Preparation method of N,N-bis(2-hydroxyethyl)isopropanolamine

CN102924301A

Abstract

The invention relates to a preparation method of N,N-bis(2-hydroxyethyl)isopropanolamine, which

comprises the following steps: weighing diethanolamine, polymerization inhibitor, water and
epoxypropane according to a preset ratio; adding the diethanolamine, the polymerization inhibitor and the
water into a reactor with a stirring device, and evenly stirring; and then, dropwisely adding the
epoxypropane, controlling the reaction temperature at 35-95 DEG C, stirring to react for 2-10 hours, and
performing reduced pressure distillation to obtain the N,N-bis(2-hydroxyethyl)isopropanolamine product,
wherein the mol ratio of the diethanolamine to the epoxypropane to the water is (0.5-1.5):(0.5-1.5):(1-1.8),
and the amount of the polymerization inhibitor is 0.01-0.2% of the mass sum of the diethanolamine and
the epoxypropane. The preparation method has the advantages of simple operation process, low
production cost and high yield, and is suitable for industrial production.

Description

A kind of preparation method of di-alcohol monoisopropanolamine

Technical field

The present invention relates to a kind of preparation method of di-alcohol monoisopropanolamine.

Background technology

The alcamines material is the important organic compound of a class, and the structure that it is unique
and charge distribution are used as tensio-active agent usually, are widely used in industrial chemicals,
each field such as pigment, medicine, material of construction.China realizes suitability for industrialized
production in the sixties in 20th century.

The di-alcohol monoisopropanolamine is a kind of in numerous alcamines materials, in 20th century four
the fifties be designed research and development.Along with branch-shape polymer transports carrier at
biomedical sector from simple medicine, be applied to the complicated many aspects such as imaging of
medical, its synthetic used important source material di-alcohol monoisopropanolamine comes into one's
own.The di-alcohol monoisopropanolamine has good grinding aid and improves the cement early
strength performance as tensio-active agent, in recent years in the cement industry saliency, and enjoys
the insider to pay close attention to.

The existing method for preparing the di-alcohol monoisopropanolamine has multiple, all has some
defective:
Such as the disclosed di-alcohol monoisopropanolamine of US2649483 (1948) preparation method, be in
diethanolamine, to drip propylene oxide, below the control temperature 70 C, be stirred to and react
completely, underpressure distillation gets di-alcohol monoisopropanolamine product, yield 93.2%, its
product yield is relatively low;
Journal of the Chemical Society and for example; (1949). the disclosed di-alcohol monoisopropanolamine
of 547-552 page or leaf preparation method is that diethanolamine and chloropropane are reacted in the
aqueous solution, is heated to 100 ℃, reaction 12h, its temperature of reaction is higher, long reaction
time, cost is higher;
Journal of Organic Chemistry 1960.25.1378-1386 page or leaf also discloses a kind of di-alcohol
monoisopropanolamine preparation method: drip propylene oxide in the chloroformic solution of
diethanolamine, reaction is spent the night, steam except the chloroform solvent, it need adopt organic
solvent, and cost is higher.

Summary of the invention

Technical problem to be solved by this invention is to provide a kind of product yield higher, the
preparation method of the di-alcohol monoisopropanolamine that production cost is lower.
The technical scheme that the present invention solves its technical problem employing is: a kind of
preparation method of di-alcohol monoisopropanolamine may further comprise the steps:
After taking by weighing diethanolamine, stopper, water and propylene oxide by predetermined
proportion, in with the reactor of whipping appts, add first diethanolamine, stopper and water, stir, then
drip propylene oxide, the control temperature of reaction is at 35-95 ℃ (preferred 40-80 ℃), the preferred
6-8h of stirring reaction 2-10h(), underpressure distillation gets di-alcohol monoisopropanolamine
product;
Described diethanolamine, propylene oxide with the mol ratio of water are: (0.5-1.5): (0.5-1.5): (1-1.8) (the
preferred diethanolamine mol ratio identical with the propylene oxide mole number);
The consumption of described stopper is the 0.01%-0.2% (preferred 0.015%-0.1%) of diethanolamine and
propylene oxide quality sum.
Further, described stopper can be Resorcinol, MEHQ, cuprous chloride or thiophene piperazine.
Further, the vacuum tightness of described underpressure distillation is the preferred 0.1mmHg of 0.05-
0.2mmHg(), distillation temperature is 148-200 ℃ (preferred 150-160 ℃).
Reaction equation of the present invention is as follows:
It is reaction raw materials that the present invention adopts diethanolamine and propylene oxide, low for
the propylene oxide boiling point, easily ring-opening polymerization, the characteristics such as
exothermic heat of reaction, design alternative adds stopper, take water as reaction solvent, react under
the low temperature, the method is easy and simple to handle, and production cost is low, productive rate
high (can reach more than 94.4%) is fit to suitability for industrialized production.

Embodiment

The invention will be further described below in conjunction with embodiment.

Comparative example

In the 250mL four-hole bottle of mechanical stirrer, thermometer, reflux condensing tube, constant
pressure funnel is housed, add 31.5g (0.3mol) diethanolamine, 7g (0.38mol) water, stir; By constant
pressure funnel, in four-hole bottle, drip 17.4g (0.3mol) propylene oxide, temperature is at 45-60 ℃ in the
control reaction flask, stirring reaction, gas chromatographic analysis is carried out in every 30min
sampling, and is constant to the product quality percentage concentration, reaction times is 7h, obtain
colourless liquid, underpressure distillation, 148-152 ℃ cut when collecting 0.1mmHg, obtain di-alcohol
monoisopropanolamine product, yield 90.7%.

Embodiment 1

In the 250mL four-hole bottle of mechanical stirrer, thermometer, reflux condensing tube, constant
pressure funnel is housed, add 31.5g (0.3mol) diethanolamine, 0.04g (0.36mmol) Resorcinol, 7g
(0.38mol) water, stir; By constant pressure funnel, in four-hole bottle, drip 17.4g (0.3mol) propylene oxide,
temperature is at 45-60 ℃ in the control reaction flask, stirring reaction, gas chromatographic analysis is
carried out in every 30min s ampling, and is constant to the product quality percentage concentration,
reaction times is 8h, obtain Vandyke brown look liquid, underpressure distillation, 148-152 ℃ cut when
collecting 0.1mmHg, obtain di-alcohol monoisopropanolamine product, yield 94.4%.

Embodiment 2

In the 250mL four-hole bottle of mechanical stirrer, thermometer, reflux condensing tube, constant
pressure funnel is housed, add 31.5g (0.3mol) diethanolamine, 0.01g (0.09mmol) Resorcinol, 7g
(0.38mol) water, stir; By constant pressure funnel, in four-hole bottle, drip 17.4g (0.3mol) propylene oxide,
temperature is at 45-60 ℃ in the control reaction flask, stirring reaction, gas chromatographic analysis is
carried out in every 30min sampling, and is constant to the product quality percentage concentration,
reaction times is 8h, obtain light brown liquid, underpressure distillation, 148-152 ℃ cut when collecting
0.1mmHg, obtain di-alcohol monoisopropanolamine product, yield 97.3%.

Embodiment 3

In the 250mL four-hole bottle of mechanical stirrer, thermometer, reflux condensing tube, constant
pressure funnel is housed, add 31.5g (0.3mol) diethanolamine, 0.04g (0.32mmol) MEHQ, 7g (0.38mol)
water, stir; By constant pressure funnel, in four-hole bottle, drip 17.4g (0.3mol) propylene oxide,
temperature is at 45-60 ℃ in the control reaction flask, stirring reaction, gas chromatographic analysis is
carried out in every 30min sampling, and is constant to the product quality percentage concentration,
reaction times is 7h, obtain colourless liquid, underpressure distillation, 148-152 ℃ cut when collecting
0.1mmHg, obtain di-alcohol monoisopropanolamine product, yield 94.6%.

Embodiment 4

In the 250mL four-hole bottle of mechanical stirrer, thermometer, reflux condensing tube, constant
pressure funnel is housed, add 31.5g (0.3mol) diethanolamine, 0.01g (0.08mmol) MEHQ, 7g (0.38mol)
water, stir; By constant pressure funnel, in four-hole bottle, drip 17.4g (0.3mol) propylene oxide,
temperature is at 45-60 ℃ in the control reaction flask, stirring reaction, gas chromatographic analysis is
carried out in every 30min sampling, and is constant to the product quality percentage concentration,
reaction times is 7h, obtain colourless liquid, underpressure distillation, 148-152 ℃ cut when collecting
0.1mmHg, obtain di-alcohol monoisopropanolamine product, yield 95.5%.

Embodiment 5

In the 250mL four-hole bottle of mechanical stirrer, thermometer, reflux condensing tube, constant
pressure funnel is housed, add 31.5g (0.3mol) diethanolamine, 0.04g (0.4mmol) cuprous chloride, 7g
(0.38mol) water, stir; By constant pressure funnel, in four-hole bottle, drip 17.4g (0.3mol) propylene oxide,
temperature is at 45-60 ℃ in the control reaction flask, stirring reaction, gas chromatographic analysis is
carried out in every 30min sampling, and is constant to the product quality percentage concentration,
reaction times is 8h, obtain light blue liquid, underpressure distillation, 148-152 ℃ cut when collecting
0.1mmHg, obtain di-alcohol monoisopropanolamine product, yield 96.5%.

Embodiment 6

In the 250mL four-hole bottle of mechanical stirrer, thermometer, reflux condensing tube, constant
pressure funnel is housed, add 31.5g (0.3mol) diethanolamine, 0.01g (0.1mmol) cuprous chloride, 7g
(0.38mol) water, stir; By constant pressure funnel, in four-hole bottle, drip 17.4g (0.3mol) propylene oxide,
temperature is at 45-60 ℃ in the control reaction flask, stirring reaction, gas chromatographic analysis is
carried out in every 30min sampling, and is constant to the product quality percentage concentration,
reaction times is 7h, obtain caerulescent liquid, underpressure distillation, 148-152 ℃ cut when collecting
0.1mmHg, obtain di-alcohol monoisopropanolamine product, yield 94.7%.

Embodiment 7

In the 250mL four-hole bottle of mechanical stirrer, thermometer, reflux condensing tube, constant
pressure funnel is housed, add 31.5g (0.3mol) diethanolamine, 0.04g (0.2mmol) thiophene piperazine, 7g
(0.38mol) water, stir; By constant pressure funnel, in four-hole bottle, drip 17.4g (0.3mol) propylene oxide,
temperature is at 45-60 ℃ in the control reaction flask, stirring reaction, gas chromatographic analysis is
carried out in every 30min sampling, and is constant to the product quality percentage concentration,
reaction times is 7h, obtain lilac liquid, underpressure distillation, 148～152 ℃ cut when collecting
0.1mmHg, obtain di-alcohol monoisopropanolamine product, yield 95.1%.

Embodiment 8

In the 250mL four-hole bottle of mechanical stirrer, thermometer, reflux condensing tube, constant
pressure funnel is housed, add 31.5g (0.3mol) diethanolamine, 0.01g (0.05mmol) thiophene piperazine,
7g (0.38mol) water, stir; By constant pressure funnel, in four-hole bottle, drip 17.4g (0.3mol) propylene
oxide, temperature is at 45-60 ℃ in the control reaction flask, stirring reaction, gas chromatographic
analysis is carried out in every 30min sampling, and is constant to the product quality percentage
concentration, reaction times is 8h, obtain lilac liquid, underpressure distillation, 148-152 ℃ cut when
collecting 0.1mmHg, obtain di-alcohol monoisopropanolamine product, yield 96.3%.

The present invention selects Resorcinol, MEHQ, cuprous chloride, four kinds of stoppers of thiophene
piperazine, its different addition quantity compares experiment to the impact of reaction times and
production concentration, result's demonstration is compared (seeing Table 1) with the reacting phase
that does not add stopper, adds stopper and can obviously improve reaction conversion ratio, improves
productive rate.

Claims (5)

1. the preparation method of a di-alcohol monoisopropanolamine is characterized in that, may further

comprise the steps:

After taking by weighing diethanolamine, stopper, water and propylene oxide by predetermined
proportion, in with the reactor of whipping appts, add first diethanolamine, stopper and water, stir, then
drip propylene oxide, the control temperature of reaction is at 35-95 ℃, stirring reaction 2-10h,
underpressure distillation gets di-alcohol monoisopropanolamine product;

The mol ratio of described diethanolamine, propylene oxide and water is: (0.5-1.5): (0.5-1.5): (1-1.8);

The consumption of described stopper is the 0.01%-0.2% of diethanolamine and propylene oxide quality
sum.

2. the preparation method of di-alcohol monoisopropanolamine according to claim 1 is characterized in

that, described stopper is Resorcinol, MEHQ, cuprous chloride or thiophene piperazine.

3. the preparation method of di-alcohol monoisopropanolamine according to claim 1 and 2 is

characterized in that, the vacuum tightness of described underpressure distillation is 0.05-0.2mmHg, and
distillation temperature is 148-200 ℃.

4. the preparation method of di-alcohol monoisopropanolamine according to claim 1 and 2 is

characterized in that, the reaction times is 6-8h, and temperature of reaction is 40-80 ℃.

5. the preparation method of di-alcohol monoisopropanolamine according to claim 1 and 2 is

characterized in that, the consumption of described stopper is the 0.015%-0.1% of diethanolamine and
propylene oxide quality sum.