JP2000273060A - Manufacturing method of fluoroalcohol - Google Patents

Abstract

(57) [Problem] To provide a pure fluoroalcohol. SOLUTION: Methanol and tetrafluoroethylene or hexafluoropropylene are reacted in the presence of a radical generation source to obtain the following formula (1) H (CFR ¹ CF ₂ ) _n CH ₂ OH (1) [where n = 1 or 2 When n = 1, R ¹ indicates F or CF _3, and when n = 2, R ¹ indicates F. ] The method for producing a fluoroalcohol represented by the formula (1), wherein the reaction solution is reacted with an aldehyde conversion reagent or a halogen and then distilled.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound represented by the general formula (1) H (CFR ¹ CF ₂ ) _n CH ₂ OH (1) [where n = 1 or 2, and when n = 1, R ¹ is F or indicates CF _3, R ¹ when n = 2 denotes the F. And a method for producing a fluoroalcohol represented by the formula:

[0002]

2. Description of the Related Art H (CF ₂ CF ₂ ) _n CH ₂ O
A method for producing H (n = 1, 2) is disclosed in JP-A-54-154.
No. 707 and US Pat. No. 2,559,628, methanol and tetrafluoroethylene are converted to t
It is described that by reacting in the presence of -butyloctyl peroxide, a telomer mixture of H (CF2CF2) nCH2OH (n up to 12) is obtained.

[0003] However, even if the telomer mixture obtained by the above method is purified by distillation, the evaporation residue of about several hundred ppm cannot be removed.
When used as a solvent in the production of an information recording medium having a recording layer capable of writing and / or reading information by a laser on a substrate such as a DR, a high-quality information recording medium due to the influence of evaporation residue. There was a drawback that was not suitable for the production of

An object of the present invention is to provide a compound of the general formula (1) H (CFR ¹ CF ₂ ) _n CH ₂ OH (1) substantially free from impurities such as evaporation residues and UV absorbing components. R ¹ is as defined above. And a method for producing a fluoroalcohol represented by the formula:

[0005]

Means for Solving the Problems The inventor of the present invention has a general formula
(1) To reduce impurities of fluoroalcohol
As a result of the analysis of impurities,
Rudehid, HCF_TwoCF_TwoCHO, HCF_TwoCHFCH
O, HCF_TwoCF_TwoCF_TwoCF_TwoCHO, HCF_TwoCOOC
H _TwoCH = CHCHO, HCF_TwoCH_TwoCOOCH = CH
CHO, HCF_TwoCF_TwoCH (OH) OCH_TwoCHO etc.
Of various aldehyde components and components having unsaturated bonds
May be mixed, and they may be fluorinated depending on the rectification.
Alcohol is difficult to separate.
Reaction of aldehyde component with aldehyde conversion reagent or halogen
And rectify it after converting it to a compound that can be easily separated
That high-purity fluoroalcohol can be obtained.
Issued.

[0006] The present invention relates to items 1 to 7. Item 1. Methanol and tetrafluoroethylene or hexafluoropropylene are reacted in the presence of a radical generating source to give the following formula (1) H (CFR ¹ CF ₂ ) _n CH ₂ OH (1) [where n = 1 or 2, n When = 1, R ¹ indicates F or CF _3, and when n = 2, R ¹ indicates F. ] The method for producing a fluoroalcohol represented by the formula (1), wherein the reaction solution is reacted with an aldehyde conversion reagent or a halogen and then distilled. Item 2. Item 2. The method for producing a fluoroalcohol according to Item 1, wherein the aldehyde conversion reagent is hydrazine. Item 3. Item 2. The method for producing a fluoroalcohol according to Item 1, wherein the aldehyde conversion reagent is peroxomonosulfuric acid. Item 4. Item 2. The method for producing a fluoroalcohol according to Item 1, wherein the aldehyde conversion reagent is a silver compound or a copper compound. Item 5. Item 2. The method for producing a fluoroalcohol according to Item 1, wherein the aldehyde conversion reagent is xanthine oxidase. Item 6. Item 2. The method for producing a fluoroalcohol according to Item 1, wherein the aldehyde conversion reagent is a primary amine or a secondary amine. Item 7. Item 2. The method for producing a fluoroalcohol according to Item 1, wherein the halogen is chlorine or bromine.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the production method of the present invention, an excess amount of methanol is used with respect to tetrafluoroethylene or hexafluoropropylene. Reaction temperature is 40-14
About 0 ° C., the reaction time is about 3 to 12 hours, and the reaction pressure is
It is about 0.2 to 1.2 MPa. The reaction can be performed, for example, in a high-pressure reactor. The inside of the reaction system is preferably replaced with an inert gas such as nitrogen or argon.

After completion of the reaction, the reaction solution is reacted with an aldehyde conversion reagent or a halogen to convert the aldehyde present in the reaction mixture into a compound which can be easily separated. Prior to the reaction with the aldehyde conversion reagent or halogen, or after the reaction with the aldehyde conversion reagent or halogen, the excess methanol may be removed by distillation, if necessary, and the H (CF) present in the reaction mixture may be removed. ₂ CF ₂ )
_n CH ₂ OH (n is 3 or more) or H (CF (CF ₃ ) C
The impurities of F ₂ ) _n CH ₂ OH (n is 2 or more) may be removed by distillation.

The aldehyde conversion reagent is a reagent capable of converting an aldehyde into a derivative which can be separated from the fluoroalcohol of the present invention, and comprises (1) hydrazine, (2) peroxomonosulfuric acid, (3) a silver compound or a copper compound, (4) xanthine oxidase, (5) a primary amine or a secondary amine is exemplified, and halogen is a reagent capable of leading a component having an unsaturated bond to a derivative that can be separated from the fluoroalcohol of the present invention, chlorine or bromine. Is exemplified.

The proportion of the aldehyde in the reaction mixture of fluoroalcohol is about 0.001 to 1.0% by weight based on the product mainly composed of fluoroalcohol after methanol distillation.

The silver compound or copper compound is not particularly limited as long as it is a compound capable of oxidizing an aldehyde to lead to a carboxylic acid. Examples thereof include AgOH, Fehling solution and Benedict solution used in the Tollens reagent for silver mirror reaction. Cu (OH) _{2 and the} like.

The oxidase or dehydrogenase may be any as long as it can convert an aldehyde into a carboxylic acid, and includes, for example, xanthine oxidase.

As the primary or secondary amine, Schiff base (primary amine) or enamine (secondary amine)
Amines that form (1) Reaction of hydrazine (Wolff-Kishner reduction) In the presence of excess hydrazine with respect to aldehyde,
After reacting at 00 ° C. for 1 hour to lead the aldehyde to the hydrazone, by reacting at 200 ° C. for 2 hours, a compound in which the CHO of the aldehyde is reduced to CH ₃ can be obtained. The amount of hydrazine used is about 0.1 to 1.0 mol per kg of the reaction mixture other than methanol. (2) Reaction of peroxomonosulfuric acid (H ₂ SO ₅ ) An appropriate amount of peroxomonosulfuric acid is added to the reaction solution, and the mixture is reacted in the presence of an alcohol at, for example, 15 ° C. for 3 hours to obtain a corresponding ester from the aldehyde. . As the alcohol, ethanol, propanol, or the like may be newly added to the reaction solution. However, it is preferable to use methanol present in the reaction solution to guide the aldehyde to the corresponding methyl ester. The amount of peroxomonosulfuric acid used is about 0.1 to 1.0 mol per kg of the reaction mixture other than methanol. (3) Reaction of silver compound or copper compound Examples of silver compound include AgOH, preferably Tollens
A reagent (AgOH ammine complex) can be used.

Examples of the copper compound include Cu (OH) ₂ , preferably Fehling solution (Cu (OH) ₂ / tartaric acid chelate complex) and
Benedict liquid (Cu (OH) ₂ / citric acid chelate complex) can be used.

The amount of the silver compound and the copper compound to be used is 0.1 to 0.1 kg / kg of the reaction mixture other than methanol.
It is about 2.0 mol. The reaction can be carried out at a temperature from room temperature to about 70 ° C. for about 1 to 5 hours. (4) Reaction of xanthine oxidase Xanthine oxidase is added to the reaction solution in the form of a solution or as an enzyme immobilized on a carrier, and the aldehyde is converted to a carboxylic acid by reacting at a temperature of about room temperature to about 40 ° C. for about 1 to 10 hours. be able to. Xanthine oxidase may be used in a catalytic amount. (5) Reaction of primary amine or secondary amine As primary amine, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine,
Examples include aniline and benzylamine, and examples of the secondary amine include dimethylamine, diethylamine, diisopropylamine, morpholine, piperidine, and pyrrolidine.

As follows:

The reaction is carried out by using a primary amine or a secondary amine of about 0.1 to 1.0 mol per 1 kg of a reaction mixture other than methanol, and reacting at a reflux temperature of methanol for about 1 to 10 hours. Performed by (6) Reaction of chlorine or bromine The aldehyde contained in the reaction mixture contains a large amount of unsaturated aldehyde, and chlorine or bromine is added to the double bond of these unsaturated aldehydes to form a high boiling addition compound. Generate Chlorine or bromine is added in an amount of about 0.1 to 1.0 mol per 1 kg of a reaction mixture other than methanol, and reacted at 0 ° C. to a reflux temperature of methanol for about 1 to 10 hours to obtain an additional compound. Can be.

The reaction for producing the fluoroalcohol is preferably carried out in the presence of an acid acceptor. Examples of the acid acceptor include carbonates and bicarbonates of alkali metals or alkaline earth metals such as calcium carbonate, magnesium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate, calcium oxide, calcium hydroxide, and soda. Lime, barium carbonate and the like. The acid acceptor is composed of HF generated during the reaction without making the reaction system strongly alkaline.
Those capable of trapping an acid are preferred.

The amount of the acid acceptor used is not particularly limited.
About 0.001 to 0.1 mol can be used per 1 mol of tetrafluoroethylene or hexafluoropropylene.

The radical generating sources include a reaction initiator, U
At least one selected from the group consisting of V and heat can be used. When the radical source is UV, UV from a medium pressure or high pressure mercury lamp can be exemplified. When the radical generation source is heat, a temperature of 250 to 300 ° C. can be exemplified.
As the reaction initiator, a peroxide can be exemplified, and a reaction initiator having a half-life at the reaction temperature of about 10 hours can be preferably exemplified.

Preferred radical generating sources are perbutyl D (di-t-butyl peroxide), perbutyl O (t-butylperoxy-2-ethylhexanoate) or perbutyl I (t-butylperoxyisopropyl carbonate). Is exemplified. The amount of the reaction initiator used is usually about 0.005 to 0.1 mol per 1 mol of tetrafluoroethylene or hexafluoropropylene.

The evaporation residue of the fluorine alcohol obtained in the present invention is 50 ppm or less, preferably 25 ppm or less,
More preferably, it is 10 ppm or less.

The residue of evaporation is determined as follows.
Can be. That is, fluorinated alcohol at 40 ° C., 5 mmH
g, and the weight of the residue after concentration was measured._TwoCF_Two
CH _TwoExpressed as wt.ppm relative to OH.

The absorbance of the fluoroalcohol of the general formula (1) obtained in the present invention in methanol at 205 nm is 0.1 abs or less, preferably -0.1 abs or less, more preferably -0.2 abs or less. The absorbance in methanol is measured using a sample obtained by adding 3 ml of methanol to 1 ml of the fluoroalcohol of the general formula (1) and using methanol as a reference.

The fluoroalcohol of the present invention is suitable as a solvent for producing an information recording medium having a recording layer provided with a substrate on which information can be written and / or read by a laser.

An information recording medium in which a recording layer on which information can be written and / or read by a laser is provided on a substrate is a solvent containing a fluorine alcohol of the general formula (1) of the present invention, preferably the fluorine alcohol. Dissolve the dye in a fluorinated solvent containing, apply the resulting solution on the substrate,
It can be manufactured by forming a recording layer containing a dye according to a conventional method such as drying. Examples of the dye include a cyanine dye, a phthalocyanine dye, a pyrylium dye, a thiopyrylium dye, a squalilium dye, an azurenium dye,
Examples include indophenol dyes, indoaniline dyes, triphenylmethane dyes, quinone dyes, aluminum dyes, diimmonium dyes, and metal complex dyes. Examples of the substrate include plastics such as polycarbonate, polymethyl methacrylate, epoxy resin, amorphous polyolefin, polyester, and polyvinyl chloride, glass, and ceramics. In addition, an undercoat layer may be provided between the recording layer and the substrate for the purpose of improving flatness, improving adhesive strength, preventing deterioration of the recording layer, and a protective layer may be provided on the recording layer. .

[0027]

According to the present invention, an information recording medium (such as an optical disk such as a CD-R or a DVD-R) in which a recording layer capable of writing and / or reading information by a laser is provided on a substrate, a film, and the like. Suitable for the production of photoreceptors,
HCF ₂ CF ₂ substantially free of impurities such as aldehydes
CH ₂ OH, H (CF ₂ CF ₂ ) ₂ CH ₂ OH and HCF
(CF ₃ ) CF ₂ CH ₂ OH can be easily produced.

[0028]

The present invention will be described below in more detail with reference to examples and comparative examples. Example 1 Methanol (2 L) and Perbutyl D (45) were placed in a high-pressure reactor.
g) and calcium carbonate (30 g). After replacing the reactor with nitrogen, the initial speed of tetrafluoroethylene was 6
Charged at 00 g / hr, temperature 125 ° C, pressure 0.8MP
a, and reacted for 6 hours. After cooling, the reaction mixture was distilled to separate methanol, and then H (CF ₂ CF ₂ ) n
CH ₂ OH (n is an integer of 2 or more) is separated into HCF ₂ CF
A fraction (1.2 L) of ₂ CH ₂ OH was obtained.

The obtained HCF_TwoCF_TwoCH_TwoOH fraction
(1 kg) 30 g of hydrazine and 50 g of potassium hydroxide
And stirred at 100 ° C for 1 hour to remove impurities from hydrazone.
And stirred at 200 ° C. for 2 hours to remove N_TwoAnd then distillation
HCF substantially free from impurities_TwoCF_TwoCH_TwoOH
I got Example 2 HCF obtained in Example 1_TwoCF_TwoCH_TwoOH fraction (1k
g), add 10 g of peroxomonosulfuric acid, and at 15 ° C for 3 hours
After stirring for a while, it is distilled to remove HC substantially free of impurities.
F_TwoCF_TwoCH_TwoOH was obtained. Example 3 HCF obtained in Example 1_TwoCF_TwoCH_TwoOH fraction (1k
g), 50 g of silver (I) oxide and 5 g of potassium hydroxide are added.
After stirring at room temperature for 1 hour, distillation was carried out to substantially remove impurities.
HCF not containing_TwoCF_TwoCH_TwoOH was obtained. Example 4 HCF obtained in Example 1_TwoCF_TwoCH_TwoOH fraction (1k
g), add 100 g of Fehling solution and stir at room temperature for 1 hour
And then distilled to obtain HCF substantially free of impurities. _TwoC
F_TwoCH_TwoOH was obtained. Example 5 HCF obtained in Example 1_TwoCF_TwoCH_TwoOH fraction (1k
g), add 50 g of xanthine oxidase,
After stirring for 1 hour at, the mixture is distilled to be substantially free of impurities.
HCF_TwoCF_TwoCH_TwoOH was obtained. Example 6 HCF obtained in Example 1_TwoCF_TwoCH_TwoOH fraction (1k
g), add 5 g of potassium hydroxide, and irradiate with visible light;
Bromine (100 g) was introduced while stirring at 0 ° C. for 1 hour.
HCF which is subsequently distilled and substantially free of impurities_TwoCF_TwoC
H_TwoOH was obtained.

Claims (7)

[Claims] (1) H (CFR ¹ CF ₂ ) _n CH ₂ OH (1) wherein n = 1 or 2 is obtained by reacting methanol and tetrafluoroethylene or hexafluoropropylene in the presence of a radical generating source. When n = 1, R ¹ indicates F or CF _3, and when n = 2, R ¹ indicates F. ] The method for producing a fluoroalcohol represented by the formula (1), wherein the reaction solution is reacted with an aldehyde conversion reagent or a halogen and then distilled. 2. The method according to claim 1, wherein the aldehyde conversion reagent is hydrazine. 3. The method according to claim 1, wherein the aldehyde conversion reagent is peroxomonosulfuric acid. 4. The method according to claim 1, wherein the aldehyde conversion reagent is a silver compound or a copper compound. 5. The method according to claim 1, wherein the aldehyde conversion reagent is xanthine oxidase. 6. The method according to claim 1, wherein the aldehyde conversion reagent is a primary amine or a secondary amine. 7. The method according to claim 1, wherein the halogen is chlorine or bromine.
The method for producing a fluoroalcohol according to the above.