JP5359052B2 - Method for producing fluorine-containing monomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an easily operable industrial method of more efficiently preparing a fluorine-containing monomer useful in the field of a coating material such as a reflection preventive film or in the field of a resist material such as photolithography. <P>SOLUTION: The method of preparing a fluorine-containing monomer by esterifying a fluorine-containing diol and acrylic acid chloride each being commercially readily available, in the presence of an alkali, is characterized by employing a polycyclic nitrogen compound as the alkali. According to the above preparation method, the compound can be prepared not only with easy operability but also with high efficiency. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a fluorine-containing monomer represented by the general formula [3]

(In the formula, R ¹ is a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl substituent, and R ² is a hydrogen atom, or a linear or branched chain having 1 to 6 carbon atoms. And a fluorine-containing alkyl group). The fluorine-containing monomer represented by the general formula [3] has a hexafluoroisopropyl unit and is useful as a monomer for a coating material such as an antireflection film or a resist material such as photolithography.

  The fluorine-containing monomer is useful as a monomer for a coating material such as an antireflection film or a resist material. In particular, it is a compound that holds the key to microfabrication in the resist field such as photolithography, which is a processing technique for electric circuits, and a variety of compounds are being developed. Among them, a compound having a hexafluoroisopropyl alcohol unit has received much attention because it contains fluorine and has a hydroxyl group which is a polar group (Non-patent Document 1).

  Since these compounds introduce a polymerizable site, they are often synthesized by esterifying a polymerizable acid such as substituted acrylic acid and a functional alcohol. As the esterification method, a general method can be used. For example, (1) a reaction in the presence of an acid catalyst of a substituted acrylic anhydride and an alcohol, (2) a reaction in the presence of a base of a substituted acrylic acid chloride and an acrylic anhydride and an alcohol, (3) a substituted acrylic acid Various things such as dehydration condensation of alcohol with alcohol are known.

Patent Document 1 describes that the fluorine-containing monomer represented by the general formula [3], which is the target compound of the present invention, can be produced by the above method (1) or (2).
Resist material p57-p68, edited by Polymer Society, Hiroshi Ito, Kyoritsu Publishing JP 2005-232037 A

  The reaction in the presence of the acid catalyst of the substituted acrylic acid anhydride and the alcohol described in (1) described in Patent Document 1 proceeds with good selectivity, and a solid salt does not precipitate, so the amount of solvent is reduced. It has excellent points such as being able to improve productivity. However, in this method, in principle, one equivalent of acrylic acid is by-produced with respect to one equivalent of the product. Therefore, when expensive substituted acrylic acid is used, it is disadvantageous in terms of cost, and further, it is necessary to remove the substituted acrylic acid for commercialization, which is not necessarily a synthesis method suitable for industrial production.

  Patent Document 1 also discloses the reaction in the presence of a base of the substituted acrylic acid chlorides (2) and alcohol described above, and describes that triethylamine, pyridine, and 2,6-dimethylpyridine are used as the base. . Therefore, when the reaction between the substituted acrylic acid chlorides and the alcohol was actually performed in the presence of the base, by-products may be generated depending on the base and the selectivity may be reduced (Comparative Example 1 or 2), In some cases, the amine hydrochloride used as a mixture does not become a uniform slurry but grows while taking up the product and grows into large lumps and the operability is significantly reduced (Comparative Examples 3 to 5). There was a problem.

  Furthermore, although the dehydration condensation reaction was also attempted in the reaction of the substituted acrylic acid and alcohol in (3) above, a side reaction progressed in the reaction between the substituted acrylic acid and alcohol having a large steric hindrance, and good results were obtained. (See Comparative Example 6).

  In the step of producing the fluorine-containing monomer represented by the general formula [3] by esterifying the fluorine-containing diol represented by the general formula [1] and the fluorine-containing substituted acrylic acid chloride represented by the general formula [2] in the presence of a base. As a side reaction, the base hydrochloride is formed. Further, since the diol represented by the general formula [1] has two hydroxyl groups, there is a possibility that a bis body in which two substituted acrylic acid chlorides are esterified as a by-product may be formed.

(However, R ¹ and R ² in the formula have the same meaning as in the general formula [3].)
As described above, when the hydrochloride is agglomerated, there is a problem as a production method for industrial production because it affects stirring and the operability is lowered. Moreover, in the reaction using the base disclosed in the preceding examples, the production of by-products is recognized depending on the type of the base, and the selectivity is not necessarily good. Therefore, an industrial production method for producing the fluorine-containing monomer represented by the general formula [3] more efficiently by a method with good operability has been demanded.

  INDUSTRIAL APPLICABILITY The present invention is an industrial process for more efficiently producing a fluorine-containing monomer represented by the general formula [3], which is a compound useful for a coating material such as an antireflection film or a resist material such as photolithography, by a method with good operability. It is an object to provide a simple manufacturing method.

  In view of the problems of the prior art, the present inventors have intensively studied to establish a method for producing a fluorine-containing monomer suitable for production on an industrial scale.

  As a result, the fluorine-containing diol represented by the general formula [1]

(The meaning of R ¹ in the formula [1] is the same as described above.) The substituted acrylic acid chlorides represented by the general formula [2]

(The meaning of R ² in the formula [1] is the same as described above.) When a specific condition is applied to esterify, not only the operability is improved, but also good selectivity is obtained. Monomer for fluorine-containing resist represented by the general formula [3] with an appropriate recovery rate as the reaction proceeds

(In formula [3], R ¹ and R ^{2 have} the same meanings as described above), and the present invention has been completed.

  That is, the present invention is a novel method for producing a fluorine-containing monomer including the inventions of [Invention 1] to [Invention 4].

  [Invention 1] Fluorine-containing diol represented by the general formula [1]

In the reaction of esterifying an acrylic acid chloride represented by the general formula [2] in the presence of a base, using a polycyclic nitrogen compound as the base, the general formula [3] The manufacturing method of the fluorine-containing monomer represented by these.

(In the formula, R ¹ is a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl substituent, and R ² is a hydrogen atom, or a linear or branched chain having 1 to 6 carbon atoms. An alkyl group having a fluorine atom or a fluorine-containing alkyl group.)
[Invention 2] A polycyclic nitrogen compound is indole, isoindole, purine, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, sinoline, pteridine, carbazole, β-carboline, phenanthridine, acridine, perimidine, phenanthrin Or a method for producing a monomer for a fluorine-containing resist according to invention 1, wherein the monomer is at least one compound selected from the group consisting of phenazine.
[Invention 3] The method for producing a fluorine-containing monomer according to Invention 1 or Invention 2, wherein R ¹ is a methyl group and R ² is a trifluoromethyl group.
[Invention 4] The method for producing a fluorine-containing monomer according to any one of Inventions 1 to 3, wherein the polycyclic nitrogen compound is quinoline.

  According to the present invention, the target fluorine-containing monomer can be produced not only with good operability, but also with a higher selectivity than conventional methods. Therefore, the present invention is an extremely excellent method for producing a fluorine-containing monomer on an industrial scale.

Hereinafter, the production method of the present invention will be described in more detail.

The alkyl substituent R ¹ of the fluorine-containing diols represented by the general formula [1] targeted by this reaction is a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group. , A methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a cyclopentyl group, and a cyclohexyl group are preferable, and a methyl group is particularly preferable.

  It is also known that these fluorinated alkyl-substituted vinyl halides represented by the general formula [1] can be produced, for example, by reducing a fluorinated hydroxyketone obtained by the reaction of hexafluoroacetone and methyl ethyl ketone (Patent Document 1). Or US Pat. No. 3,660,711).

The alkyl substituent R ² of the acrylic acid chlorides represented by the general formula [2] targeted by this reaction is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorinated alkyl. And a hydrogen atom, a methyl group, an ethyl group, a propyl group, an iso-propyl group, a trifluoromethyl group and a pentafluoroethyl group are preferable, and a trifluoromethyl group is particularly preferable. For example, a method using phosgene as an acid chloride agent in the presence of a polymerization inhibitor and a catalyst (Japanese Patent Publication No. 47-13021), thionyl chloride is prepared by acid chloride of the corresponding acrylic acid. It can be produced by the method used (Japanese Examined Patent Publication No. 63-66819).

  The reaction of the present invention can be carried out in batch-type and flow-type reaction apparatuses. The batch reaction conditions will be described below, but this does not preclude changes in the reaction conditions that can be easily adjusted by those skilled in the art.

  In this reaction, the amount of acrylic acid chlorides used is preferably from 0.5 to 3, more preferably from 0.8 to 1.5, particularly preferably from 0.9 to 1.2, as the molar ratio to the substrate. If it is less than 0.5, the conversion rate of the reaction is lowered, and unreacted fluorine-containing diol remains, which is not preferable. On the other hand, if it is larger than 3, the amount of acrylic acid chlorides not involved in the reaction increases, which is not economically preferable.

  The base is preferably a polycyclic nitrogen compound, indole, isoindole, purine, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, sinoline, pteridine, carbazole, β-carboline, phenanthridine, acridine, perimidine, phenanthrin. Phenazine is more preferred, and quinoline is most preferred. By using these polycyclic nitrogen compounds as the base, the esterification reaction proceeds efficiently. Further, the hydrochloride produced by the side reaction becomes a uniform slurry in the system, so that the operability is good without hindering stirring.

  In this reaction, when a polycyclic nitrogen compound is used as the base, the molar ratio of the base to the substrate is preferably 0.5 to 3, more preferably 0.8 to 1.5, and preferably 0.00. 9 to 1.2 are particularly preferred. If it is less than 0.5, the conversion rate of the reaction is lowered, and unreacted fluorine-containing diol remains, which is not preferable. On the other hand, if it is larger than 3, the amount of the polycyclic nitrogen compound not involved in the reaction increases, which is not economically preferable.

  In this reaction, a solvent can be used for the purpose of improving the reaction selectivity, reaction rate, and operability. Nitrile solvents such as acetonitrile, propionitrile or benzonitrile, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide or N, N-dimethylimidazolidinone, sulfoxide solvents such as dimethyl sulfoxide, Ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether or tetrahydrofuran, halogenated solvents such as methylene chloride, chloroform or carbon tetrachloride, aromatic hydrocarbon solvents such as benzene, toluene or xylene, pentane, hexane or heptane At least one compound selected from the aliphatic hydrocarbon solvents is preferred, and diisopropyl ether, toluene, and heptane are more preferred.

  When a solvent is used, the effect varies depending on the solvent used, and therefore the amount of the solvent cannot be uniquely determined, but is preferably 30% to 1000% by weight, preferably 100% by weight based on the raw material substrate. % To 500% by weight is more preferred. If it is less than 30% by weight, the effect of adding is not preferred. On the other hand, when the amount exceeds 1000% by weight, good reaction selectivity can be expected, but the productivity per batch is lowered, and the labor for removing the solvent is increased, which is not economically preferable.

  In this reaction, for the purpose of preventing polymerization of the substituted acrylic acid chloride or the product (fluorinated monomer), it may be carried out in the presence of a polymerization inhibitor, and it is usually desirable to use a polymerization inhibitor. . Polymerization inhibitors used are hydroquinone, methoquinone, 2,5-di-t-butylhydroquinone, 1,2,4-trihydroxybenzene, 2,5-bistetramethylbutylhydroquinone, leucoquinizarin, nonflex F, nonflex H , Non-flex DCD, non-flex MBP, ozonone 35, phenothiazine, tetraethylthiuram disulfide, 1,1-diphenyl-2-picrylhydrazyl, 1,1-diphenyl-2-picrylhydrazine, Q-1300, Q-1301 Is at least one compound selected from the group consisting of The above polymerization inhibitors are commercially available products and can be easily obtained.

  The amount of the polymerization inhibitor used in the present invention is usually 0.00001 to 0.1 mol, and 0.0001 to 0.05 mol per mol of the fluorine-containing diol represented by the raw material formula [1]. Preferably, 0.001 to 0.01 mol is more preferable. Even if the amount of the polymerization inhibitor exceeds 0.1 mol relative to 1 mol of the fluorine-containing diol represented by the formula [1] of the raw material, there is no significant difference in the ability to prevent polymerization, and this is economically undesirable. .

  There are three types of reagents involved in this reaction: raw material fluorinated diols, substituted acrylic acid chlorides, and polycyclic nitrogen compounds. If these are added to the reactor at once, it will be difficult to control the reaction. It is desirable to mix any two kinds of reagents in the presence of a solvent, and sequentially add the remaining one kind of reagent.

  The rate of sequential addition of reagents involved in the main reaction of the reagent is difficult to determine uniquely because the possible range varies depending on the heat removal efficiency of the reactor, but from 30 minutes from the start of addition to the end of addition. It is preferable to take 24 hours. If it is shorter than 30 minutes, it is difficult to remove the heat, and the reaction runs out of control. If it exceeds 24 hours, heat is removed sufficiently, but only time is used, which is not preferable in terms of cost.

  Although there is no special restriction | limiting in the reaction temperature at the time of implementing this reaction, Usually, it is -50-200 degreeC, -20-100 degreeC is preferable, and 0 degreeC-50 degreeC is especially preferable. If it is less than −50 ° C., it is not desirable because it costs cooling. On the other hand, when the temperature exceeds 200 ° C., since the raw material and the product are both monomers, side reactions such as polymerization are likely to proceed, and it is difficult to achieve selective synthesis.

  The reactor for carrying out the reaction is preferably a reactor made of tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass or the like, a glass container, or stainless steel.

  The reaction of the present invention is preferably carried out at normal pressure because it does not require pressurizing conditions. However, with the aim of preventing the vapor of the compound used in the reaction from being discharged out of the system, It is also possible to carry out the reaction by sealing the inside of the system using a sex reactor.

  Although the reaction of the present invention can be carried out under an inert gas atmosphere, there is no significant difference from the reaction under an inert gas atmosphere even when the reaction is carried out in the atmosphere, and the synthesis is performed particularly on a large scale. In the case of performing the reaction, it is preferable in terms of cost to perform the reaction in the atmosphere.

[Examples of desirable embodiments]
Although the method for carrying out the present invention is not limited, details will be described with respect to an example of a desirable embodiment.

  A predetermined amount of a polycyclic nitrogen compound as a raw material fluorine-containing diol, a solvent, and a base is added to a reactor that can withstand the reaction conditions of this reaction, and heated or cooled as necessary to set a predetermined temperature.

  It is preferable to add a predetermined amount of acrylic acid chloride dropwise and successively monitor the production of the target product by sampling or the like.

  As the reaction proceeds, the desired fluorine-containing monomer is produced by esterification, but at the same time, the hydrochloride of the base is also produced. Even if the hydrochloride of the polycyclic nitrogen compound used as a base in the present invention is formed in a uniform slurry, it does not become a lump and can be reacted with good operability. Further, in the organic composition of the solution after the reaction, the target fluorine-containing monomer can be produced with a conversion rate of 99% and a selectivity higher by 95% or more.

  The fluorine-containing monomer represented by the general formula [3] produced by the production method of the present invention can be purified by applying a known method. For example, the crude fluorine-containing resist monomer solution taken out from the reaction vessel is filtered. Thus, after removing the hydrochloride of the polycyclic nitrogen compound, the filtrate is treated with an aqueous hydrochloric acid solution, and the solvent is distilled off to obtain a crude organic material. If the polycyclic nitrogen compound remains in the reaction solution, it can be removed by filtration after treatment with an aqueous hydrochloric acid solution, so the order of filtration and treatment with an aqueous hydrochloric acid solution is appropriate depending on the situation of the remaining base. Can be changed. The obtained crude organic matter can be purified by column chromatography, distillation purification or the like to obtain a high purity fluorine-containing monomer.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it is not restricted to these embodiments.
Here, “%” of the compositional analysis value refers to an organic component obtained by collecting a part of the reaction mixture or product and measuring the organic component dissolved in diethyl ether by gas chromatography. This represents the “area%” of the raw material and product, and this value was used as the selectivity. A value obtained by subtracting the numerical value of GC% of the raw material from 100 was defined as the conversion rate.

  In a 1 L (liter) four-necked flask equipped with a thermometer and a stirrer, 50.0 g of 1,1,1-trifluoro-2-trifluoromethyl-pentane-2,4-diol, 31.4 g of quinoline, toluene 200 mL was added and cooled with water.

Using a dropping funnel, 41.9 g of 2- (trifluoromethyl) acrylic acid chloride was added to the reaction mixture over 1 hour, and after the addition was completed, the mixture was further stirred for 1 hour.
Formation of hydrochloride of quinoline was observed during the reaction, but the reaction proceeded without being disturbed by stirring in a slurry state. The composition of the organic substance in the reaction solution was 2-trifluoromethylacrylic acid 1,1,1-trifluoro-2-hydroxy-2-trifluoromethyl-pentan-4-yl 95.9%, 1,1,1-trimethyl. Fluoro-2-trifluoromethyl-pentane-2,4-diol was 0.7%, and other impurities were found to be 3.4% in total. The resulting quinoline hydrochloride was removed by filtration, the resulting solution of the product was washed with 200 g of 5% hydrochloric acid and water, and the solvent toluene was distilled off to obtain 61.6 g of a crude organic material.

The resulting crude organic matter was subjected to precision distillation, and a fraction having a boiling point of 83 to 88 ° C. (10 Torr = 1.33 kPa) was collected. As a result, 40.2 g of 2-trifluoromethylacrylic acid 1,1,1-trimethyl was obtained. Fluoro-2-hydroxy-2-trifluoromethyl-pentan-4-yl was obtained. The purity was 98%. The yield from the raw material 1,1,1-trifluoro-2-trifluoromethyl-pentane-2,4-diol was 67%.
“Comparative Example 1—Comparative Example 5”
The same reaction as in the examples was performed by changing the type of base and the type of solvent. The reaction conditions and results are summarized in Table 1 together with Example 1.

[Comparative Example 1]
To a 50 mL two-necked flask equipped with a thermometer and a stirrer piece was added 5 g of 1,1,1-trifluoro-2-trifluoromethyl-pentane-2,4-diol, 2.7 g of triethylamine, and 20 mL of toluene, followed by water cooling. did.

  Using a dropping funnel, 4.2 g of 2- (trifluoromethyl) acrylic acid chloride was added to the reaction mixture over 30 minutes. After the addition was completed, the mixture was further stirred for 1 hour. The reaction mixture was sampled and the composition of the organic substance was examined. As a result, 1,1,1-trifluoro-2-hydroxy-2-trifluoromethyl-pentan-4-yl 2-trifluoromethylacrylate 63% 1,1-trifluoro-2-trifluoromethyl-pentane-2,4-diol, and other impurities were confirmed to be 32% in total.

[Comparative Example 2]
The reaction was carried out under the same conditions as in Comparative Example 1 except that the base was changed to 2.8 g of 2,6-dimethylpyridine. The results are shown in Table 1.

[Comparative Example 3]
The reaction was performed under the same conditions as in Comparative Example 1 except that the base was changed to 2.1 g of pyridine. Pyridine hydrochloride formed during the dropwise addition of 2-trifluoromethylacrylic acid chloride became a highly viscous mass, and stirring became difficult. After the dropping, the mixture was further stirred for 1 hour. The results are shown in Table 1.

  [Comparative Example 4] The reaction was performed under the same conditions as in Comparative Example 1 except that 2.1 g of pyridine and 20 mL of diisopropyl ether were used as the solvent. During the dropwise addition of 2-trifluoromethylacrylic acid chloride, the produced pyridine hydrochloride became a highly viscous mass, and stirring was difficult, so the reaction was stopped.

[Comparative Example 5]
The reaction was performed under the same conditions as in Comparative Example 1 except that the base was changed to 2.5 g of 4-methylpyridine. During the dropwise addition of 2-trifluoromethylacrylic acid chloride, the produced 4-methylpyridine hydrochloride became a highly viscous mass, and stirring was difficult, so the reaction was stopped.

[Comparative Example 6]
In a 50 mL two-necked flask equipped with a thermometer, stirrer piece, and Dean-Stark refluxer, 25 g of 1,1,1-trifluoro-2-trifluoromethyl-pentane-2,4-diol and paratoluenesulfonic acid 5 g and 17.0 g of 2- (trifluoromethyl) acrylic acid were added and heating to reflux was started. After 25 hours, the reaction mixture was sampled and the composition of the organic matter was examined. 1,1,1-trifluoro-2-hydroxy-2-trifluoromethyl-pentan-4-yl 2-trifluoromethyl acrylate They were 52%, 1,1,1-trifluoro-2-trifluoromethyl-pentane-2,4-diol 28.2%, and other impurities 19.8% were confirmed.

Claims (2)

Fluorine-containing diol represented by the general formula [1]

In the general formula with an acrylic acid chloride compound represented by [2] to esterification in the presence of a base reaction is represented by wherein the as a base using a quinoline of the general formula [3] A method for producing a fluorine-containing monomer.

(In the formula, R ¹ is a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl substituent, and R ² is a hydrogen atom, or a linear or branched chain having 1 to 6 carbon atoms. An alkyl group having a fluorine atom or a fluorine-containing alkyl group.) The method for producing a fluorine-containing monomer according to claim 1, wherein R ¹ is a methyl group and R ² is a trifluoromethyl group.