JP2007039347A - Method for producing glycerol carbonate - Google Patents
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Abstract
Description
本発明はグリセリンカーボネートの製造法に関する。 The present invention relates to a process for producing glycerin carbonate.
グリセリンカーボネートは、ポリエステルやポリカーボネート、ポリウレタン等のポリマー合成原料や、活性剤・潤滑油等応用分野が広く、例えば特許文献１や特許文献２には化粧料組成物としての用途が開示されており、また特許文献３にはデオドラント剤としての有用性が開示されている。一方、グリセリンカーボネートは工業用有機合成原料としても有用であり、特許文献４に記載されているように、容易にグリシドールへと変換することが可能である。 Glycerin carbonate has a wide range of application fields such as polymer synthesis raw materials such as polyester, polycarbonate, polyurethane, and activator / lubricating oil. For example, Patent Document 1 and Patent Document 2 disclose uses as cosmetic compositions, Patent Document 3 discloses the usefulness as a deodorant agent. On the other hand, glycerin carbonate is useful as an industrial organic synthesis raw material, and can be easily converted to glycidol as described in Patent Document 4.
従来、グリセリンからグリセリンカーボネートを製造する方法として、ホスゲンを反応させる方法やジアルキルカーボネートとの交換反応等が知られている。また、特許文献５に開示されているように、グリセリンに一酸化炭素及び酸素を特定の触媒を用いて高圧下で反応させる方法も知られている。しかしながら、これらのグリセリンを用いる方法では、反応剤に由来するハロゲン化物が混入する可能性や望ましい収率が得られていない等、工業的な観点からは幾つかの解決すべき課題があり、より安全性の高い反応剤を用いた、安価で、より簡便な方法の開発が望まれていた。 Conventionally, as a method for producing glycerin carbonate from glycerin, a method of reacting phosgene, an exchange reaction with dialkyl carbonate, and the like are known. Moreover, as disclosed in Patent Document 5, a method of reacting glycerin with carbon monoxide and oxygen using a specific catalyst under high pressure is also known. However, in these methods using glycerin, there are some problems to be solved from an industrial point of view, such as the possibility that the halide derived from the reactant is mixed and the desired yield is not obtained. Development of an inexpensive and simpler method using a highly safe reactant has been desired.
一方、特許文献６や特許文献７には、グリセリンに極めて安価な尿素を反応させることにより、簡便且つ安価にグリセリンカーボネートを合成できることが開示されている。この反応における未反応グリセリンは、グリシドール等の他の合成原料に変換する際に回収・再使用することができるため、反応剤として尿素を用いるこの手法は、グリセリンカーボネート合成法として工業的にも極めて有用である。 On the other hand, Patent Literature 6 and Patent Literature 7 disclose that glycerol carbonate can be synthesized easily and inexpensively by reacting glycerol with extremely inexpensive urea. Since unreacted glycerin in this reaction can be recovered and reused when converted to other synthetic raw materials such as glycidol, this method using urea as a reactant is extremely industrially used as a glycerol carbonate synthesis method. Useful.
しかしながらこの手法では、グリセリンが過剰に反応したジグリセリン等の副生物が生じるが、これらは回収・再使用することができないという問題がある。
本発明の課題は、グリセリンと尿素を反応させるグリセリンカーボネートの製造法において、ジグリセリン等の副生物を低減させるグリセリンカーボネートの製造法を提供することにある。 The subject of this invention is providing the manufacturing method of glycerol carbonate which reduces by-products, such as diglycerol, in the manufacturing method of glycerol carbonate which makes glycerol and urea react.
本発明者らは、この課題を解決すべく鋭意研究した結果、グリセリンと尿素を反応させるグリセリンカーボネートの製造法において、特定の溶媒を用いることで副生物の生成を低減できることを見出した。 As a result of intensive studies to solve this problem, the present inventors have found that the production of by-products can be reduced by using a specific solvent in the method for producing glycerin carbonate in which glycerin and urea are reacted.
すなわち本発明は、一般式（１）で表される溶媒の存在下、グリセリンと尿素を反応させるグリセリンカーボネートの製造法を提供するものである。 That is, this invention provides the manufacturing method of the glycerol carbonate which makes glycerol and urea react in presence of the solvent represented by General formula (1).
（式中、Ｒ1及びＲ2は同一もしくは異なって、炭素数２〜３の直鎖又は分岐鎖のアルキル基を示し、ｎは１又は２を示す。） (In the formula, R 1 and R 2 are the same or different, represents a linear or branched alkyl group having 2 to 3 carbon atoms, n represents 1 or 2.)
本発明の方法によると、グリセリンと尿素から、ジグリセリン等の副生物の少ないグリセリンカーボネートを簡便且つ安価に製造することができる。 According to the method of the present invention, glycerin carbonate with few by-products such as diglycerin can be easily and inexpensively produced from glycerin and urea.
本発明で用いられる一般式（１）で表される溶媒は、グリセリンとグリセリンカーボネートの混合物に対して、前者よりも後者を優先的に分配・溶解させるものである。 The solvent represented by the general formula (1) used in the present invention distributes and dissolves the latter preferentially over the former with respect to the mixture of glycerin and glycerin carbonate.
一般式（１）において、Ｒ1及びＲ2は同一もしくは異なって、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基等の炭素数２〜３の直鎖又は分岐鎖のアルキル基を示すが、エチル基が好ましい。 In the general formula (1), R 1 and R 2 are the same or different and each represents a linear or branched alkyl group having 2 to 3 carbon atoms such as an ethyl group, an n-propyl group, or an iso-propyl group. An ethyl group is preferred.
一般式（１）で表される溶媒の具体例としては、ジエチレングリコール又はエチレングリコールの両末端が炭素数２〜３の直鎖又は分岐鎖のアルキル基でエーテル化されたジエチルエーテル体、ジプロピルエーテル体、エチルプロピルエーテル体等が挙げられ、それらの混合物でも構わない。具体的にはジエチレングリコールジエチルエーテル、エチレングリコールジエチルエーテルが好ましく、ジエチレングリコールジエチルエーテルが更に好ましい。 Specific examples of the solvent represented by the general formula (1) include diethylene glycol or a diethyl ether form in which both ends of ethylene glycol are etherified with a linear or branched alkyl group having 2 to 3 carbon atoms, dipropyl ether Body, ethylpropyl ether body, etc., and a mixture thereof may be used. Specifically, diethylene glycol diethyl ether and ethylene glycol diethyl ether are preferable, and diethylene glycol diethyl ether is more preferable.
本発明の製造法において、一般式（１）で表される溶媒の使用量は、グリセリンに対し０．１〜１０重量倍、特に０．５〜５重量倍が好ましい。 In the manufacturing method of this invention, the usage-amount of the solvent represented by General formula (1) is 0.1-10 weight times with respect to glycerol, Especially 0.5-5 weight times is preferable.
また本発明の製造法におけるグリセリンと尿素の仕込み比は、グリセリンに対し尿素を０．２〜２．０モル倍、特に０．５〜１．０モル倍用いるのが好ましい。 In the production method of the present invention, it is preferable that urea is used in an amount of 0.2 to 2.0 moles, particularly 0.5 to 1.0 moles, based on glycerol.
本発明の反応は、触媒は特に必要とはしないが、酸化亜鉛や、酸化マグネシウム等のアルカリ土類金属酸化物等の金属酸化物を触媒として用いると反応は良好に進行する。また、使用する触媒量はグリセリンに対し０．００１〜２０モル％が好ましい。 The reaction of the present invention does not require a catalyst, but the reaction proceeds well when a metal oxide such as zinc oxide or an alkaline earth metal oxide such as magnesium oxide is used as the catalyst. Further, the amount of catalyst used is preferably 0.001 to 20 mol% with respect to glycerin.
また本発明において、グリセリンは十分に脱水したものを用いるのが好ましく、特に硫酸マグネシウム等の脱水剤を反応時に用いることも好ましい。反応時に脱水剤を用いる場合の脱水剤の使用量は、グリセリンに対して０．０１〜５０重量％となる量が好ましく、０．１〜１０重量％となる量が更に好ましい。 In the present invention, it is preferable to use glycerin that has been sufficiently dehydrated, and it is particularly preferable to use a dehydrating agent such as magnesium sulfate during the reaction. When the dehydrating agent is used during the reaction, the amount of the dehydrating agent used is preferably 0.01 to 50% by weight, more preferably 0.1 to 10% by weight, based on glycerin.
また発生するアンモニアを効率良く除去するため窒素を流通させる等の方法や減圧下で反応させる方法も好ましい。流通させる窒素の量はアンモニアや余分な水分が除去できるのであれば特に限定されず、窒素はグリセリン液相中に導入させるのが好ましい。また減圧下で反応を行う場合は、１３．３〜１０１ｋＰａの範囲で行うのが好ましい。また、本発明における反応温度は８０〜１６０℃が好ましく、特に１００〜１４０℃が好ましい。 Moreover, in order to efficiently remove the generated ammonia, a method of circulating nitrogen or a method of reacting under reduced pressure is also preferable. The amount of nitrogen to be circulated is not particularly limited as long as ammonia and excess water can be removed, and nitrogen is preferably introduced into the glycerin liquid phase. Moreover, when reacting under reduced pressure, it is preferable to carry out in the range of 13.3 to 101 kPa. The reaction temperature in the present invention is preferably 80 to 160 ° C, particularly preferably 100 to 140 ° C.
比較例１
フラスコにグリセリン９２ｇを仕込み、窒素流通下１２０℃に昇温し、２時間攪拌した後、８０℃まで冷却した。尿素６０ｇを溶解させ、更に無水硫酸マグネシウム７ｇを加えた後、１２０℃に昇温した。そのまま２４時間反応させた後、ガスクロマトグラフィーで分析した結果、グリセリンカーボネートの生成率は５９％、ジグリセリンの副生は８.２％となり、グリセリンカーボネートとジグリセリンとの生成比率で表した選択性は、８８％であった。
Comparative Example 1
The flask was charged with 92 g of glycerin, heated to 120 ° C. under nitrogen flow, stirred for 2 hours, and then cooled to 80 ° C. After dissolving 60 g of urea and adding 7 g of anhydrous magnesium sulfate, the temperature was raised to 120 ° C. The reaction was allowed to proceed for 24 hours, and as a result of gas chromatography analysis, the production rate of glycerin carbonate was 59% and the by-product of diglycerin was 8.2%, which was selected by the production ratio of glycerin carbonate and diglycerin. The sex was 88%.
実施例１
フラスコにグリセリン９２ｇおよびジエチレングリコールジエチルエーテル１３０ｇを仕込み、窒素流通下１２０℃に昇温し、２時間攪拌した後、尿素６０ｇを溶解させ、更に無水硫酸マグネシウム７ｇを加えて１２０℃に昇温した。そのまま２４時間反応させた後、ガスクロマトグラフィーで分析した結果、グリセリンカーボネートの生成率は５８％、ジグリセリンの副生は２．３％となり、グリセリンカーボネートとジグリセリンとの生成比率で表した選択性は、９６％であった。
Example 1
The flask was charged with 92 g of glycerin and 130 g of diethylene glycol diethyl ether, heated to 120 ° C. under nitrogen flow, stirred for 2 hours, dissolved 60 g of urea, further added with 7 g of anhydrous magnesium sulfate, and heated to 120 ° C. The reaction was allowed to proceed for 24 hours, and as a result of gas chromatography analysis, the production rate of glycerin carbonate was 58%, and the by-product of diglycerin was 2.3%. Selection represented by the production ratio of glycerin carbonate and diglycerin The sex was 96%.
実施例２
フラスコにグリセリン１２０ｇおよびジエチレングリコールジエチルエーテル２４０ｇを仕込み、窒素流通下１２０℃に昇温し、２時間攪拌した後、尿素６０ｇを溶解させ、更に無水硫酸マグネシウム１０ｇを加えて１２０℃に昇温した。そのまま２４時間反応させた後、ガスクロマトグラフィーで分析した結果、グリセリンカーボネートの生成率は５４％、またジグリセリンの副生は１．６％となり、グリセリンカーボネートとジグリセリンとの生成比率で表した選択性は、９７％であった。
Example 2
The flask was charged with 120 g of glycerin and 240 g of diethylene glycol diethyl ether, heated to 120 ° C. under nitrogen flow, stirred for 2 hours, dissolved 60 g of urea, further added with 10 g of anhydrous magnesium sulfate, and heated to 120 ° C. After reacting as it is for 24 hours, as a result of analysis by gas chromatography, the production rate of glycerin carbonate was 54%, and the by-product of diglycerin was 1.6%, which was represented by the production ratio of glycerin carbonate and diglycerin. The selectivity was 97%.
Claims (3)
The process according to claim 1 or 2, wherein the reaction is carried out in the presence of a dehydrating agent.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2005222721A JP4732058B2 (en) | 2005-08-01 | 2005-08-01 | Method for producing glycerin carbonate |
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| JP2005222721A JP4732058B2 (en) | 2005-08-01 | 2005-08-01 | Method for producing glycerin carbonate |
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| JP2007039347A true JP2007039347A (en) | 2007-02-15 |
| JP4732058B2 JP4732058B2 (en) | 2011-07-27 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008285457A (en) * | 2007-05-21 | 2008-11-27 | Kao Corp | Method for producing glycerol carbonate |
| JP2010527976A (en) * | 2007-05-24 | 2010-08-19 | アルケマ フランス | Simultaneous production of cyclic carbonates and aliphatic nitriles and / or amines |
| US9474916B2 (en) | 2013-08-08 | 2016-10-25 | Evonik Degussa Gmbh | Carbamates from glycerine carbonate for pearlization |
| US9518035B2 (en) | 2015-02-23 | 2016-12-13 | Korea Institute Of Science And Technology | Method for preparing glycidol using glycerol and glycidol obtained thereby |
| CN110672768A (en) * | 2019-10-24 | 2020-01-10 | 无限极（中国）有限公司 | Method for determining diethoxydiol in oral care product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04211075A (en) * | 1990-02-20 | 1992-08-03 | Texaco Chem Co | Preparation of alkylene carbonate |
| JPH069610A (en) * | 1993-02-02 | 1994-01-18 | Neos Co Ltd | Production of substituted 1,3-dioxolan-2-one derivative |
| JPH10195067A (en) * | 1996-12-28 | 1998-07-28 | Lion Corp | Production of 4-hydroxymethyl-1,3-dioxolane compound |
| JP2000247967A (en) * | 1999-02-24 | 2000-09-12 | Kao Corp | Production of glycerol carbonate |
-
2005
- 2005-08-01 JP JP2005222721A patent/JP4732058B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04211075A (en) * | 1990-02-20 | 1992-08-03 | Texaco Chem Co | Preparation of alkylene carbonate |
| JPH069610A (en) * | 1993-02-02 | 1994-01-18 | Neos Co Ltd | Production of substituted 1,3-dioxolan-2-one derivative |
| JPH10195067A (en) * | 1996-12-28 | 1998-07-28 | Lion Corp | Production of 4-hydroxymethyl-1,3-dioxolane compound |
| JP2000247967A (en) * | 1999-02-24 | 2000-09-12 | Kao Corp | Production of glycerol carbonate |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008285457A (en) * | 2007-05-21 | 2008-11-27 | Kao Corp | Method for producing glycerol carbonate |
| JP2010527976A (en) * | 2007-05-24 | 2010-08-19 | アルケマ フランス | Simultaneous production of cyclic carbonates and aliphatic nitriles and / or amines |
| US9474916B2 (en) | 2013-08-08 | 2016-10-25 | Evonik Degussa Gmbh | Carbamates from glycerine carbonate for pearlization |
| US9518035B2 (en) | 2015-02-23 | 2016-12-13 | Korea Institute Of Science And Technology | Method for preparing glycidol using glycerol and glycidol obtained thereby |
| CN110672768A (en) * | 2019-10-24 | 2020-01-10 | 无限极（中国）有限公司 | Method for determining diethoxydiol in oral care product |
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