JP2016150909A - Method for producing diol - Google Patents
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Abstract
Description
本発明は脂環骨格を有するジオールの製造方法に関する。 The present invention relates to a method for producing a diol having an alicyclic skeleton.
シクロヘキサンジメタノールに代表される脂環骨格を有するジオールは、主にポリエステルに誘導され、コーティング剤、塗料、成形材料、粘接着剤などに用いられている。従来、脂環骨格を有するジオールの製造方法としては、脂環骨格を有するアルデヒドとホルムアルデヒドによるアルドール反応およびカニッツァーロ反応を利用する方法が知られている（特許文献１）。 Diols having an alicyclic skeleton typified by cyclohexanedimethanol are mainly derived from polyester and used for coating agents, paints, molding materials, adhesives and the like. Conventionally, as a method for producing a diol having an alicyclic skeleton, a method utilizing an aldol reaction and a Cannizzaro reaction using an aldehyde having an alicyclic skeleton and formaldehyde is known (Patent Document 1).
特許文献１では、原料の脂環骨格を有するアルデヒドとホルムアルデヒド、炭酸カリウムを一度に仕込み、撹拌しながら還流温度まで昇温することで、脂環骨格を有するジオールを合成している。しかしながら当該方法では、反応温度が十分でない場合、粘着性の高い中間体である脂環骨格を有するβ−ヒドロキシアルデヒドの濃度上昇に伴う反応系中の粘度増大が問題となる。一方、当該中間体の溶解度を高め、濃度上昇を防ぐために反応温度を上昇させると、副反応による急な発熱や温度暴走の危険性がある。
本発明の目的は、上記事情に鑑み、反応系中の粘度上昇が生じず、かつ急な発熱や温度暴走が生じない、脂環骨格を有するジオールの高収率な製造方法を提供することにある。
In Patent Document 1, an aldehyde having an alicyclic skeleton is synthesized by charging an aldehyde having an alicyclic skeleton, formaldehyde, and potassium carbonate at a time and raising the temperature to a reflux temperature while stirring. However, in this method, when the reaction temperature is not sufficient, an increase in viscosity in the reaction system accompanying an increase in the concentration of β-hydroxyaldehyde having an alicyclic skeleton, which is an intermediate having high tackiness, becomes a problem. On the other hand, if the reaction temperature is increased in order to increase the solubility of the intermediate and prevent the concentration from increasing, there is a risk of sudden heat generation or temperature runaway due to side reactions.
In view of the above circumstances, an object of the present invention is to provide a high-yield production method of a diol having an alicyclic skeleton that does not cause an increase in viscosity in a reaction system and does not cause sudden heat generation or temperature runaway. is there.
本発明者らは鋭意検討した結果、脂環骨格を有するアルデヒドとホルムアルデヒドを先に混合し、その後にブレンステッド塩基を添加する方法によれば、反応温度を上昇させても急な発熱や温度暴走が起こらないことを見出し、本発明を完成した。
すなわち、本発明は、下記［１］〜［５］を提供する。
［１］下記一般式（１）
As a result of intensive studies, the inventors of the present invention first mixed an aldehyde having an alicyclic skeleton with formaldehyde, and then added a Bronsted base, and even if the reaction temperature was increased, sudden exotherm or temperature runaway occurred. As a result, the present invention has been completed.
That is, the present invention provides the following [1] to [5].
[1] The following general formula (1)
（式中、Ｒは炭素数１〜４のアルキル基により置換されていてもよい炭素数２〜１０のアルキレン基を表す。）
で表されるアルデヒドとホルムアルデヒドの存在下、反応温度１０〜８０℃でブレンステッド塩基を添加する工程を含む、下記一般式（２）
(In the formula, R represents an alkylene group having 2 to 10 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms.)
In the presence of aldehyde represented by the formula and formaldehyde, a step of adding a Bronsted base at a reaction temperature of 10 to 80 ° C.
（式中、Ｒは前記定義の通りである。）
で表されるジオールの製造方法。
［２］アルデヒドが下記一般式（３）
(Wherein R is as defined above.)
The manufacturing method of diol represented by these.
[2] The aldehyde is represented by the following general formula (3)
（式中、Ｒ１〜Ｒ１０はそれぞれ独立して炭素数１〜４のアルキル基又は水素原子を表す。）
で表されるアルデヒドである、［１］の製造方法。
［３］反応温度が３５〜６５℃である、［１］、［２］の製造方法。
［４］ブレンステッド塩基として、アルカリ金属水酸化物、アルカリ土類金属水酸化物または炭酸塩を用いる、［１］〜［３］の製造方法。
［５］さらに、得られた生成物を５０〜７０℃で水と接触させる工程を含む、［１］〜［４］の製造方法。
(Wherein, R 1 to R 10 each independently represents an alkyl group or a hydrogen atom having 1 to 4 carbon atoms.)
The production method of [1], which is an aldehyde represented by the formula:
[3] The production method of [1] and [2], wherein the reaction temperature is 35 to 65 ° C.
[4] The production method of [1] to [3], wherein an alkali metal hydroxide, alkaline earth metal hydroxide or carbonate is used as the Bronsted base.
[5] The production method of [1] to [4], further comprising a step of contacting the obtained product with water at 50 to 70 ° C.
本発明によれば、反応系中の粘度増大を抑制するために反応温度を上昇させても、急な発熱や温度暴走なしに、脂環骨格を有するアルデヒドから高収率で脂環骨格を有するジオールを製造できる。 According to the present invention, even if the reaction temperature is increased in order to suppress an increase in viscosity in the reaction system, the alicyclic skeleton is obtained in a high yield from the aldehyde having the alicyclic skeleton without sudden heat generation or temperature runaway. Diol can be produced.
本発明に係る製造方法では、下記一般式（１） In the production method according to the present invention, the following general formula (1)
（式中、Ｒは炭素数１〜４のアルキル基により置換されていてもよい炭素数２〜１０のアルキレン基を表す。）
で表される脂環骨格を有するアルデヒド（以下、アルデヒド（１）と称する。）とホルムアルデヒドを混合した後、反応温度１０〜８０℃でブレンステッド塩基を添加することで脂環骨格を有するジオールを製造する。その際、脂環骨格を有するβ−ヒドロキシアルデヒドが生成する段階（ａ）と、該脂環骨格を有するβ−ヒドロキシアルデヒドとホルムアルデヒドのカニッツァーロ反応により、脂環骨格を有するジオールが生成する段階（ｂ）の二段階の反応が連続して進行する。
(In the formula, R represents an alkylene group having 2 to 10 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms.)
After mixing an aldehyde having an alicyclic skeleton represented by the formula (hereinafter referred to as aldehyde (1)) and formaldehyde, a diol having an alicyclic skeleton is added by adding a Bronsted base at a reaction temperature of 10 to 80 ° C. To manufacture. At that time, a step (a) in which a β-hydroxyaldehyde having an alicyclic skeleton is generated, and a step in which a diol having an alicyclic skeleton is generated by a Cannizzaro reaction of the β-hydroxyaldehyde having the alicyclic skeleton and formaldehyde (b) ) The two-stage reaction proceeds continuously.
（式中、Ｒは炭素数１〜４のアルキル基により置換されていてもよい炭素数２〜１０のアルキレン基を表す。） (In the formula, R represents an alkylene group having 2 to 10 carbon atoms which may be substituted by an alkyl group having 1 to 4 carbon atoms.)
［アルデヒド（１）］
アルデヒド（１）のＲを構成する炭素数２〜１０のアルキレン基としては、炭素数１〜４のアルキル基により置換されていてもよいｎ−ブチレン基、ｎ−ペンチレン基、ｎ−ヘキシレン基が好ましく、炭素数１〜４のアルキル基により置換されていてもよいｎ−ペンチレン基が特に好ましい。
すなわち、アルデヒド（１）としては、下記一般式（３）で表される化合物が特に好ましい。
[Aldehyde (1)]
Examples of the alkylene group having 2 to 10 carbon atoms constituting R of the aldehyde (1) include an n-butylene group, an n-pentylene group and an n-hexylene group which may be substituted with an alkyl group having 1 to 4 carbon atoms. An n-pentylene group which may be substituted with an alkyl group having 1 to 4 carbon atoms is particularly preferable.
That is, as the aldehyde (1), a compound represented by the following general formula (3) is particularly preferable.
（式中、Ｒ１〜Ｒ１０はそれぞれ独立して炭素数１〜４のアルキル基又は水素原子を表す。）
Ｒ１〜Ｒ１０としてはメチル基または水素原子が好ましく、水素原子が特に好ましい。
(Wherein, R 1 to R 10 each independently represents an alkyl group or a hydrogen atom having 1 to 4 carbon atoms.)
R 1 to R 10 are preferably a methyl group or a hydrogen atom, and particularly preferably a hydrogen atom.
アルデヒド（１）の入手方法に特に制限はない。工業的に入手してもよいし、公知の方法（例えば、シクヘキサンメタノールを酸化する方法、シクロヘキセンをヒドロホルミル化する方法等）またはそれに準ずる方法によって合成することもできる。 There is no restriction | limiting in particular in the acquisition method of aldehyde (1). It may be obtained industrially, or may be synthesized by a known method (for example, a method of oxidizing cyclohexane methanol, a method of hydroformylating cyclohexene, or the like) or a method analogous thereto.
［ホルムアルデヒド］
本発明で使用するホルムアルデヒドは、工業的に入手可能な５〜６０質量％のホルムアルデヒド水溶液をそのまま使用できる。生成物の溶液損失や排水処理量を低減させる観点からは１５〜５０質量％が好ましく、３０〜４０質量％がより好ましい。６０質量％より高濃度のものを用いると、ホルムアルデヒドの揮発が問題となる。
[Formaldehyde]
As the formaldehyde used in the present invention, an industrially available 5 to 60% by mass aqueous formaldehyde solution can be used as it is. From the viewpoint of reducing the solution loss of the product and the amount of wastewater treatment, 15 to 50% by mass is preferable, and 30 to 40% by mass is more preferable. When a concentration higher than 60% by mass is used, volatilization of formaldehyde becomes a problem.
ホルムアルデヒドの使用量は、１モルのアルデヒド（１）に対して理論量ないし過剰量、すなわち、２．０〜４．０モルが好ましく、２．５〜３．５モルがより好ましい。４．０モルを超えて使用すると、反応終了時にホルムアルデヒドが残存し、排水処理にかかるコストが増大する。 The amount of formaldehyde used is preferably a theoretical amount or an excess amount, that is, 2.0 to 4.0 mol, more preferably 2.5 to 3.5 mol, relative to 1 mol of aldehyde (1). If the amount exceeds 4.0 mol, formaldehyde remains at the end of the reaction, and the cost for wastewater treatment increases.
［ブレンステッド塩基］
本発明で用いるブレンステッド塩基としては、例えば水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物；水酸化カルシウム、水酸化バリウムなどのアルカリ土類金属水酸化物；炭酸ナトリウム、炭酸カリウムなどの炭酸塩などが挙げられる。中でも、反応成績および価格を考慮すると水酸化ナトリウムが好ましい。
ブレンステッド塩基は１種を単独で用いてもよく、２種以上を併用してもよい。
[Bronsted base]
Examples of the Bronsted base used in the present invention include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; sodium carbonate, And carbonates such as potassium carbonate. Among these, sodium hydroxide is preferable in view of reaction results and price.
One Bronsted base may be used alone, or two or more may be used in combination.
ブレンステッド塩基は水溶液として使用するのが好ましい。ブレンステッド塩基の濃度に特に制限はないが、通常１質量％から飽和溶液までであり、生成物の溶液損失や排水処理量を低減させる観点からは１〜６０質量％が好ましく、５〜５５質量％がより好ましく、１０〜５０質量％がさらに好ましい。
ブレンステッド塩基の使用量は１モルのアルデヒド（１）に対して理論量ないし過剰量、すなわち１．０〜２．０モルが好ましく、１．２５〜１．７５モルがより好ましい。
ブレンステッド塩基の添加時間は１〜２０時間が好ましく、特に２〜１２時間が好ましい。添加時間が１時間より短いと反応温度の制御が困難となり、２０時間より長いと製造効率が悪くなる。
ブレンステッド塩基の添加方法は特に制限されないが、添加時間が上記時間に収まるよう、できるだけ等速で添加する方法、例えば滴下などが好ましい。
The Bronsted base is preferably used as an aqueous solution. Although there is no restriction | limiting in particular in the density | concentration of a Bronsted base, Usually, it is from 1 mass% to a saturated solution, and 1-60 mass% is preferable from a viewpoint of reducing the solution loss of a product and a waste-water treatment amount, 5-55 mass. % Is more preferable, and 10 to 50% by mass is more preferable.
The amount of Bronsted base used is preferably a theoretical amount or an excess amount, that is, 1.0 to 2.0 mol, more preferably 1.25 to 1.75 mol, relative to 1 mol of aldehyde (1).
The addition time of the Bronsted base is preferably 1 to 20 hours, particularly preferably 2 to 12 hours. When the addition time is shorter than 1 hour, it is difficult to control the reaction temperature, and when it is longer than 20 hours, the production efficiency is deteriorated.
The method for adding the Bronsted base is not particularly limited, but a method of adding at a constant speed, for example, dropping, is preferable so that the addition time is within the above time.
［その他の反応条件］
反応溶媒は基本的には水であるが、必要に応じて有機溶媒を添加してもよい。有機溶媒としては、反応を阻害しなければ特に制限はなく、例えばベンゼン、トルエン、エチルベンゼン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、１，２，３−トリメチルベンゼン、１，２，４−トリメチルベンゼン、メシチレンなどの芳香族系溶媒；メタノール、エタノール、プロパノール、イソプロピルアルコール、ブタノール、ｓ−ブチルアルコール、イソブチルアルコール、ｔ−ブチルアルコール、エチレングリコールなどのアルコール系溶媒；テトラヒドロフラン、２−メチルテトラヒドロフラン、３−メチルテトラヒドロフラン、テトラヒドロピラン、２−メチルテトラヒドロピラン、３−メチルテトラヒドロピラン、４−メチルテトラヒドロピラン、１，４−ジオキサン、シクロペンチルメチルエーテル、１，２−ジメトキシエタン、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、プロピレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、トリプロピレングリコールジメチルエーテルなどのエーテル系溶媒などが挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。
[Other reaction conditions]
The reaction solvent is basically water, but an organic solvent may be added as necessary. The organic solvent is not particularly limited as long as it does not inhibit the reaction. For example, benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, 1,2,3-trimethylbenzene, 1,2,4- Aromatic solvents such as trimethylbenzene and mesitylene; alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol, s-butyl alcohol, isobutyl alcohol, t-butyl alcohol, and ethylene glycol; tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, tetrahydropyran, 2-methyltetrahydropyran, 3-methyltetrahydropyran, 4-methyltetrahydropyran, 1,4-dioxane, cyclopentylmethyl ether, 1,2-dimethyl Kishietan, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and ether solvents such as tripropylene glycol dimethyl ether. These may be used alone or in combination of two or more.
反応温度は通常１０〜８０℃の範囲であり、３５〜６５℃の範囲が好ましい。反応温度が１０℃より低いと反応速度が極端に遅くなる上、粘着性の高い中間体である脂環骨格を有するβ−ヒドロキシアルデヒドの濃度が上昇し、反応系中の粘度が増大しやすくなる。また８０℃より高いとホルムアルデヒドが揮発する恐れがある。 The reaction temperature is usually in the range of 10 to 80 ° C, preferably in the range of 35 to 65 ° C. When the reaction temperature is lower than 10 ° C., the reaction rate becomes extremely slow, and the concentration of β-hydroxyaldehyde having an alicyclic skeleton, which is a highly adhesive intermediate, increases, and the viscosity in the reaction system tends to increase. . If it is higher than 80 ° C., formaldehyde may be volatilized.
反応圧力に特に制限はなく、常圧下でも加圧下でも実施できる。反応装置・設備の簡略化の観点から、常圧下が好ましい。また、反応は窒素雰囲気下で行うのが好ましい。 There is no restriction | limiting in particular in reaction pressure, It can implement even under a normal pressure or pressurization. Normal pressure is preferable from the viewpoint of simplification of the reaction apparatus / equipment. The reaction is preferably performed in a nitrogen atmosphere.
［分離および洗浄］
反応終了後、静置して油水分離し、ギ酸塩が含まれる水層を除去する。その後、湿結晶などを含む有機層に水を加え、撹拌水洗を行うことで、残存するギ酸塩、ブレンステッド塩基およびホルムアルデヒドを除去することができる。水量は通常有機層の０．０１〜１０質量倍であり、０．０５〜５質量倍が好ましい。水洗時の温度は通常１０〜１００℃であり、５０〜７０℃が好ましい。特に水洗時の温度を５０〜７０℃とした場合、ギ酸塩、ブレンステッド塩基およびホルムアルデヒドを非常に効率よく除去できる。水洗時間に特に限定はないが、通常１０分以上行うことで十分にギ酸塩、ブレンステッド塩基およびホルムアルデヒドを除去できる。さらに念入りに行う場合には、３０分以上が好ましく、１時間以上がさらに好ましく、３時間以上が特に好ましい。水洗は必要に応じて複数回行ってもよい。
水洗の効果は、例えばＣｏｎｔｒｏｌｌｅｄ Ｐｏｌｙｍｅｒｉｚａｔｉｏｎ ｒａｔｅ ｖａｌｕｅ（ＣＰＲ）値の測定により評価することができる。ＣＰＲ値は試料３０ｇ中に含まれる塩基性物質のマイクロ当量値を表し、試料３０ｇを溶解させたメタノール５０ｍｌに、０．００５ｍｏｌ／Ｌの希塩酸を滴下していき、その滴定曲線の変曲点から算出する（ＪＩＳ Ｋ１５５７−４）。
水洗を終了した反応液を蒸留または晶析により精製し、高純度のジオールを得ることができる。
[Separation and washing]
After completion of the reaction, the mixture is allowed to stand to separate oil and water, and the aqueous layer containing formate is removed. Thereafter, the remaining formate, Bronsted base and formaldehyde can be removed by adding water to the organic layer containing wet crystals and washing with stirring. The amount of water is usually 0.01 to 10 times by mass of the organic layer, preferably 0.05 to 5 times by mass. The temperature at the time of water washing is 10-100 degreeC normally, and 50-70 degreeC is preferable. In particular, when the temperature during washing with water is 50 to 70 ° C., formate, Bronsted base and formaldehyde can be removed very efficiently. Although there is no particular limitation on the washing time, the formate, Bronsted base and formaldehyde can be sufficiently removed by usually performing the washing for 10 minutes or more. Further, in the case of carrying out carefully, it is preferably 30 minutes or longer, more preferably 1 hour or longer, particularly preferably 3 hours or longer. Washing with water may be performed a plurality of times as necessary.
The effect of washing with water can be evaluated, for example, by measuring the Controlled Polymerization rate value (CPR) value. The CPR value represents the micro equivalent value of the basic substance contained in 30 g of the sample. 0.005 mol / L dilute hydrochloric acid is added dropwise to 50 ml of methanol in which 30 g of the sample is dissolved, and from the inflection point of the titration curve. Calculate (JIS K1557-4).
The reaction solution that has been washed with water can be purified by distillation or crystallization to obtain a high-purity diol.
以下、実施例により本発明を詳細に説明するが、本発明は以下の例により何ら限定されない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by the following examples.
（実施例１）
内容積３００ｍｌの三口フラスコに、シクロヘキサンカルボキシアルデヒド（ＣＨＣＡ）３９．４ｇ（０．３５ｍｏｌ）、３７質量％ホルムアルデヒド水溶液９６．１ｇ（１．１８ｍｏｌ）を仕込み、窒素雰囲気下、４０℃に加熱した。攪拌下、滴下ロートを用いて２５質量％水酸化ナトリウム水溶液８５．４ｇ（０．５３ｍｏｌ）を３時間３０分かけて添加した。添加終了後、６０℃でさらに２時間撹拌を続けた。反応終了後１５℃に冷却し、撹拌を停止し、生じた固体を濾過して水層を除去した。得られた湿結晶６９．６ｇに対し水を１３９．２ｇ加え６０℃にて３０分撹拌水洗した。洗浄後、固体を濾過して水層を除去し、湿結晶を６８．２ｇ得た。この湿結晶に対しアセトニトリルを９０．７ｇ加え、６０℃まで加熱し溶解させた後５℃に冷却して固体を析出させ晶析精製を行った。湿結晶を乾燥させることで精製１，１−シクロヘキサンジメタノール（ＣＨＤ）を３７．１ｇ得た（収率７２．１％）。
１Ｈ−ＮＭＲ分析（４００ＭＨｚ，ＣＤＣｌ３，ＴＭＳ，ｐｐｍ） δ １．３４〜１．３５（ｍ，−ＣＨ２−，４Ｈ），１．４４〜１．４７（ｍ，−ＣＨ２−，６Ｈ），２．７５（ｔ，−ＯＨ，２Ｈ），３．６１（ｄ，−ＣＨ２−Ｏ，４Ｈ）
Example 1
A three-necked flask having an internal volume of 300 ml was charged with 39.4 g (0.35 mol) of cyclohexanecarboxaldehyde (CHCA) and 96.1 g (1.18 mol) of a 37% by mass aqueous formaldehyde solution and heated to 40 ° C. in a nitrogen atmosphere. Under stirring, 85.4 g (0.53 mol) of 25 mass% aqueous sodium hydroxide solution was added using a dropping funnel over 3 hours and 30 minutes. After the addition was complete, stirring was continued for an additional 2 hours at 60 ° C. After completion of the reaction, the reaction mixture was cooled to 15 ° C., stirring was stopped, and the resulting solid was filtered to remove the aqueous layer. 139.2 g of water was added to 69.6 g of the obtained wet crystals, and the mixture was stirred and washed with water at 60 ° C. for 30 minutes. After washing, the solid was filtered to remove the aqueous layer to obtain 68.2 g of wet crystals. 90.7 g of acetonitrile was added to the wet crystals, heated to 60 ° C. and dissolved, and then cooled to 5 ° C. to precipitate a solid for crystallization purification. The wet crystals were dried to obtain 37.1 g of purified 1,1-cyclohexanedimethanol (CHD) (yield 72.1%).
1 H-NMR analysis (400 MHz, CDCl 3 , TMS, ppm) δ 1.34 to 1.35 (m, —CH 2 —, 4H), 1.44 to 1.47 (m, —CH 2 —, 6H) ), 2.75 (t, -OH, 2H), 3.61 (d, -CH 2 -O, 4H)
（比較例１）
内容積５００ｍｌの三口フラスコに、３７質量％ホルムアルデヒド水溶液１５１．９５ｇ（１．８７ｍｏｌ）を仕込み、窒素雰囲気にて撹拌下、２０℃で滴下ロートを用いて２５質量％水酸化ナトリウム水溶液１４９．８ｇ（０．９４ｍｏｌ）を２時間かけて添加した。その後、窒素雰囲気にて撹拌下、２０℃で滴下ロートを用いてＣＨＣＡ７０．０ｇ（０．６２ｍｏｌ）を１時間３０分かけて添加した。添加終了後、反応温度が２３℃まで上昇し系中の粘度が増大した。その後６０℃に加熱しさらに４時間撹拌を続けた。反応終了後１５℃に冷却し、撹拌を停止し、生じた固体を濾過して水層を除去した。得られた湿結晶９２．９ｇに対し水を１８５．５ｇ加え６０℃にて３０分撹拌水洗した。洗浄後、固体を濾過して水層を除去し、湿結晶を７８．１ｇ得た。この湿結晶に対しアセトニトリルを１０３．９ｇ加え、６０℃まで加熱し溶解させた後５℃に冷却して固体を析出させ晶析精製を行った。湿結晶を乾燥させることで精製ＣＨＤを６１．５ｇ得た（収率６８．３％）。
(Comparative Example 1)
A three-necked flask with an internal volume of 500 ml was charged with 151.95 g (1.87 mol) of a 37% by weight aqueous formaldehyde solution and stirred at 20 ° C. using a dropping funnel at 14 ° C. 0.94 mol) was added over 2 hours. Then, CHCA 70.0g (0.62mol) was added over 1 hour 30 minutes using the dropping funnel at 20 degreeC under stirring in nitrogen atmosphere. After completion of the addition, the reaction temperature rose to 23 ° C. and the viscosity in the system increased. Thereafter, the mixture was heated to 60 ° C. and further stirred for 4 hours. After completion of the reaction, the reaction mixture was cooled to 15 ° C., stirring was stopped, and the resulting solid was filtered to remove the aqueous layer. 185.5 g of water was added to 92.9 g of the obtained wet crystals, and the mixture was stirred and washed with water at 60 ° C. for 30 minutes. After washing, the solid was filtered to remove the aqueous layer to obtain 78.1 g of wet crystals. To this wet crystal, 103.9 g of acetonitrile was added and heated to 60 ° C. to dissolve, then cooled to 5 ° C. to precipitate a solid for crystallization purification. The wet crystals were dried to obtain 61.5 g of purified CHD (yield 68.3%).
（比較例２）
内容積５００ｍｌの三口フラスコに、３７質量％ホルムアルデヒド水溶液１５１．９５ｇ（１．８７ｍｏｌ）を仕込み、窒素雰囲気にて撹拌下、４０℃で滴下ロートを用いて２５質量％水酸化ナトリウム水溶液１４９．８ｇ（０．９４ｍｏｌ）を２時間かけて添加した。この時内温が７４℃まで上昇したことを確認し、反応を中止した。
(Comparative Example 2)
A three-necked flask with an internal volume of 500 ml was charged with 151.95 g (1.87 mol) of a 37% by weight aqueous formaldehyde solution, and stirred with a nitrogen atmosphere at 40 ° C. using a dropping funnel at 149.8 g of a 25% by weight aqueous sodium hydroxide solution ( 0.94 mol) was added over 2 hours. At this time, it was confirmed that the internal temperature rose to 74 ° C., and the reaction was stopped.
（製造例１）
反応器にＣＨＣＡ６６．１０ｋｇ（５８９ｍｏｌ）、３７質量％ホルムアルデヒド水溶液１５３．９０ｋｇ（１８９８ｍｏｌ）を仕込み、窒素雰囲気下、４０℃に加熱した。攪拌下、２５質量％水酸化ナトリウム水溶液１４１．８０ｋｇ（８８６ｍｏｌ）を１２時間かけて添加した。滴下終了後、６０℃でさらに４時間撹拌を続けた。反応終了後１５℃に冷却し、撹拌を停止し、生じた固体を濾過して水層を除去し、粗ＣＨＤを８２．１４ｋｇ得た。
(Production Example 1)
The reactor was charged with 66.10 kg (589 mol) of CHCA and 153.90 kg (1898 mol) of a 37% by mass aqueous formaldehyde solution, and heated to 40 ° C. in a nitrogen atmosphere. Under stirring, 141.80 kg (886 mol) of a 25% by mass aqueous sodium hydroxide solution was added over 12 hours. After completion of the dropwise addition, stirring was further continued at 60 ° C. for 4 hours. After completion of the reaction, the reaction mixture was cooled to 15 ° C., the stirring was stopped, the resulting solid was filtered to remove the aqueous layer, and 82.14 kg of crude CHD was obtained.
（実施例２）
製造例１で得られた粗ＣＨＤ７１．３ｋｇを、水３５０．０ｋｇを用いて６０℃で９時間撹拌水洗した後に、アセトニトリル２３１．３ｋｇを用いて晶析した結果、純度９９．８％の精製ＣＨＤを５３．０ｋｇ得た。含有ナトリウム量は７５．５ｐｐｂであり、ＣＰＲ値は０．１１であった。
(Example 2)
After 71.3 kg of crude CHD obtained in Production Example 1 was stirred and washed with 350.0 kg of water at 60 ° C. for 9 hours and crystallized using 231.3 kg of acetonitrile, purified CHD having a purity of 99.8% was obtained. 53.0 kg was obtained. The sodium content was 75.5 ppb and the CPR value was 0.11.
（比較例３）
製造例１で得られたＣＨＤ８２．１ｋｇを、水２２５．４ｋｇを用いて１５℃で３時間撹拌水洗した後に、アセトニトリル２２９．５ｋｇを用いて晶析した結果、純度９９．８６％の精製ＣＨＤを６０．３ｋｇ得た。含有ナトリウム量は６６４６２ｐｐｂであり、ＣＰＲ値は１０５．５６であった。
(Comparative Example 3)
82.1 kg of CHD obtained in Production Example 1 was stirred and washed with 225.4 kg of water at 15 ° C. for 3 hours, and then crystallized with 229.5 kg of acetonitrile. As a result, purified CHD having a purity of 99.86% was obtained. 60.3 kg was obtained. The amount of sodium contained was 66462 ppb, and the CPR value was 105.56.
本発明により得られる脂環骨格を有するジオールは、コーティング剤、塗料、成形材料、粘接着剤等に用いられるポリエステルの原料等として有用な化合物である。 The diol having an alicyclic skeleton obtained by the present invention is a useful compound as a raw material for polyesters used for coating agents, paints, molding materials, adhesives and the like.
Claims (5)
で表されるアルデヒドとホルムアルデヒドの存在下、反応温度１０〜８０℃でブレンステッド塩基を添加する工程を含む、下記一般式（２）
で表されるジオールの製造方法。 The following general formula (1)
In the presence of aldehyde represented by the formula and formaldehyde, a step of adding a Bronsted base at a reaction temperature of 10 to 80 ° C.
The manufacturing method of diol represented by these.
で表されるアルデヒドである、請求項１に記載の製造方法。 The aldehyde is represented by the following general formula (3)
The manufacturing method of Claim 1 which is an aldehyde represented by these.
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| WO2020004455A1 (en) * | 2018-06-27 | 2020-01-02 | Ｋｈネオケム株式会社 | Alicyclic diol and method for producing same |
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