KR101911131B1 - Method for the production process of methacryl acid ester - Google Patents

Method for the production process of methacryl acid ester Download PDF

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KR101911131B1
KR101911131B1 KR1020150069390A KR20150069390A KR101911131B1 KR 101911131 B1 KR101911131 B1 KR 101911131B1 KR 1020150069390 A KR1020150069390 A KR 1020150069390A KR 20150069390 A KR20150069390 A KR 20150069390A KR 101911131 B1 KR101911131 B1 KR 101911131B1
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alcohol
acid ester
methacrylic acid
buo
ester
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KR1020150069390A
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KR20160067017A (en
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공명진
남현
정소이
이경무
이원재
최용진
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주식회사 엘지화학
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention relates to a process for producing a methacrylic acid ester in which a methacrylic acid ester is produced by an ester exchange reaction while air-blowing an alkyl methacrylate ester and an alcohol under a catalyst represented by the following formula (1).
[Chemical Formula 1]
Ti (BuO) n (HQ) 4-n (n = 1, 2, 3)
The production method of the methacrylic acid ester of the present invention can prevent the formation of polymer in the production of the methacrylic acid ester and increase the yield without using a separate polymerization inhibitor.

Description

METHOD FOR THE PRODUCTION PROCESS OF METHACRYL ACID ESTER [0002]

The present invention relates to a methacrylic acid ester, and more particularly, to a method for producing methacrylic acid ester, which can dramatically increase the yield and conversion rate without using a polymerization inhibitor.

A method conventionally used for producing a methacrylic acid ester is a method in which an alcohol is added to an alkyl methacrylate ester as shown in Reaction Scheme 1 below, followed by addition of a polymerization inhibitor together with a catalyst.

[Reaction Scheme 1]

Figure 112015047651799-pat00001

In such a conventional production method, a polymerization inhibitor such as phenothiazine (PT), hydroquinone (HQ), mono-methyl ether hydroquinone (MEHQ) or the like is used to prevent polymerization between the formed methacrylic acid esters.

However, in accordance with the use of the polymerization inhibitor, there is a problem that impurities are generated and the yield and the conversion ratio are lowered. Therefore, there is a need to improve the yield and conversion ratio without using the polymerization inhibitor.

US 8067633

In order to solve the above problems of the prior art,

It is an object of the present invention to provide a process for producing a novel methacrylic acid ester which can prevent the polymerization reaction and improve the yield without using a separate polymerization inhibitor.

In order to achieve the above object,

The present invention provides a process for producing a methacrylic ester in which a methacrylic acid ester is produced by subjecting an alkyl methacrylate ester and an alcohol to an ester exchange reaction under a catalyst represented by the following general formula (1).

[Chemical Formula 1]

Ti (BuO) n (HQ) 4-n (n = 1, 2, 3)

(Wherein BuO represents butoxide anion and HQ represents hydroquinone).

According to the method for producing methacrylic acid ester of the present invention,

It is possible not only to prevent the polymerization reaction but also to prevent the formation of an insoluble solid due to the use of the polymerization inhibitor because the polymerization inhibitor is not used and the yield and conversion rate can be improved There is no addition step of the polymerization inhibitor, so that the manufacturing process is simpler than that of the prior art, thereby reducing the overall process time and process cost.

1 is a 13 C NMR graph showing the peak of HQ (hydroquinone).
Figure 2 is a 13 C NMR graph showing the peak of Titanium Buotoxide.
3 is a 13 C NMR graph showing the peak of butanol.
4 is a 13 C NMR graph showing the peaks of the catalyst compounds used in the examples of the present invention.

Hereinafter, a method for producing the methacrylic acid ester of the present invention will be described in detail.

The present invention is not limited to adding a polymerization inhibitor such as HQ (hydroquinone) to the reaction of an alkyl methacrylate ester and an alcohol separately from a catalyst as in the case of the conventional invention, but by adding a polymerization inhibitor To a methacrylic acid ester.

To this end, the methacrylic acid ester of the present invention is produced by reacting a mixture of an alkyl methacrylate ester and an alcohol under a catalyst represented by the following formula (1).

[Chemical Formula 1]

Ti (BuO) n (HQ) 4-n (n = 1, 2, 3)

(Wherein BuO represents butoxide anion and HQ represents hydroquinone).

The compound of Formula 1 is prepared by reacting Ti (BuO) 4 with HQ,

Can be prepared by a process comprising the following steps.

a) stirring Ti (BuO) 4 and HQ at room temperature for 0.5 to 24 hours;

b) stirring the mixture in the step a), adding 2 to 50 parts by weight of methylene chloride, and stirring the mixture for 30 minutes to 2 hours;

c) stirring the mixture in step b), adding acetone, stirring the mixture, and filtering the mixture; And

d) filtering, washing, and then drying in step c)

In the preparation step, Ti (BuO) 4 and HQ may be reacted at a molar ratio of 1: 0.1 to 1:20. If the reaction molar ratio of Ti (BuO) 4 and HQ is less than 1: 0.1, the yield is lowered. If the molar ratio is higher than 1:20, unreacted HQ is increased, which is not economical.

In the method for producing a methacrylic acid ester of the present invention, the alkyl methacrylic acid ester may be at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like And most preferably methyl methacrylate can be used.

In the method for producing a methacrylic acid ester of the present invention, the alcohol may be appropriately determined according to the objective methacrylic acid ester, but is preferably selected from methanol, ethanol, n-propanol, i-propanol, n-butanol, i Butanol, t-butanol, n-pentanol, t-amyl alcohol, n-hexanol, n-heptanol, n-octanol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,4-butanediol, 1,4-butanediol, 5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonene diol, 1,10-decane diol, 1,12-dodecane di Aliphatic saturated alcohols such as oligo, glycerol and the like; Aliphatic unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol, prenol, and isoprenol; Cyclohexane-1,4-dimethanol, norbornene-2-methanol, 5-norbornene-2-methanol, 1-adamantanol, 2-methyl- Aliphatic cyclic alcohols such as ethanol; Functional alcohols such as glycidol, isopropylidene glycerol, and glycerin carbonate; Phenols such as phenol and 2-phenylphenol; And allyl group-containing alcohols such as benzyl alcohol, 1-phenylethyl alcohol and 2-phenylethyl alcohol, and most preferably n-butanol can be used.

In addition, the methacrylic acid ester of the present invention may preferably be subjected to air blowing during the reaction of the alkyl methacrylate ester and the alcohol. Oxygen in the air reacts with HQ to generate radicals. The radicals thus generated react with radicals present in the reactor to form stable compounds, thereby preventing the subsequent reaction from proceeding.

In the method for producing a methacrylic acid ester of the present invention, the molar ratio of the alkyl methacrylate ester to the alcohol is preferably 1: 1 to 5: 1. If the molar ratio of the alkyl methacrylate ester to the alcohol is less than 1: 1, the yield decreases. If the molar ratio exceeds 5: 1, unreacted alkyl methacrylate esters increase, resulting in poor economical efficiency.

In the method for producing a methacrylic acid ester of the present invention, the reaction temperature of the alkyl methacrylate ester and the alcohol is preferably 80 to 150 ° C. If the reaction temperature of the alkyl methacrylic acid ester and the alcohol is lower than 80 ° C, the yield decreases. If the reaction temperature exceeds 150 ° C, the risk of polymer formation increases and the conversion rate to the vaporization of unreacted materials decreases.

The yield of methacrylic acid ester prepared by the production method of the present invention is 65% or more.

In the process for producing a methacrylic acid ester of the present invention, the alkyl methacrylate ester and the alcohol can be used without any particular limitation, and those having a purity of 60 to 99.5% can be used.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

Example

Preparation of Catalyst Compounds

[Synthesis Example 1]

After 1.5 g of Ti (BuO) 4 and 0.5 g of HQ (hydroquinone) were stirred at room temperature for 15 hours, 20 g of methylene chloride was added and the mixture was stirred for 1 hour. After that, acetone was added, and the mixture was stirred for 3 hours, filtered, washed again with acetone, and dried in a vacuum oven at 100 ° C for 15 hours to prepare a titanium compound.

Preparation of methacrylic acid ester

[Example 1]

2000 ppm of the titanium compound prepared in Synthesis Example 1 was added as a catalyst to prepare a mixed solution of methyl methacrylate and n-butanol in a ratio of 1.5: 1, followed by air blowing at 115 ° C for 1 hour To prepare a methacrylic acid ester.

[Example 2]

butyric acid was used in place of n-butanol, methacrylic acid ester was prepared.

[Example 3]

A methacrylic acid ester was prepared by reacting in the same manner as in Example 1 except that methacrylic acid was used instead of methylmethacrylate.

[Comparative Example 1]

2000 ppm of Ti (BuO) 4 as a catalyst, 10,000 ppm of HQ (Hydroquinone) as a polymerization inhibitor, and a mixed solution of methyl methacrylate and n-butanol in a ratio of 1.5: (Air blowing) for 1 hour to prepare a methacrylic acid ester.

[Comparative Example 2]

The reaction was carried out in the same manner as in Example 1 except that the reaction was carried out without air blowing, thereby preparing a methacrylic acid ester.

[Comparative Example 3]

1000 ppm of Ti (BuO) 4 was added as a catalyst, 1,000 ppm of HQ (Hydroquinone) was added as a polymerization inhibitor, and a mixed solution of methyl methacrylate and n-butanol in a ratio of 1.5: (Air blowing), and reacted for 1 hour to prepare a methacrylic acid ester.

[Comparative Example 4]

Methyl methacrylate and n-butanol in a ratio of 0.5: 1 was used in place of the methacrylic acid ester.

[Comparative Example 5]

Methyl methacrylate and n-butanol in a ratio of 7.0: 1 was used in place of the methacrylic acid ester.

[Comparative Example 6]

Methacrylic acid ester was prepared by reacting a mixture of methyl methacrylate and n-butanol in the same manner as in Example 1, except that the mixture was reacted at 70 ° C with air blowing.

[Comparative Example 7]

Methacrylic acid ester was prepared by reacting a mixture of methyl methacrylate and n-butanol in the same manner as in Example 1, except that the mixture was reacted while air-blowing at 180 ° C.

Experimental Example  One

In order to examine the structure of the prepared titanium compound, 13 C NMR peak of each compound was confirmed using the following spectrometer.

Varian 400 MHz SSNMR / 4 mm MAS probe

- 13 C MAS NMR (Static)

- 13 C MAS NMR (Spinning rate = 10 kHz)

First, 13 C NMR peaks for HQ (hydroquinone) were found at 115.29 (ppm), 121.40 (ppm) and 153.23 (ppm), and a 13 C NMR graph thereof was shown in Fig.

13 C NMR peaks for titanium butoxide (Titanium Buotoxide) has, 18.65 (ppm), 23.96 ( ppm), 40.49 (ppm), were found at 79.36 (ppm), also indicated in the 2 to 13 C NMR graph for this .

13 C NMR peaks for butanol were found at 18.65 (ppm), 23.60 (ppm), 39.36 (ppm) and 66.02 (ppm), and a 13 C NMR graph thereof was shown in Fig.

Finally the titanium compound peaks, 82.52 (ppm), 115.28 ( ppm), 120.91 (ppm), 153.71 (ppm), were found in 164.89 (ppm), it shows a 13 C NMR graph for it in Fig.

1 to 4, it was confirmed that the titanium compound prepared in the examples was Ti (BuO) 3 (HQ).

Experimental Example  2

The methacrylic acid esters prepared in Examples 1 to 3 and Comparative Examples 1 to 7 were immersed in MeOH and quantified using gas chromatography (GC 6890N, agilent) to determine the conversion of BuOH and the yield of methacrylic acid ester And the formation of polymer was visually confirmed.

Alcohol Conversion Rate (%) yield(%) Whether polymers are produced Example 1 75.92 71.03 Not created Example 2 76.21 68.99 Not created Example 3 98.12 92.11 Not created Comparative Example 1 61.60 57.92 Created Comparative Example 2 61.04 20.33 Created Comparative Example 3 68.62 60.77 Created Comparative Example 4 38.58 37.44 Not created Comparative Example 5 76.77 52.10 Created Comparative Example 6 20.62 18.88 Not created Comparative Example 7 40.15 19.11 Created

As shown in Table 1, the yield of the Example 1 prepared by the methacrylic acid ester producing method of the present invention was 71.03%, which was higher than that of the conventional method by more than 10% Did not appear. In addition, the yield of the Example 2 using the but-butanol and the methacrylic acid was also as high as 10-30%, and no polymer was produced. On the other hand, in Comparative Examples 1 to 3, 5 and 7, the production of polymer was observed, and the effect of preventing polymerization was not sufficient. Therefore, it was confirmed that the methacrylic acid ester production methods according to Examples 1 to 3 can improve the yield while showing the polymerization inhibiting effect, as compared with the case of using the conventional polymerization inhibitor.

Claims (10)

Under the presence of a catalyst represented by the following general formula (1), an alkylmethacrylate ester and an alcohol are subjected to ester exchange reaction by air blowing to produce methacrylic acid ester,
Wherein the reaction molar ratio of the alkyl methacrylate ester to the alcohol is from 1: 1 to 5: 1,
Wherein the reaction temperature of the alkyl methacrylate ester with the alcohol is 80 to 150 ° C.
[Chemical Formula 1]
Ti (BuO) n (HQ) 4-n (n = 1, 2, 3)
(Wherein BuO represents a butoxide anion, and HQ represents hydroquinone). The method according to claim 1,
Wherein the compound of Formula 1 is prepared by reacting Ti (BuO) 4 with HQ. The method of claim 2,
Wherein the compound of Formula 1 is prepared by a process comprising the steps of:
a) stirring Ti (BuO) 4 and HQ at room temperature for 0.5 to 24 hours;
b) adding 2 to 50 parts by weight of methylene chloride to 1 part by weight of the mixture of Ti (BuO) 4 and HQ, followed by stirring for 30 minutes to 2 hours;
c) stirring the mixture in step b), adding acetone, stirring the mixture, and filtering the mixture; And
d) filtering, washing, and then drying in step c) The method of claim 2,
And reacting the Ti (BuO) 4 with HQ in a molar ratio of 1: 0.1 to 1:20. delete delete The method according to claim 1,
Wherein the yield of the methacrylic acid ester is 65% or more. The method according to claim 1,
Wherein the alkyl methacrylate ester is at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. The method according to claim 1,
The alcohol may be at least one selected from the group consisting of methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, N-decanol, n-undecanol, n-dodecanol, lauryl alcohol, stearyl alcohol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, Indole, 1,10-decane diol, 1,12-dodecane diol, glycerol, allyl alcohol, 1,1-dimethylallyl alcohol, prenol, isoprenol, cyclohexanol, methyl Cyclohexane-1,4-dimethanol, norbornene-2-methanol, 5-norbornene-2-methanol, 1-adamantanol, 2- , Isopropylidene glycerol, glycerin carbonate, phenol, 2-phenylphenol, benzyl alcohol, 1-phenylethyl alcohol and 2- One method of producing a methacrylic acid ester, characterized in that at least selected from the group consisting of carbonyl ethyl alcohol. The method of claim 9,
Wherein the alcohol is n-butanol.
KR1020150069390A 2014-12-03 2015-05-19 Method for the production process of methacryl acid ester KR101911131B1 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014043414A (en) * 2012-08-27 2014-03-13 Osaka Organic Chem Ind Ltd Method for producing (meth)acrylate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3686268A (en) * 1970-02-24 1972-08-22 Ugine Kuhlmann Process of manufacture of acrylic and methacrylic higher esters
FR2184545B1 (en) * 1972-05-17 1980-03-14 Rhone Poulenc Ind
DE10026644A1 (en) * 2000-05-29 2001-12-06 Basf Ag Process for the preparation of esters of unsaturated carboxylic acids
FR2909377A1 (en) 2006-12-05 2008-06-06 Arkema France Synthesis of (meth)acrylic ester, useful to prepare e.g. acrylate of dimethylaminoethyl, comprises reacting alkyl (meth)acrylate with alcohol, in the presence of transesterification catalyst and at least a polymerization inhibitor
CN104540837A (en) * 2012-06-28 2015-04-22 沙特基础工业公司 Novel titanium catalyst end process for the preparation thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014043414A (en) * 2012-08-27 2014-03-13 Osaka Organic Chem Ind Ltd Method for producing (meth)acrylate

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