JP2002047218A - Method for purifying fluorinated hydrocarbon, solvent, lubricative polymer-containing liquid, and article having lubricative polymer film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for purifying fluorinated hydrocarbon, capable of decreasing a hydrogen fluoride concentration contained in the fluorinated hydrocarbon, so that the production facility therefor, a container packed with the purified product and an article to which the purified product is applied are prevented from being corroded, to provide a solvent, to provide a lubricative polymer-containing liquid, and to provide an article having a lubricative polymer film. SOLUTION: This method for purifying the 4-8C fluorinated hydrocarbon comprises contacting the 4-8C fluorinated hydrocarbon which contains the hydrogen fluoride with a hydrogen fluoride-removing material. The solvent contains one, two or more kinds of the 4-8C fluorinated hydrocarbons, wherein the concentration of the hydrogen fluoride contained in the solvent is not more than 5 ppb. The lubricative polymer- containing liquid is obtained by dissolving or dispersing a lubricative polymer having film-forming ability into the solvent. The article having the lubricative polymer film is obtained by applying the lubricative polymer-containing liquid to an article and drying the liquid-applied article.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for purifying a fluorinated hydrocarbon, a solvent containing the fluorinated hydrocarbon, and a lubricating polymer-containing liquid obtained by dissolving or dispersing a lubricating polymer in the solvent. , And an article having a film of the lubricating polymer on the surface, more specifically, by contacting the concentration of hydrogen fluoride contained in the fluorinated hydrocarbon with a hydrogen fluoride removing material to reduce hydrogen fluoride as much as possible. A method for purifying fluorinated hydrocarbons that can prevent corrosion of manufacturing equipment, filled containers, or used articles, a solvent containing the fluorinated hydrocarbons, and a lubricating polymer dissolved or dispersed in the solvent. The present invention relates to a lubricating polymer-containing liquid and an article having a film of the lubricating polymer on a surface.

[0002]

2. Description of the Related Art Conventionally, fluorinated saturated hydrocarbons such as hydrofluorocarbons and hydrofluoroethers have been used as solvents for lubricating polymers and as washing solvents. Further, the fluorinated unsaturated hydrocarbon is useful as a raw material monomer of fluorinated polymer, a substitute for chlorofluorocarbon, an etching gas for semiconductor production, a drug, an agricultural chemical, a liquid crystal, and an intermediate for producing these.

[0003] Methods for producing these fluorinated hydrocarbons include, for example, (1) an unsaturated hydrocarbon in which a carbon atom having a carbon-carbon double bond in the molecule is substituted with a chlorine atom, A method for producing a fluorinated unsaturated hydrocarbon by reacting an alkali metal fluoride such as potassium fluoride in a polar solvent (US Pat. No. 3,024,290, US Pat. No. 3567)
No. 78, J.P. Org. Chem. , 28 , 112 (19
(2) a method for producing hydrofluorocarbons by catalytic hydrogen reduction of fluorinated unsaturated hydrocarbons in the presence of a hydrogenation catalyst (see WO 99/33771, etc.); Of acid fluoride and alkyl halide or alkyl sulfonate in the presence of a compound (Japanese Patent Application Laid-Open No. 11-505249); (4) a saturated hydrocarbon (hydrocarbon) having a fluorine atom capable of substituting fluorine in the molecule or A method of producing a hydrofluorocarbon or a hydrofluoroether by allowing a fluorinating agent to act on hydroether.

[0004] The target product obtained by these production methods is isolated and purified by distillation or the like, but the obtained target product often contains a trace amount of hydrogen halide. Hydrogen halides, especially hydrogen fluoride, are highly corrosive, and even when contained in trace amounts, have the property of corroding glass or metal manufacturing equipment, filled containers, used equipment, and the like. In particular, if moisture is mixed, the environment is more likely to be corroded, so that the presence of hydrogen fluoride often causes inconvenience.

In recent years, fluorinated unsaturated hydrocarbons have been increasingly used as etching gases in semiconductor production. Since gases for semiconductor use are required to have high purity standards, it is necessary to remove impurities as much as possible. In addition, hydrofluorocarbons and hydrofluoroethers are used as solvents for lubricating polymers that impart lubricity to sliding parts and surfaces of electronic devices, mechanical devices, and the like, or as solvents for cleaning these materials. With miniaturization and high precision, high durability and high reliability are required. Therefore, these hydrofluorocarbons and hydrofluoroethers used as solvents need to remove hydrogen fluoride and the like as much as possible.

[0006] In connection with the present invention, as a technique for removing hydrogen fluoride in a fluorinated hydrocarbon, for example, (1) Japanese Patent Application Laid-Open No. 6-184014 discloses a fluorine-based inert liquid containing hydrogen fluoride. A method for purifying a fluorine-based inert liquid, which is characterized by being brought into contact with allophane (an amorphous clay mineral which is a hydrous silicate of aluminum), is described.
(2) JP-A-8-3075 describes a method of purifying a fluorine-based inert liquid by contacting it with water or an aqueous alkali solution in the presence of silica, alumina or silicate.

However, in any of the above-mentioned methods, the fluorine-based liquid to be purified is limited to perfluoro compounds such as perfluoroalkanes, perfluoroethers, and perfluorotertiary amines.
No effect is described for hydrofluorocarbons and hydrofluoroethers containing hydrogen bonds in the molecule or fluorinated hydrocarbons such as fluorinated unsaturated hydrocarbons. Further, since the method (2) includes a step of bringing the fluorine-based inert liquid into contact with water, a step of drying the treated solvent again is required.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been made by reducing the concentration of hydrogen fluoride contained in hydrofluorocarbons, hydrofluoroethers, and fluorinated unsaturated hydrocarbons. Provide a method for purifying fluorinated hydrocarbons that can prevent corrosion of these fluorinated hydrocarbon production facilities, filling containers, and articles used, a solvent, a liquid containing a lubricating polymer, and an article having a lubricating polymer film. The purpose is to do.

[0009]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have used fluorocarbons having 4 to 8 carbon atoms such as hydrofluorocarbons, hydrofluoroethers and fluorinated unsaturated hydrocarbons. The inventors have found that the concentration of hydrogen fluoride contained can be remarkably reduced by contacting with a hydrogen hydride removing material, and have completed the present invention.

The present invention firstly provides a method for producing a fluorinated hydrocarbon having 4 to 8 carbon atoms, which comprises contacting a fluorinated hydrocarbon having 4 to 8 carbon atoms containing hydrogen fluoride with a hydrogen fluoride removing material. A purification method is provided. In the first invention, it is preferable to use at least one selected from the group consisting of zeolite, alumina, silica, activated carbon and an ion exchange resin as the hydrogen fluoride removing material. The fluorinated hydrocarbon is preferably one or more selected from the group consisting of hydrofluorocarbons, hydrofluoroethers, and fluorinated unsaturated hydrocarbons.

Secondly, the present invention relates to a solvent containing one or two or more fluorocarbons having 4 to 8 carbon atoms, wherein the concentration of the contained hydrogen fluoride is 5 ppb or less. A solvent is provided.

[0013] Thirdly, the present invention provides a lubricating polymer-containing liquid obtained by dissolving or dispersing a lubricating polymer having film forming ability in the solvent of the second invention. Further, the present invention fourthly provides an article having a lubricating polymer film obtained by applying the liquid containing the lubricating polymer of the third invention to the surface and drying the liquid.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (1) The invention of the first refining method is characterized by including a step of contacting a fluorinated hydrocarbon having 4 to 8 carbon atoms including hydrogen fluoride with a hydrogen fluoride removing material. The fluorinated hydrocarbon to be refined has 4 to 8 carbon atoms,
There is no particular limitation as long as the hydrocarbon has a carbon-fluorine bond in the molecule, for example, hydrofluorocarbon,
Hydrofluoroethers and fluorinated unsaturated hydrocarbons are preferred.

Hydrofluorocarbons are fluorinated hydrocarbons in which some of the hydrogen atoms of the hydrocarbon are substituted with only fluorine atoms, and hydrofluoroethers are those in which some of the hydrogen atoms of the ethers are substituted with only fluorine atoms. Fluorinated ether. The hydrofluorocarbon or hydrofluoroether used in the present invention has a boiling point of 3
Those at 0 ° C. or higher are preferred. If the boiling point is less than 30 ° C., the distillation loss during purification is large, and the purification yield may be reduced. Further, the hydrofluorocarbon or hydrofluoroether may be a chain or a ring.

Of these, the hydrofluorocarbon used in the present invention includes —CH ₂ —CHF—
A chain or alicyclic compound having 4 to 8 carbon atoms having a group is preferred. 4 carbon having such a -CH ₂ -CHF- group
As the compound of No. 8, for example, 1,1,1,2,4,
4,4-heptafluoro-n-butane, 1,1,1,
2,2,3,5,5,5-nonafluoro-n-pentane, 1,1,1,2,2,3,3,4,6,6,6-undecafluoro-n-hexane, 1, 1,1,2,2
3,3,4,4,5,7,7,7-tridecafluoro-
chain hydrofluorocarbons such as n-heptane; 1,
1,2,2,3-pentafluorocyclobutane, 1,
And cyclic hydrofluorocarbons such as 1,2,2,3,3,4-heptafluorocyclopentane and 1,1,2,2,3,3,4,4,5-nonafluorocyclohexane.

As the hydrofluoroether, heptafluoropropyl-methyl ether, 1,1,
2,2,2-tetrafluoroethyl heptafluoropropyl ether, ethyl-1,1,2,2-tetrafluoroethyl ether, nonafluorobutyl-methyl ether, nonafluorobutyl-ethyl ether, 1,1,
1,2,3,3-hexafluoro-2-heptafluoropropoxy-3- (1,2,2,2-tetrafluoroethoxy) -1-propane and the like can be mentioned. These may be used alone, or a mixture of two or more of hydrofluorocarbons,
A mixture of two or more kinds or a mixture of hydrofluorocarbon and hydrofluoroether can be used.

The fluorinated unsaturated hydrocarbon used in the present invention has at least one carbon-carbon double bond in the molecule, and at least one fluorine atom is bonded to a carbon atom constituting the double bond. And is an unsaturated hydrocarbon having 4 to 8 carbon atoms. The structure of the unsaturated hydrocarbon is not particularly limited, and may be a chain or have a cyclic structure.

Preferred examples of the unsaturated hydrocarbon used in the present invention include compounds represented by the formula: R ¹ -C (X) = C (F) -R ² . In the formula, X represents a fluorine atom or a chlorine atom. R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 8 carbon atoms. All or a part of the alkyl group having 1 to 8 carbon atoms may be fluorinated. However, at least one of R ¹ and R ² is an optionally fluorinated alkyl group having 1 to 8 carbon atoms, and the sum of the carbon numbers of both R ¹ and R ² is at least 2.

Further, R ¹ and R ² may be combined together to form a hydrocarbon group having 2 to 8 carbon atoms —R ¹ —R ² — to form an alicyclic compound. Divalent hydrocarbon group -R ^1-
All or part of the hydrogen atom of R ² — may be fluorinated. Such alicyclic compounds include, for example,
Examples thereof include a cyclobutene compound, a cyclopentene compound, a cyclohexene compound, a cycloheptene compound, a cyclooctene compound, and the like.

Specific examples of such a fluorinated unsaturated hydrocarbon include 1-chloroheptafluoro-2-butene and 2-chloroheptafluoro-2-butene.
Chloro-1,1,1,3,4,4,4-heptafluoro-2-butene, 1,2-dichloro-1,1,3,4
4,4-hexafluoro-2-butene, 1,3-dichloro-1,1,2,4,4,4-hexafluoro-2-butene, 1,1,2-trichloro-3,4,4, 4-tetrafluoro-2-butene, 1,1,3-trichloro-
2,4,4,4-tetrafluoro-2-butene, 1,
1,1,2,4-pentachloro-3,4,4-trifluoro-2-butene, 1,1,1,3,4-pentachloro-2,4,4-trifluoro-2-butene, 1, 1,
1,2,4,4,4-heptachloro-3-fluoro-2
-Butene, 1-chlorononafluoro-2-pentene, 2
-Chlorononafluoro-2-pentene, 3-chlorononafluoro-2-pentene, 1-chloroundecafluoro-2-hexene, 2-chloroundecafluoro-2-hexene, 3-chloroundecafluoro-2- Linear unsaturated hydrocarbons such as hexene;

1-chloropentafluorocyclobutene,
1-chloro-2,3,3,4,4,5,5-heptafluorocyclopentene, 1-chloro-2,3,3,4,
4,5-hexafluorocyclopentene, 1-chloro-
2,3,3,4,5,5-hexafluorocyclopentene, 1-chloro-2,3,3,4,4-pentafluorocyclopentene, 1-chloro-2,3,3,5,5-pentafluoro Cyclopentene, octafluorocyclopentene, 1-chloro-nonafluorocyclohexene, 1
Cyclic unsaturated hydrocarbons such as -chloro-2,3,3,4,4,5,5,6-octafluorocyclohexene; Among them, cyclic fluorinated unsaturated hydrocarbons having 4 to 8 carbon atoms are preferable.

The refining method of the present invention is characterized in that a fluorinated hydrocarbon containing hydrogen fluoride as an impurity is brought into contact with a hydrogen fluoride removing material. As a hydrogen fluoride removing material,
Zeolites, alumina, silica, activated carbon or ion exchange resins can be used. Among them, zeolite, silica, and alumina are preferably used, and zeolite,
Alumina is most preferred.

As the zeolite, faujasite,
Natural zeolites such as shabasite, gmelinite, erionite, and levinite, and A such as 3A, 4A, and 5A
Mold and X of molecular sieves 10X, 13X etc.
And synthetic zeolites such as F-type, H-type and Y-type. Of the zeolites, molecular sieves which are easily available are preferred. Molecular sieves are not limited in type, and can be appropriately selected as many types are commercially available. Molecular sieves 3A, molecular sieves 4A, molecular sieves 5A, molecular sieves 13X, and the like can be used. , Molecular sieves 3A, 4A and 5A are preferred, and molecular sieves 4A and 5A are most preferred.

The type of alumina is not particularly limited, and amorphous alumina, crystalline alumina, alumina hydrate and the like can be used. Of these, alumina having low crystallinity is preferable, and specific examples thereof include catalysts (trade name: N
612N, manufactured by JGC Corporation). The type of silica is not particularly limited, and amorphous silica, crystalline silica, silica hydrate and the like can be used. Specifically, silica gel, diatomaceous earth, or the like can be used. More specifically, CARiACT, Q-15 (all manufactured by Fuji Devison Co., Ltd.) and the like can be mentioned. There is no particular limitation on the type of activated carbon, and plant-based, calcareous, and petroleum-based activated carbon can be used. In particular, a plant-based material made from wood, charcoal, and coconut shell charcoal, or a calcareous activated carbon made from bituminous coal, lignite, or the like is preferably used. As the ion exchange resin, various types of cation exchange resins can be used without particular limitation. For example, those having a chemical structure in which a sulfonic acid group is bonded to a polymer substrate having a fine three-dimensional network structure made of a copolymer of styrene and divinylbenzene are exemplified. Further, as a counter ion of the sulfonic acid group, an alkali metal ion such as a sodium ion is preferable. Specifically, a gel-type ion exchange resin (trade name: Diaion SKIB, manufactured by Mitsubishi Chemical Corporation) and the like can be mentioned. These zeolites, alumina, silica, activated carbon and ion exchange resin can be used alone or in combination of two or more.

The shape of the hydrogen fluoride removing material is not particularly limited, and for example, a powder, a granule, and a granular material can be used. The particle size of zeolite, alumina, silica and activated carbon is preferably small from the viewpoint of the contact efficiency with the fluorinated hydrocarbon, and those having an average particle size of 10 mm or less are preferably used. 0.3-5mm from a practical point of view
Is appropriate. The use amount of the hydrogen fluoride removing material is not particularly limited, but is usually 2 to 10 parts by weight, preferably 3 to 7 parts by weight, based on 100 parts by weight of the fluorinated hydrocarbon.

The method of contacting the fluorinated hydrocarbon containing hydrogen fluoride with the hydrogen fluoride removing material is performed under pressure or normal pressure.
Any of a batch type, a continuous type, a counter-current type, and a co-current type may be performed. For example, a method of passing a fluorinated hydrocarbon through a column filled with a hydrogen fluoride removing material such as zeolite, alumina, silica, or an ion exchange resin may be mentioned.
The fluorinated hydrocarbon may be in a gas state or a liquid state. Further, in order to enhance the efficiency of removing hydrogen fluoride, it is also preferable to circulate the hydrogen fluoride removing material in the packed tower using a pump or the like.

The column filled with the hydrogen fluoride removing material is not particularly limited as long as it is made of a material stable to hydrogen fluoride or fluorinated hydrocarbon. For example, a column made of Teflon is used. The contact temperature varies depending on the boiling point of the fluorinated hydrocarbon used. However, if the temperature is higher than the boiling point, the yield may be reduced. Therefore, the contact is preferably performed at a temperature lower than the boiling point by 20 ° C. or more. Normal-
The temperature ranges from 20 ° C to 150 ° C, preferably from 0 ° C to 100 ° C. The contact time is not particularly limited, but is usually 0.1 seconds to 50 hours, preferably 0.1 seconds to 7 hours.
Time.

According to the present invention, the above-mentioned (1) a fluorinated hydrocarbon having a significantly reduced hydrogen fluoride concentration is brought into contact with a hydrogen fluoride removing material before the fluorinated hydrocarbon is actually used. In addition to the case where it is desired to obtain, (2) an unsaturated hydrocarbon having a carbon-carbon double bond and having a chlorine atom capable of being replaced by fluorine bonded to a carbon constituting the double bond is used as a raw material, A fluorinated unsaturated hydrocarbon is obtained by allowing a fluorinating agent to act on a saturated hydrocarbon, and then the obtained fluorinated hydrocarbon is brought into contact with a hydrogen fluoride removing material, thereby reducing the concentration of hydrogen fluoride. When producing fluorinated unsaturated hydrocarbons, or (3) fluorinated unsaturated hydrocarbons are subjected to catalytic hydrogen reduction in the presence of a hydrogenation catalyst to obtain fluorinated hydrocarbons. Hydrocarbon fluoride to hydrocarbon By contacting with Sazai, is preferably applied in the production of hydrogen fluoride concentration has been reduced fluorinated saturated hydrocarbon.

In the above (2), it is used as a raw material.
The unsaturated hydrocarbon represented by the formula: R ^Three−C (X) = C
(Cl) -R^FourPreferred examples of the compound represented by
You. In the formula, X represents a fluorine atom or a chlorine atom. R^ThreePassing
And R^FourAre each independently a hydrogen atom, a fluorine atom,
Or an alkyl group having 1 to 8 carbon atoms. 1-8 carbon atoms
Alkyl groups are fully or partially fluorinated
Is also good. Where R^ThreeAnd R^FourAt least one of which is fluorine
An alkyl group having 1 to 8 carbon atoms which may be
And R^ThreeAnd R^FourThe sum of both carbon numbers is at least two.

Further, R ³ and R ⁴ may be combined together to form a hydrocarbon group having 2 to 8 carbon atoms —R ³ —R ⁴ — to form an alicyclic compound. Divalent hydrocarbon group -R ^3-
All or a part of the hydrogen atom of R ⁴ — may be fluorinated. Such alicyclic compounds include, for example,
Examples thereof include a cyclobutene compound, a cyclopentene compound, a cyclohexene compound, a cycloheptene compound, a cyclooctene compound, and the like.

Specific examples of such fluorinated unsaturated hydrocarbons include 2,3-dichlorohexafluoro-2-butene, 1,2,3-trichloro-1,1,4,4,4-pentafluoro- 2-butene, 1,1,2,3-tetrachloro-4,4,4-trifluoro-2-butene, 1,
1,1,2,3,4-hexachloro-4,4-difluoro-2-butene, 1,2,3-trichlorooctafluoro-2-pentene, 2,3-dichlorooctafluoro-
Chain unsaturated hydrocarbons such as 2-pentene and 2,3-dichlorodecafluoro-2-hexene;

1,2-dichlorotetrafluorocyclobutene, 1-chloroheptafluorocyclopentene, octachlorocyclopentene, 1,2-dichlorohexafluorocyclopentene, 1,2-dichloro-3,3,4,
4,5-pentafluorocyclopentene, 1,2-dichloro-3,3,4,4-tetrafluorocyclopentene, 1,2-dichloro-octafluorocyclohexene, 1,2-dichloro-3,3,4,4,4 5,5,6-
Cyclic unsaturated hydrocarbons such as heptafluorocyclohexene;

The fluorinating agent acting on the unsaturated hydrocarbon is not particularly limited as long as it is a compound capable of releasing fluorine ions. Examples of the fluorinating agent include metal fluorides, anhydrous or aqueous hydrofluoric acid, and hydrofluoric acid. And an amine or quaternary ammonium salt, and an association between hydrofluoric acid and a polar solvent. Among them, metal fluoride is preferable.

The metal fluoride includes, for example, metal fluorides such as alkali metals, alkaline earth metals, and transition metals, and is preferably an alkali metal fluoride. Specific examples of the alkali metal fluoride include sodium fluoride, potassium fluoride, lithium fluoride, cesium fluoride, rubidium fluoride and the like. Also, two or more of these can be used in combination. In addition, these alkali metal fluorides, commercially available products can be used as they are, but in order to enhance the reaction activity,
A mechanically pulverized product can also be used. The amount of the fluorinating agent to be used is generally at least 1 molar equivalent, preferably 1 to 5 equivalents, more preferably 1 to 3 equivalents, most preferably 1 to 2 equivalents to chlorine atoms in the unsaturated hydrocarbon used as the raw material.
The range of equivalents.

The fluorination reaction may be carried out by a liquid phase reaction or a gas phase reaction. When the above-mentioned alkali metal fluoride is used, the fluorination reaction is generally carried out by a liquid phase reaction. The liquid phase reaction is preferably performed by diluting an unsaturated hydrocarbon with a suitable solvent. As the solvent used, an aprotic polar solvent is usually preferred. For example, N-methylpyrrolidone,
N, N-dimethylformamide, N, N-dimethylacetamide, N, N′-dimethylimidazolidinone, and the like. Among these, N-pyrrolidone, N, N-
Particular preference is given to using dimethylformamide. These aprotic polar solvents can be used alone or in combination of two or more. Further, if necessary, an aromatic hydrocarbon such as benzene, toluene, xylene, and mesitylene which is compatible with the aprotic polar solvent can be used. The amount of the solvent to be used is generally 0 to 1,000 parts by weight based on 100 parts by weight of the unsaturated hydrocarbon.

The reaction temperature is 20 ° C. in the case of a liquid phase reaction.
To 200 ° C, preferably 50 ° C to 150 ° C. The reaction is preferably carried out in a reaction vessel equipped with a rectification column and in a solvent in which metal fluoride is dispersed. In this case,
Only the target product can be concentrated and isolated with high purity from the top of the rectification column. In the case of a gas phase reaction, the reaction temperature is 100 ° C to 500 ° C. In this case, a batch system or a continuous system in which the raw material is continuously supplied to the reactor and the reaction product is continuously extracted from the reactor is employed. Also,
In the case of a gas phase reaction, it is preferable that after the reaction is completed, unreacted fluorinating agent or the like is removed by absorption or neutralization. Upon removal, an additive such as an alkali metal or alkaline earth metal hydroxide, oxide, weak acid salt, or organic acid salt can be added to the system if necessary.

The obtained fluorinated unsaturated hydrocarbon can have a high purity by a purification method such as distillation, if necessary, but usually contains a trace amount of hydrogen fluoride. Therefore, in the present invention, a step of contacting with the hydrogen fluoride removing material is further provided.

As the hydrogen fluoride removing material that can be used, the zeolites, alumina, silica, activated carbon, and ion exchange resins listed in the purification method (1) can be used. Further, the conditions of the hydrogen fluoride removal treatment such as the amount of the hydrogen fluoride removal material used and the treatment temperature are the same as those described in the above-mentioned purification method (1).

In the above (3), the fluorinated unsaturated hydrocarbon which can be used as a raw material includes the fluorinated unsaturated hydrocarbon obtained in the above (2). The hydrogenation catalyst used is a noble metal simple substance or a noble metal compound. The noble metal catalyst is preferably used in a form supported on a carrier. As a noble metal, for example,
Palladium, rhodium, ruthenium, rhenium, platinum and the like can be mentioned, and among them, palladium, rhodium and ruthenium are preferable. Examples of the noble metal compound include palladium acetate, palladium sulfate, palladium nitrate, palladium chloride, platinum oxide and the like. These hydrogenation catalysts may be composed of a single metal, or may be used as two or more kinds of metals, so-called bimetallic catalysts.

The type of the carrier on which the noble metal catalyst is supported, and the shape and size of the carrier are not particularly limited. As the type of the carrier, activated carbon, alumina, silica, titania, zirconia, and those obtained by treating these with hydrogen fluoride are preferable. The shape of the carrier may be a powder or a granular material such as a sphere or a pellet. The amount of the noble metal supported on the carrier is usually 0.05 to
The range is 20% by weight, preferably 0.1 to 10% by weight.

The hydrogen used for the hydrogenation may be gaseous. Hydrogen is preferably used in an excess amount with respect to the fluorinated unsaturated hydrocarbon. For example, 2 mol or more, preferably 2 to 50 mol of hydrogen may be used per 1 mol of the fluorinated unsaturated hydrocarbon.

As a method of hydrogenation, a liquid phase reaction or a gas phase reaction can be mentioned. In the liquid phase reaction, a solvent can be used. In the gas phase reaction, a diluent can be used if necessary. As the diluent, any inert gas may be used, and examples thereof include nitrogen gas, argon gas, helium gas, methane gas, ethane gas, propane gas, pentafluoroethane, pentafluoropropane, and hexafluorobutane. These diluent gases can be used alone or
More than one kind can be mixed and used. In the gas phase reaction, a fixed bed type gas phase reaction, a fluidized bed type gas phase reaction or the like can be employed.

The solvent used in the liquid phase reaction is not particularly limited, and aliphatic hydrocarbons, aromatic hydrocarbons, hydrofluorocarbons, alcohols, ethers, ketones, esters, water and the like can be used. it can.

The pressure of the reaction system for the hydrogenation reaction is usually from normal pressure to 50 kgf / cm ² , preferably from normal pressure to 20 kf / cm ^2.
gf / cm ² . The reaction temperature is usually from room temperature to
The temperature is 350 ° C, preferably room temperature to 200 ° C. In this reaction, stirring or shaking is performed as necessary. In addition, the hydrogenation reaction preferably employs a batch reaction or a continuous reaction in which raw materials are continuously supplied to a reactor and a reaction product is extracted from the reactor.

In this reaction, acidic components such as hydrogen chloride gas are generated as by-products. This acidic component is preferably absorbed or neutralized and removed during the reaction. What is necessary is just to add an additive to a system as a removal method. Such additives include hydroxides of alkali metals or alkaline earth metals,
Oxides, weak acid salts, organic acid salts and the like can be mentioned. These may be added alone or as a mixture of two or more. After completion of the reaction, if necessary, the desired component can be isolated by a conventional purification method such as distillation after absorbing or neutralizing the acidic component with an additive.

The obtained hydrofluorocarbon has high purity, but contains a trace amount of hydrogen fluoride and the like. Therefore, in the present invention, the concentration of hydrogen fluoride is reduced as much as possible by bringing the obtained reaction product into contact with a hydrogen fluoride removing material.

As the hydrogen fluoride removing material that can be used, the zeolites, alumina, silica, activated carbon and ion exchange resins listed in the purification method (1) can be used. The conditions for the hydrogen fluoride removal treatment, such as the amount of the hydrogen fluoride removal material and the treatment temperature, are the same as those described in the purification method (1).

After the contact with the hydrogen fluoride removing material, rectification is preferably performed. The rectification is preferably performed in an inert gas belonging to Group 0 of the periodic table. The theoretical number of plates in the rectification column can be appropriately selected depending on the type of fluorinated hydrocarbon and the type of impurities contained, but is usually 30 or more, preferably 50 or more. The pressure during rectification is usually -0.5 atm or more in gauge pressure, preferably from normal pressure to 1 atm.
The range is 0 atm. The reflux ratio is not particularly limited, and it is usually 2 or more, preferably 5 or more, where the reflux ratio can be appropriately selected according to the capacity of the rectification column. The rectification may be any of a batch type and a continuous type, and the extraction distillation may be performed by adding an extraction solvent.

Thus, the concentration of hydrogen fluoride contained in the fluorinated hydrocarbon can be remarkably reduced.
That is, the concentration of hydrogen fluoride after the treatment with the hydrogen fluoride removing material can be reduced to 5 ppb or less.

The concentration of hydrogen fluoride in the fluorinated hydrocarbon is
For example, (1) ultrapure water (electric conductivity, 18 MΩ / c
m ² ) to extract fluorine ions in the fluorinated hydrocarbon,
The extract can be determined by measuring the concentration of fluorine ion in an ion chromatograph analyzer and converting it to the concentration of hydrogen fluoride. Further, (2) the concentration can be determined by measuring the concentration of fluorine ions contained in the fluorinated hydrocarbon obtained using a commercially available fluorine ion electrode and converting the concentration into hydrogen fluoride concentration.

The fluorinated hydrocarbon thus obtained is useful for various uses. For example, fluorinated unsaturated hydrocarbons are used as raw material monomers for high-purity etching gases and fluorine-based polymers in semiconductor production, and hydrofluorocarbons and hydrofluoroethers are used as cleaning solvents or lubricating polymers described below. It is preferably used as a solvent.

The solvent of the present invention is a solvent containing one or more of a fluorinated hydrocarbon having 4 to 8 carbon atoms, preferably a hydrofluorocarbon having 4 to 8 carbon atoms and / or a hydrofluoroether. Wherein the concentration of hydrogen fluoride contained is 5 ppb or less. In the solvent of the present invention, the hydrogen fluoride concentration is 5 pp
As a method for reducing the content to b or less, it is preferable to bring the solvent of the present invention into contact with the above-described hydrogen fluoride removing material.

The solvent of the present invention is preferably used, for example, as a solvent for an article cleaning composition or a lubricating polymer. When used with an article cleaning composition, the carbon number is 4 to
It is preferable to use one or a mixture of two or more of the hydrofluorocarbon and / or hydrofluoroether of No. 8 and a mixture of these with another organic solvent.

As the organic solvent, a hydrogen fluoride concentration of 5 p
Organic solvents having a boiling point of 25 to 300 ° C., which are not higher than pb, are preferred. As the organic solvent, those having a small change in composition when contacted with a hydrocarbon (that is, having the same solubility as a cyclic fluorinated hydrocarbon), and having a small change in the composition of a cleaning solution even after distillation and regeneration. Is preferred. When the cyclic fluorinated hydrocarbon and the organic solvent form an azeotropic composition,
Use near the formation of the azeotropic composition is desirable.

Examples of such organic solvents include saturated hydrocarbons such as hexane, octane, isooctane, cyclopentane and cyclohexane; lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol and isopropyl alcohol; acetone, methyl ethyl ketone and methyl Ketones such as isopropyl ketone, methyl isobutyl ketone and diethyl ketone; ethers such as dimethyl ether and diethyl ether; esters such as ethyl acetate and vinyl acetate;
Chain hydrofluorocarbons such as 2,3,4,5,5,5-decafluoropentane; perfluorocarbons such as perfluorohexane and perfluoroheptane; and the like. These organic solvents can be used alone or in combination of two or more.

The object to be cleaned is not particularly limited. For example, processed products such as metals, ceramics, glass, plastics, and elastomers in the precision machine industry, metal processing industry, optical machine industry, electronic industry, plastic industry, and the like. And the like. Since the solvent of the present invention is made of a fluorinated hydrocarbon having a hydrogen fluoride concentration reduced to 5 ppb or less, even when the object to be cleaned is continuously cleaned, it does not corrode the cleaning equipment.

The lubricating polymer-containing liquid of the present invention is characterized in that a lubricating polymer having a film forming ability is dissolved or dispersed in the solvent of the present invention. The lubricating polymer,
There is no particular limitation as long as a uniform film can be formed on the substrate surface. In addition, the properties of the polymer are not particularly limited, and any polymer having a property conventionally required when a film having lubricity, non-adhesion, or water repellency is formed may be used. Examples of the lubricating polymer having such a film forming ability include a fluoropolymer, a silicone resin, a phenol resin, and a polyolefin resin, and among them, the fluoropolymer is preferable. The fluorine-based polymer is not particularly limited as long as it has a fluorine atom in the molecule. For example, fluorinated olefin polymers; fluorinated olefin polymers; And the like.

Of these, a fluorine-containing polymer containing a hetero atom is particularly preferred in the present invention. Examples of the hetero atom of the fluorine-containing polymer containing a hetero atom include atoms belonging to the second to third periods of the periodic table and belonging to Group 4B, 5B, or 6B. More specifically, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom and the like can be mentioned, and an oxygen atom is preferable. Examples of the fluorine-based polymer containing a fluorine atom include perfluoroalkylsulfonic acid polyesters; perfluoroalkylpolyethers; polyimides having a perfluoroalkyl group; partially fluorinated modified silicone oils; . Of these, perfluoroalkyl polyethers are particularly preferred.

The perfluoroalkyl polyethers are not particularly limited as long as they are generally used as a material for forming a water-repellent film. For example, JP-A-61-12
No. 6627, JP-A-63-97264, JP-A-64-31642, JP-A-4-21969, JP-A-5-342570, JP-A-7-18
Perfluoroalkyl polyethers such as those described in US Pat. Suitable perfluoroalkyl polyethers include, for example, CH ₃ O
— (CF ₂ CF ₂ O) _a —CH ₃ , PhOCH ₂ CH ₂ OCH
₂ O— (CF ₂ CF ₂ O) _b —CH ₃ , CF ₃ — [(OCF
_{(CF 3) CF 2) c} - (OCF 2) d] -OCF 3, CF 3
_{- [(OCF 2 CF 2)} e - (OCF 2) f] include those represented by the general formula _3, such as -OCF (wherein, a to f represents an arbitrary positive integer.).

Further, a fluorine-based polymer having a cyclic structure in the main chain, for example, a cyclic perfluorocarbon, a cyclic perfluoroether, and a partial fluorine of the cyclic perfluorocarbon described in JP-A-6-305151 A cyclic fluorochlorocarbon polymer in which atoms are substituted with chlorine atoms can also be used.

The form of the lubricating polymer used in the present invention is not particularly limited, and may be in the form of particles, grease, or wax. These polymers having film forming ability can be used alone or in combination of two or more.

The lubricating polymer described in, for example,
As described in JP-A-182652 and JP-A-7-182653, a compounding agent such as a lubricant can be added for the purpose of further reducing the friction coefficient. Such lubricants include, for example, paraffinic, aromatic, and naphthenic mineral oils; silicone oils; higher alcohols such as lauryl alcohol, dodecyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, eicosyl alcohol, and seryl alcohol; tridecane Acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, higher fatty acids such as arachinic acid, and salts of these higher fatty acids such as Li, Na, K, Mg, Ca, Ba; and methyl myristate , Ethyl myristate, isopropyl pentadecanoate, methyl palmitate, hexyl palmitate, butyl margallate, methyl stearate, ethyl stearate, propyl stearate, isopropyl stearate, stearin Amyl, isoamyl stearate, higher fatty acid esters of hexyl stearate;
CF ₃ described in JP-A-7-125219
(CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ , CF ₃ (CH ₂ ) ₂ Si
(OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (C
F ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ Cl, CF ₃ (CF ₂ )
₇ (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅
A fluorine-containing silane compound such as (CH ₂ ) ₂ Si (NH ₂ ) ₃ ,
And phosphazene compounds. Among them, mineral oil, silicone oil, higher alcohol, higher fatty acid, higher fatty acid salt, higher fatty acid ester, phosphazene compound and the like are preferable. The amount of the lubricant used is appropriately selected within a range that does not impair the properties of the lubricating polymer film, and is usually 0.01 to 50 parts by weight, based on 100 parts by weight of the solvent.
Preferably 0.1-30 parts by weight, more preferably 1-1.
The range is 5 parts by weight.

The lubricating polymer-containing liquid of the present invention can be prepared by dissolving or dispersing the polymer in the solvent composition of the present invention. That is, the lubricating polymer and, if desired, the compounding agent may be put into the solvent composition of the present invention and stirred. If necessary, means such as heating and ultrasonic irradiation can be employed. When a dispersion of a dissolved polymer is obtained, it is preferable to use a polymer in the form of fine particles.

The content of the lubricating polymer in the lubricating polymer-containing liquid of the present invention is appropriately determined in consideration of the type of the polymer, the type of the substrate to be coated, the coating workability, the thickness of the coating film, and the like. Selected. The concentration also changes depending on whether the polymer is dissolved or dispersed in the liquid. When the lubricating polymer is dissolved in the liquid containing the lubricating polymer, it is usually 0.0001 to 10% by weight, preferably 0.001 to 1% by weight, more preferably 0.0001 to 1% by weight, based on the total amount of the liquid containing the lubricating polymer. Is 0.005
It is in the range of 0.5% by weight. When the polymer is dispersed in the solution, it is usually 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight.
It is in the range of 5% by weight.

The article (substrate to be coated) to which the lubricating polymer-containing liquid of the present invention is applied is not particularly limited, and is appropriately selected depending on the purpose of use. Examples of the material of the article to be coated include natural rubber, isoprene polymer, butadiene polymer rubber (BR), styrene-butadiene copolymer gum (SBR), hydrogenated styrene-butadiene copolymer rubber (hydrogen SBR), rubber such as acrylonitrile-butadiene copolymer rubber (NBR), hydrogenated acrylonitrile-butadiene copolymer rubber (hydrogenated NBR), chloroprene polymer rubber, silicone rubber; aluminum, iron, stainless steel, titanium, Metals such as copper; inorganic materials such as carbon, glass, ceramics and silicon; and polycarbonate, polyimide, polysulfone, polyester, polyethersulfone polyester, polyphenylene sulfide, polyurethane, polyolefin, hydrogenated polynorbornene, and hydrogenated polystyrene And the like are; down, bakelite, resin such as polyacetal photosensitive resin.

The lubricating polymer-containing liquid of the present invention is suitable for applying to a magnetic substrate. As a magnetic substrate,
Directly on various non-magnetic substrates or through an underlayer of nickel / phosphorus, titanium, silicon, chromium, alumite, etc.
The ferromagnetic metal thin films may be used alone or in combination of two or more. As the material of the ferromagnetic metal thin film, for example, Co, Co-N
i, Co-Cr, Co-Fe, Co-Ni-Fe, Co
-Ni-Cr, Co-Ni-P, Co-Ni-Ti, C
o-Ni-Ta and their partially oxidized ones. These metal thin films can be formed by, for example, a vacuum evaporation method, a sputtering method, an ion plating method, a plating method, or the like. The thickness of the ferromagnetic metal thin film including the underlayer is usually 0.005 μm to 1 μm.
00 μm, preferably in the range of 0.01 μm to 50 μm.

The ferromagnetic metal thin film may have, on its surface, a protective film layer generally used in ordinary magnetic recording media, if necessary. Examples of the protective film include a metal protective film layer made of, for example, Cr, W, and Ni; an inorganic protective film layer made of silicon oxide, SiC, graphite, diamond-like carbon (Japanese Patent Application Laid-Open No. 61-126627, Japanese Patent Application Laid-Open No. 342570, etc.); carbon number 8
To 28 linear saturated fatty acids and their alkali metal salts or alkaline earth metal salts (see Japanese Patent Publication No. 56-30609, etc.), silicone resins (Japanese Patent Application Laid-Open No. 61-131231).
And organic protection film layers or composite protection film layers such as epoxy resins, polyamide resins, plasma polymerization products, and radiation polymerization products.

Specific examples of the articles made of the above materials include an ink jet recording head; a cleaning blade for office equipment such as a rubber cleaning blade for removing residual toner on a photoreceptor of an electrophotographic copying apparatus;
Cameras, office equipment, medical equipment, precision equipment, vacuum equipment such as vacuum pumps, electronic parts, precision car parts, small motors, ultrasonic motors, sliding parts such as micromachines; hard disks, digital video tapes and other magnetic disks A magnetic recording medium; between a film and a rubber or resin sheet;

An article having a lubricating polymer film (polymer film) on the surface can be obtained by applying the lubricating polymer-containing liquid on the surface and then removing the solvent. The method for applying the lubricating polymer-containing liquid may be a conventional method, such as a dipping method, a spin coating method, or a spraying method using a spray. Solvent contained in the coating film of the lubricating polymer-containing liquid, generally at room temperature or under heating,
It can be removed by drying in an inert gas such as nitrogen gas or in air. When heating, it can be performed under reduced pressure. Further, the removal of the solvent can be promoted by applying energy such as light or an electron beam.
Further, if desired, after drying the coating film, energy such as heat, light, and electron beam may be applied to increase the degree of polymerization of the lubricating polymer constituting the coating film or to form a cross-linking bond.

The thickness of the lubricating polymer film is usually 0.000
1 μm to 10 μm, preferably 0.0005 μm to 5 μm
m, more preferably in the range of 0.001 μm to 3 μm. Note that the thickness of the film varies depending on the use.
For example, the thickness of the polymer film formed on the ink jet recording head is usually 0.001 μm to 10 μm, preferably 0.005 μm to 5 μm, more preferably 0.01 μm.
The thickness of the polymer film formed on the cleaning blade of the electrophotographic copying machine is usually 0.01 μm to 2 μm.
10 μm, preferably 0.01 μm to 5 μm, more preferably 0.1 μm to 5 μm, and the thickness of the polymer film formed on the magnetic recording hard disk is usually 0.0001 μm.
m to 10 μm, preferably 0.0001 μm to 5 μm,
More preferably, it is in the range of 0.0005 μm to 3 μm.

The lubricating polymer-containing liquid of the present invention uses a fluorinated hydrocarbon having a hydrogen fluoride concentration reduced to 5 ppb or less as a solvent, so that a lubricating polymer film is formed on the surface of an article whose surface is easily corroded. Even if formed, the surface of the article will not corrode.

[0072]

Next, the present invention will be described in more detail by way of examples. The present invention is not limited to the following examples, and the type and amount of the fluorinated hydrocarbon and the hydrogen fluoride removing material can be freely selected and changed without departing from the gist of the present invention. Can be.

(Example 1) Under a nitrogen stream, potassium fluoride (trade name: Kurocat F, manufactured by Morita Chemical Industry Co., Ltd.) was placed in a 5 L four-necked flask equipped with a dropping funnel, a rectification tower and a stirrer. 988 g (17 mol) and 3 L of N, N-dimethylformamide (DMF) were charged, a −20 ° C. refrigerant was passed through a Dimroth condenser provided at the top of the rectification tower, and the fraction trap was cooled to −70 ° C. . On the other hand, 1,2-dichloro-3,3,4,4,4
1,658 g of 5,5-hexafluorocyclopentene
(6.77 mol), and the temperature in the flask was raised to 135 ° C. over 0.5 hours. After the start of the temperature increase, the raw materials were dropped from the dropping funnel for 0.5 to 4 hours. After the temperature at the top of the column was stabilized at the boiling point of the product (−27 ° C.), when 0.7 hour (1.5 hours from the start of the reaction) had elapsed, the column was provided between the top of the rectification column and the Dimroth condenser. Extraction of the fraction was started from the extraction port. Withdrawal was performed until the temperature at the top of the column started to rise and reached the vicinity of the boiling point of DMF (8 hours from the start of the reaction).
Purity 99.80%). The concentration of hydrogen fluoride was measured using a fluorine ion electrode (trade name: Ion Meter Ti-5101, manufactured by Toko Chemical Co., Ltd.) and found to be 37 ppm.

Next, 60 g of alumina (trade name: N612N, manufactured by Nikki Chemical Co., Ltd.) was charged with an inner diameter of 2.2 cm and a length of 40 cm.
cm of Teflon (registered trademark) column, and 1200 g of octafluorocyclopentene obtained above was passed through at a flow rate of 30 ml / min at a temperature of 15 ° C., and trapped in a cooled stainless steel container cooled to 0 ° C. Gathered. When about 1000 g of octafluorocyclopentene was passed, the concentration of hydrogen fluoride in the octafluorocyclopentene collected in the container was measured and found to be 0.4 ppb. In addition, gas chromatography (Shimaz
u GC-14A), the purity was 99.
83%, and no generation of a new impurity of octafluorocyclopentene was confirmed. 1000 g of octafluorocyclopentene obtained above was charged into a 2 L glass round flask, and rectification was performed under a nitrogen atmosphere using a rectification tower having 55 theoretical plates. As a result of extraction at a tower top temperature of 27 ° C. and a reflux ratio of 40: 1, 900 g of octafluorocyclopentene having a purity of 99.99% was obtained.

(Example 2) In place of alumina used in Example 1, a cation exchange resin of Na ⁺ foam (trade name:
The procedure was performed in the same manner as in Example 1 except that 60 g of Diaion SKIB (manufactured by Mitsubishi Chemical Corporation) was used. The octafluorocyclopentene before passing through the cation exchange resin had a hydrogen fluoride concentration of 45 ppm, and the octafluorocyclopentene after passing through the cation exchange resin had a hydrogen fluoride concentration of 5 pp.
b. In addition, gas chromatography (Shim
azu GC-14A), the purity was 9
9.83%, and the generation of new impurities of octafluorocyclopentene was not confirmed.

Example 3 In a nitrogen stream, potassium fluoride (trade name: Kurocat F, Morita Chemical Industry Co., Ltd.) was placed in a 5 L four-necked flask equipped with a dropping funnel, a rectification tower, a thermometer and a stirrer. G), 500 g (8.6 mol), DMF
500 ml of toluene and 500 ml of toluene were charged, a −10 ° C. refrigerant was passed through a Dimroth condenser provided at the top of the rectification tower, the fraction trap was cooled to −70 ° C., and 72.1% of 1,2 was added to a dropping funnel. -Dichloro-3,3,4
4,5,5-hexafluorocyclopentene, 20.7
% Of trichloropentafluorocyclopentenes and 5.4% of tetrachlorotetrafluorocyclopentenes. After raising the temperature in the flask to 130 ° C., the raw material compounds were continuously dropped from the dropping funnel over 5 hours. After 2 hours from the start of the reaction (start of dropping), the temperature at the top of the rectification column became the boiling point of the target product (56 ° C.) and became stable. From that time until the temperature at the top of the tower rose to 110 ° C. (13 hours from the start of the reaction), the reaction products were continuously extracted, and as a result, two types of fractions were obtained. When each fraction was analyzed by gas chromatography (Shimazu GC-14A), the fraction having a boiling point of 56 ° C. (fraction 1) was 1-chloro-2,3,3,4,4,5 , 5-heptafluorocyclopentene 1106 g (4.8 mol
The yield was 80.7% and the purity was 98.82%).

Next, 60 g of alumina (trade name: N612N, manufactured by Nikki Chemical Co., Ltd.) was weighed at 2.2 cm in inner diameter and 40 cm in length.
cm of Teflon PFA column, and 1-chloro-2,3,3,4,4,
1050 g of 5,5-heptafluorocyclopentene was passed at a flow rate of 30 ml / min at 15 ° C.
And collected in a cooled stainless steel container. After passing about 1000 g, 1-chloro-
When the hydrogen fluoride concentration of 2,3,3,4,4,5,5-heptafluorocyclopentene was measured, the hydrogen fluoride concentration was 0.4 ppb. Moreover, when analyzed by gas chromatography (Shimazu GC-14A), the purity was 98.85%, and 1-chloro-2,
Generation of new impurities due to decomposition of 3,3,4,4,5,5-heptafluorocyclopentene was not confirmed. 1-chloro-2,3,3,4,4,5,5 obtained
-1000 g of heptafluorocyclopentene was charged into a 2 L glass round flask, and rectification was carried out under a nitrogen atmosphere using a rectification column having 55 theoretical plates. As a result of extraction at a tower top temperature of 56 ° C. and a reflux ratio of 40: 1, the purity was 99.
950 g of 83% of 1-chloro-2,3,3,4,4,5,5-heptafluorocyclopentene was obtained (yield 92%).

Example 4 In a 50 L autoclave equipped with a stirrer, octafluorocyclopentene (99.9%
(Purity) 42.4 kg (200 mol), 2.12 kg of 5% palladium carbon, 50 ° C., hydrogen pressure 0.
Hydrogenation was performed under an atmosphere of 6 MPa. 15 hours later,
When the absorption of hydrogen was completely stopped, the heating was stopped to stop the reaction. After sufficiently neutralizing with saturated aqueous sodium bicarbonate,
The organic layer was separated, 20 L of a 1 mol aqueous sodium carbonate solution was added, and the mixture was stirred at 30 ° C for 10 hours. The reaction solution was separated into two layers, and the obtained organic layer was again subjected to 50 L with a stirrer.
In autoclave, 5% palladium carbon 1.78k
g and 1 kg of tridecane. The reaction was carried out at 50 ° C. for 15 hours in the same manner as above, and when the absorption of hydrogen was completely stopped, the heating was stopped, and neutralization was performed with saturated aqueous sodium hydrogen carbonate. After that, when the organic layer was distilled, 1,1,2,2
2,3,3,4-heptafluorocyclopentane
0 kg (99.0% purity) were obtained.

5.0 kg of the obtained 1,1,2,2,3,3,4-heptafluorocyclopentane was put into a 5 L polypropylene bottle, and molecular sieves 5A having an average particle diameter of 4 mm (Union Showa (Co., Ltd.) )) Packed with 150 g of Teflon (2.5 cm ID x 40 c length)
m) was pump-circulated at a flow rate of 100 ml / min. After circulating for 3 hours, the pump was stopped, and the 1,1,2,2,3,3,4-
200 g of heptafluorocyclopentane was extracted.
150 g of the extracted 1,1,2,2,3,3,4-heptafluorocyclopentane was transferred to a separating funnel having a capacity of 300 ml, and ultrapure water (electric conductivity: 18 MΩ / cm)
^{In step 2} ), fluorine ions were extracted. The extract was analyzed for the concentration of fluorine ions with an ion chromatograph (trade name: DX-120, manufactured by Dionex) and converted to the concentration of hydrogen fluoride.

Using 50 g of the remaining 1,1,2,2,3,3,4-heptafluorocyclopentane, water content and purity were analyzed. The water content was analyzed by a Karl Fischer moisture meter (trade name: AQ-5, manufactured by Hiranuma Sangyo Co., Ltd.), and the purity was determined by gas chromatography (trade name: HP-6).
890, manufactured by Hewlett-Backer Co.). In the same manner, the concentration of hydrogen fluoride, the amount of water, and the purity of 1,1,2,2,3,3,4-heptafluorocyclopentane before the treatment with the molecular sieve 5A were analyzed. Table 1 shows the measurement results. In addition, as a result of measurement by gas chromatography, before and after treatment with Molecular Sieves 5A, 1,1,2,2,3,3,4
-No change in the purity of heptafluorocyclopentane was observed, and no new decomposition products were observed.

(Example 5) The procedure of Example 4 was repeated, except that the molecular sieve 5A was replaced by the molecular sieve 4A, and the 1,1,2,2,3 Hydrogen fluoride concentration, water content and purity in 3,3,4-heptafluorocyclopentane were analyzed. Table 1 shows the measurement results. In addition, as a result of measurement by gas chromatography, molecular sieves 4A
Before and after treatment with 1, no change in the purity of 1,1,2,2,3,3,4-heptafluorocyclopentane was observed,
No new decomposition products were observed.

Example 6 Nonafluorobutyl-ethyl ether in a pail can (trade name: HFE-7200,
Sumitomo 3M Co., Ltd.) (5 kg) was placed in a 5 L polypropylene bottle, and molecular sieves 5A having an average particle size of 4 mm were used.
Flow rate 100 in a Teflon column (2.5 cm × 40 cm inside diameter) packed with 150 g (manufactured by Union Showa).
The pump was circulated at a rate of ml / min. After circulating for 3 hours, the pump was stopped, and 200 g of nonafluorobutyl-ethyl ether was withdrawn from the polypropylene bottle. 150 g of the extracted nonafluorobutyl-ethyl ether was transferred to a 300-ml separating funnel, and fluorine ions were extracted with ultrapure water (electric conductivity: 18 MΩ / cm ² ). The extract was analyzed for the concentration of fluorine ions by ion chromatography (trade name: DX-120, manufactured by Dionex) and converted to the concentration of hydrogen fluoride.

Using 50 g of the remaining nonafluorobutyl-ethyl ether, the water content and the purity were analyzed in the same manner as in Example 4. In addition, hydrogen fluoride concentration, water content and purity in nonafluorobutyl-ethyl ether before contact with Molecular Sieves 5A were also analyzed. Table 1 shows the results of these measurements. Further, as a result of measurement by gas chromatography, no change was observed in the purity of nonafluorobutyl-ethyl ether before and after the treatment with Molecular Sieves 5A, and no new decomposition products were observed.

[0084]

[Table 1]

(Comparative Example) 1,1, synthesized in Example 3
Put 1 kg of 2,2,3,3,4-heptafluorocyclopentane in a polyethylene bottle having a capacity of 3 L,
Further, allophane (trade name: Secard KW, manufactured by Shinagawa Brick Co., Ltd.) having a molar ratio of silicate SiO ₂ / Al ₂ O ₃ of 1.97 and an average particle size of 2 mm, and 10% by weight of hydroxide 500 ml of an aqueous sodium solution was charged, and the whole
The mixture was stirred at 5 ° C. and a stirring speed of 300 rpm for 3 hours. After stopping the stirring, the treatment liquid was filtered to remove allophane,
By separating using a separating funnel, 1,1,2,2
2,3,3,4-heptafluorocyclopentane was fractionated. As a result of analysis by gas chromatography,
26% of 1,2,2,3,3,4-heptafluorocyclopentane was decomposed and a new product was observed.

Example 7 20 kg of 1,1,2,2,3,3,4-heptafluorocyclopentane obtained by purifying in the same manner as in Example 4 (hydrogen fluoride concentration = 0.2 pp
To b), 20 g of a linear perfluoropolyether-based lubricating polymer (molecular weight 1,500) and 5 g of a phosphazene-based lubricant (trade name: X-1P, manufactured by Dow Chemical Company) were added. A clear, homogeneous solution was obtained upon addition.
This was passed through a Teflon filter having a pore size of 0.2 micron to obtain a lubricating polymer-containing liquid.

Then, the obtained liquid containing a lubricating polymer is put into a dipping tank of a lubricant coating device on the surface of a hard disk, and a magnetic layer is provided in a head portion in the dipping tank. Then, ten hard disks each having a carbon layer formed on the surface of the substrate were introduced. After the hard disk was allowed to stand in the dipping tank for 3 minutes,
The lubricating polymer-containing liquid was withdrawn at a constant rate so as to decrease at a rate of mm / sec. After the liquid was drawn out, the hard disk was naturally dried at room temperature to obtain a hard disk having a lubricating polymer film formed on the surface.

Out of the ten hard disks obtained above, three arbitrary disks were taken out, and the surfaces of the respective hard disks were extracted with ultrapure water (electric conductivity: 18 MΩ / cm ² ), and the extract was subjected to ion chromatography. (Product name:
DX-120, manufactured by Dionex Corporation). Fluorine ions were not detected from any of the three hard disks. From this, it was found that even when a lubricating polymer film was formed on the surface of a hard disk using the lubricating polymer-containing liquid obtained in this example, dirt and corrosion of the hard disk head were reduced.

[0089]

As described above, according to the method for purifying fluorinated hydrocarbons of the present invention, the concentration of hydrogen fluoride can be reduced remarkably easily and efficiently. According to the present invention,
Even when the fluorinated hydrocarbon is brought into contact with the hydrogen fluoride removing material, decomposition of the fluorinated hydrocarbon does not occur, and the hydrogen fluoride can be removed. Therefore, the present invention is particularly suitable for purifying fluorinated hydrocarbons that are not stable to alkali. Since the fluorinated unsaturated hydrocarbon of the present invention contains much less hydrogen fluoride, it is particularly useful as an etching gas in the production of semiconductors that require high purity.
The solvent of the present invention contains a fluorinated hydrocarbon whose concentration of hydrogen fluoride is reduced to 5 ppb or less as a main component. Therefore, even when the solvent of the present invention is used as a cleaning solvent, the cleaning equipment does not corrode. Further, when the solvent of the present invention is used as a solvent for a lubricating polymer, even when the resulting lubricating polymer-containing liquid is applied to the surface of an article to form a lubricating polymer film, Does not corrode the surface of the article. Therefore, the lubricating polymer-containing liquid of the present invention is particularly preferably used when high durability is required and a lubricating polymer film is formed on the surface of a magnetic substrate or the like whose surface is easily corroded. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C10M 107/32 C10M 107/32 107/38 107/38 107/44 107/44 107/46 107/46 107 / 50 107/50 // C10N 30:12 C10N 30:12 40:02 40:02 40:18 40:18 50:02 50:02 (72) Inventor Mitsuru Sugawara 1-2-2 Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa No. 1 F-term in the Zeon Corporation General Development Center (reference) 4H006 AA02 AD17 DA10 DA60 GP01 GP20 4H104 CA01A CB12A CD04A CE13A CG03A CJ02A CJ13A LA06 PA01 PA16 QA08

Claims (6)

[Claims] 1. A method for purifying a fluorinated hydrocarbon having 4 to 8 carbon atoms, comprising contacting a fluorinated hydrocarbon having 4 to 8 carbon atoms containing hydrogen fluoride with a hydrogen fluoride removing material. 2. The method for purifying a fluorinated hydrocarbon according to claim 1, wherein at least one selected from the group consisting of zeolite, alumina, silica, activated carbon and an ion exchange resin is used as said hydrogen fluorinated material. 3. The fluorinated hydrocarbon according to claim 1, wherein the fluorinated hydrocarbon is at least one member selected from the group consisting of hydrofluorocarbons, hydrofluoroethers, and fluorinated unsaturated hydrocarbons. A method for purifying carbon. 4. A solvent containing one or more fluorinated hydrocarbons having 4 to 8 carbon atoms, wherein the concentration of hydrogen fluoride contained is 5 ppb or less. . 5. A lubricating polymer-containing liquid obtained by dissolving or dispersing a lubricating polymer having film forming ability in the solvent according to claim 4. 6. An article having a lubricating polymer film obtained by applying the liquid containing the lubricating polymer according to claim 5 to the surface and drying the liquid.