CN1091094C - Process for preparing 2,2,4-trimethyl-1,3-pentadiol monoisobutyrate - Google Patents

Abstract

The present invention provides a method for preparing 2, 2, 4-trimethyl-1, 3-pentanediol-monoisobutyric butyrate. One key point of the present invention is that Ba(OH)2.8H2O is directly adopted for reaction in ester synthesis, and the selectivity of the generation of 2, 2, 4-trimethyl-1, 3-pentanediol-monoisobutyric butyrate is improved to more than 96% from 89%. Besides, the colority (platinum and cobalt) of products is changed to below No. 20 from original No. 50, and the quality of products is improved greatly. The other key point of the present invention is that the charging sequence of an aldol condensation process is changed, water and the aqueous solution of sodium hydroxide are filled in a reaction kettle firstly, isobutyraldehyde is slowly added under stirring subsequently, and the phenomenon that reaction can not be controlled easily, for the heat release of reaction is too concentrated, can not be generation.

Description

2,2,4-trimethylammonium-1, the preparation method of 3-pentanediol mono isobutyrate

The present invention relates to a kind of 2,2,4-trimethylammonium-1, the preparation method of 3-pentanediol mono isobutyrate.

That the present invention and previous patent ZL.94 1.06092.6 are raw material equally with the isobutyric aldehyde is synthetic through aldol condensation, ester, azeotropic full gear, underpressure distillation or rectification under vacuum operation realize.That adopts is still two-step process (aldol reaction, ester synthesis reaction), and reaction is easy to control, is suitable for suitability for industrialized production.

Characteristics of the present invention are that the ester synthesis procedure directly adopts solid hydrogen barium oxide Ba (OH) ₂8H ₂O makes catalyzer, makes to generate 2,2, and 4-trimethylammonium-1, the selectivity of 3-pentanediol mono isobutyrate (abbreviation monoesters) is brought up to more than 96% by 89%.And making the look number (platinum cobalt) of product become No. 20 by original No. 50, color and luster is more shallow.

Clear 58-65245 compares with day disclosure special permission communique, and the present invention has raw material isobutyric aldehyde content and the moisture and very not strict advantage of isopropylformic acid requirement.

Clear 58-65245 speaks of, and generates 2,2 if make, 4-trimethylammonium-1, and 3-pentanediol mono isobutyrate selectivity reaches 94.9%, and just palpus use content is 99.85% isobutyric aldehyde.And moisture requirement contains isopropylformic acid below 0.12% (weight) below 0.03% (weight).And isobutyric aldehyde content used in the present invention is 93.66%, to moisture, contain isopropylformic acid and also do not have very strict requirement, generate the principal product selectivity and reach more than 96%.

According to the present invention, the aldol condensation operation is earlier water and aqueous sodium hydroxide solution to be added reactor, chuck leads to water coolant then, under agitation, slowly add isobutyric aldehyde, the limit adds the reaction of isobutyric aldehyde limit, thereby has controlled the aldol reaction temperature effectively, just for increasing the volume of aldol condensation still, expanding the scale of production provides favourable condition for this.Illustrate below in conjunction with process flow sheet of the present invention 2,2,4-trimethylammonium-1, the preparation method of 3-pentanediol mono isobutyrate.Accompanying drawing is 2,2,4-trimethylammonium-1, the preparation method's of 3-pentanediol mono isobutyrate process flow sheet.

The aldol condensation operation:

Water and aqueous sodium hydroxide solution are dropped into the aldol condensation still, chuck water flowing cooling, under agitation slowly add isobutyric aldehyde, control reaction solution pH=12-13, temperature of reaction 28-52 ℃, add and expect that counting the reaction times is 10 minutes-2 hours, reaction solution is cooled to 20-25 ℃ afterwards, left standstill 30 minutes-6 hours, it is standby to get the upper strata oil reservoir.Each material feeding quantity is in following ratio: isobutyric aldehyde: water=1: 0.1-10 (weight)

Reaction formula:

The ester synthesis procedure:

Aldol condensation operation gained oil reservoir is dropped into the ester synthesis reactor, start stirring, chuck leads to steam-heated cal(l)andria, makes reaction solution be warming up to 45 ℃, adds catalyst B a (OH) ₂8H ₂O, its consumption is calculated as follows:

Isobutyric aldehyde: Ba (OH) ₂8H ₂O=100: 1-10 (weight)

In the following formula: Ba (OH) ₂8H ₂O content is more than 98%, control reaction temperature 50-72 ℃, reacts 30 minutes-10 hours.Hou Jiashui is finished in reaction, and its consumption is calculated as follows:

Isobutyric aldehyde: water=6: 1 (weight)

Fully stir and be cooled to 25 ℃, left standstill 1-4 hour, divide the sub-cloud water layer to recycle then, the upper strata oil reservoir is standby.Reaction formula is as follows:

Full gear and underpressure distillation operation:

Ester synthesis procedure gained oil reservoir is dropped into the full gear still, and chuck lead to steam, when gas phase temperature rises to 59 ℃, overhead product is arranged just, collects phlegma, treat layering after, as water of productive use, upper strata aldehyde layer can be used as the use of raw material isobutyric aldehyde with lower aqueous layer.When the still temperature reached 145 ℃, full gear finished.Slow gas clean-up is collected foreshot then, when vacuum tightness reach-during 0.095MPa, collect 140-146 ℃ of fraction, be finished product.

The rectification under vacuum operation:

With underpressure distillation gained content is that product more than 96% drops into the rectification under vacuum still, and after rectifying, product content can reach more than 99%.

Embodiment 1:

(1) aldol condensation:

With 90 kilograms in water and concentration is that 12 kilograms of inputs of 40% sodium hydroxide volume is 1000 liters a stainless steel still, chuck feeds water coolant, starts stirring, when below the liquid temperature drop to 20 ℃, slowly add 360 kilograms of (content 93.66% of isobutyric aldehyde, acid number 15.51mgKOH/g), 35 ℃ of reactions 1 hour, make reaction solution be cooled to 25 ℃ then, it is 1000 liters standing demix groove that reaction solution is moved into volume, left standstill 2 hours, and divided the sub-cloud water layer to recycle, the upper strata oil reservoir is standby.

(2) ester is synthetic:

It is in 1000 liters the synthetic enamel still of ester, to start stirring that 351 kilograms in the oil reservoir that the aldol condensation operation is obtained drops into volume, and chuck lead to steam, makes the liquid temperature rise to 45 ℃, stops then heating, and when the liquid temperature no longer rises, under agitation adds catalyst B a (OH) ₂8H ₂16 kilograms of O (content 98%).The liquid temperature rises to more than 65 ℃ by reaction heat, intermittently heating then, kept 1.5 hours at 65-70 ℃, add 60 kilograms in water then, after fully stirring, it is 1000 liters standing demix groove that reaction solution is moved into volume, leaves standstill 4 hours, divide sub-cloud water and 80 kilograms of recyclings of catalyzer, 343 kilograms in upper strata oil reservoir is standby.

(3) azeotropic full gear and underpressure distillation:

It is that the logical pressure of chuck is the following steam-heated cal(l)andria of 0.6MPa, slowly heats up in 1000 liters the stainless steel full gear and underpressure distillation still that 343 kilograms in the synthetic oil reservoir that obtains of ester is moved into volume, and the liquid temperature finally is controlled at below 145 ℃.Overhead product left standstill 1 hour.Layering then, lower layer of water is as the reaction water, and the upper strata oil reservoir is used as the raw material isobutyric aldehyde for 85 kilograms, and gas clean-up is gradually collected foreshot then.When vacuum tightness bring up to-during 0.095MPa, collecting gas phase temperature is 140-146 ℃ of fraction, is finished product.Product weight is 223 kilograms, and it is composed as follows:

2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate are 96.78%, 2,2, and 4-trimethylammonium-1,3-pentanediol are 2.94%, and isobutyric aldehyde is 0.16%.

Calculation of yield:

$=\frac{223\×96.78\%}{360\×93.66\%}\×100\%=64.01\%$

$=\frac{223\×96.78\%}{(360\×93.66\%)-(85\×90.00\%)}\×100\%=82.79\%$

Rectifying: it is 1000 liters of rectification under vacuum stills that this product is dropped into volume, during rectifying vacuum tightness be-more than the 0.098MPa, reflux ratio R=3-4, what at first obtain is 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate, its content are more than 99%.

Embodiment 2:

Ester synthesis procedure catalyst system therefor Ba (OH) ₂8H ₂The O consumption is 8 kilograms.Other is all identical with embodiment 1.Products therefrom weight is 205 kilograms, and it is composed as follows:

2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate content 96.03%; 2,2,4-trimethylammonium-1,3-pentanediol content 1.59%; Isobutyric aldehyde content 0.75%; Other is 1.63%.

One-pass yield: 58.39%

Overall yield: 81.08%

Embodiment 3:

Ester synthesis procedure catalyst system therefor is Ba (OH) ₂H ₂O, its consumption are 9.6 grams, and all weight of material are the thousandth of embodiment 1, and other is all identical with embodiment 1.

Products therefrom heavily is 202.9 grams, and product contains 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate 96.01%; 2,2,4-trimethylammonium-1,3-pentanediol 2.10%; Isobutyric aldehyde 0.80%; Other is 1.10% years old.

One-pass yield: 57.80%

Overall yield: 79.26%

Embodiment 4:

Ester synthesis procedure catalyst system therefor is BaO, and its consumption is 7.8g, and all weight of material are the thousandth of embodiment 1, and other is all identical with embodiment 1, and products therefrom heavily is 145 grams.

Product contains 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate 94.97%;

2,2,4-trimethylammonium-1,3-pentanediol 2.85%; Isobutyric aldehyde 0.49%; Other is 1.69% years old.

One-pass yield: 40.84%

Overall yield: 81.82%

Claims (2)

1, a kind of 2,2,4-trimethylammonium-1, the preparation method of 3-pentanediol mono isobutyrate is to be raw material with the isobutyric aldehyde, carries out according to following operation:

Aldol condensation, ester are synthetic, azeotropic full gear and underpressure distillation, rectification under vacuum, it is characterized in that:

(1), in the aldol condensation operation, earlier water and aqueous sodium hydroxide solution are dropped into the aldol condensation still, chuck water flowing cooling then, under agitation slowly add isobutyric aldehyde, control reaction solution pH=12-13, temperature of reaction 28-52 ℃, add and expect that counting the reaction times is 10 minutes-2 hours, reaction solution is cooled to 20-25 ℃ afterwards, leaves standstill 30 minutes-6 hours, and it is standby to get the upper strata oil reservoir;

Each material feeding quantity is in following ratio:

Isobutyric aldehyde: water=1: 0.1-10 (weight)

(2), in the ester synthesis procedure, be that aldol condensation operation gained oil reservoir is dropped into the ester synthesis reactor, start stirring, chuck lead to steam-heated cal(l)andria, makes reaction solution be warming up to 45 ℃, adding catalyst B a (OH) ₂8H ₂O, its consumption is calculated as follows:

Isobutyric aldehyde: Ba (OH) ₂8H ₂O=100: 1-10 (weight)

In the following formula: Ba (OH) ₂8H ₂O content is more than 98%, and control reaction temperature 50-72 ℃ was reacted 30 minutes-10 hours, added water then, stirs, and standing demix divides the sub-cloud water layer, and it is standby to obtain the upper strata oil reservoir;

(3), oil reservoir that the ester synthesis procedure is obtained drops into full gear and underpressure distillation still, taken off aldehyde after underpressure distillation acquisition content is 2,2 more than 96%, 4-trimethylammonium-1,3-pentanediol mono isobutyrate;

(4), rectification under vacuum: the underpressure distillation product drops into the rectification under vacuum still, and obtaining content through rectifying is more than 99% 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate.

2, a kind of 2,2 according to claim 1,4-trimethylammonium-1, the preparation method of 3-pentanediol mono isobutyrate is characterized in that ester catalyzer that synthesis procedure adds is Ba (OH) ₂8H ₂O or Ba (OH) ₂H ₂O or BaO.