JPH0262836A - Production of 2-n-butyl-2-ethyl-1,3-propanediol - Google Patents
Production of 2-n-butyl-2-ethyl-1,3-propanediolInfo
- Publication number
- JPH0262836A JPH0262836A JP63212149A JP21214988A JPH0262836A JP H0262836 A JPH0262836 A JP H0262836A JP 63212149 A JP63212149 A JP 63212149A JP 21214988 A JP21214988 A JP 21214988A JP H0262836 A JPH0262836 A JP H0262836A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- ethyl
- butyl
- propanediol
- ethylhexanal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000000034 method Methods 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000012044 organic layer Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- BPOSPHPRYDVTFU-UHFFFAOYSA-N 2-ethylheptane-1,3-diol Chemical compound CCCCC(O)C(CC)CO BPOSPHPRYDVTFU-UHFFFAOYSA-N 0.000 claims 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims 1
- 239000008098 formaldehyde solution Substances 0.000 claims 1
- 229960004592 isopropanol Drugs 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000001298 alcohols Chemical class 0.000 abstract description 3
- 229920000180 alkyd Polymers 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 2
- 239000004814 polyurethane Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 abstract 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 abstract 1
- 235000019256 formaldehyde Nutrition 0.000 description 12
- 239000010410 layer Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HYFFNAVAMIJUIP-UHFFFAOYSA-N 2-ethylpropane-1,3-diol Chemical compound CCC(CO)CO HYFFNAVAMIJUIP-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- -1 2-n-butyl Chemical group 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical group OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は２−エチルヘキサナールとホルムアルデヒドを
アルカリ金属水酸化物の存在下に反応させて２−ｎ−ブ
チル−２−エチル−１゜３−プロパンジオールを製造す
る方法に関する。Detailed Description of the Invention (Industrial Application Field) The present invention produces 2-n-butyl-2-ethyl-1゜3- by reacting 2-ethylhexanal and formaldehyde in the presence of an alkali metal hydroxide. The present invention relates to a method for producing propanediol.
（式中、Ｒ３及びＲ２は脂肪族炭化水素基である）で示
される物質として、工業的にはイソブチルアルデヒドか
らネオペンチルグリコールが大量に製造されている。ネ
オペンチルグリコルはアルキッド樹脂、ポリウレタン、
ポリエステルの原料として使用されている。２−エチル
ヘキサナールから得られる２−ｎ−ブチル−２−エチル
−１，３−プロパンジオールも、ネオペンチルグリコー
ルと同様の用途への利用が期待されている。As a substance represented by the formula (wherein R3 and R2 are aliphatic hydrocarbon groups), neopentyl glycol is industrially produced in large quantities from isobutyraldehyde. Neopentyl glycol is alkyd resin, polyurethane,
Used as a raw material for polyester. 2-n-butyl-2-ethyl-1,3-propanediol obtained from 2-ethylhexanal is also expected to be used for the same purposes as neopentyl glycol.
（従来技術）
２−エチルヘキサナールとホルムアルデヒドをアルカリ
金属水酸化物の存在下に反応させて２−ｎ−ブチル−２
−エチル−１，３−プロパンジオールが得られることは
既に知られている。(Prior art) 2-ethylhexanal and formaldehyde are reacted in the presence of an alkali metal hydroxide to form 2-n-butyl-2.
It is already known that -ethyl-1,3-propanediol can be obtained.
しかし、２−エチルヘキサナール及び目的物が水に実質
的に不溶であるので、この合成反応は通常の方法では水
溶液中において均一相で実施することができない。その
為、種々の方法が提案されている。その方法の一つとし
て、溶媒としてアルコールを大量に使用して、均一相で
１５〜３０℃といった比較的低温で反応させる方法（Ｕ
ＳＰ２４１３８０３号）が知られている。更に、２−エ
チルヘキサナールとホルムアルデヒドをアルカリ金属水
酸化物の存在下先ず１反応器度３０〜６０℃で（１）式
のアルドール縮合反応をさせた後、続いて、反応温度６
５〜９０℃で（２）式の交叉力ニラアロ反応をさせる実
質的に２段階の反応工程に区別された方法（特公昭４８
−４３０８５）が知られている。However, since 2-ethylhexanal and the target product are substantially insoluble in water, this synthetic reaction cannot be carried out in a homogeneous phase in an aqueous solution by conventional methods. Therefore, various methods have been proposed. One method is to use a large amount of alcohol as a solvent and conduct the reaction in a homogeneous phase at a relatively low temperature of 15 to 30°C (U
SP2413803) is known. Furthermore, 2-ethylhexanal and formaldehyde were first subjected to the aldol condensation reaction of formula (1) in the presence of an alkali metal hydroxide at 30 to 60°C in one reactor, and then the reaction temperature was 60°C.
A method that is essentially divided into two reaction steps (Japanese Patent Publication No. 48
-43085) is known.
（１）式：
（２）式・
（式中、Ｍはアルカリ金属を示す）
（発明が解決しようとする課題）
しかしながら、ＵＳＰ２４１３８０３号の方法は、１６
時間もの長時間反応させても、目的物の収率は７３％に
しかすぎない。また、大量のアルコールを溶媒として用
いるので反応器が過大となる欠点がある。(1) Formula: (2) Formula (In the formula, M represents an alkali metal) (Problem to be solved by the invention) However, the method of USP 2413803 is
Even if the reaction is carried out for many hours, the yield of the target product is only 73%. Furthermore, since a large amount of alcohol is used as a solvent, there is a drawback that the reactor becomes too large.
また、特公昭４８−４３０８５の方法は、２段階で反応
させるので操作が煩雑という欠、屯がある。Furthermore, the method disclosed in Japanese Patent Publication No. 48-43085 has the disadvantage that the reaction is complicated in two steps.
（課題を解決するための手段）
本発明者等は、従来技術の問題点を解決するため鋭意研
究を重ねた。その結果、２−エチルヘキサナールとホル
ムアルデヒドをアルカリ金属水酸化物の存在下に、油層
と水層とからなる不均一相で反応させて２−ｎ−ブチル
−２−エチル−１，３−プロパンジオールを製造するに
際し、反応系に炭素数１〜４のアルコールを存在させる
ことにより、反応が大幅に促進されることを見出し本発
明を完成させた。(Means for Solving the Problems) The present inventors have conducted extensive research in order to solve the problems of the prior art. As a result, 2-ethylhexanal and formaldehyde were reacted in the presence of an alkali metal hydroxide in a heterogeneous phase consisting of an oil layer and an aqueous layer, and 2-n-butyl-2-ethyl-1,3-propanediol was produced. The present inventors have completed the present invention by discovering that the reaction is significantly accelerated by the presence of an alcohol having 1 to 4 carbon atoms in the reaction system.
即ち、本発明は２−エチルヘキサナールとホルムアルデ
ヒドをアルカリ金属水酸化物の存在下に、不均一相で反
応させて２−ｎ−ブチル−２−エチル−１，３−プロパ
ンジオールを製造するに際し、反応系に２−エチルヘキ
サナールに対して２重量％以上好ましくは、５重量％以
上の炭素数１〜４のアルコールを存在させることを特徴
とする２−ｎ−ブチル−２−エチル−１，３−プロパン
ジオールの製造方法である。That is, in the present invention, when producing 2-n-butyl-2-ethyl-1,3-propanediol by reacting 2-ethylhexanal and formaldehyde in the presence of an alkali metal hydroxide in a heterogeneous phase, 2-n-butyl-2-ethyl-1,3, characterized in that 2% by weight or more, preferably 5% by weight or more of an alcohol having 1 to 4 carbon atoms is present in the reaction system based on 2-ethylhexanal. - A method for producing propanediol.
本発明によれば、前記した米国特許記載のようにアルコ
ールを大量に用いて均一相で反応しなくても、不均一相
の反応で、反応系に少量の炭素数１〜４のアルコールを
存在させるだけで、しかも収率は大幅に向上し反応時間
も大幅に短縮することができる。According to the present invention, even if a large amount of alcohol is not used to react in a homogeneous phase as described in the above-mentioned US patent, a small amount of alcohol having 1 to 4 carbon atoms is present in the reaction system by a reaction in a heterogeneous phase. In addition, the yield can be greatly improved and the reaction time can be significantly shortened.
又１不均−相での反応において、少量の炭素数１〜４の
アルコールの存在によって、大幅に反応が促進されるこ
とは、従来の公知方法には提供されていない新しい知見
である。Furthermore, in the reaction in one heterogeneous phase, the presence of a small amount of an alcohol having 1 to 4 carbon atoms greatly accelerates the reaction, which is a new finding not provided in conventional known methods.
本発明において、炭素数１〜４のアルコールを反応系に
存在させることの効果は、実施例と比較例から明らかで
ある。例えば、２−エチルヘキサナールに対しメタノー
ル量が７９重量％の（実施例−１）と０．９５重量％の
（比較例）では、その他の条件が同一でも１反応終了液
中の未反応２−エチルヘキサナールは、前者が痕跡にだ
いし後者は仕込の１５％も残存する。しかも、収率は前
者が９４．４％に対し後者は８０％である。In the present invention, the effect of the presence of an alcohol having 1 to 4 carbon atoms in the reaction system is clear from Examples and Comparative Examples. For example, when the amount of methanol is 79% by weight (Example-1) and 0.95% by weight (Comparative Example) based on 2-ethylhexanal, even if other conditions are the same, unreacted 2- As for ethyl hexanal, the former remains in traces, while the latter remains as much as 15% of the original amount. Moreover, the yield is 94.4% for the former and 80% for the latter.
本発明において、炭素数１〜４のアルコールとしては例
えばメタノール、エタノール、ｎ−プロパツール、ｉｓ
ｏ−プロパノール、ｎ−ブタノール、５ｅｃ−ブタノー
ルが挙げられる。これらのアルコールを単独又は複数で
使用することができる。炭素数１〜４のアルコールの使
用量は２−エチルヘキサナールにだい、化２重量％以上
、好ましくは５重量％以上であればよく、大量に用いる
必要はない。大量に用いることは反応器が過大になるし
、又加えたアルコールの回収伽こ多大なエネルギーを必
要とするので、出来るだけ少量にするほうが有利である
。本発明方法は不均一相で反応を行なうものであるので
、溶媒としては水を用いる。水の使用量は反応系の水分
として、１５重量％〜７５重量％の範囲内である。In the present invention, alcohols having 1 to 4 carbon atoms include, for example, methanol, ethanol, n-propanol, is
Examples include o-propanol, n-butanol, and 5ec-butanol. These alcohols can be used alone or in combination. The amount of alcohol having 1 to 4 carbon atoms to be used may be at least 2% by weight, preferably at least 5% by weight, based on 2-ethylhexanal, and there is no need to use a large amount. If a large amount is used, the reactor becomes too large, and recovery of the added alcohol requires a large amount of energy, so it is advantageous to use as little amount as possible. Since the method of the present invention involves a reaction in a heterogeneous phase, water is used as the solvent. The amount of water used is within the range of 15% to 75% by weight as water in the reaction system.
本発明において、アルカリ金属水酸化物としては水酸化
ナトリウム、水酸化カリウムが挙げられる。In the present invention, examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.
反応温度は４０〜８０℃の範囲が好ましく更に好ましく
は５０〜７０℃である。４０℃未満では反応速度が極め
て遅く反応を完結させるのに長時間を必要とする。又、
８０℃を越えると、ホルムアルデヒド同志の反応により
ホルムアルデヒドが目的物の生成に有効に用いられない
。The reaction temperature is preferably in the range of 40 to 80°C, more preferably 50 to 70°C. Below 40°C, the reaction rate is extremely slow and a long time is required to complete the reaction. or,
If the temperature exceeds 80°C, formaldehyde will not be effectively used to produce the target product due to reactions between formaldehydes.
い。stomach.
反応に使用するホルムアルデヒドの量は、２−エチルヘ
キサナールに対し理論モル以上で、好ましくは理論モル
比の１〜１．５倍モルである。反応に使用するアルカリ
金属水酸化物の量は２−エチルヘキサナールに対し理論
モル以上で、好ましくは１〜１，５培モルである。The amount of formaldehyde used in the reaction is at least the theoretical molar amount relative to 2-ethylhexanal, preferably 1 to 1.5 times the theoretical molar ratio. The amount of alkali metal hydroxide used in the reaction is at least a theoretical mole, preferably 1 to 1.5 moles, based on 2-ethylhexanal.
本発明方法では、メタノールを含有するホルムアルデヒ
ド水溶液と２−エチルヘキサナールとからなり且つ４０
〜８０℃好ましくは５０〜７０″Ｃに保たれた混合液中
に、アルカリ金属水酸化物水溶液を連続的に２〜５時間
で供給しながら反応させるのが好ましい。In the method of the present invention, a formaldehyde aqueous solution containing methanol and 2-ethylhexanal are used.
It is preferable to carry out the reaction while continuously feeding an aqueous alkali metal hydroxide solution into the mixture maintained at a temperature of ~80°C, preferably 50~70''C for 2 to 5 hours.
本発明方法により得られた２−ｎ−ブチル−２−エチル
−１，３−プロパンジオールの反応液から２−ｎ−ブチ
ル−２−エチル−１１３−プロパンジオールの精製分離
は、下記の方法を実施することにより達成される。The following method can be used to purify and separate 2-n-butyl-2-ethyl-113-propanediol from the reaction solution of 2-n-butyl-2-ethyl-1,3-propanediol obtained by the method of the present invention. This is achieved through implementation.
即ち反応終了後、残存するアルカリ金属水酸化物を中和
するため、有機酸又は鉱酸を添加する。中和後静置し、
油水分離を行なう。分離した有機層には少量の蟻酸塩が
残存している。この蟻酸塩によって蒸留時に２−ｎ−ブ
チル２−エチル−１，３−プロパンジオールの熱分解が
促進されるので、これを防止するため、リン酸の添加に
より有機層のｐＨを４５〜５．５に調整する。このｐ［
（調整により残存する蟻酸塩が実質的に全てリン酸塩に
なり、前記熱分解が防止されるものと推察される。リン
酸の使用量は通常残存蟻酸塩に対して０，５倍モル程度
である。リン酸は油水分離した有機層に直ちに添加して
もよいが、水を加え撹拌水洗を行い、残存蟻酸基量を低
下させた後に添加してもよい。リン酸添加によりｐＨ調
整された有機層を、必要ならば水洗後、減圧下での精留
に供することにより、精製２−ｎ−ブチル−２−エチル
−１，３−プロパンジオールを得ることが出来る。That is, after the reaction is completed, an organic acid or mineral acid is added to neutralize the remaining alkali metal hydroxide. After neutralization, let stand,
Perform oil/water separation. A small amount of formate remains in the separated organic layer. This formate accelerates thermal decomposition of 2-n-butyl-2-ethyl-1,3-propanediol during distillation, so to prevent this, phosphoric acid is added to adjust the pH of the organic layer to 45-5. Adjust to 5. This p[
(It is presumed that by adjustment, substantially all of the remaining formate becomes phosphate, and the above thermal decomposition is prevented. The amount of phosphoric acid used is usually about 0.5 times the mole of the remaining formate. Phosphoric acid may be added immediately to the oil-water separated organic layer, but it may also be added after adding water and stirring and washing with water to reduce the amount of residual formic acid groups.The pH is adjusted by adding phosphoric acid. Purified 2-n-butyl-2-ethyl-1,3-propanediol can be obtained by washing the organic layer with water if necessary and subjecting it to rectification under reduced pressure.
（発明の効果）
本発明によれば、少量の炭素数１〜４のアルコールを反
応系に存在させることにより、−段の反応で、しかも副
反応を抑制して高収率で高品質の２−ｎ−ブチル−２−
エチル−１゜３−プロパンジオールを効率よく製造する
ことができる。(Effects of the Invention) According to the present invention, by allowing a small amount of alcohol having 1 to 4 carbon atoms to exist in the reaction system, high yield and high quality 2-stage reaction can be achieved by suppressing side reactions. -n-butyl-2-
Ethyl-1°3-propanediol can be efficiently produced.
又、加えるアルコールも少量で効果が顕著であるので、
大量に用いて均一反応を行う公知方法に比べ反応器が小
さくなる利点がある。Also, since the effect is noticeable even with a small amount of alcohol added,
There is an advantage that the reactor is smaller than the known method in which a large amount is used to carry out a homogeneous reaction.
以下、本発明の実施例を示すが、本発明はこれに限定さ
れるものではない。Examples of the present invention will be shown below, but the present invention is not limited thereto.
（実施例）
実施例−１
２−エチルヘキサナール５１３ｇ（４モル）及びメタノ
ール含量５重量％のホルムアルデヒド３７重量％水溶液
８１２ｇ（１０モル）を２℃の反応フラスコに仕込み（
メタノール量は２−エチルヘキサナールに対し７９重量
％）、６０℃に保ちながら、撹拌下に４８重量％水酸化
ナトリウム３９０ｇ （４，６８モル）を３時間かけて
等速滴下した。滴下終了後、その温度で攪拌を１時間続
けた。その後、硫酸的３ｇで中和して反応を終了させた
。この反応液を静置微分液し、油層７７４ｇを得た。こ
の油層をガスクロマトグラフィーで分析したところ、未
反応の２−エチルヘキサナールは痕跡であった。一方、
この油層に水１５ｃＩｇを加え６０℃で撹拌洗浄した。(Example) Example-1 513 g (4 mol) of 2-ethylhexanal and 812 g (10 mol) of a 37 wt% aqueous solution of formaldehyde with a methanol content of 5 wt% were charged into a reaction flask at 2°C (
The amount of methanol was 79% by weight based on 2-ethylhexanal), and 390 g (4.68 mol) of 48% by weight sodium hydroxide was added dropwise at a constant speed over 3 hours with stirring while maintaining the temperature at 60°C. After the dropwise addition was completed, stirring was continued at that temperature for 1 hour. Thereafter, the reaction was terminated by neutralization with 3 g of sulfuric acid. This reaction solution was subjected to static differentiation to obtain 774 g of an oil layer. When this oil layer was analyzed by gas chromatography, traces of unreacted 2-ethylhexanal were found. on the other hand,
15 cIg of water was added to this oil layer and washed with stirring at 60°C.
１０分間撹拌後、静置、分液した。得られた油層に８５
重量％リン酸１．５ｇを加えｐｈを５．０に調整し減圧
下に精留し、１０５−１０７℃／ｌｍｍＨｇの留分とし
て２−ｎ−ブチル−２−エチル−１゜３−プロパンジオ
ール６０５ｇ （２−エチルヘキサナールに対し、収率
９４４％）を得た。After stirring for 10 minutes, the mixture was allowed to stand and the liquids were separated. 85 to the obtained oil layer
Add 1.5 g of wt% phosphoric acid to adjust the pH to 5.0, and rectify under reduced pressure to obtain 2-n-butyl-2-ethyl-1°3-propanediol as a fraction of 105-107°C/lmmHg. 605 g (yield 944% based on 2-ethylhexanal) was obtained.
得られた２−ｎ−ブチル−２−エチル−１゜３−プロパ
ンジオールの溶融色はハーゼン色数５であった。The melt color of the obtained 2-n-butyl-2-ethyl-1°3-propanediol was Hazen color number 5.
実施例−２
メタノール含Ｎ３，３重２％のホルムアルデヒド３７重
量％水、＠液を使用（メタノール量は２−エチルヘキサ
ナールに対し、５．２重量％）した以外は実施例−１と
同様にして、２−ｎ−ブチルへ２−エチル−１，３−プ
ロパンジオール５９６ｇ （収率９３％）を得た。得ら
れた２−ｎ−ブチル−２−エチル−１３−プロパンジオ
ールの溶融色はハーゼン色数５であった。Example-2 Same as Example-1 except that methanol-containing N3,3 2% formaldehyde 37% water, @ solution was used (the amount of methanol was 5.2% by weight based on 2-ethylhexanal). Thus, 596 g (yield: 93%) of 2-ethyl-1,3-propanediol to 2-n-butyl was obtained. The melt color of the obtained 2-n-butyl-2-ethyl-13-propanediol was Hazen color number 5.
尚、反応終了後の油層中の未反応２−エチルヘキサナー
ルは、４％（仕込２−エチルヘキサナールに対し）であ
った。Incidentally, the amount of unreacted 2-ethylhexanal in the oil layer after the completion of the reaction was 4% (based on the charged 2-ethylhexanal).
比較例
メタノール含量０．６重１％のホルムアルデヒド３７１
１１％水溶液を使用（メタノール量は２−エチルヘキサ
ナールに対し、０．９５重量％）した以外は実施例−１
と同様に反応を行なった。反応終了液の油層中の未反応
２−エチルヘキサナールは、１５％（仕込２−エチルヘ
キサナールに対し）も残存していた。この油層を実施例
−１と同様の処理を行なったところ。Comparative example Formaldehyde 371 with methanol content of 0.6% by weight
Example-1 except that a 11% aqueous solution was used (the amount of methanol was 0.95% by weight based on 2-ethylhexanal)
The reaction was carried out in the same manner. As much as 15% (based on the charged 2-ethylhexanal) of unreacted 2-ethylhexanal remained in the oil layer of the reaction-completed liquid. This oil layer was subjected to the same treatment as in Example-1.
得られた２−ｎ−ブチル−２−エチル−１゜３−プロパ
ンジオールは５１３ｇ（収率８０゜０％）であった。The amount of 2-n-butyl-2-ethyl-1.3-propanediol obtained was 513 g (yield: 80.0%).
実施例−３
メタノールの代りにエタノールを使用（エタノール量は
、２−エチルヘキサナールに対し７．９重量％）した以
外は、実施例−１と全く同様にして、２−ｎ−ブチル−
２−エチル１．３−プロパンジオール６０３ｇ （収率
９４６１％）を得た。Example-3 2-n-butyl-
603 g (yield: 9461%) of 2-ethyl 1,3-propanediol was obtained.
得られた２−ｎ−ブチル−２−エチル−１゜３−プロパ
ンジオールの溶融色、ハーゼン色数５であった。The melt color of the obtained 2-n-butyl-2-ethyl-1°3-propanediol had a Hazen color number of 5.
Claims (5)
ルカリ金属水酸化物の存在下に、不均一相で反応させて
２−ｎ−ブチル−２−エチル−１，３−プロパンジオー
ルを製造するに際し、反応系に２−エチルヘキサナール
に対して２重量％以上、好ましくは５重量％以上の炭素
数１〜４のアルコールを存在させることを特徴とする２
−ｎ−ブチル−２−エチル−１，３−プロパンジオール
の製造方法。(1) When producing 2-n-butyl-2-ethyl-1,3-propanediol by reacting 2-ethylhexanal and formaldehyde in the presence of an alkali metal hydroxide in a heterogeneous phase, the reaction system 2, characterized in that an alcohol having 1 to 4 carbon atoms is present in an amount of 2% by weight or more, preferably 5% by weight or more based on 2-ethylhexanal.
- A method for producing n-butyl-2-ethyl-1,3-propanediol.
ール、ｉｓｏ−プロパノール及びブタノールからなる群
より選ばれる少なくとも１種以上のアルコールである請
求項１記載の方法。(2) The method according to claim 1, wherein the alcohol having 1 to 4 carbon atoms is at least one alcohol selected from the group consisting of methanol, ethanol, iso-propanol, and butanol.
記載の方法。(3) Claim 1 or 2, wherein the reaction temperature is 40 to 80°C.
Method described.
２−エチルヘキサナールとからなり且つ４０〜８０℃好
ましくは５０〜７０℃に保たれた混合液中にアルカリ水
酸化物水溶液を連続的に供給しながら反応させることを
特徴とする請求項１記載の方法。(4) Reaction is carried out while continuously supplying an aqueous alkali hydroxide solution to a mixed solution consisting of an aqueous formaldehyde solution containing methanol and 2-ethylhexanal and maintained at a temperature of 40 to 80°C, preferably 50 to 70°C. 2. A method according to claim 1, characterized in that:
後、リン酸を加えて有機層のｐＨを４．５〜５．５に調
整する工程及び ［ｄ］［ｃ］工程で得られた有機層を減圧蒸留に付して
精製２−ｎ−ブチル−２−エチル−１，３−プロパンジ
オールを得る工程 からなることを特徴とする請求項１、２、３または４記
載の方法。(5) The separation and purification method for 2-n-butyl-2-ethyl-1,3-propanediol includes [a] neutralizing the reaction solution with an organic acid or mineral acid, [b] the neutralized reaction solution [c] Adding phosphoric acid to the separated organic layer, after washing the organic layer with water, if desired, to adjust the pH of the organic layer to 4.5 to 5.5; d] [C] The organic layer obtained in step [c] is subjected to vacuum distillation to obtain purified 2-n-butyl-2-ethyl-1,3-propanediol. 2. The method described in 2, 3 or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63212149A JP2649555B2 (en) | 1988-08-26 | 1988-08-26 | Method for producing 2-n-butyl-2-ethyl-1,3-propanediol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63212149A JP2649555B2 (en) | 1988-08-26 | 1988-08-26 | Method for producing 2-n-butyl-2-ethyl-1,3-propanediol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0262836A true JPH0262836A (en) | 1990-03-02 |
| JP2649555B2 JP2649555B2 (en) | 1997-09-03 |
Family
ID=16617701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63212149A Expired - Lifetime JP2649555B2 (en) | 1988-08-26 | 1988-08-26 | Method for producing 2-n-butyl-2-ethyl-1,3-propanediol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2649555B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5618985A (en) * | 1993-06-28 | 1997-04-08 | Neste Oy | Process for the preparation of 2-n-butyl-2-ethyl-1,3-propane diol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4843085A (en) * | 1971-09-29 | 1973-06-22 | ||
| JPS4933169A (en) * | 1972-07-31 | 1974-03-27 | ||
| JPS5557528A (en) * | 1978-10-21 | 1980-04-28 | Huels Chemische Werke Ag | Continuous manufacture of butanedioll1*4 |
| JPS62129233A (en) * | 1985-11-11 | 1987-06-11 | Chisso Corp | Production of purified 2-n-butyl-2-ethyl-1,3-propanediol |
-
1988
- 1988-08-26 JP JP63212149A patent/JP2649555B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4843085A (en) * | 1971-09-29 | 1973-06-22 | ||
| JPS4933169A (en) * | 1972-07-31 | 1974-03-27 | ||
| JPS5557528A (en) * | 1978-10-21 | 1980-04-28 | Huels Chemische Werke Ag | Continuous manufacture of butanedioll1*4 |
| JPS62129233A (en) * | 1985-11-11 | 1987-06-11 | Chisso Corp | Production of purified 2-n-butyl-2-ethyl-1,3-propanediol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5618985A (en) * | 1993-06-28 | 1997-04-08 | Neste Oy | Process for the preparation of 2-n-butyl-2-ethyl-1,3-propane diol |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2649555B2 (en) | 1997-09-03 |
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