JP2007308459A - Manufacturing method of 2-methyl-2-adamantyl (meth)acrylate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing 2-alkyl-2-adamantyl (meth)acrylate with a high efficiency on an industrial scale. <P>SOLUTION: The method for manufacturing 2-methyl-2-adamantyl (meth)acrylate comprises causing a magnesium halide salt of 2-methyl-2-adamantanol to react with a (meth)acrylic acid halide, where 2-methyl-2-adamantanol and the (meth)acrylic acid halide are separately and simultaneously added dropwise in a solution to the reactor, and the dropwise addition and the reaction are carried out with continuous or intermittent withdrawal of the reaction liquid out of the reactor. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing 2-methyl-2-adamantyl (meth) acrylate useful as a photoresist raw material.

  Resin copolymerized with 2-alkyl-2-adamantyl (meth) acrylate, especially 2-methyl-2-adamantyl (meth) acrylate as an acid dissociable monomer, has high dry etching resistance, high resolution, It is known as a photoresist material having excellent performance such as good adhesion.

  As a production method of 2-alkyl-2-adamantyl (meth) acrylate, 2-alkyl-2-adamantanol or a metal salt of 2-alkyl-2-adamantanol, an anhydride or halide of (meth) acrylic acid In general, a method of esterifying by reacting is carried out (see Patent Document 1 and Patent Document 2, respectively).

  A metal salt of 2-alkyl-2-adamantanol is usually synthesized by alkylating 2-position with an alkylating agent such as an organometallic reagent using 2-adamantanone as a starting material. For example, in the example of Patent Document 2, a method of synthesizing a magnesium bromide salt of 2-methyl-2-adamantanol by reacting 2-adamantanone with methylmagnesium bromide in a tetrahydrofuran (hereinafter also simply referred to as THF) solvent. Is disclosed.

In addition, as a conventional method for charging the reagent, a method in which methylmagnesium bromide is charged in advance into a reactor and a solution of 2-adamantanone is added dropwise thereto, or a solution of 2-adamantanone is previously added. For example, a method in which a solution of methylmagnesium bromide is dropped into a reactor. That is, the method in which the charged reagent and the solvent remained in the reactor in the whole amount was the mainstream.
JP 2000-229911 A JP 2002-53522 A

  However, the present inventors have revealed that such a conventional technique has a considerable problem when applied to production on an industrial scale as it is.

  Specifically, since the reaction of the carboxylic acid halide with the metal salt of 2-alkyl-2-adamantanol is an exothermic reaction, heat removal is required during the reaction, but when a large amount is produced on an industrial scale As the reaction scale increases, the heat removal efficiency decreases and the reaction solution accumulates heat. Therefore, if the temperature of the reaction system is controlled within an allowable range, the addition rate of the raw material cannot be increased. As a result, the problem that the production efficiency of 2-methyl-2-adamantyl (meth) acrylate deteriorates became clear.

  Therefore, an object of the present invention is to provide a method for producing 2-methyl-2-adamantyl (meth) acrylate with high efficiency on an industrial scale.

  As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by devising the addition of raw materials to the reaction vessel and the extraction of reactants from the reaction vessel, and the present invention has been completed. That is, the first aspect of the present invention is a method for producing 2-methyl-2-adamantyl (meth) acrylate by reacting a magnesium halide salt of 2-methyl-2-adamantanol with (meth) acrylic acid halide. The magnesium halide salt of 2-methyl-2-adamantanol and the (meth) acrylic acid halide are dropped into the reaction vessel separately and simultaneously, and the reaction solution is continuously or intermittently removed from the reaction vessel. The above-mentioned problems are solved by providing a method for producing 2-methyl-2-adamantyl (meth) acrylate, characterized in that the dropping and reaction are carried out while being extracted.

  According to this invention, 2-methyl-2-adamantyl (meth) acrylate can be produced with high efficiency on an industrial scale.

  According to a second aspect of the present invention, the magnesium halide salt of 2-methyl-2-adamantanol is prepared by adding dropwise the raw materials 2-adamantanone and methylmagnesium halide to the reaction vessel separately and simultaneously, and The production of 2-methyl-2-adamantyl (meth) acrylate according to claim 1, wherein the reaction solution is dropped and reacted while being continuously or intermittently extracted from the reaction vessel. A method is provided to solve the problem.

  According to this invention, 2-methyl-2-adamantanol can be produced more efficiently on an industrial scale.

  According to the production method of the present invention, since the entire amount of raw materials is not charged into the reaction vessel at a time, the capacity of the reaction vessel can be reduced. As a result, heat removal can be performed more efficiently than before, and the addition rate of raw materials can be increased, and thus the reaction time can be shortened. Also, the amount charged per time can be increased. As a result, even in production on an industrial scale, 2-methyl-2-adamantyl (meth) acrylate can be produced efficiently, and as a result, production can be performed at low cost.

  Such an operation and a gain of the present invention will be clarified from the best mode for carrying out the invention described below.

  The present invention relates to a method for producing 2-methyl-2-adamantyl (meth) acrylate by reacting a magnesium halide salt of 2-methyl-2-adamantanol with a (meth) acrylic acid halide. It is characterized by the addition of raw materials to the reaction vessel and the removal of the reaction product from the reaction vessel in the reaction of the magnesium halide salt of methyl-2-adamantanol and (meth) acrylic acid halide. The present invention will be described in detail below.

  The magnesium halide salt of 2-methyl-2-adamantanol, which is the first raw material, can be synthesized by methylating 2-position of 2-adamantanone with methyl magnesium halide, which is a Grignard reagent (for example, Patent Document 2). The reaction conditions are the same as in a general Grignard reaction. Examples of the methylmagnesium halide include methylmagnesium iodide, methylmagnesium bromide, and methylmagnesium chloride. The solvent used in the reaction is an aprotic solvent. Preferably, ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, 1,4-dioxane and tetrahydrofuran are used.

  The (meth) acrylic acid halide which is the other raw material can be exemplified by (meth) acrylic acid chloride, (meth) acrylic acid bromide, and (meth) acrylic acid iodide. From the viewpoint of production or availability, ( Meth) acrylic acid chloride is preferred. Although these can also obtain a commercial item, they can be easily manufactured with a corresponding halogenating agent. For example, (meth) acrylic acid chloride can be synthesized by reacting (meth) acrylic acid with benzoyl chloride, phosphorus trichloride, or thionyl chloride in an ether solvent or a hydrocarbon solvent.

  The solvent used in the reaction can be used without particular limitation as long as the raw material is an inert solvent. Specifically, ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, and tetrahydrofuran are used. Hydrocarbons such as toluene and xylene are preferably used. These may be used singly or may be a mixed solvent of two or more, and each raw material added to the reaction system may be dissolved in a different solvent. Tetrahydrofuran is most preferably used from the viewpoint of balance of solubility, safety, cost and the like.

  In the present invention, the addition of magnesium halide salt of 2-methyl-2-adamantanol and (meth) acrylic acid halide to the reaction vessel is performed separately and simultaneously by dropwise addition with a solution. A solvent may be put in the reaction vessel in advance, or it may be dropped into an empty reaction vessel. From the viewpoint of controlling the stirring efficiency and the reaction temperature, it is preferable that a solvent capable of stirring is previously placed in the reaction vessel. The concentration of each solution at the time of dropping varies greatly depending on the type of solvent, so it cannot be generally stated, but it may be diluted to such a concentration that precipitation does not occur depending on the temperature at the time of addition.

  The addition ratio of the magnesium halide salt of 2-methyl-2-adamantanol and the (meth) acrylic acid halide is usually (meth) acrylic acid halide 1 per 1 mol of the magnesium halide salt of 2-methyl-2-adamantanol. It is -2.0 mol, Preferably it is 1-1.5 mol, More preferably, it is 1-1.3 mol. When the addition ratio is high, (meth) acrylic acid halide remains in the system more than necessary, so a large amount of hydrogen chloride is generated during the quenching after the reaction and heat is generated. Since a magnesium halide salt of 2-adamantanol remains, the purification load increases, which is not preferable.

  From the viewpoint of preventing the deactivation of 2-methyl-2-adamantanol or (meth) acrylic acid halide, the reaction is desirably performed in an inert atmosphere such as nitrogen or argon. In addition, a polymerization inhibitor for preventing polymerization of the (meth) acrylic acid skeleton, a base for capturing an acid, and the like may be added to the reaction system.

  The dropping is carried out at such a rate that the solute magnesium halide salt of 2-methyl-2-adamantanol and (meth) acrylic acid halide are ideally always in this addition ratio. That is, the concentration of each solution may be the same or different, but when the concentration of the solution is different, the magnesium halide of 2-methyl-2-adamantanol is set at a set addition ratio by changing the dropping speed. It adjusts so that salt and (meth) acrylic acid halide may be added in reaction container. For this reason, the magnesium halide salt of 2-methyl-2-adamantanol and (meth) acrylic acid halide are always added to the reaction vessel without excess or deficiency, and the reaction described later Even if the addition is continued while extracting the liquid, only one of the raw materials does not remain in an excessive ratio in the reaction liquid. Note that the deviation allowed from the set addition ratio when actually performing the reaction is relative to the numerical value of the molar ratio of (meth) acrylic acid halide to the magnesium halide salt of 2-methyl-2-adamantanol, Preferably it is within ± 15%, more preferably within ± 10%. The method for adding the reagent to the reactor at a predetermined rate is not particularly limited, and a method using a dropping funnel or a method using a feed pump can be employed.

  The dropping of the raw material and the reaction are performed while continuously or intermittently extracting the reaction solution from the reaction vessel. The reaction solution may be extracted from an extraction port provided in the reaction vessel or using an extraction means such as a pump. Here, “continuous” means that the reaction solution is always withdrawn while dropping and reacting, and “intermittent” means repeatedly withdrawing the reaction solution from the reactor and stopping the withdrawal.

  In the case of continuous extraction, the extraction may always be performed at a constant speed, or the extraction may be performed by appropriately changing the speed while observing the remaining amount of reaction liquid in the reaction vessel, the temperature, the reaction speed, and the like. In addition, even when intermittently withdrawing, the amount of reaction liquid withdrawn and the interval between withdrawals may be appropriately changed while taking into account the remaining amount of reaction liquid in the reaction vessel, temperature, reaction rate, etc. Alternatively, the amount of extraction and the interval between extractions may be determined, and the extraction of a certain amount at intervals of a certain time may be repeated. In any case, from the viewpoint of stirring efficiency, the reaction solution is not completely withdrawn, and until the end of the reaction, the reaction vessel always has a certain amount or more of the reaction solution and can be stirred. It is.

  The reaction between the magnesium halide salt of 2-methyl-2-adamantanol and (meth) acrylic acid halide proceeds rapidly by mixing in a solvent, but the reaction solution is continuously withdrawn or reacted. When the reaction liquid is withdrawn intermittently within a shorter time than the completion time, the withdrawn reaction liquid may be sent to another reaction vessel for further continuing the reaction. By using two reaction vessels, cooling efficiency and reaction time can be shortened.

  The reaction temperature is 100 ° C. or lower, preferably 70 ° C. or lower, more preferably 40 ° C. or lower from the viewpoint of suppressing side reactions such as polymerization and obtaining the desired product with high purity. On the other hand, since the reaction becomes too slow at low temperatures, from the viewpoint of efficient production on an industrial scale, the lower limit is −10 ° C. or higher, preferably 0 ° C. or higher, more preferably 10 ° C. or higher. preferable.

  The reaction between the magnesium halide salt of 2-methyl-2-adamantanol and the (meth) acrylic acid halide is an exothermic reaction and is adjusted to the above temperature as appropriate. In the present invention, the addition of the raw material to the reaction vessel and the extraction of the reaction liquid from the reaction vessel are performed in parallel, and the entire amount of the raw material is not charged into the reaction vessel at one time. The capacity can be reduced, and the reaction can be efficiently cooled to an appropriate reaction temperature. Therefore, 2-methyl-2-adamantyl (meth) acrylate can be efficiently produced even in mass production on an industrial scale.

  The extracted reaction solution or sent to another reaction vessel where the reaction is completed is combined with the reaction solution remaining in the reaction vessel after completion of the reaction, filtered, washed, extracted, concentrated, The target 2-methyl-2-adamantyl (meth) acrylate can be obtained by processing by known separation and purification means such as distillation and column chromatography. When performing distillation, thin film distillation may be used in order to reduce the thermal history of the target product.

  In the present invention, the magnesium halide salt of 2-methyl-2-adamantanol, which is one of the raw materials, is the 2-methyl-2-adamantyl (meth) described above in the Grignard reaction at the time of synthesis. As with the synthesis of acrylate, 2-adamantanone and methylmagnesium halide as raw materials are dropped into the reaction vessel separately and simultaneously, and the reaction solution is dropped continuously or intermittently from the reaction vessel. It is preferable that the reaction has been performed.

  Since this reaction also requires heat removal in order to prevent side reactions, as in the synthesis of 2-methyl-2-adamantyl (meth) acrylate, the addition of raw materials to the reaction vessel and the reaction solution from the reaction vessel It is possible to efficiently cool to an appropriate reaction temperature by performing extraction in parallel. In addition, when 2-methyl-2-adamantyl (meth) acrylate is industrially produced continuously using 2-adamantanone as a starting material, the addition of the raw material to the reaction vessel and the reaction vessel are conducted in two reactions. By using this method of extracting the reaction solution in parallel, 2-methyl-2-adamantyl (meth) acrylate, which is the target product, can be synthesized very efficiently as a whole.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples unless the gist of the present invention is exceeded.

(Synthesis Example 1)
Into a 300 mL reactor having an extraction port so that the reaction solution can be continuously extracted, 100 mL of THF was charged, and a solution of 68.4 g (455 mmol) of 2-adamantanone dissolved in 200 mL of THF and a concentration of 3.0 mol / L. 177 mL (532 mmol) of a solution of methylmagnesium chloride in THF was added dropwise over 1 hour so that the molar ratio of both compounds was the same as the total charge ratio of the reagents. During this time, a reaction solution having the same volume as that charged in the reactor was continuously withdrawn from the reactor. During this time, the internal temperature of the reactor was kept at 40 ° C. or lower. After completion of the dropwise addition, stirring in the reactor was continued for another hour. The reaction solution thus obtained and the extracted solution were combined to obtain a THF solution of 2-methyl-2-adamantanol magnesium chloride salt.

Example 1
100 mL of THF was charged into a 300 mL reactor equipped with an extraction port so that the reaction solution could be continuously extracted, and a THF solution of 2-methyl-2-adamantanol magnesium chloride salt prepared in Synthesis Example 1 and (meth) Using a dropping funnel while maintaining 62.8 g (601 mmol) of acrylic acid chloride so that the internal temperature of the reactor is 25 ° C., and the molar ratio of both reagents added is the same as the total charge ratio of the reagents. It was dripped. During this time, a reaction liquid having the same volume as that charged in the reactor was continuously withdrawn from the reactor. As a result, the addition of the reagent was completed in 1 hour. After completion of the addition, the reaction solution in the reactor was further stirred for 1 hour while maintaining this temperature. The obtained reaction solution and the extracted solution were combined, 50 mL of a saturated aqueous ammonium chloride solution was added thereto, and THF was distilled off. 700 mL of toluene was added to the concentrate, and washed with 500 mL of saturated aqueous ammonium chloride solution, 500 mL of 1N aqueous sodium hydroxide solution, and 500 mL of demineralized water. The toluene solution was concentrated with an evaporator to obtain 89.0 g (380 mmol; yield 84%) of the desired 2-methyl-2-adamantyl (meth) acrylate.

(Comparative Example 1)
A total amount of 2-methyl-2-adamantanol solution obtained in Synthesis Example 1 (about 720 mL; 455 mmol) was charged into a 1 L three-necked flask in which nitrogen was circulated, and 62.8 g of (meth) acrylic acid chloride (here) 601 mmol) was added dropwise while keeping the internal temperature of the reactor at 25 ° C. or lower. In order to prevent the temperature in the reactor from rising, the dropping was performed slowly, and thus it took 1 hour 30 minutes to complete the dropping. 50 mL of saturated aqueous ammonium chloride solution was added to the resulting reaction solution, and THF was distilled off. 700 mL of toluene was added to the concentrate, and washed with 500 mL of saturated aqueous ammonium chloride solution, 500 mL of 1N aqueous sodium hydroxide solution, and 500 mL of demineralized water. The toluene solution was concentrated with an evaporator to obtain 90.0 g (384 mmol; yield 84%) of the desired 2-methyl-2-adamantyl (meth) acrylate.

  Although the present invention has been described with reference to the most practical and preferred embodiments at the present time, the present invention is not limited to the embodiments disclosed herein. The present invention can be appropriately changed without departing from the spirit or idea of the invention that can be read from the claims and the entire specification, and a manufacturing method involving such a change is also understood to be included in the technical scope of the present invention. It must be.

Claims (2)

A process for producing 2-methyl-2-adamantyl (meth) acrylate by reacting a magnesium halide salt of 2-methyl-2-adamantanol with a (meth) acrylic acid halide, wherein the 2-methyl-2- The dropwise addition and reaction of the magnesium halide salt of adamantanol and the (meth) acrylic acid halide to the reaction vessel are performed separately and simultaneously in solution, and the reaction solution is continuously or intermittently extracted from the reaction vessel. Is performed, The manufacturing method of 2-methyl-2-adamantyl (meth) acrylate characterized by the above-mentioned. The magnesium halide salt of 2-methyl-2-adamantanol is prepared by dropping the raw materials 2-adamantanone and methylmagnesium halide into the reaction vessel separately and simultaneously, and continuously or intermittently from the reaction vessel. The method for producing 2-methyl-2-adamantyl (meth) acrylate according to claim 1, wherein the dropping and the reaction are performed while the reaction solution is withdrawn.