.46 to −87.22 (1F), −130.07 to −130.19 (2F), −132.26 to −132.47 (1F).
[0075]
[Example 3] CF by fluorination reaction ₂ ClCFClCF (OCF _Three CF ₂ OCOCF (CF _Three OCF ₂ CF ₂ CF _Three Example of manufacturing
In a 3000cc nickel autoclave, CF _Three CF ₂ CF ₂ OCF (CF _Three CF ₂ OCF (CF _Three ) COF (3523 g, hereinafter referred to as Solvent A) was added and stirred and kept at 5 ° C. A cooler maintained at −10 ° C. was installed at the autoclave gas outlet. After blowing nitrogen gas for 3.5 hours, fluorine gas diluted to 20% with nitrogen gas (hereinafter referred to as diluted fluorine gas) was blown for 1 hour at a flow rate of 26.52 L / h. Next, the CH obtained in Example 2 while blowing fluorine gas at the same flow rate. ₂ ClCHClCH (OCH _Three ) CH ₂ OCOCF (CF _Three OCF ₂ CF ₂ CF _Three A portion (415 g) of was injected over 22.5 hours. 261 g of the reaction crude liquid was extracted.
[0076]
Next, while blowing diluted fluorine gas at the same flow rate, CH ₂ ClCHClCH (OCH _Three ) CH ₂ OCOCF (CF _Three OCF ₂ CF ₂ CF _Three (642 g) was injected over 22.0 hours. 533 g of reaction crude liquid was extracted.
[0077]
Furthermore, while blowing diluted fluorine gas at the same flow rate, CH ₂ ClCHClCH (OCH _Three ) CH ₂ OCOCF (CF _Three OCF ₂ CF ₂ CF _Three (471 g) was injected over 22.8 hours. 270 g of the reaction crude liquid was extracted.
[0078]
Next, the reaction temperature was adjusted to 25 ° C. for 22 hours while diluting fluorine gas at the same flow rate. Next, nitrogen gas was blown in for 3.0 hours. The reaction crude liquid 3530g was recovered. As a result of analyzing the reaction crude liquid by GC-MS, solvent A and the title compound were obtained as main components. The reaction yield of the title compound was 71%.
[0079]
[Example 4] CF by liquid phase pyrolysis ₂ ClCFClCF (OCF _Three ) Production example of COF CF obtained in Example 3 was added to a 300 mL four-necked flask equipped with a stirrer and a reflux condenser. ₂ ClCFClCF (OCF _Three CF ₂ OCOCF (CF _Three OCF ₂ CF ₂ CF _Three (200 g, 0.31 mol) was charged with 9.0 g (0.155 mol) of KF powder, and heated in an oil bath at 90 to 95 ° C. for 0.5 to 1 hour while thoroughly stirring. After confirming the reflux caused by the progress of the reaction, the reaction system was decompressed, and the product was recovered by distilling over 5 hours and withdrawing from the reaction system. Further, the crude product was distilled to obtain the title compound (74 g) having a GC purity of 99.9% or more (yield: 79%). From the NMR spectrum, it was confirmed that the title compound was the main component.
[0080]
¹⁹ F-NMR (282.7 MHz, solvent: CDCl _Three Standard: CFCl _Three ) Δ (ppm): 28.4, 28.0 (1F), −55.1, −55.4 (3F), −61.6 to −63.9 (2F), −121.9, −123 .9 (1F), -128.7, -129.0 (1F).
[0081]
Boiling point: 62 ° C./33.3 kPa.
[0082]
【The invention's effect】
According to the present invention, a novel and useful vic-dichloro acid fluoride compound is provided. The compound of the present invention has a terminal CF ₂ It has a ClCFCl- moiety. This part is led to a polymerizable carbon-carbon double bond by a known method, and by polymerizing this, a useful fluororesin having excellent heat resistance and chemical resistance and being transparent can be obtained. In addition, —CF (CF _Three ) The COF end is -CF = CF by a known reaction. ₂ Can be converted to the end. The compound is also useful as a fluororesin raw material. Moreover, the compound of this invention does not have the problem that it is difficult to control the amount of the isomer byproduced as a by-product in a manufacturing process like the conventional vic-dichloro acid fluoride compound, or a by-product. Moreover, there are few reaction processes, raw materials are inexpensive, and it is economically advantageous. Furthermore, handling of the reaction reagent is easy.

Claims (2)

A compound represented by the following formula (1).
CF ₂ ClCFClCF (OR ^f ) COF (1)
^Rf represents a perfluoroalkyl group. The compound according to claim 1, wherein R ^f is —CF ₃ .