CN105646434A - Method for reducing acidity and moisture content of caprolactone product - Google Patents
Method for reducing acidity and moisture content of caprolactone product Download PDFInfo
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- CN105646434A CN105646434A CN201410642741.XA CN201410642741A CN105646434A CN 105646434 A CN105646434 A CN 105646434A CN 201410642741 A CN201410642741 A CN 201410642741A CN 105646434 A CN105646434 A CN 105646434A
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Abstract
The present invention discloses a method for reducing acidity and moisture content of a caprolactone product, the caprolactone product is deacidified by an adsorption column filled with base anion-exchanged resin, and then is dehydrated by an adsorption column filled with 3A or 4A molecular sieve, liquid space velocity of the adsorption column filled with the base anion-exchanged resin is 0.1 to 1.0h<-1>, liquid space velocity of the adsorption column filled with the molecular sieve is 0.1 to 2.0 h<-1>. The moisture content of the caprolactone treated by the method can be reduced to 50mg / kg or less, and the acidity of the caprolactone treated by the method can be reduced to 0.06mgKOH / g or less.
Description
Technical field
The invention discloses a kind of method reducing caprolactone product acidity and moisture, belong to technical field of organic synthesis.
Background technology
6-caprolactone (��-CL) is a kind of important organic synthesis intermediate, such as can be used to synthesize polycaprolactone and polycaprolactone polyol, also can with other esters copolymerization or blending and modifying, polycaprolactone and polymer-modified because it has good biocompatibility, avirulence, biodegradable and good oozes the property of medicine, obtains good application in degradative plastics and biomedicine. Polycaprolactone polyol is one of initiation material of high-grade polyurethane material, and owing to caprolactone is relatively more active, minor amount of water, acid etc. can promote the reaction of caprolactone, is unfavorable for that the long period of caprolactone stores and transport. Apparent result is that most that caprolactone places its colour changed into yellow after a period of time, colourity increases, and acidity also increases simultaneously, if such caprolactone is used for being polymerized, can affect the color of polyreaction and polymerization product. In order to solve this problem, industrial usually employing rectification mode, by rotten caprolactone re-distillation, which adds energy resource consumption; US Patent No. 4360682 reports the method that a kind of dihydroxy benzene compound such as hydroquinone stablizes caprolactone, but it mainly plays the effect of stable caprolactone colourity, but owing to hydroquinone is noxious substance, boiling point is higher, stay in polymerization product after caprolactone polymerization reacts, affect the use scope of polymerization product; CN101781280A reports a kind of preparation method preparing colour stable caprolactone, utilize the adsorption of activated carbon, by caprolactone higher for colourity and activated carbon at 25-80 DEG C haptoreaction 0.1-10 hour, thus the colourity of caprolactone being dropped to 10 platinum cobalt colourities and following. Although the colourity of stable caprolactone is had certain effect by the method, but can not play good effect to reducing acidity and moisture in caprolactone, and needs stirring reaction, solid-liquid separation in course of reaction, operate not easy.
Summary of the invention
Present invention aim at providing a kind of simple to operate, method that caprolactone product acidity and moisture can be reduced, by reducing caprolactone product acidity and moisture, make caprolactone be more convenient for storing and long-distance sand transport.
The invention discloses a kind of method reducing caprolactone product acidity and moisture, described method carries out according to following steps: by caprolactone product by equipped with basic anion exchange resin adsorption column deacidification;Then again through equipped with 3A or 4A molecular sieve adsorption post dehydration, wherein, the liquid air speed in basic anion exchange resin adsorption column is 0.1-1.0h-1, the liquid air speed in molecular sieve adsorption post is 0.1-2.0h-1��
Liquid air speed in described basic anion exchange resin adsorption column is preferably 0.1-0.8h-1; Liquid air speed in molecular sieve adsorption post is preferably 0.2-1.5h-1��
Liquid air speed more preferably 0.1-0.5h in described basic anion exchange resin adsorption column-1; Liquid air speed more preferably 0.2-1.0h in molecular sieve adsorption post-1��
One of most preferred scheme is:
Liquid air speed in strong-base anion-exchange resin adsorption column is 0.1h-1; Liquid air speed in 4A molecular sieve adsorption post is 0.2h-1��
By above-mentioned preferably, it is possible to obtain simultaneously the best deacidification and dehydrating effect.
The basic anion exchange resin used is strong-base anion-exchange resin or weak-base anion-exchange resin.
Strong-base anion-exchange resin is preferably used.
Strong-base anion-exchange resin D201, D301 type resin etc. that present invention preferably uses.
If the acidity not carrying out the caprolactone product of deacidification, processed is generally 0.18-0.25mgKOH/g, water content is 0.15-0.20%.
Beneficial effects of the present invention
Collaborative by basic anion exchange resin adsorption column deacidification and 3A or 4A molecular sieve adsorption post dehydration of the present invention, and plus the cooperation of the restriction of liquid air speed in two steps, the moisture in caprolactone product can be made to be reduced to below 50mg/kg, acidity is reduced to below 0.06mgKOH/g, it is thus achieved that be far superior to deacidification and the dehydrating effect of prior art. And the present invention is simple to operate, it is possible to be used for processing large batch of caprolactone, be suitable for industrial applications. After present invention deacidification effectively and dehydration, it is simple to caprolactone produces, stores and long-distance sand transport. The present invention solves puzzlement caprolactone industry problem for a long time by design cleverly, has huge value from the angle of economic benefit.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the absorbing process of the present invention, I is wherein basic anion exchange resin adsorption column, II for 3A or 4A molecular sieve adsorption post; I and II series connection.
Detailed description of the invention
Following example are intended to that the invention will be further described, rather than the restriction present invention.
Embodiment 1
By caprolactone (purity 99.96%, acidity 0.2mgKOH/g, moisture 1500mg/kg) squeeze into I adsorption column (�� 25 �� 500mm as shown in Figure 1 with pump, built-in strong basic ion exchange resin) and II adsorption column (�� 25 �� 500mm, built-in 4A molecular sieve), in I adsorption column, liquid air speed is 0.1, in II adsorption column, liquid air speed is 0.2, sample analysis II adsorption column outlet caprolactone acidity and moisture, moisture is 0mg/kg, acidity 0.03mgKOH/g.
Embodiment 2
By caprolactone (purity 99.96%, acidity 0.2mgKOH/g, moisture 1500mg/kg) squeeze into I adsorption column (�� 25 �� 500mm as shown in Figure 1 with pump, built-in strong basic ion exchange resin) and II adsorption column (�� 25 �� 500mm, built-in 4A molecular sieve), in I adsorption column, liquid air speed is 0.5, in II adsorption column, liquid air speed is 1.0, sample analysis II adsorption column outlet caprolactone acidity and moisture, moisture is 50mg/kg, acidity 0.06mgKOH/g.
Embodiment 3
By caprolactone (purity 99.96%, acidity 0.2mgKOH/g, moisture 1500mg/kg) squeeze into I adsorption column (�� 25 �� 500mm as shown in Figure 1 with pump, built-in strong basic ion exchange resin) and II adsorption column (�� 25 �� 500mm, built-in 4A molecular sieve), in I adsorption column, liquid air speed is 1.0, in II adsorption column, liquid air speed is 2.0, sample analysis II adsorption column outlet caprolactone acidity and moisture, moisture is 80mg/kg, acidity 0.1mgKOH/g.
Comparative example 1
By caprolactone (purity 99.96%, acidity 0.2mgKOH/g, moisture 1500mg/kg) squeeze into I adsorption column (�� 25 �� 500mm as shown in Figure 1 with pump, built-in strong basic ion exchange resin) and II adsorption column (�� 25 �� 500mm, built-in 4A molecular sieve), in I adsorption column, liquid air speed is 2.5, in II adsorption column, liquid air speed is 5.0, sample analysis II adsorption column outlet caprolactone acidity and moisture, moisture is 500mg/kg, acidity 0.18mgKOH/g.
Comparative example 2
By caprolactone (purity 99.96%, acidity 0.2mgKOH/g, moisture 1500mg/kg) squeeze into I adsorption column (�� 25 �� 500mm as shown in Figure 1 with pump, built-in strong basic ion exchange resin), liquid air speed is 0.5, sample analysis I adsorption column outlet caprolactone acidity and moisture, moisture is 1400mg/kg, acidity 0.06mgKOH/g.
Comparative example 3
By caprolactone (purity 99.96%, acidity 0.2mgKOH/g, moisture 1500mg/kg) squeeze into II adsorption column (�� 25 �� 500mm as shown in Figure 1 with pump, built-in 4A molecular sieve), liquid air speed is 1.0, sample analysis II adsorption column outlet caprolactone acidity and moisture, moisture is 80mg/kg, acidity 0.22mgKOH/g.
Comparative example 4
By caprolactone (purity 99.96%, acidity 0.2mgKOH/g, moisture 1500mg/kg) squeeze into adsorption column (�� 25 �� 500mm with pump, built-in activated carbon), liquid air speed is 0.5, sample analysis adsorption column outlet caprolactone acidity and moisture, moisture is 1300mg/kg, acidity 0.16mgKOH/g.
Effect example 1
The caprolactone processed without the present invention is stored placement at normal temperatures and pressures, becomes cloudy after 6 months; Under the same conditions, without muddy after being placed 6 months by the caprolactone after processed by the invention, colourity is unchanged.
Claims (5)
1. the method reducing caprolactone product acidity and moisture, it is characterised in that by caprolactone product by equipped with basic anion exchange resin adsorption column deacidification; Then again through equipped with 3A or 4A molecular sieve adsorption post dehydration, wherein, the liquid air speed in basic anion exchange resin adsorption column is 0.1-1.0h-1, the liquid air speed in molecular sieve adsorption post is 0.1-2.0h-1��
2. method according to claim 1, it is characterised in that the liquid air speed in basic anion exchange resin adsorption column is 0.1-0.8h-1; Liquid air speed in molecular sieve adsorption post is 0.2-1.5h-1��
3. method according to claim 1, it is characterised in that the liquid air speed in basic anion exchange resin adsorption column is 0.1-0.5h-1; Liquid air speed in molecular sieve adsorption post is 0.2-1.0h-1��
4. the method according to any one of claim 1-3, it is characterised in that described basic anion exchange resin adsorption column is strong-base anion-exchange resin adsorption column.
5. method according to claim 1, it is characterised in that employing is strong-base anion-exchange resin adsorption column, the liquid air speed in post is 0.1h-1; Liquid air speed in 4A molecular sieve adsorption post is 0.2h-1��
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5337679A (en) * | 1976-09-16 | 1978-04-06 | Mitsubishi Chem Ind Ltd | Purification of epsilon-caprolactone |
| JPH11140075A (en) * | 1997-11-07 | 1999-05-25 | Daicel Chem Ind Ltd | Purification of epsilon-caprolactone |
| CN101993386A (en) * | 2010-11-03 | 2011-03-30 | 天津大学 | Method for preparing electronic-grade N, N-dimethylformamide by ion exchange resin method |
| CN102391238A (en) * | 2011-09-28 | 2012-03-28 | 江苏飞翔化工股份有限公司 | Method for preparing epsilon-caprolactone by catalyzing oxidation of cyclohexanone |
-
2014
- 2014-11-11 CN CN201410642741.XA patent/CN105646434B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5337679A (en) * | 1976-09-16 | 1978-04-06 | Mitsubishi Chem Ind Ltd | Purification of epsilon-caprolactone |
| JPH11140075A (en) * | 1997-11-07 | 1999-05-25 | Daicel Chem Ind Ltd | Purification of epsilon-caprolactone |
| CN101993386A (en) * | 2010-11-03 | 2011-03-30 | 天津大学 | Method for preparing electronic-grade N, N-dimethylformamide by ion exchange resin method |
| CN102391238A (en) * | 2011-09-28 | 2012-03-28 | 江苏飞翔化工股份有限公司 | Method for preparing epsilon-caprolactone by catalyzing oxidation of cyclohexanone |
Non-Patent Citations (3)
| Title |
|---|
| 吴炜亮 等: "改性脂质的阴离子交换树脂脱酸工艺研究", 《食品工业科技》 * |
| 张敏 等: "乙酰丙酸、甲酸、葡萄糖在碱性树脂上的静态吸附性能", 《江南大学学报(自然科学版)》 * |
| 邵彤 等: "有机羧酸在强碱性阴离子交换树脂上的超当量吸附", 《离子交换与吸附》 * |
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