KR100948498B1 - An alkyl 2-t-butoxyethoxy-acetate compound and a method for preparing the same - Google Patents

Abstract

The present invention relates to a novel compound represented by the following formula (I), methyl 2-t-butoxyethoxy-acetate (MTBEA) or ethyl 2-t-butoxyethoxy-acetate (ETBEA) and a process for preparing the same. :

(I)

(I)

[Wherein R 'is a methyl or ethyl group].

The compound represented by the formula (I) reacts with a compound such as a solvent used in peeling agent, ink, paint, etc., ammonia, amine, etc. to peel off the photoresist film on the wafer surface in the manufacture of a semiconductor or LCD to produce an amide compound. It can be used as an intermediate that can be.

Alkyl 2-t-butoxyethoxy-acetate (alkyl is a methyl or ethyl group), stripper, para-dioxanone

Description

Alkyl 2-tet-butoxyethoxy-acetate compound and preparation method thereof {AN ALKYL 2-T-BUTOXYETHOXY-ACETATE COMPOUND AND A METHOD FOR PREPARING THE SAME}

The present invention is a novel compound represented by the following general formula (I):

(I)

(I)

[Wherein R 'is methyl or ethyl group]

And to a method for producing the same.

To date, methyl 2-t-butoxyethoxy-acetate represented by the formula (I) (when R 'is a methyl group; hereinafter MTBEA) or ethyl 2-t-butoxyethoxy-acetate (R' is an ethyl group In the following cases, no ETBEA) compounds and preparation methods thereof have been reported. The inventors have therefore found that MTBEA or ETBEA can be prepared from para-dioxanone as in the following scheme:

Regarding the raw material para-dioxanone, the present inventors have described the para-dioxanone as catalytically inexpensive from diethylene glycol as a petrochemical by-product, as described in patent KR 2005-0011383, incorporated herein by reference. We have developed an economical way to manufacture. Para-dioxanone, which is a raw material, is a raw material of mainly biocompatible materials, such as a polymerization raw material of poly (para-dioxanone), which is used as a monofilament type surgical suture having bioabsorption properties, or a pharmaceutical raw material or a drug delivery system. As an expensive substance used as a substance, it has not been used to manufacture general-purpose products until now. However, considering that para-dioxanone is used as a biocompatible material or that a material based on it is biodegradable, it is possible to apply para-dioxanone to manufacturing eco-friendly products. Thus, the present invention has been completed.

The lactone group of para-dioxanone reacts easily with an alcohol, an amine compound, etc., and is substituted, and becomes an alkyl 2-hydroxyethoxy acetate or a 2-hydroxyethoxy acetamide compound. At this time, compounds and amide compounds in which the alkyl group has methyl ethyl and other alkyl groups have already been reported (USP 3,929,847, WO 2007/066164).

However, the alkyl 2-hydroxyethoxy-acetate and amide compounds have problems in chemical stability for use in solvents and other applications because reversible reactions occur easily and are not thermally stable as in Scheme 1 below.

Accordingly, the present inventors have reacted hydroxy groups with isobutylene in an alkyl 2-hydroxyethoxy acetate compound (alkyl is methyl or ethyl) to ester compounds into which t-butyl groups have been introduced, ie alkyl 2-t-butoxy. By converting into oxy-acetate compounds (MTBEA, ETBEA), new compounds with stability were prepared.

MTBEA and ETBEA are intermediates that can produce amide compounds by reacting with compounds such as ammonia, amines, solvents used for peeling photoresist films on wafer surfaces, solvents used for inks, paints, etc. in the manufacture of semiconductors or LCDs. Can be used.

It is an object of the present invention to provide novel MTBEA, ETBEA compounds prepared from para-dioxanone and methods for preparing these compounds.

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

Method for producing MTBEA or ETBEA represented by the formula (I) according to the present invention, para-dioxanone represented by the formula (II) in the presence of an acid catalyst and methanol or ethanol:

(II)

(II)

Reacting a compound represented by the following formula (III), ie, methyl t-butyl ether or (hereinafter MTBE) or ethyl t-butyl ether (hereinafter ETBE):

(III)

(III)

[Wherein R 'is a methyl or ethyl group].

In addition, the method for producing MTBEA or ETBEA according to the present invention uses MTBE or ETBE as a solvent in the presence of an acid catalyst and methanol or ethanol,

(1) An alkyl 2-hydroxyethoxy acetate compound represented by the following formula (IV) with MTBEA or ETBEA by reacting para-dioxanone with methanol or ethanol in the presence of MTBE or ETBE represented by formula (III) Obtaining a mixture of:

(IV)

(IV)

[Wherein R 'is a methyl or ethyl group];

(2) reacting isobutylene with a hydroxyl group of the compound of formula (IV) in the solution obtained in step (1) to convert the compound of formula (I).

Para-dioxanone is easily prepared as an ester compound while the lactone ring is ring-opened by alcohol. In order to form an ether compound by reacting the hydroxy group of 2-hydroxyethoxy acetate, a hydration reaction with olefins such as propylene or isobutylene is more advantageous than dehydration with primary, secondary and tertiary alcohols. Reaction which introduce | transduces a tertiary group is easier than the compound which has an (iso) group.

This is because the reaction for the preparation of ether compounds is carried out under mild conditions as possible, such that the reverse reaction in which 2-hydroxyethoxy acetate as described above is decomposed into para-dioxanone and alcohol and para-dioxanone or 2- This is important because the intermolecular condensation of the hydroxyethoxy acetate compound itself can be minimized.

Such ether compound preparation reaction is promoted under an acid catalyst. Possible acid catalysts include sulfuric acid, para toluene-sulfonic acid, heteropoly acids such as PMo ₁₂ and PW ₁₂ , strongly acidic ion exchange resins into which sulfonic acid groups are introduced, and zeolites such as H-ZSM-5. More preferably, in order to facilitate the separation of the catalyst from the product after the reaction, a strong acid ion exchange resin catalyst or a solid acid catalyst such as H-ZSM-5 is used.

In preparing MTBEA or ETBEA from para-dioxanone, a feature of the present invention is that MTBE or ETBE act as a reaction solvent and at the same time as a reactant. Since MTBE or ETBE are decomposed into isobutylene and methanol or isobutylene and ethanol under the acid catalyst, the decomposition products of MTBE or ETBE act as reactants to react with para-dioxanone to produce MTBEA or ETBEA.

The molar ratio of MTBE or ETBE to para-dioxanone used in the reaction is 1-10, preferably 1-5. Too little is undesirable because the reaction rate is slow, and in many cases the reactor volume must be large.

After a certain degree of reaction, it will compete with decomposition of the product MTBEA or ETBEA under an acid catalyst, so it is preferable to further supply methanol, ethanol or isobutylene to promote the forward reaction.

The amount of methanol or ethanol added is 0.1 to 10, preferably 0.2 to 3, in a molar ratio of methanol or ethanol to para-dioxanone, if less than this, the effect is small, and in many cases methanol and ethanol react with isobutylene Conversion to MTBE or ETBE lowers the isobutylene concentration in the reaction system, resulting in a lower conversion.

The amount of isobutylene added is 0.1 to 10, preferably 0.5 to 5 in molar ratio of isobutylene to para-dioxanone. When too much, dimer (2,5-dimethylhexane) production between isobutylene proceeds and thus may be uneconomical against the conversion of para-dioxanone.

At this time, the additionally supplied isobutylene is C4-rapinate-1 (isobutylene, 1-butene, 2-) using a compound of isobutylene alone or removing butadiene from a C4 stream produced in a petrochemical naphtha process. Butene, butane, etc.) can be used.

The reaction temperature for producing the MTBEA or ETBEA is from room temperature to 100 ℃, preferably 30 ~ 70 ℃. If the temperature is low, the reaction rate is slow. If the temperature is higher, the yield is lowered because the decomposition reaction of the product is promoted under an acid catalyst.

In the reaction pressure, it is necessary to pressurize in order to maximize the dissolution of isobutylene in the reaction solution, it is carried out at atmospheric pressure to 30 atm, preferably 5 to 20 atm.

The compound of the formula (I) according to the present invention can be used as a solvent used in peeling agents, inks, paints and the like for peeling the photoresist film on the wafer surface in the manufacture of a semiconductor or LCD.

In addition, the compound of formula (I) can be selectively produced in high yield by the production method of the present invention.

In addition, the MTBEA or ETBEA thus obtained can be used not only as it is itself but also as an intermediate for preparing various compounds. For example, ammonia, monoalkylamines (such as methylamine, monoethylamine and C ₃ to C ₁₀ straight or branched alkyl amines), dialkylamines (such as dimethylamine, diethylamine and C ₃ to C ₁₀ linear or branched alkyl amines), diamines (eg ethylenediamine, propylenediamine, butylenediamine, hexylenediamine), triamines (eg diethylenetriamine), tetraamines (eg triethylenetetraamine) Various amide compounds can be manufactured easily by reacting with such compounds.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are only for helping understanding of the present invention, but do not limit or limit the protection scope of the present invention.

<Example 1>

Methyl 2-t- Butoxyethoxy-acetate  Produce

41.5 g (0.4708 mole) of MTBE solution was added to a 100 ml high-pressure reactor, 7.52 g (0.2350 mole) of MeOH solution was added, followed by 12 g (0.1175 mole) of para-dioxanone solution, and Rohm & Hass Amberlyst, an acid catalyst. 36 g 2 dry were added. It was stirred at 50 ° C. for 2 hours under 10 atmospheres of nitrogen. In this case, gas chromatography (GC) analysis showed that the conversion of para-dioxanone was 94.5%, the selectivity of methyl 2-hydroxyethoxy acetate was 45.5%, and methyl 2-t-butoxyethoxy-acetate. The selectivity of was 50.8%.

After 2 hours had elapsed, the reaction was stopped and the temperature was decreased to room temperature. Then, 13.19 g (0.2351 mole) of isobutylene was injected and stirred at 30 ° C. for 2 hours under nitrogen at 10 atmospheres. As a result of analysis through GC, the conversion of para-dioxanone was 97.7%, the selectivity of methyl 2-hydroxyethoxy acetate was 2.8%, and the selectivity of methyl 2-t-butoxyethoxy-acetate was 85.8. Appeared in%. After refine | purifying this, the analyzed NMR result is shown in FIG.

<Example 2>

Preparation of ethyl 2-t-butoxyethoxy-acetate

Into a 100 ml autoclave, 32.07 g (0.3139 mole) of ETBE solution was added, 7.22 g (0.1568 mole) of EtOH solution was added, followed by 8 g (0.0784 mole) of para-dioxanone solution, followed by Rohm & Hass as an acid catalyst. 2 g of Amberlyst 36dry was added. It was stirred at 50 ° C. for 2 hours under 10 atmospheres of nitrogen. As a result of analysis through GC, the conversion of para-dioxanone was 99.5%, the selectivity of ethyl 2-hydroxyethoxy acetate was 31.8%, and the selectivity of ethyl 2-t-butoxyethoxy-acetate was 63.3. Appeared in%.

After 2 hours had elapsed, the reaction was stopped and the temperature was lowered to room temperature. Then, 8.8 g (0.1568 mole) of isobutylene was injected and stirred at 30 ° C. for 10 hours under nitrogen at 10 atmospheres. As a result of analysis through GC, the conversion of para-dioxanone was 98.9%, the selectivity of ethyl 2-hydroxyethoxy acetate was 3.0%, and the selectivity of ethyl 2-t-butoxyethoxy-acetate was 90.3. Appeared in%. After refine | purifying this, the analyzed NMR result is shown in FIG.

<Example 3>

41.45 g (0.4702 mole) of MTBE solution was added to a 100 ml autoclave, 5.64 g (0.1763 mole) of MeOH solution was added, followed by 12 g (0.1175 mole) of para-dioxanone solution, followed by Rohm & Hass as an acid catalyst. 2 g of Amberlyst 36dry was added. It was stirred at 50 ° C. for 2 hours under 10 atmospheres of nitrogen. At this time, the total exchange rate of para-dioxanone was 96.9%, the selectivity of methyl 2-hydroxyethoxy acetate was 34.7%, the selectivity of methyl 2-t-butoxyethoxy-acetate was 59.5%.

<Example 4>

310.8 g (3.5258 mole) of MTBE solution was added to a 1 L high-pressure reactor, 37.6 g (1.1750 mole) of MeOH solution was added, 120 g (1.1754 mole) of para-dioxanone solution was added, and 20 g of Rohm & Hass Amberlyst 36dry was added. The reactor was fastened. After injection of 131.9 g (2.3507 mole) of isobutylene while the inside of the reactor was nitrogenized, the reaction was stirred at 50 ° C. for 2 hours at 10 atm. After the reaction, the conversion of para-dioxanone was 93.4%, the selectivity of methyl 2-t-butoxyethoxy-acetate was 84.5%.

Example 5

Methyl 2-t- Butoxyethoxy Acetate peeling effect

On the surface of the silicon wafer (Primer grade, Wafernet, Inc.), about 3 ml of the photoresist solution was evenly applied to the surface by spin method, and then baked at 150 ° C. for 90 seconds on a hot plate. After the baking process, the silicon wafer was cut into 5 mm x 5 mm width x length.

To put the methyl 2-t-butoxyethoxy-acetate compound into the sample bottle at about 20 ml, preheat the sample to 70 ° C. in a water bath, and compare the photoresist stripping effect of the compound. NMP (N-methylpyrrolidone) solution or BDG (2- (2-t-butoxyethoxy) ethanol) solution, which is currently used as a release agent, was preheated under the same conditions.

First, the wafer piece coated with the photoresist thin film is placed in a sample bottle containing an NMP solution or a BDG solution, and the peeling time is confirmed. Then, the wafer piece is placed in a sample bottle containing a methyl 2-t-butoxyethoxy-acetate compound. Was added, and the effect of peeling was confirmed by time. The degree of peeling of the photoresist film was confirmed by electron microscopy. As a result, the total time to completely peel off was 15 seconds in the NMP solution and 100 seconds in the BDG solution, respectively, whereas the methyl 2-t-butoxyethoxy-acetate compound was used. The total time taken to completely peel off the photoresist thin film was found to be 30 seconds. As a result, the novel substance methyl 2-t-butoxyethoxy-acetate compound of the present invention showed a superior peeling effect comparable to that of currently available photoresist strippers. In addition, since it does not contain N element, it is judged that the corrosion degree with respect to Cu and Al is weaker compared with the compound containing N element.

<Example 6>

The MTBEA prepared in Example 4 was distilled and purified, and thereto was slowly added an aqueous dimethylamine solution (50 wt% solution in water) at a room temperature of 1: 1.1 molar ratio, followed by reaction at 50 ° C. for 3 hours, where N, N-dimethyl 2-t-butoxyethoxy acetamide compound was prepared. After distillation and purification, the peeling ability of the photoresist was examined under the same conditions and method as in Example 5, and it took about 80 seconds for the thin film to be completely peeled off.

1 is NMR data of methyl 2-t-butoxyethoxy-acetate prepared according to Example 1. FIG.

2 is NMR data of ethyl 2-t-butoxyethoxy-acetate prepared according to Example 2. FIG.

Claims (15)

A compound of formula (I)

(I) [Wherein R 'is a methyl or ethyl group]. In the presence of an acid catalyst, para-dioxanone of formula (II)

(II) And a compound of formula (III)

(III) [Wherein R 'is a methyl or ethyl group], A method for preparing a compound of formula (I) according to claim 1, comprising the step of reacting. A process for preparing a compound of formula (I) according to claim 1 in the presence of an acid catalyst comprising the following steps: (1) in the presence of a compound of formula (III)

(III) [Wherein R 'is a methyl or ethyl group], Para-dioxanone of formula (II)

(II) Reacting with methanol or ethanol to obtain a mixture of a compound of formula (I) and a compound of formula (IV)

(IV) [Wherein R 'is a methyl or ethyl group]; (2) converting the hydroxy group of the compound of formula (IV) to isobutylene to convert the compound of formula (I) in the solution obtained in step (1). The process according to claim 2 or 3, wherein the molar ratio of the compound of formula (III) to para-dioxanone is 1 to 10. 4. A process according to claim 2 or 3, further comprising the step of feeding at least one compound selected from the group consisting of isobutylene, methanol and ethanol. The production method according to claim 5, wherein the molar ratio of methanol or ethanol to be supplied to para-dioxanone is 0.1 to 10. 6. The process according to claim 5, wherein the molar ratio of further isobutylene to para-dioxanone is from 0.1 to 10. 4. The process according to claim 2 or 3, wherein the acid catalyst is at least one acid catalyst selected from the group consisting of sulfuric acid, para toluene-sulfonic acid, heteropoly acid, strong acidic ion exchange resin into which sulfonic acid groups are introduced and zeolite. . The production method according to claim 8, wherein a strong acidic ion exchange resin catalyst having a sulfonic acid group introduced therein is used. The method of claim 8, wherein the heteropolyacid is PMo ₁₂ or PW ₁₂ or the zeolite is H-ZSM-5. The production method according to claim 2 or 3, wherein the reaction temperature is from room temperature to 100 ° C. The process according to claim 2 or 3, wherein the reaction pressure is from atmospheric pressure to 30 atmospheres. A release agent for peeling a photoresist film on the wafer surface in the manufacture of a semiconductor or LCD, comprising the compound according to claim 1. A solvent used in ink or paint, comprising the compound according to claim 1. A process for preparing an amide compound obtained by reacting a compound according to claim 1 with at least one compound selected from the group consisting of ammonia, monoalkylamines, dialkylamines, diamines, triamines and tetraamines.

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