KR101727332B1 - Method for producing hydroxyalkyl(meth)acrylic acid ester - Google Patents
Method for producing hydroxyalkyl(meth)acrylic acid ester Download PDFInfo
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Abstract
번잡한 정제 공정을 필요로 하지 않고 효율적으로 히드록시알킬(메타)아크릴산 에스테르를 제조할 수 있는 제조 방법을 제공한다. 비닐에테르 함유 알코올을 에스테르 교환법에 의해 (메타)아크릴화하여 비닐에테르 함유 (메타)아크릴산 에스테르로 한 후, 산촉매 존재 하, 탈비닐화 반응을 실시할 때에, 물을 공존시키는 것을 특징으로 하는, 히드록시알킬(메타)아크릴산 에스테르의 제조 방법이다.(Meth) acrylic acid ester can be efficiently produced without requiring a complicated purification step. A process for producing a vinyl ether-containing (meth) acrylic acid ester, which comprises reacting a vinyl ether-containing alcohol with a vinyl ether-containing (meth) acrylic acid ester- (Meth) acrylic acid ester.
Description
본 발명은, 비닐에테르 함유 알코올을 이용하는 히드록시알킬(메타)아크릴산 에스테르의 제조 방법에 관한 것이다.The present invention relates to a process for producing a hydroxyalkyl (meth) acrylic acid ester using a vinyl ether-containing alcohol.
히드록시알킬(메타)아크릴산 에스테르의 제조 방법으로서 일반적으로는 알칸디올로부터 에스테르화 반응에 의해 디올, 모노에스테르, 디에스테르 혼합체를 얻은 후, 모노에스테르체만을 추출 분리하는 방법이 주류이다. 구체적으로는, 아크릴산과 알칸디올을 강산 존재 하에서 반응시키는 방법(예를 들어, 특허문헌 1 참조)이 보고되고 있지만, 강산에 의한 부생성물이 생성되고, 수율이 저하하는 등의 불리한 점을 가지고 있다. 이 문제를 해결하는 방법으로서, 알칸디올과 (메타)아크릴산 에스테르와의 에스테르 교환 반응에 관하여 여러 가지의 보고가 있다(예를 들어, 특허문헌 2~4 참조). 또한, 4-히드록시부틸(메타)아크릴레이트에 관하여, 효율적으로 추출 및 정제하는 방법(예를 들어, 특허문헌 5~6 참조) 등도 보고되고 있다. 그러나, 알칸디올로부터의 에스테르 교환법에서는, 얻어지는 생성물이 혼합물이기 때문에, 모노에스테르만을 분리하는데 과잉의 추출 용제가 필요하여, 효율적이지 않다.As a method for producing a hydroxyalkyl (meth) acrylic acid ester, a method is generally used in which a diol, a monoester and a diester mixture are obtained from an alkane diol by an esterification reaction, and then a monoester is extracted and separated. Specifically, a method of reacting acrylic acid with an alkane diol in the presence of a strong acid (see, for example, Patent Document 1) has been reported, but it has disadvantages such as generation of by-products from strong acids and reduction in yield. As a method for solving this problem, there have been various reports on the transesterification reaction between an alkanediol and a (meth) acrylic acid ester (see, for example, Patent Documents 2 to 4). Also, methods for efficiently extracting and purifying 4-hydroxybutyl (meth) acrylate (see, for example, Patent Documents 5 to 6) have also been reported. However, in the ester exchange method from the alkane diol, since the obtained product is a mixture, an excessive extraction solvent is required to separate only the monoester, which is not efficient.
히드록시알킬(메타)아크릴산 에스테르를 2단계로 얻는 방법으로서는, 비닐에테르 함유 알코올을 에스테르 교환한 후, 산촉매와 알코올 존재 하에 탈비닐화하는 방법이 보고되고 있다(예를 들어, 특허문헌 7 참조). 그러나, 이 방법에서는 탈비닐화 반응 시에 아세탈 화합물이 생성되기 때문에 아세탈 화합물을 제거할 필요가 있지만, 반응 중의 아세탈 화합물을 제거하는 작업을 하는 것이 용이하지 않다. 또한, 이 반응 시에 과잉으로 이용한 알코올은 수세 제거에 의해 폐기하지 않으면 안되어, 효율이지 않다.As a method for obtaining a hydroxyalkyl (meth) acrylic acid ester in two steps, there has been reported a method in which a vinyl ether-containing alcohol is ester-exchanged and then debenzylated in the presence of an acid catalyst and an alcohol (see, for example, Patent Document 7). However, in this method, since the acetal compound is produced during the de-vinylation reaction, it is necessary to remove the acetal compound, but it is not easy to work to remove the acetal compound in the reaction. In addition, the alcohol used excessively in this reaction must be discarded by washing with water, which is not efficient.
특허문헌 1: 독일 특허 제 15118572호 공보Patent Document 1: German Patent No. 15118572
특허문헌 2: 일본국 특허공개공보 평10-298143호Patent Document 2: JP-A-10-298143
특허문헌 3: 일본국 특허공개공보 평11-43466호Patent Document 3: Japanese Patent Application Laid-Open No. 11-43466
특허문헌 4: 일본국 특허공개공보 2000-159727호Patent Document 4: Japanese Patent Application Laid-Open No. 2000-159727
특허문헌 5: 일본국 특허공개공보 평8-53392호Patent Document 5: JP-A-8-53392
특허문헌 6: 일본국 특허공개공보 2005-194201호Patent Document 6: JP-A-2005-194201
특허문헌 7: 일본국 특허공개공보 평10-182555호Patent Document 7: JP-A-10-182555
본 발명은, 번잡한 정제 공정을 필요로 하지 않으며, 효율적으로 히드록시알킬(메타)아크릴산 에스테르를 제조할 수 있는 제조 방법을 제공하는 것을 과제로 한다.It is an object of the present invention to provide a production method capable of efficiently producing a hydroxyalkyl (meth) acrylic acid ester without requiring a complicated purification step.
본 발명자들은 여러가지로 검토한 결과, 비닐에테르 함유 알코올을 (메타)아크릴화하여 비닐에테르 함유 (메타)아크릴산 에스테르로 한 후, 산촉매 존재하, 물을 공존시키는 것에 의한 탈비닐화법에 의해, 고순도의 히드록시알킬(메타)아크릴산 에스테르를 고수율로 얻을 수 있으며, 또한 탈비닐화 후에 분리 회수되는 수층은, 재이용 가능하다는 것을 발견하였다.As a result of various investigations, the inventors of the present invention have found that a vinyl ether-containing (meth) acrylic ester is obtained by (meth) acrylating a vinyl ether-containing alcohol and then subjecting the vinyl ether- It has been found that an alkyl (meth) acrylic acid ester can be obtained in high yield, and that the water layer, which is separated and recovered after deprivinylation, is reusable.
즉, 본 발명은 이하와 같다.That is, the present invention is as follows.
(1) 비닐에테르 함유 알코올을 에스테르 교환법에 의해 (메타)아크릴화하여 비닐에테르 함유 (메타)아크릴산 에스테르로 한 후, 산촉매 존재 하, 탈비닐화 반응을 실시할 때에, 물을 공존시키는 것을 특징으로 하는, 히드록시알킬(메타)아크릴산 에스테르의 제조 방법.(1) A process for producing a vinyl ether-containing (meth) acrylic ester by (meth) acrylating a vinyl ether-containing alcohol with an ester exchange method to give a vinyl ether- (Meth) acrylic acid ester.
(2) 탈비닐화 반응 시의 반응 온도가 60℃ 이하인, 상기 (1)에 기재된 히드록시알킬(메타)아크릴산 에스테르의 제조 방법.(2) The process for producing a hydroxyalkyl (meth) acrylic acid ester according to the above (1), wherein the reaction temperature during the de-vinylation reaction is 60 占 폚 or lower.
(3) 비닐에테르 함유 알코올이 하기 일반식 (I) 또는 (II)로 표시되는, 상기 (1) 또는 (2)에 기재된 히드록시알킬(메타)아크릴산 에스테르의 제조 방법.(3) The process for producing a hydroxyalkyl (meth) acrylic acid ester according to (1) or (2), wherein the vinyl ether-containing alcohol is represented by the following general formula (I) or (II)
[화학식 1][Chemical Formula 1]
(일반식 (I) 중, n는 3~11의 정수를 나타낸다.)(In the general formula (I), n represents an integer of 3 to 11.)
[화학식 2](2)
(일반식 (II) 중, A는 시클로펜틸렌기 또는 시클로헥실렌기를 나타낸다.)(In the general formula (II), A represents a cyclopentylene group or a cyclohexylene group.)
본 출원은, 동출원인에 의해 먼저 출원된 일본특허출원, 즉, 특원2008-306256(출원일 2008년 12월 1일)에 근거하는 우선권 주장을 수반하는 것으로서, 이들 명세서를 참조를 위해 여기에 포함시키기로 한다.This application is a continuation-in-part of US patent application Ser. No. 08 / 292,754, filed on Dec. 1, 2008, which is hereby incorporated by reference in its entirety for all purposes. do.
본 발명에 의하면, 증류 등의 번잡한 정제 공정을 거치는 일 없이 효율적으로 히드록시알킬(메타)아크릴산 에스테르를 얻을 수 있으며, 또한, 탈비닐화 공정에서 사용하는 물을 재이용할 수 있기 때문에, 공정이 짧고 또한 경제적인 히드록시알킬(메타)아크릴산 에스테르의 제조 방법을 제공할 수 있다.According to the present invention, hydroxyalkyl (meth) acrylic acid ester can be efficiently obtained without complicated purification steps such as distillation, and water used in the debinylation step can be reused, so that the process is short It is also possible to provide a process for producing economical hydroxyalkyl (meth) acrylic acid esters.
본 발명의 히드록시알킬(메타)아크릴산 에스테르의 제조 방법의 실시의 형태에 관하여 상세하게 설명한다.[0033] The embodiment of the process for producing the hydroxyalkyl (meth) acrylic acid ester of the present invention will be described in detail.
본 발명의 히드록시알킬(메타)아크릴산 에스테르의 제조 방법은, 비닐에테르 함유 알코올을 에스테르 교환법에 의해 (메타) 아크릴화하여 비닐에테르 함유 (메타)아크릴산 에스테르로 한 후, 산촉매 존재 하, 탈비닐화 반응을 실시할 때에, 물을 공존시키는 것을 특징으로 한다.The process for producing the hydroxyalkyl (meth) acrylic acid ester of the present invention is a process for producing a vinyl ether-containing (meth) acrylic acid ester by subjecting a vinyl ether-containing alcohol to a (meta) acrylic ester by a transesterification method, And water is caused to coexist when it is carried out.
본 발명에서는 우선, 비닐에테르 함유 알코올의 수산기를 에스테르화하여, 비닐에테르 함유 (메타)아크릴산 에스테르를 얻는다. 에스테르화의 방법으로서는 주로, (메타)아크릴산을 사용하는 탈수 에스테르화법, 저급 (메타)아크릴산 에스테르를 사용하는 에스테르 교환법, (메타)아크릴산 클로라이드를 사용하는 산할로겐법을 들 수 있는데, 이 중, 탈수 에스테르화법에서는 산촉매를 사용하기 때문에, 탈비닐화가 동시에 일어나므로 적용할 수 없다. 또한, 산할로겐법은 반응에 의해 할로겐이 이탈하여 계(系) 내에 잔존하기 때문에, 수세, 흡착 또는 증류 등의 정제 처리가 필요하다. 한편, 에스테르 교환법은 불순물이 적고 정제 작업도 필요없다는 점에서, 본 발명에서는 에스테르 교환법을 채용하고 있다.In the present invention, first, the hydroxyl group of the vinyl ether-containing alcohol is esterified to obtain a vinyl ether-containing (meth) acrylic acid ester. Examples of the esterification method include a dehydration esterification method using (meth) acrylic acid, an ester exchange method using a lower (meth) acrylic acid ester, and an acid halogen method using (meth) acrylic acid chloride. In the esterification method, since an acid catalyst is used, devinylation can occur at the same time and therefore it can not be applied. Further, the acid halogen method requires purification treatment such as washing with water, adsorption or distillation because the halogen is released and remains in the system through the reaction. On the other hand, the ester exchange method employs the ester exchange method in the present invention in that impurities are small and a purification operation is not necessary.
본 발명에서 사용하는 비닐에테르 함유 알코올로서는, 예를 들어, 4-히드록시부틸비닐에테르, 6-히드록시헥실비닐에테르, 9-히드록시노닐비닐에테르, 10-히드록시데카닐비닐에테르, 12-히드록시도데실비닐에테르 등의 하기 일반식 (I)로 표시되는 화합물; 시크로헥산디메탄올모노비닐에테르 등의 하기 일반식 (II)로 표시되는 화합물; 페닐디메탄올모노비닐에테르 등을 들 수 있다.Examples of the vinyl ether-containing alcohol used in the present invention include 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, 9-hydroxynonyl vinyl ether, 10-hydroxydecanyl vinyl ether, A compound represented by the following general formula (I) such as hydroxydodecyl vinyl ether; A compound represented by the following general formula (II) such as cyclohexanedimethanol monovinyl ether; Phenyldimethanol monovinyl ether, and the like.
[화학식 3](3)
(일반식 (I) 중, n는 3~11의 정수를 나타낸다.)(In the general formula (I), n represents an integer of 3 to 11.)
[화학식 4][Chemical Formula 4]
(일반식 (II) 중, A는 시클로펜틸렌기 또는 시클로헥실렌기를 나타낸다.)(In the general formula (II), A represents a cyclopentylene group or a cyclohexylene group.)
에스테르 교환법에 사용하는 저급 (메타)아크릴산 에스테르로서 구체적으로는, (메타)아크릴산메틸, (메타)아크릴산에틸, (메타)아크릴산프로필, (메타)아크릴산부틸 등을 들 수 있다. 즉, 본원에서 말하는 저급 (메타)아크릴산 에스테르란, 에스테르 치환기로서 탄소수가 4 이하의 알킬기를 갖는 것을 말한다.Specific examples of the lower (meth) acrylic acid ester used in the ester exchange method include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate. That is, as used herein, the lower (meth) acrylic acid ester refers to an ester substituent having an alkyl group having 4 or less carbon atoms.
에스테르 교환 반응 시에는, 단시간 반응, 고에스테르 전환율, 반응 후의 후처리의 관점에서, 저급 (메타)아크릴산 에스테르를 비닐에테르 함유 알콜화합물에 대해서, 등량부터 과잉으로 사용하는 것이 바람직하다. 구체적으로는, 통상 비닐에테르 함유 알콜화합물이 갖는 수산기 1몰에 대해서, 저급 (메타)아크릴산 에스테르를 1.0~20몰의 범위에서 사용하는 것이 바람직하다. 저급 (메타)아크릴산 에스테르의 사용량이 비닐에테르 함유 알콜화합물의 수산기 1몰에 대해서, 1.0몰 미만이면 반응이 충분히 진행하지 않고, 또한 20몰을 넘으면 반응 후의 농축 공정에 장시간을 필요로 하여 생산성이 악화된다.From the viewpoint of short-time reaction, high ester conversion, and post-treatment after the reaction, it is preferable to use the lower (meth) acrylic acid ester in excess from the same amount with respect to the vinyl ether-containing alcohol compound. Concretely, it is preferable to use a lower (meth) acrylic acid ester in an amount of 1.0 to 20 moles per mole of the hydroxyl group of the vinyl ether-containing alcohol compound. When the amount of the lower (meth) acrylic acid ester used is less than 1.0 mol based on 1 mol of the hydroxyl group of the vinyl ether-containing alcohol compound, the reaction does not proceed sufficiently. When the amount is more than 20 mol, a long time is required for the concentration step after the reaction, do.
에스테르 교환법에 사용되는 촉매로서는, 수산화리튬, 수산화나트륨, 수산화칼륨 등의 알칼리 금속 수산화물; 탄산리튬, 탄산나트륨, 탄산칼륨 등의 알칼리 금속 탄산 화물; 리튬메톡시드, 나트륨메톡시드, 나트리움에톡시드, 칼륨t-부톡시드등의 알칼리 금속 알콕시드; 리튬아미드, 나트륨아미드, 칼륨아미드 등의 알칼리 금속 아미드; 오르토티탄산테트라메틸, 오르토티탄산테트라에틸, 오르토티탄산테트라프로필, 오르토티탄산테트라이소프로필, 오르토티탄산테트라 부틸 등의 티탄알콕시드; 그 외 알루미늄알콕시드; 주석알콕시드; 등을 들 수 있다. 이 중 부반응이 극력 억제되고, 반응 종료 후에 물을 첨가함으로써 용이하게 촉매 제거할 수 있다는 점에서, 티탄알콕시드 또는 알루미늄알콕시드가 보다 바람직하다.Examples of the catalyst used in the ester exchange method include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; Alkali metal alkoxides such as lithium methoxide, sodium methoxide, sodium triethoxide, potassium t-butoxide and the like; Alkali metal amides such as lithium amide, sodium amide and potassium amide; Titanium alkoxides such as tetramethyl ortho titanate, tetraethyl ortho titanate, tetra propyl ortho titanate, tetraisopropyl ortho titanate, and tetrabutyl ortho titanate; Other aluminum alkoxide; Tin alkoxide; And the like. A titanium alkoxide or an aluminum alkoxide is more preferable in that the side reaction is suppressed to the utmost and the catalyst can be easily removed by adding water after completion of the reaction.
또한, 촉매의 사용량은, 저급 (메타)아크릴산 에스테르와 비닐에테르 함유 알콜화합물의 합계량에 대해서, 통상 0.01~5.0중량%의 범위가 바람직하다. 촉매량이 필요 이상으로 많아져도 반응속도에는 거의 영향이 없고, 반대로 촉매 제거 시에 대량의 물이 필요하게 되는 등, 비경제적으로 될 뿐이다.The amount of the catalyst to be used is preferably in the range of usually 0.01 to 5.0% by weight based on the total amount of the lower (meth) acrylic acid ester and the vinyl ether-containing alcohol compound. Even if the amount of the catalyst is increased more than necessary, there is almost no influence on the reaction rate, and on the contrary, a large amount of water is required in removing the catalyst.
본 발명에 있어서의 에스테르 교환 반응에 있어서, 공지의 중합 금지제를 첨가, 병용할 수 있다. 중합 금지제로서는, 예를 들어, 하이드로퀴논, 하이드로퀴논모노메틸에테르(「메토퀴논」이라고도 한다) 등의 페놀류; 페노치아딘, 에틸렌티오요소 등의 유황 화합물; 디부틸디티오카르바민산동 등의 동염; 아세트산망간 등의 망간염; 니트로 화합물, 니트로소 화합물, 4-히드록시-2,2,6,6-테트라메틸피페리디노옥실 등의 N-옥실 화합물; 등을 들 수 있다. 중합 금지제의 첨가량은, 생성 에스테르에 대해서 0.1중량% 이하가 바람직하다. 0.1중량%를 넘으면 첨가제에 기인하는 착색이 생기는 경우가 있다.In the transesterification reaction in the present invention, a known polymerization inhibitor may be added and used in combination. Examples of the polymerization inhibitor include phenols such as hydroquinone and hydroquinone monomethyl ether (also referred to as " methoquinone "); Sulfur compounds such as phenothiazine, ethylene thiourea and the like; Copper salts such as dibutyldithiocarbamate and the like; Manganese salts such as manganese acetate; N-oxyl compounds such as nitro compounds, nitroso compounds, and 4-hydroxy-2,2,6,6-tetramethylpiperidinoxyl; And the like. The addition amount of the polymerization inhibitor is preferably 0.1% by weight or less with respect to the produced ester. When the amount exceeds 0.1% by weight, coloring due to the additive may occur.
에스테르 교환 반응 시에는, 반응 중의 반응액의 중합을 방지하기 위해서 소량의 분자상(分子狀) 산소를 불어 넣는 것이 바람직하다. 분자상 산소로서는, 희석된 상태로 사용하는 것이 바람직하고, 공기를 이용하는 것이 적합하다. 또한, 분자상 산소의 불어 넣기는, 증발하여 증기로서 존재하거나 상부의 가마 벽면 등에 응축한 (메타)아크릴산 에스테르류의 중합을 방지하거나 하기 위해서도 바람직하다.In the transesterification reaction, it is preferable to breathe a small amount of molecular oxygen to prevent polymerization of the reaction solution during the reaction. The molecular oxygen is preferably used in a diluted state, and air is preferably used. In addition, the blowing of molecular oxygen is also preferable in order to prevent polymerization of (meth) acrylic acid esters which are evaporated and are present as a vapor or condensed on a wall surface of the upper furnace or the like.
분자상 산소란, 2개의 산소 원자에 의해서 만들어진 기저 상태의 삼중항산소 분자(02)를 의미하며, 반응에 그대로의 상태로 직접 관여도 할 수 있지만, 촉매나 반응시제(反應試劑)와의 상호작용에 의해, 일중항산소 분자나 산소 원자, 슈퍼옥시드, 페르옥시드 등의 상태로 변환된 후, 반응에 관여할 수도 있는 산소 분자를 의미한다. 분자상 산소의 도입량으로서는, 반응기의 형상이나 교반동력에 의해서도 영향을 받지만, 원료 비닐에테르 함유 알코올 1몰에 대해서 5~500ml/분(공기로서 25~2500ml/분)의 속도로 불어 넣으면 된다. 분자상 산소 도입량이 5ml/분 미만의 경우는, 중합 금지의 효과가 충분하지 않고, 500ml/분을 넘으면, 저급 (메타)아크릴산 에스테르를 계 밖으로 밀어 내 버리는 효과가 강해져, 원료로서의 저급 (메타) 아크릴산 에스테르의 손실(loss)을 초래한다.Molecular oxygen means a ground state triplet oxygen molecule (0 2 ) made by two oxygen atoms, and can be directly involved in the reaction, but it can interact directly with the catalyst or the reaction reagent Refers to an oxygen molecule that may be involved in the reaction after being converted into a state of singlet oxygen, an oxygen atom, a superoxide, a peroxide, and the like. The amount of molecular oxygen to be introduced is influenced by the shape of the reactor and the agitating power, but it may be blown at a rate of 5 to 500 ml / min (25 to 2500 ml / min as air) per mole of the raw vinyl ether-containing alcohol. When the amount of molecular oxygen introduced is less than 5 ml / min, the effect of inhibiting polymerization is not sufficient. When the amount of molecular oxygen introduced is more than 500 ml / min, the effect of pushing off the lower (meth) Resulting in loss of acrylic acid ester.
본 발명에 있어서의 에스테르 교환 반응은, 상압 또는 감압 하 60~120℃에서 실시하는 것이 바람직하다. 온도가 60℃ 미만이면 반응속도가 극단적으로 반응이 늦어지고, 또한 120℃를 넘으면, 에스테르 교환 반응에서 얻어지는 비닐에테르 함유 (메타)아크릴산 에스테르의 중합이 일어나기 쉬우며, 또한 착색을 일으키기 쉽다.The transesterification reaction in the present invention is preferably carried out at 60 to 120 ° C under atmospheric pressure or reduced pressure. If the temperature is less than 60 ° C, the reaction rate becomes extremely slow, and if it exceeds 120 ° C, the polymerization of the vinyl ether-containing (meth) acrylic acid ester obtained in the transesterification reaction tends to occur and tends to cause coloring.
에스테르 교환 반응의 형태로서는, (메타)아크릴산 에스테르를 제조하는 당업자 사이에 일반적으로 알려진 방법으로 실시할 수 있다. 에스테르 교환 반응 시에는, 부생하는 저급 알코올을 저급 (메타)아크릴산 에스테르 및/또는 용매로 공비 증류 제거하는 것이 필요하다. 이 때문에, 반응 장치로서는 예를 들어 정류탑 부속 회분식 반응조가 사용된다.The transesterification reaction can be carried out in a manner generally known to those skilled in the art of producing (meth) acrylic acid esters. In the ester exchange reaction, it is necessary to azeotropically remove the by-produced lower alcohol with a lower (meth) acrylic acid ester and / or a solvent. For this reason, as the reaction apparatus, for example, a batch type reaction vessel with a rectification column attached thereto is used.
에스테르 교환 반응 종료 후는, 촉매를 물에 의해 실활시켜, 과잉의 저비성분을 농축 장치로 증류 제거한다. 저비성분의 농축 장치에 의한 증류 제거는, 상압 또는 감압 하, 액체의 온도를 90℃ 이하로 유지하면서 실시하는 것이 바람직하고, 보다 바람직하게는 50~70℃의 범위 내이다. 액체의 온도가 90℃를 넘으면 비닐에테르 함유 (메타)아크릴산 에스테르의 착색이나 중합을 일으킬 가능성이 높아진다.After completion of the ester exchange reaction, the catalyst is deactivated by water, and the excess low-boiling component is distilled off with a concentrating apparatus. The distillation by a low-boiling-point concentrating apparatus is preferably carried out under normal pressure or reduced pressure while maintaining the temperature of the liquid at 90 占 폚 or lower, more preferably in the range of 50 to 70 占 폚. When the temperature of the liquid exceeds 90 캜, the possibility of causing coloring or polymerization of the vinyl ether-containing (meth) acrylic acid ester increases.
저비성분의 증류 제거가 완료된 비닐에테르 함유 (메타)아크릴산 에스테르는, 여과를 실시함으로써 잔존하는 실활촉매 등의 불용분을 없앨 수 있다. 여과 시에는 효율 좋게 불용분을 없애기 위해서, 규조토 등의 여과조제를 이용하는 것이 바람직하다.The vinyl ether-containing (meth) acrylic acid ester in which the low-boiling component has been removed by distillation can be filtered to eliminate insoluble components such as remaining inactivated catalysts. In filtering, it is preferable to use a filter aid such as diatomaceous earth in order to efficiently remove insolubles.
계속해서, 비닐에테르 함유 (메타)아크릴산 에스테르의 탈비닐화 반응을 실시하여, 히드록시알킬(메타)아크릴산 에스테르를 얻는 방법에 관하여 설명한다.Next, a method for obtaining a hydroxyalkyl (meth) acrylic acid ester by subjecting a vinyl ether-containing (meth) acrylic acid ester to a de-vinylation reaction will be described.
본 발명에 있어서는, 탈비닐화 반응을 산촉매 존재 하에서 실시하지만, 사용 가능한 산촉매로서는 통상, 황산, 황산수소나트륨, 파라톨루엔설폰산, 벤젠설폰산, 메탄설폰산, 고체산(제올라이트, 앰버라이트, 앰버리스트, 나피온 등)을 들 수 있다. 또한, 사용하는 촉매량은, 반응시키는 비닐에테르 함유 (메타)아크릴산 에스테르에 대해서 0.01중량%~10중량%가 바람직하고, 0.1중량%~5중량%가 보다 바람직하다.사용하는 촉매량이 0.01중량% 미만의 경우, 반응성이 현저하게 저하하여, 탈비닐화 반응이 극단적으로 늦어지는 경우가 있다. 또한, 10중량%보다 많은 경우는, 반응속도에는 거의 영향이 없는 한편, 불순물이 생성될 우려가 있다.In the present invention, the devinylation reaction is carried out in the presence of an acid catalyst. As the acid catalyst that can be used, sulfuric acid, sodium hydrogen sulphate, paratoluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid and a solid acid (zeolite, amberlite, , Nafion, etc.). The amount of the catalyst to be used is preferably 0.01% by weight to 10% by weight, more preferably 0.1% by weight to 5% by weight, based on the vinyl ether-containing (meth) acrylate ester to be reacted. , The reactivity is remarkably lowered, and the de-vinylation reaction may be extremely delayed. On the other hand, if it is more than 10% by weight, impurities may be generated while there is almost no influence on the reaction rate.
본 발명과 관련되는 탈비닐화 반응은, 물을 공존시켜 실시하는 것이 특징이다. 물을 공존시켜 실시함으로써, 탈비닐화 반응 시에 부생하는 알데히드를 용이하게 제거할 수 있다. 물의 사용량으로서는, 비닐에테르 함유 (메타)아크릴산 에스테르를 기준으로 하여 등몰 이상이면 특별히 제한은 없지만, 바람직하게는, 비닐에테르 함유 (메타)아크릴산 에스테르를 기준으로 하여 2배몰 이상 이용함으로써 반응이 신속하게 진행한다. 물을 등몰보다 적은 비율로 사용했을 경우는, 반응이 도중에 정지한다.The de-vinylation reaction according to the present invention is characterized in that water is coexistent. By carrying out water in the coexistence, the by-produced aldehyde can be easily removed during the debinylation reaction. The amount of water to be used is not particularly limited as far as it is equal to or more than the equimolar amount based on the vinyl ether-containing (meth) acrylic acid ester. Preferably, the reaction is rapidly proceeded by using 2-fold molar amount or more based on the vinyl ether-containing (meth) do. When water is used at a smaller ratio than the equimolar amount, the reaction stops in the middle.
본 발명과 관련되는 탈비닐화 반응은, 발열 반응이다. 이 때, 반응 온도를 60℃ 이하, 바람직하게는 0℃~40℃로 제어함으로써 고순도의 히드록시알킬(메타)아크릴산 에스테르를 얻는 것이 가능해진다. 반응 온도를 제어하는 방법으로서는, 반응기를 냉각하거나 또는, 촉매 수용액에 비닐에테르 함유 (메타)아크릴산 에스테르를 서서히 첨가하는 방법을 들 수 있다. 또한, 반응 시는 아세트알데히드가 부생하지만, 계 내를 감압하로 함으로써 아세트알데히드를 신속하게 제거할 수 있으며, 반응을 촉진할 수 있다.The debinylation reaction according to the present invention is an exothermic reaction. At this time, by controlling the reaction temperature to 60 占 폚 or less, preferably 0 占 폚 to 40 占 폚, it becomes possible to obtain a hydroxyalkyl (meth) acrylic acid ester of high purity. As a method of controlling the reaction temperature, there can be mentioned a method of cooling the reactor or gradually adding a vinyl ether-containing (meth) acrylic acid ester to the aqueous catalyst solution. In addition, acetaldehyde is produced as a by-product at the time of the reaction, but acetaldehyde can be rapidly removed by decompression in the system, and the reaction can be promoted.
탈비닐화 반응 종료 후에는, 반응 잔액으로부터 수층을 분리 제거한다. 그 때, 분리능을 올리기 위해서, 예를 들어 톨루엔이나 크실렌 등의 용매를 단독 또는 2종 이상 조합해서 이용할 수 있다. 분리 제거하여 얻은 수층의 물은, 다음 번 이후의 제조에 있어서 탈비닐화 반응으로 공존시키는 물로서 재이용할 수 있다.After completion of the de-vinylation reaction, the aqueous layer is separated and removed from the reaction residue. At this time, in order to raise the resolution, for example, solvents such as toluene and xylene may be used alone or in combination of two or more. The water in the water layer obtained by separating and removing can be reused as water coexisting in the devinylation reaction in the subsequent production.
분리한 유기층은 촉매를 포함하기 때문에, 염기로 중화하여 분리 제거한다. 염기로서는 예를 들어, 수산화칼륨, 수산화나트륨, 탄산칼륨, 탄산나트륨, 탄산수소칼륨, 탄산수소나트륨 등의 알칼리 금속, 알칼리 토류 금속의 수산화물 또는 염을 들 수 있다. 이들을 수용액으로서 이용하고, 중화 후에 분리 제거하여 이용하는 방법이 바람직하다.Since the separated organic layer contains a catalyst, it is neutralized with a base and separated and removed. Examples of the base include hydroxides or salts of alkali metals and alkaline earth metals such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate and sodium hydrogencarbonate. It is preferable to use them as an aqueous solution and separate and remove them after neutralization.
중화 후는, 과잉의 알칼리를 물 또는 중성염 수용액에 의해 세정하여 제거한 후, 농축에 의해 과잉의 수분이나, 용매를 사용하고 있는 경우는 용매를 증류 제거한다. 농축은 상압 또는 감압 하, 액체의 온도를 90℃ 이하로 유지하면서 실시하는 것이 바람직하고, 보다 바람직하게는 50℃~80℃의 범위 내이다. 액체의 온도가 90℃를 넘으면, 히드록시알킬(메타)아크릴산 에스테르의 착색이나 중합을 일으킬 가능성이 높아진다.After neutralization, excess alkali is removed by washing with water or a neutral salt aqueous solution, and excess water is removed by concentration, or when the solvent is used, the solvent is distilled off. Concentration is preferably carried out under normal pressure or reduced pressure while maintaining the temperature of the liquid at 90 占 폚 or lower, more preferably in the range of 50 占 폚 to 80 占 폚. If the temperature of the liquid exceeds 90 占 폚, the possibility of causing coloration or polymerization of the hydroxyalkyl (meth) acrylic acid ester becomes high.
농축 후는, 여과를 실시함으로써 잔존하는 중화 염 등의 불용분을 없앨 수 있다. 여과 시에는 효율 좋게 불용분을 없애기 위하여, 규조토 등의 여과조제를 이용하는 것이 바람직하다.After the concentration, the insoluble matter such as neutralized salts remaining can be removed by filtration. It is preferable to use a filter aid such as diatomaceous earth in order to efficiently remove insolubles during filtration.
본 발명의 히드록시알킬(메타)아크릴산 에스테르의 제조 방법은, 탈비닐화 반응 시에 물을 이용하기 때문에, 고순도의 히드록시알킬(메타)아크릴산 에스테르를 얻을 수 있으므로, 증류 등의 정제 공정은 필요없다.The method for producing the hydroxyalkyl (meth) acrylic acid ester of the present invention does not require a purification step such as distillation since water is used in the de-vinylation reaction and a hydroxyalkyl (meth) acrylic acid ester of high purity can be obtained .
실시예Example
이하에, 실시예를 들어 본 발명을 더욱 구체적으로 설명하지만, 본 발명은 이들에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto.
[실시예 1][Example 1]
(비닐옥시부틸 메타크릴레이트의 합성)(Synthesis of vinyloxybutyl methacrylate)
4L의 4구 환저 세퍼러블 플라스크에 4-히드록시부틸비닐에테르(마루젠석유화학 제 HBVE) 1000g, 메타크릴산 메틸 3000g, 메토퀴논 0.65g을 넣고, 정류탑(15단), 교반기, 공기 도입관, 온도계를 설치하였다. 교반 하, 건조공기를 100ml/분으로에 도입하면서 가열을 시작하고, 환류 시의 플라스크 내의 액체의 온도가 75℃가 되도록 압력을 40kPa 정도로 조정하여, 계 내의 수분을 제거하였다. 계 내의 수분이 300ppm 이하인 것을 확인한 후, 촉매로서 티탄테트라이소프로폭시드 8.6g을 넣고, 반응 온도가 95±5℃가 되도록 플라스크 내 압력을 60kPa 정도로 제어하였다. 가열 환류 시에 정류탑 상부의 온도(탑정온도)를 감시하고 있으면, 생성하는 메탄올과 메타크릴산 메틸의 공비온도에 가까워지므로, 탑정온도가 60℃정도가 되도록 환류비를 조절하여 메탄올을 메타크릴산 메틸과의 공비물로서 증류 제거하면서 반응을 실시하였다.1000 g of 4-hydroxybutyl vinyl ether (HBVE manufactured by Maruzen Petrochemical Co., Ltd.), 3000 g of methyl methacrylate and 0.65 g of methoquinone were placed in a 4 L four-necked round bottom separable flask, and a rectifying column (15- Tube, and a thermometer. Heating was started while introducing dry air at 100 ml / min with stirring, and the pressure was adjusted to about 40 kPa so that the temperature of the liquid in the flask at the time of reflux was 75 캜 to remove water in the system. After confirming that the water content in the system was 300 ppm or less, 8.6 g of titanium tetraisopropoxide as a catalyst was added and the pressure in the flask was controlled to about 60 kPa so that the reaction temperature was 95 ± 5 ° C. When the temperature (overhead temperature) of the upper portion of the rectifying column is monitored during the heating and refluxing, the reflux ratio is adjusted so that the top temperature is about 60 ° C since methanol is close to the azeotropic temperature between methanol and methyl methacrylate. Methanol The reaction was carried out while distilling off as an azeotropic mixture with methyl.
반응 4시간을 경과했을 무렵으로부터 탑정온도가 상승하기 시작했으므로, 환류비를 서서히 크게 하여 반응을 계속하였다. 반응 5시간째의 반응액을 가스크로마토그래피로 분석한 바, 에스테르 전환율이 99.2%였으므로, 반응 종료로 하였다. 반응액을 냉각하여, 액체의 온도가 75℃가 된 시점에서 17중량% 식염수 250g을 가하여 촉매를 가수분해하였다. 15분 정치한 후, 경사법(decantation)에 의해 유기층을 가지형 플라스크에 취하고, 회전증발기(rotary evaporator)를 이용하여, 과잉인 메타크릴산 메틸 감압하 증류 제거하고 나서, 흡인 여과에 의해 가지형 플라스크 내 액(液)을 여과하여, 목적으로 하는 비닐옥시부틸 메타크릴레이트를 1522g 얻었다.Since the top temperature began to rise from the time when the reaction time had elapsed after 4 hours, the reflux ratio was gradually increased and the reaction was continued. When the reaction solution at the fifth hour of the reaction was analyzed by gas chromatography, the ester conversion was 99.2%, and the reaction was terminated. The reaction solution was cooled, and when the temperature of the liquid reached 75 캜, 250 g of 17% by weight of saline was added to hydrolyze the catalyst. After the mixture was allowed to stand for 15 minutes, the organic layer was taken in an eggplant type flask by decantation, and the excess methyl methacrylate was distilled off under reduced pressure using a rotary evaporator. Then, The liquid in the flask was filtered to obtain 1522 g of the target vinyl oxybutyl methacrylate.
(4-히드록시부틸메타크릴레이트의 합성)(Synthesis of 4-hydroxybutyl methacrylate)
1L의 4구 세퍼러블 플라스크에 파라톨루엔설폰산 16g, 순수한 물 200g을 투입하고, 교반기, 온도계, 공기 도입관, 냉각 트랩 부착 진공 펌프를 설치하였다. 상술한 바와 같이 하여 합성한 비닐옥시부틸 메타크릴레이트 500g을 플라스크에 천천히 첨가하였다. 계 내 압력을 20kPa로 하고, 교반 하, 생성하는 아세트알데히드를 계내로부터 제거하면서, 반응을 진행시켰다. 이 때, 플라스크는 얼음물로 냉각하면서 반응 온도를 15~30℃로 유지하였다. 반응 3시간 후, 가스크로마토그래피에 의한 분석에 의해 반응 전환율이 거의 100%였기 때문에, 반응 종료로 하였다. 반응 완료액에 톨루엔 100g, 17중량% 식염수 50g을 넣어 유수 분리하고, 유기층만을 꺼냈다(수층은 실시예 4로 사용). 유기층은 분액깔때기를 사용하여 5중량% 탄산수소나트륨 수용액 70g으로 세정한 후, 17중량% 식염수 70g으로 세정하였다. 유기층을 가지형 플라스크에 취하고, 회전증발기를 이용하여, 과잉인 톨루엔을 감압 하 증류 제거하고 나서, 흡인 여과에 의해 여과하여, 목적으로 하는 4-히드록시부틸메타크릴레이트 395g(수율 92.2%, 순도 991%)을 얻었다.16 g of paratoluenesulfonic acid and 200 g of pure water were charged into a 1 L four-neck separable flask, and a stirrer, a thermometer, an air inlet tube, and a vacuum pump with a cooling trap were provided. 500 g of vinyloxybutyl methacrylate synthesized as described above was slowly added to the flask. The pressure in the system was adjusted to 20 kPa and the reaction proceeded while stirring the acetaldehyde produced. At this time, the flask was cooled with ice water and the reaction temperature was maintained at 15 to 30 ° C. After 3 hours of the reaction, the reaction conversion was almost 100% by analysis by gas chromatography, and the reaction was terminated. 100 g of toluene and 50 g of 17% by weight of saline were added to the reaction completion solution, and the resultant was subjected to oil-water separation. Only the organic layer was taken out (the water layer was used as Example 4). The organic layer was washed with 70 g of a 5 wt% sodium hydrogencarbonate aqueous solution using a separatory funnel, followed by washing with 70 g of 17 wt% saline. The organic layer was taken in an eggplant type flask and the excess toluene was distilled off under reduced pressure using a rotary evaporator and then filtered by suction filtration to obtain 395 g of a target 4-hydroxybutyl methacrylate (yield: 92.2%, purity 991%).
[실시예 2][Example 2]
(비닐옥시부틸 아크릴레이트의 합성)(Synthesis of vinyloxybutyl acrylate)
4L의 4구 환저 세퍼러블 플라스크에 4-히드록시부틸비닐에테르(마루젠석유화학 제 HBVE) 1000g, 아크릴산 에틸 3000g, 메토퀴논 0.65g을 넣고, 정류탑(15단), 교반기, 공기 도입관, 온도계를 설치하였다. 교반 하, 건조공기를 100ml/분으로 도입하면서 가열을 시작하고, 환류 시의 플라스크 내의 액체의 온도가 75℃가 되도록 압력을 40kPa 정도로 조정하여, 계 내의 수분을 제거하였다. 계내의 수분이 300ppm 이하인 것을 확인한 후, 촉매로서 티탄테트라이소프로폭시드 8.6g을 넣고, 반응 온도가 95±5℃가 되도록 플라스크 내 압력을 60kPa 정도로 제어하였다. 가열 환류 시에 정류탑 상부의 온도(탑정온도)를 감시하고 있으면, 생성하는 에탄올과 아크릴산 에틸의 공비온도에 가까워지므로, 탑정온도가 70℃정도가 되도록 환류비를 조절하여 에탄올을 아크릴산에틸과의 공비물로서 증류 제거하면서 반응을 실시하였다.1000 g of 4-hydroxybutyl vinyl ether (HBVE manufactured by Maruzen Petrochemical Co., Ltd.), 3000 g of ethyl acrylate and 0.65 g of methoquinone were placed in a 4 L four-necked round bottom separable flask, and a rectifying column (15- A thermometer was installed. Heating was started while introducing dry air at 100 ml / min with stirring, and the pressure was adjusted to about 40 kPa so that the temperature of the liquid in the flask at reflux was 75 캜 to remove water in the system. After confirming that the water content in the system was 300 ppm or less, 8.6 g of titanium tetraisopropoxide as a catalyst was added and the pressure in the flask was controlled to about 60 kPa so that the reaction temperature was 95 ± 5 ° C. When the temperature (overhead temperature) of the upper portion of the rectifying column is monitored during the heating and refluxing, the reflux ratio is adjusted so that the top temperature is about 70 ° C because the temperature is close to the azeotropic temperature between the produced ethanol and ethyl acrylate. The reaction was carried out while distilling off as water.
반응 4시간을 경과했을 무렵으로부터 탑정온도가 상승하기 시작했으므로, 환류비를 서서히 크게 하여 반응을 계속하였다. 반응 5시간째의 반응액을 가스크로마토그래피로 분석한 바, 에스테르 전환율이 99.0%였으므로, 반응 종료로 하였다. 반응액을 냉각하여, 액체의 온도가 75℃가 된 시점에서 17중량% 식염수 250g을 가하여 촉매를 가수분해하였다. 15분 정치한 후, 경사법에 의해 유기층을 가지형 플라스크에 취하고, 회전증발기를 이용하여, 과잉인 아크릴산에틸 감압 하 증류 제거하고 나서, 흡인 여과에 의해 가지형 플라스크 내 액을 여과하여, 목적으로 하는 비닐옥시부틸 아크릴레이트를 1376g 얻었다.Since the top temperature began to rise from the time when the reaction time had elapsed after 4 hours, the reflux ratio was gradually increased and the reaction was continued. When the reaction solution at the fifth hour of the reaction was analyzed by gas chromatography, the ester conversion was 99.0%, and the reaction was terminated. The reaction solution was cooled, and when the temperature of the liquid reached 75 캜, 250 g of 17% by weight of saline was added to hydrolyze the catalyst. After the mixture was allowed to stand for 15 minutes, the organic layer was taken up in an egg-shaped flask by a tilting method, and the excess ethyl acrylate was distilled off under reduced pressure using a rotary evaporator. Then, the liquid in the egg plant type flask was filtered by suction filtration, Of vinyloxybutyl acrylate was obtained.
(4-히드록시부틸아크릴레이트의 합성)(Synthesis of 4-hydroxybutyl acrylate)
1L의 4구 세퍼러블 플라스크에 파라톨루엔설폰산 16g, 순수한 물 200g을 투입하고, 교반기, 온도계, 공기 도입관, 냉각 트랩 부착 진공 펌프를 설치하였다. 상술한 바와 같이 하여 합성한 비닐옥시부틸 아크릴레이트 500g을 플라스크에 천천히 첨가하였다. 계 내 압력을 20kPa로 하고, 교반 하, 생성되는 아세트알데히드를 계 내로부터 제거하면서, 반응을 진행시켰다. 이 때, 플라스크는 얼음물로 냉각하면서 반응 온도를 15~30℃로 유지하였다. 반응 3시간 후, 가스크로마토그래피에 의한 분석에 의해 반응 전환율이 99.9%였기 때문에, 반응 종료로 하였다. 반응 완료액에 톨루엔 200g, 17중량% 식염수 50g을 넣어 유수 분리하여, 유기층만을 꺼냈다. 유기층은 분액깔때기를 사용하여 5중량% 탄산수소나트륨 수용액 70g으로 세정한 후, 17중량% 식염수 70g으로 세정하였다. 유기층을 가지형 플라스크에 취하고, 회전증발기를 이용하여, 과잉인 톨루엔을 감압 하 증류 제거하고 나서, 흡인 여과에 의해 여과하여, 목적으로 하는 4-히드록시부틸아크릴레이트 389g(수율 92.0%, 순도 99.0%)을 얻었다.16 g of paratoluenesulfonic acid and 200 g of pure water were charged into a 1 L four-neck separable flask, and a stirrer, a thermometer, an air inlet tube, and a vacuum pump with a cooling trap were provided. 500 g of vinyloxybutyl acrylate synthesized as described above was slowly added to the flask. The pressure in the system was adjusted to 20 kPa, and the reaction proceeded while stirring the acetaldehyde produced. At this time, the flask was cooled with ice water and the reaction temperature was maintained at 15 to 30 ° C. Three hours after the reaction, the reaction conversion was 99.9% by analysis by gas chromatography, and the reaction was terminated. 200 g of toluene and 50 g of 17% by weight of saline were added to the reaction completion solution, and water separation was performed to remove only the organic layer. The organic layer was washed with 70 g of a 5 wt% sodium hydrogencarbonate aqueous solution using a separatory funnel, followed by washing with 70 g of 17 wt% saline. The organic layer was taken in an eggplant-shaped flask, and the excess toluene was distilled off under reduced pressure using a rotary evaporator, and then filtered by suction filtration to obtain 389 g (yield: 92.0%, purity: 99.0%) of the target 4-hydroxybutyl acrylate %).
[실시예 3][Example 3]
(시클로헥산디메탄올비닐에테르 메타크릴레이트의 합성)(Synthesis of cyclohexanedimethanol vinyl ether methacrylate)
1L의 4구 환저플라스크에 시클로헥산디메탄올모노비닐에테르(마루젠석유화학 제 CHMVE) 300g, 메타크릴산메틸 600g, 메토퀴논 0.20g를 넣고, 정류탑(15단), 교반기, 공기 도입관, 온도계를 설치하였다. 교반 하, 건조공기를 100ml/분으로 도입하면서 가열을 시작하여, 환류 시의 플라스크 내의 액체의 온도가 75℃가 되도록 압력을 40kPa 정도로 조정하여, 계 내의 수분을 제거하였다. 계 내의 수분이 300 ppm 이하인 것을 확인한 후, 촉매로서 티탄테트라이소프로폭시드 2.6g을 넣고, 반응 온도가 95±5℃가 되도록 플라스크 내 압력을 60kPa 정도로 제어하였다. 가열 환류 시에 정류탑 상부의 온도(탑정온도)를 감시하고 있으면, 생성하는 메탄올과 메타크릴산 메틸의 공비온도에 가까워졌으므로, 탑정온도가 60℃ 정도가 되도록 환류비를 조절하여 메탄올을 메타크릴산 메틸과의 공비물로서 증류 제거하면서 반응을 실시하였다.300 g of cyclohexanedimethanol monovinyl ether (CHMVE, manufactured by Maruzen Petrochemical Co., Ltd.), 600 g of methyl methacrylate and 0.20 g of methoquinone were placed in a 1 L four-neck round bottom flask, A thermometer was installed. Heating was started while introducing dry air at 100 ml / min with stirring, and the pressure was adjusted to about 40 kPa so that the temperature of the liquid in the flask at the time of reflux was 75 캜 to remove water in the system. After confirming that the water content in the system was 300 ppm or less, 2.6 g of titanium tetraisopropoxide as a catalyst was added, and the pressure in the flask was controlled to about 60 kPa so that the reaction temperature was 95 ± 5 ° C. When the temperature (overhead temperature) of the upper portion of the rectifying column was monitored at the time of heating and refluxing, the reflux ratio was adjusted so that the temperature at the top of the column was about 60 ° C because methanol was close to the azeotropic temperature between methanol and methyl methacrylate. The reaction was carried out while distilling off as an azeotropic mixture with methyl.
반응 2시간을 경과했을 무렵부터 탑정온도가 상승하기 시작했으므로, 환류비를 서서히 크게 하여 반응을 계속하였다. 반응 3시간째의 반응액을 가스크로마토그래피로 분석한 바, 에스테르 전환율이 99.4%였으므로, 반응 종료로 하였다. 반응액을 냉각하여, 액체의 온도가 75℃가 되었을 때, 17중량% 식염수 100g을 가하여 촉매를 가수분해하였다. 15분 정치한 후, 경사법에 의해 유기층을 가지형 플라스크에 취하고, 회전증발기를 이용하여, 과잉인 메타크릴산메틸 감압 하 증류 제어하고 나서, 흡인 여과에 의해 가지형 플라스크 내 액을 여과하여, 목적으로 하는 시클로헥산디메탄올비닐에테르 메타크릴레이트를 385g 얻었다.Since the overhead temperature started to increase from the time when 2 hours of reaction had elapsed, the reflux ratio was gradually increased and the reaction was continued. When the reaction solution at the third hour of the reaction was analyzed by gas chromatography, the ester conversion was 99.4%, and the reaction was terminated. The reaction solution was cooled, and when the temperature of the liquid reached 75 캜, 100 g of 17% by weight saline was added to hydrolyze the catalyst. After the mixture was allowed to stand for 15 minutes, the organic layer was taken up in an egg-shaped flask by a tilting method, the excess methyl methacrylate was distilled under reduced pressure using a rotary evaporator, and the liquid in the egg- 385 g of cyclohexanedimethanol vinyl ether methacrylate was obtained.
(시클로헥산디메탄올모노메타크릴레이트의 합성)(Synthesis of cyclohexanedimethanol monomethacrylate)
500mL의 4구 세퍼러블 플라스크에 파라톨루엔설폰산 6.4g, 순수한 물 80g을 투입하고, 교반기, 온도계, 공기 도입관, 냉각 트랩 부착 진공 펌프를 설치하였다. 상술한 바와 같이 하여 합성한 시클로헥산디메탄올비닐에테르 메타크릴레이트 200g을 플라스크에 천천히 첨가하였다. 계 내 압력을 20kPa로 하고, 교반 하, 생성되는 아세트알데히드를 계 내로부터 제거하면서, 반응을 진행시켰다. 이 때, 플라스크는 얼음물로 냉각하면서 반응 온도를 15~30℃로 유지하였다. 반응 2시간 후, 가스크로마토그래피에 의한 분석에 의해 반응 전환율이 99.9%였기 때문에, 반응 종료로 하였다. 반응 완료액에 톨루엔 80g, 17중량% 식염수 30g을 넣어 유수 분리하여, 유기층만을 꺼냈다. 유기층은 분액깔때기를 사용하여 5중량% 탄산수소나트륨 수용액 20g으로 세정한 후, 17중량% 식염수 30g으로 세정하였다. 유기층을 가지형 플라스크에 취하고, 회전증발기를 이용하여, 과잉인 톨루엔을 감압하 증류 제거하고 나서, 흡인 여과에 의해 여과하여, 목적으로 하는 시클로헥산디메탄올모노메타크릴레이트 163g(수율 91.5%, 순도 99.4%)을 얻었다.6.4 g of paratoluenesulfonic acid and 80 g of pure water were put into a 500 mL four-neck separable flask, and a stirrer, a thermometer, an air inlet tube, and a vacuum pump with a cooling trap were provided. 200 g of cyclohexanedimethanol vinyl ether methacrylate synthesized as described above was slowly added to the flask. The pressure in the system was adjusted to 20 kPa, and the reaction proceeded while stirring the acetaldehyde produced. At this time, the flask was cooled with ice water and the reaction temperature was maintained at 15 to 30 ° C. Two hours after the reaction, the reaction conversion was 99.9% by analysis by gas chromatography, and the reaction was terminated. 80 g of toluene and 30 g of 17% by weight saline solution were added to the reaction completion solution, followed by water separation to remove only the organic layer. The organic layer was washed with 20 g of a 5 wt% sodium hydrogencarbonate aqueous solution using a separatory funnel, and then washed with 30 g of 17 wt% saline solution. The organic layer was taken in an eggplant type flask and the excess toluene was distilled off under reduced pressure using a rotary evaporator and then filtered by suction filtration to obtain 163 g of the desired cyclohexanedimethanol monomethacrylate (yield: 91.5%, purity 99.4%).
[실시예 4][Example 4]
(물 재이용에 의한 4-히드록시부틸메타크릴레이트의 제조 방법)(Method for producing 4-hydroxybutyl methacrylate by water reuse)
1L의 4구 세퍼러블 플라스크에 실시예 1에서 반응 후에 분리한 수층(전량)을 투입하고, 교반기, 온도계, 공기 도입관, 냉각 트랩 부착 진공 펌프를 설치하였다. 실시예 1에서 합성한 비닐옥시부틸메타크릴레이트 500g을 플라스크에 천천히 첨가하였다. 계 내 압력을 20kPa로 하고, 교반 하, 생성되는 아세트알데히드를 계 내로부터 제거하면서, 반응을 진행시켰다. 이 때, 플라스크는 얼음물로 냉각하면서 반응 온도를 15~30℃로 유지하였다. 반응 3시간 후, 가스크로마토그래피에 의한 분석에 의해 반응 전환율이 99.9%였기 때문에, 반응 종료로 하였다. 반응 완료액에 톨루엔 100g을 넣고 유수 분리하여, 유기층만을 꺼냈다. 유기층은 분액깔때기를 사용하여 5중량% 탄산수소나트륨 수용액 70g으로 세정한 후, 17중량% 식염수 70g으로 세정하였다. 유기층을 가지형 플라스크에 취하고, 회전증발기를 이용하여, 과잉인 톨루엔을 감압하 증류 제거하고 나서, 흡인 여과에 의해 여과하여, 목적으로 하는 4-히드록시부틸메타크릴레이트 398g(수율 92.8%, 순도 99.2%)을 얻었다.In a 1 L four-neck separable flask, an aqueous layer (whole amount) separated after the reaction in Example 1 was charged, and a stirrer, a thermometer, an air inlet tube, and a vacuum pump with a cooling trap were provided. 500 g of vinyloxybutyl methacrylate synthesized in Example 1 was slowly added to the flask. The pressure in the system was adjusted to 20 kPa, and the reaction proceeded while stirring the acetaldehyde produced. At this time, the flask was cooled with ice water and the reaction temperature was maintained at 15 to 30 ° C. Three hours after the reaction, the reaction conversion was 99.9% by analysis by gas chromatography, and the reaction was terminated. 100 g of toluene was added to the reaction completion solution, and the organic layer was taken out by water separation. The organic layer was washed with 70 g of a 5 wt% sodium hydrogencarbonate aqueous solution using a separatory funnel, followed by washing with 70 g of 17 wt% saline. The organic layer was taken in an eggplant type flask and the excess toluene was distilled off under reduced pressure using a rotary evaporator and then filtered by suction filtration to obtain 398 g of 4-hydroxybutyl methacrylate (yield: 92.8%, purity 99.2%).
[실시예 5][Example 5]
(반응 온도 60℃이상의 경우의 4-히드록시부틸메타크릴레이트의 제조 방법)(A method for producing 4-hydroxybutyl methacrylate in the case of a reaction temperature of 60 ° C or more)
1L의 4구 세퍼러블 플라스크에 파라톨루엔설폰산 16g, 순수한 물 200g을 투입하고, 교반기, 온도계, 공기 도입관, 냉각 트랩 부착 진공 펌프를 설치하였다. 실시예 1에서 합성한 비닐옥시부틸메타크릴레이트 500g을 플라스크에 한꺼번에 첨가한 후, 즉시 계 내 압력을 20kPa로 하고, 교반 하, 생성하는 아세트알데히드를 계 내로부터 제거하면서 반응을 진행시켰다. 이 때, 플라스크는 냉각하지 않고 방치한 바, 반응 온도는 65℃까지 상승하였다. 반응 3시간 후, 가스크로마토그래피에 의한 분석에 의해 반응 전환율이 거의 100%였기 때문에, 반응 종료로 하였다. 반응 완료액에 톨루엔 100g, 17중량% 식염수 50g을 넣고 유수 분리하여, 유기층만을 꺼냈다. 유기층은 분액깔때기를 사용하여 5중량% 탄산수소나트륨 수용액 70g으로 세정한 후, 17중량% 식염수 70g으로 세정하였다. 유기층을 가지형 플라스크에 취하고, 회전증발기를 이용하여, 과잉인 톨루엔을 감압 하 증류 제거하고 나서, 흡인 여과에 의해 여과하여, 목적으로 하는 4-히드록시부틸메타크릴레이트 385g(수율 89.9%, 순도 97.0%)을 얻었다.16 g of paratoluenesulfonic acid and 200 g of pure water were charged into a 1 L four-neck separable flask, and a stirrer, a thermometer, an air inlet tube, and a vacuum pump with a cooling trap were provided. 500 g of vinyloxybutyl methacrylate synthesized in Example 1 was added all at once to the flask, and the pressure was immediately set to 20 kPa, and the reaction proceeded with stirring while removing the generated acetaldehyde from the system. At this time, the flask was left without cooling, and the reaction temperature rose to 65 占 폚. After 3 hours of the reaction, the reaction conversion was almost 100% by analysis by gas chromatography, and the reaction was terminated. 100 g of toluene and 50 g of 17% by weight saline were added to the reaction completion solution, and the organic layer was taken out by water separation. The organic layer was washed with 70 g of a 5 wt% sodium hydrogencarbonate aqueous solution using a separatory funnel, followed by washing with 70 g of 17 wt% saline. The organic layer was taken in an eggplant-shaped flask, and the excess toluene was distilled off under reduced pressure using a rotary evaporator, and then filtered by suction filtration to obtain 385 g of a target 4-hydroxybutyl methacrylate (yield: 89.9% 97.0%).
이와 같이, 반응 온도가 60℃를 넘을 경우, 실시예 1과 비교하여 수율이 약간 저하한 것을 알 수 있다.As described above, when the reaction temperature exceeds 60 ° C, the yield is slightly lower than that of Example 1.
[비교예 1][Comparative Example 1]
(디올 공존 하에서의 4-히드록시부틸메타크릴레이트의 제조 방법)(Production method of 4-hydroxybutyl methacrylate in the coexistence of diol)
1L의 4구 세퍼러블 플라스크에 파라톨루엔설폰산 16g, 에틸렌글리콜 200g을 투입하고, 교반기, 온도계, 공기 도입관, 냉각 트랩 부착 진공 펌프를 설치하였다. 합성예 1에서 합성한 비닐옥시부틸메타크릴레이트 500g을 플라스크에 천천히 첨가하였다. 계 내 압력을 20kPa로 하고, 교반 하, 생성되는 아세탈을 계 내로부터 제거하면서, 반응을 진행시켰다.이 때, 플라스크는 얼음물로 냉각하면서 반응 온도를 15~30℃로 유지하였다. 반응 3시간 후, 가스크로마토그래피에 의한 분석에 의해 반응 전환율은 78%였다. 또한, 분석에 의해 반응계 내에 아세탈 화합물이 잔존하고 있었기 때문에, 50℃까지 가열하여 반응을 계속했다. 가열 개시 후 1시간에서의 반응 전환율이 98.4%였기 때문에, 반응을 종료로 하였다. 반응 완료액에 톨루엔 200g, 5중량% 식염수 150g을 넣고 유수 분리하여, 유기층만을 꺼냈다. 유기층은 분액깔때기를 사용하여 5중량% 탄산수소나트륨 수용액 70g으로 세정한 후, 17중량% 식염수 70g으로 세정하였다. 유기층을 가지형 플라스크에 취하고, 회전증발기를 이용하여, 과잉인 톨루엔을 감압하 증류 제거하고 나서, 흡인 여과에 의해 여과하여, 목적으로 하는 4-히드록시부틸메타크릴레이트 395g(수율 87.6%, 순도 92.3%)을 얻었다.16 g of paratoluenesulfonic acid and 200 g of ethylene glycol were charged into a 1 L four-neck separable flask, and a stirrer, a thermometer, an air inlet tube, and a vacuum pump with a cooling trap were provided. 500 g of vinyloxybutyl methacrylate synthesized in Synthesis Example 1 was slowly added to the flask. The reaction was allowed to proceed while the produced acetal was removed from the system under stirring at a pressure of 20 kPa. At this time, the flask was maintained at a temperature of 15 to 30 캜 while cooling with ice water. Three hours after the reaction, the reaction conversion rate was 78% by analysis by gas chromatography. Further, since the acetal compound remained in the reaction system by the analysis, the reaction was continued by heating to 50 占 폚. Since the reaction conversion rate at 1 hour after the start of heating was 98.4%, the reaction was terminated. 200 g of toluene and 150 g of 5 wt% saline were added to the reaction completion solution, and the organic layer was taken out by water separation. The organic layer was washed with 70 g of a 5 wt% sodium hydrogencarbonate aqueous solution using a separatory funnel, followed by washing with 70 g of 17 wt% saline. The organic layer was taken in an egg yolk flask and the excess toluene was distilled off under reduced pressure using a rotary evaporator and then filtered by suction filtration to obtain 395 g of the target 4-hydroxybutyl methacrylate (yield: 87.6%, purity 92.3%).
이상의 결과로부터, 히드록시알킬(메타)아크릴레이트를 얻기 위한 탈비닐화 반응 시에, 물을 공존시킴으로써, 고순도의 히드록시알킬(메타)아크릴산 에스테르를 고수율로 얻을 수 있다. 또한, 실시예 4로부터, 탈비닐화 후에 분리 회수되는 수층은 다음 번 이후의 제조에 있어서의 탈비닐화 반응에 재이용 가능하다는 것을 알 수 있다.
From the above results, high purity hydroxyalkyl (meth) acrylic acid ester can be obtained in high yield by allowing water to coexist during the debinylation reaction to obtain hydroxyalkyl (meth) acrylate. In addition, it can be seen from Example 4 that the water layer which is separated and recovered after the debinylation is reusable in the devinylation reaction in the subsequent production.
Claims (3)
[화학식 1]
(일반식 (I) 중, n는 3~11의 정수를 나타낸다.)
[화학식 2]
(일반식 (II) 중, A는 시클로펜틸렌기 또는 시클로헥실렌기를 나타낸다.)The vinyl ether-containing alcohol represented by the following general formula (I) or (II) is (meth) acrylated by a transesterification method to give a vinyl ether-containing (meth) acrylic acid ester, (Meth) acrylate having a vinyl ether group in the presence of an acid catalyst in an amount of from 0.01 to 10% by weight based on the vinyl ether-containing (meth) ) ≪ / RTI >
[Chemical Formula 1]
(In the general formula (I), n represents an integer of 3 to 11.)
(2)
(In the general formula (II), A represents a cyclopentylene group or a cyclohexylene group.)
탈비닐화 반응 시의 반응 온도가 60℃ 이하인, 히드록시알킬(메타)아크릴산 에스테르의 제조 방법.The method according to claim 1,
Wherein the reaction temperature during the de-vinylation reaction is 60 占 폚 or lower.
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