CN113354805B - Modified polyether amine nonionic surfactant, and preparation method and application thereof - Google Patents

Abstract

The invention relates to the technical field of surfactants, in particular to a modified polyetheramine nonionic surfactant, a preparation method and application thereof. The present invention provides a method for preparing a modified polyetheramine type nonionic surfactant, which comprises dissolving polyetheramine type substances in organic solvent A to obtain a polyetheramine type solution; dissolving reducing sugar type substances in water , to obtain an aqueous solution of reducing sugars; after ultrasonically mixing the polyetheramine solution and the aqueous solution of reducing sugars, heating and stirring to fully react to obtain a crude product; dissolving the crude product in organic solvent B, recrystallization by cooling and rotary evaporation The modified polyetheramine nonionic surfactant is obtained after treatment. The surfactant obtained by the invention not only has the advantages of higher surface activity, foaming performance, foam stabilization performance, emulsifying performance and wetting performance than traditional polyether nonionic surfactants, but also has a relatively simple synthesis process and is suitable for industrial production. , has a wide range of application prospects.

Description

Modified polyetheramine nonionic surfactant, its preparation method and application

technical field

The invention relates to the technical field of surfactants, in particular to a modified polyetheramine nonionic surfactant, a preparation method and application thereof.

Background technique

Surfactants are a class of compounds that contain both hydrophilic and hydrophobic groups in the molecule. It can be aligned on the boundary (surface) surface of the solution. A small amount of surfactant can significantly reduce the surface tension of a solvent (usually water) or change the interfacial state between systems. As an important type of fine chemical products, surfactants are developing rapidly, with rich varieties and large demand. Their application fields have developed from traditional fields such as daily chemicals, oil extraction, and food additions to nanomaterials and pharmaceutical materials. , biotechnology and other new high-tech fields.

Traditional polyetheramine nonionic surfactants have been widely used in spraying, epoxy resin curing agents and gasoline detergents, etc., but such surfactants have high critical micelle concentration (CMC) and foaming. The shortcomings of performance, foam stabilization, wetting and emulsifying properties need to be further improved.

SUMMARY OF THE INVENTION

In order to solve the above technical problems, the technical idea of the present invention is to modify polyetheramines by reducing sugars to synthesize modified polyetheramines nonionic surfactants with a novel structure of sugar amine Schiff base bonds molecules, thereby significantly reducing the critical micelle concentration (CMC) of surfactants, and improving the foaming performance, foam stabilization, wetting and emulsifying properties of surfactants.

The first object of the present invention is to provide a kind of modified polyetheramine nonionic surfactant, and its molecular structure is shown in the following formula:

where R is

The second object of the present invention is to provide a method for preparing the aforementioned modified polyetheramine nonionic surfactant, comprising the following steps:

Dissolving polyetheramines in organic solvent A to obtain polyetheramines solution;

Dissolving reducing sugars in water to obtain reducing sugars aqueous solution;

After ultrasonically mixing the polyetheramine solution and the reducing sugar aqueous solution, heating and stirring to fully react to obtain a crude product;

The crude product was dissolved in organic solvent B, and then the modified polyetheramine nonionic surfactant was obtained by cooling, recrystallization and rotary evaporation.

Among them, the polyetheramine substances and reducing sugar substances used in the present invention are existing compounds, which can be obtained from commercially available products or prepared by existing methods.

)。As an embodiment of the present invention, the polyetheramine substance is polyetheramine M2070 (its molecular structure is

).

As an embodiment of the present invention, the molar ratio of the reducing sugar substance to the polyetheramine M2070 is 1:(1-3).

As an embodiment of the present invention, the temperature of the heating reaction is 50 to 100°C.

As an embodiment of the present invention, the heating reaction time is 6-48 h.

As an embodiment of the present invention, the organic solvent A is at least one of methanol, ethanol, isopropanol, n-butanol, and isoamyl alcohol.

As an embodiment of the present invention, the organic solvent B is ethanol.

The third object of the present invention is to provide the application of a modified polyetheramine nonionic surfactant in daily chemical industry, textile washing, food, pesticide preparation, and medicine preparation.

The fourth object of the present invention is to provide a detergent containing the aforementioned modified polyetheramine-based nonionic surfactant.

Beneficial effects of the present invention:

1. The present invention uses reducing sugars to modify polyetheramines to synthesize a novel sugar-modified polyetheramines nonionic surfactant. The synthesized sugar-modified polyetheramine nonionic surfactants have sugar amine Schiff base bonds, which not only have higher surface activity than traditional polyetheramine nonionic surfactants (the critical micelle concentration is reduced to 10 ^-3 orders of magnitude), also has the advantages of non-toxic, green environmental protection, easy biodegradation and mild properties, is a kind of surfactant with broad application prospects.

2. Compared with the traditional polyetheramine type nonionic surfactant, the modified polyetheramine type nonionic surfactant of the present invention has significantly improved emulsifying performance, foaming performance and wetting performance.

3. The present invention provides a method for preparing a modified polyetheramine nonionic surfactant. The method adopts a one-step reaction, and the crude product can be separated by cooling and layering purification. The preparation process is relatively simple, the operation is convenient, and the whole process is To avoid the use of toxic solvents, it is convenient to realize industrial production. The yield of the modified polyetheramine nonionic surfactant is generally above 40%, and can reach 85% under optimal conditions, which meets the basic requirements of industrial-scale production.

4. The modified polyetheramine nonionic surfactant prepared by the present invention can be applied to the fields of daily chemical industry, textile washing, food, pesticide preparation, medicine preparation, etc. Use requirements for foam properties and wetting properties.

Description of drawings

Fig. 1 is the Fourier transform infrared spectrogram of polyetheramine M2070 and the pale yellow liquid obtained in Example 1.

2 is the Fourier transform infrared spectrum of polyetheramine M2070 and the brown liquid obtained in Example 3.

FIG. 3 is the γ-c curve of the surface tension test results of polyetheramine M2070 and the glucose-modified polyetheramine nonionic surfactants prepared in Examples 1 and 3. FIG.

Detailed ways

The present invention will be further described below with reference to specific embodiments. It should be understood that the following examples are only used to illustrate the present invention rather than to limit the scope of the present invention, and those skilled in the art can make some non-essential improvements and adjustments according to the content of the present invention.

Example 1 (Glucose-modified polyetheramine nonionic surfactant)

Preparation of glucose-modified polyetheramine nonionic surfactant: dissolve 60 g (about 30 mmol) of polyetheramine M2070 in 90 mL of ethanol; dissolve 1.98 g (10 mmol) of glucose in 50 mL of water; dissolve the aforementioned two solutions After ultrasonic mixing, it was added to a 250 mL three-necked flask, the temperature was controlled at 50 °C, and the reaction was stirred for 24 h: it could be observed that as the reaction progressed, the color of the solution gradually turned yellowish. After the reaction was completed, the obtained crude product was added to ethanol for cooling and recrystallization, and 10.06 g of a light yellow liquid (that is, a glucose-modified polyetheramine nonionic surfactant) was obtained by rotary evaporation, and the glucose modification was calculated. The yield of the polyetheramine nonionic surfactant was 48%.

The NMR test results of the pale yellow liquid obtained in Example 1 are as follows:

¹ H NMR (400MHz, D ₂ O) δ 5.29 (d, J=3.7Hz, 0.63H), 4.70 (d, J=7.9Hz, 1.13H), 3.92 (d, J=43.6Hz, 13.15H) ,3.77(s,124H),3.67(d,J＝33.5Hz,20.83H),3.55(s,8.74H),3.45(s,5.14H),1.25(dd,J＝9.9,6.8Hz,30.43H ), 1.12 (d, J=6.5Hz, 1.92H).

In the mass spectrometry test result of the pale yellow liquid obtained in Example 1, m/z: 2161.14 is a molecular ion peak, which proves that the synthesized substance is a glucose-modified polyetheramine nonionic surfactant.

The Fourier transform infrared spectra of polyetheramine M2070 and the pale yellow liquid obtained in Example 1 are shown in Figure 1: 1648cm ^-1 is the sugar amine Schiff base bond formed by the reaction between polyetheramine M2070 and glucose, ^{3457cm- One} is the OH bond of the modified polyetheramine nonionic surfactant.

The specific reaction formula is as follows:

Example 2 (Glucose-modified polyetheramine nonionic surfactant)

Preparation of glucose-modified polyetheramine nonionic surfactant: dissolve 40g (about 20mmol) of polyetheramine M2070 in 100mL of isopropanol; 1.81g (10mmol) of D-anhydrous glucose is dissolved in 50mL of water ; After ultrasonically mixing the aforementioned two solutions, add them to a 250 mL three-necked flask, control the temperature to 60 °C, and stir for 48 h: it can be observed that with the progress of the reaction, the color of the solution becomes slightly yellow. After the reaction was completed, the obtained crude product was added to ethanol for cooling and recrystallization, and 16.67 g of a light yellow liquid (glucose-modified polyetheramine nonionic surfactant) was obtained by rotary evaporation, and the modified glucose was calculated. The yield of polyetheramine nonionic surfactant was 80%.

Example 3 (lactose-modified polyetheramine nonionic surfactant)

Preparation of lactose-modified polyetheramine nonionic surfactant: dissolve 40g (about 20mmol) of polyetheramine M2070 in 100mL of ethanol; dissolve 3.80g (10mmol) of lactose monohydrate in 50mL of water; dissolve the aforementioned two solutions After ultrasonic mixing, it was added to a 250 mL round-bottomed flask, the temperature was controlled at 80 °C, and the reaction was stirred for 6 h: it was observed that the color of the solution changed to brown as the reaction proceeded. After the reaction was completed, the obtained crude product was added to ethanol for cooling and recrystallization, and 8.34 g of a brown liquid (lactose-modified polyetheramine nonionic surfactant) was obtained by rotary evaporation. The yield of polyetheramine nonionic surfactant was 40%.

The NMR test results of the brown liquid obtained in Example 3 are as follows:

¹ H NMR (400MHz, DMSO)δ3.91(d, J=196.6Hz, 11.76H), 3.54(s, 14.25H), 3.51(s, 124H), 3.43(d, J=10.2Hz, 20.03H) , 3.34(dd, J=26.0, 5.2Hz, 16.74H), 3.24(s, 5.07H), 1.04(d, J=6.1Hz, 29.62H).

In the mass spectrometry test result of the brown liquid obtained in Example 3, m/z: 2341.31 is a molecular ion peak, which proves that the synthesized substance is a lactose-modified polyetheramine nonionic surfactant.

The Fourier transform infrared spectra of polyetheramine M2070 and the brown liquid obtained in Example 3 are shown in Figure 2: where 1634 cm ^-1 is the sugar amine Schiff base bond formed by the reaction between polyetheramine M2070 and glucose, 3532 cm ^-1 It is the OH bond of the modified polyetheramine nonionic surfactant.

The specific reaction formula is as follows:

Example 4 (lactose-modified polyetheramine nonionic surfactant)

Preparation of lactose-modified polyetheramine nonionic surfactant: dissolve 20g (about 10mmol) of polyetheramine M2070 in 100mL of isopropanol; dissolve 3.80g (10mmol) of lactose monohydrate in 50mL of water; The two solutions were ultrasonically mixed, added to a 250 mL round-bottomed flask, the temperature was controlled at 80 °C, and the reaction was stirred for 24 h: it was observed that the color of the solution changed to brown as the reaction proceeded. After the reaction was completed, the obtained crude product was added to ethanol for cooling and recrystallization, and 17.71 g of a brown liquid (lactose-modified polyetheramine nonionic surfactant) was obtained after rotary evaporation, and the lactose modification was calculated. The yield of polyetheramine nonionic surfactant was 85%.

Comparative Example 1 (Glucose-modified polyetheramine nonionic surfactant)

Preparation of glucose-modified polyetheramine nonionic surfactant: dissolve 20g (about 10mmol) of polyetheramine M2070 in 90mL of ethanol; 1.98g (10mmol) of glucose is dissolved in 50mL of water; ultrasonically sonicate the above two solutions After mixing, it was added to a 250 mL three-necked flask, the temperature was controlled at 120 °C, and the reaction was stirred for 72 h: it was observed that the color of the solution changed to scorch yellow as the reaction proceeded. After the reaction was completed, the obtained crude product was added to ethanol for cooling and recrystallization, and 4.56 g of a scorched yellow liquid was obtained by rotary evaporation, and the yield of the glucose-modified polyetheramine nonionic surfactant was calculated to be 21.9%. . This is because the reaction temperature is too high and the reaction time is too long, which will cause the increase of side reactions.

Comparative Example 2 (lactose-modified polyetheramine nonionic surfactant)

Preparation of lactose-modified polyetheramine nonionic surfactant: dissolve 20g (about 10mmol) of polyetheramine M2070 in 90mL of ethanol; dissolve 3.80g (10mmol) of lactose monohydrate in 50mL of water; dissolve the aforementioned two solutions After ultrasonic mixing, it was added to a 250 mL round-bottomed flask, the temperature was controlled at 120 °C, and the reaction was stirred for 72 h: it could be observed that the color of the solution changed to yellow-brown as the reaction proceeded. After the reaction was completed, the obtained crude product was added to ethanol for cooling and recrystallization, and 3.17 g of a yellow-brown liquid (lactose-modified polyetheramine nonionic surfactant) was obtained by rotary evaporation, and the lactose modification was calculated. The yield of polyetheramine nonionic surfactant was 15.2%. Because the reaction temperature is too high and the reaction time is too long, side reactions will occur.

Example 5 (Surface Tension Test of Surfactant)

Taking the unmodified polyetheramine M2070 polyetheramine nonionic surfactant and the modified polyetheramine nonionic surfactant prepared in Example 1 and Example 3 as examples, the traditional polyetheramine The surface tension of the nonionic surfactant and the modified polyetheramine nonionic surfactant of the present invention were tested.

Surface tension test method: Using a BZY-2 surface tensiometer, the surface tension of different concentrations of polyetheramine nonionic surfactants was measured by the platinum plate method at 25.0±0.1°C. The instrument was calibrated with ultrapure water before measurement. Place the vessel containing the liquid on the sample stage so that it is directly below the platinum plate and zero the reading on the instrument. Adjust the sample stage to make the solution rise slowly until the bottom of the platinum plate just touches the surface of the solution, and record the stable reading of the surface tensiometer. Clean the platinum plate, and then repeat the measurement for 3 consecutive times, take the average value as the measurement result, and the error of the two consecutive measurements is not more than 0.5mN/m. The experimental data are shown in Table 1 and Figure 3:

Table 1 Surface Tension Test Results

When the solution reaches the critical micelle concentration (cmc), the surface tension of the solution decreases to the lowest value. At this time, if the surfactant concentration is increased again, the surface tension of the solution is no longer reduced but a large number of micelles are formed. At this time, the surface tension of the solution is The minimum surface tension that the surfactant can achieve. The critical micelle concentration (cmc) can be used as a measure of the surface activity of surfactants. The smaller the cmc, the lower the concentration required for the active agent to form micelles, and the lower the concentration to achieve surface saturation adsorption. Therefore, the concentration required to change the surface properties to play the role of wetting, emulsifying, solubilizing, foaming, etc. is also lower.

It can be seen from Table 1 and Figure 1 that the critical micelle concentration (cmc) of the unmodified polyetheramine M2070 nonionic surfactant is 10 ^-2 mol·L ^-1 , while the sugar-modified polyether of the present invention has a critical micelle concentration (cmc) of 10 -2 mol·L -1 . The critical micelle concentration (cmc) of amine nonionic surfactants is reduced to the order of 10 ^-3 mol·L ^-1 . Specifically, the critical micelle concentration (cmc) of the glucose-modified polyetheramine nonionic surfactant prepared in Example 1 was about 1/3 of that of the unmodified polyetheramine M2070 nonionic surfactant; implementation The critical micelle concentration (cmc) of the lactose-modified polyetheramine nonionic surfactant prepared in Example 3 is about 1/2 of that of the unmodified polyetheramine M2070 nonionic surfactant. The above results prove that the sugar-based The modification significantly improved the surface properties of polyetheramine nonionic surfactants (eg, polyetheramine M2070 nonionic surfactant).

Example 6 (Foamability and Foam Stabilization Test of Surfactant)

Taking the unmodified polyetheramine M2070 polyetheramine nonionic surfactant and the modified polyetheramine nonionic surfactant prepared in Example 1 and Example 3 as examples, the traditional polyetheramine The foamability and foam stabilization of the nonionic surfactant and the modified polyetheramine nonionic surfactant of the present invention were verified.

Test method for foamability and foam stabilization of surfactants: Take 10mL, 1g/L of polyetheramine nonionic surfactant solution and add it to a 100mL graduated cylinder with stopper, and shake vigorously for 100 times within 1min. The height of the foam layer at the time of stopping represents the foamability, and the ratio of the height of the foam layer when the vibration stops for 5 min and the height of the foam layer when the vibration stops is used to characterize the foam stability of the foam. The experimental data are shown in Table 2 and Table 3 (3 parallel experiments were performed):

Table 2. The height of the foam layer when the shaking stopped and the result of the height of the foam layer when it stood for 5min

M2070 Example 1 Example 3 When the shaking stops 13mm 40mm 55mm 5min 5mm 35mm 51mm

Table 3 Test results of foamability and foam stability

Compared with the unmodified polyetheramine M2070 nonionic surfactant, the foaming and foam stabilization properties of the modified polyetheramine nonionic surfactants prepared in Examples 1 and 3 were extremely good. Great improvement (foamability: Example 1 is 2.1 times higher than M2070, and Example 3 is 3.2 times higher than M2070; foam stability: Example 1 is 1.3 times higher than M2070, and Example 3 is 1.4 times higher than M2070 ), wherein the polyetheramine nonionic surfactant whose sugar base is lactose in Example 3 has the greatest improvement in performance.

Example 7 (emulsification performance test of surfactant)

Taking the unmodified polyetheramine M2070 polyetheramine nonionic surfactant and the modified polyetheramine nonionic surfactant prepared in Example 1 and Example 3 as examples, the traditional polyetheramine The emulsifying properties of the nonionic surfactant and the modified polyetheramine nonionic surfactant of the present invention were tested for verification.

Emulsifying performance test method of surfactant: Pour 40 mL of 0.1% surfactant aqueous solution and 40 mL of liquid paraffin oil into a 100 mL graduated cylinder with a stopper, cover with a stopper, and keep it in a water bath at 25 °C for 5 minutes, then take it out up and down vigorously. Shake 5 times, then put it in a 25°C water bath and let it stand for 1 min, then take it out and shake it up and down vigorously 5 times, repeat the same steps 5 times, then let it stand, start the stopwatch, and record the time required for the bottom water phase to separate out 10 mL. Repeat the above steps three times to obtain the average value. The experimental data are shown in Table 4:

Table 4 Emulsifying performance test results of surfactants

M2070 Example 1 Example 3 Water separation time (s) 239 742 816

Compared with the unmodified surfactant M2070 polyetheramine nonionic surfactant, the water separation time of the modified polyetheramine nonionic surfactant prepared in Example 1 and Example 3 was significantly improved, while The longer the water separation time, the better the emulsifying performance, which indicates that the emulsifying performance of the polyetheramine nonionic surfactant has been improved.

Example 8 (Wetting performance test of surfactant)

Taking the unmodified polyetheramine M2070 polyetheramine nonionic surfactant and the modified polyetheramine nonionic surfactant prepared in Example 1 and Example 3 as examples, the traditional polyetheramine The wetting properties of the nonionic surfactant and the modified polyetheramine nonionic surfactant of the present invention were tested.

Wetting performance test method: The surfactants were prepared into aqueous solutions with a mass concentration of 1, 5, and 10 g/L, respectively, and the wetting performance of the surfactants was tested by the canvas sedimentation method: The standard fine canvas was cut into a diameter of about 35mm disc (quality should be 0.38 ~ 0.39g). Follow the same steps to put them into the prepared solution (the solution is contained in a container of the same size), avoid the canvas to contact the container wall during the sedimentation process so as not to affect the sedimentation result, and record the time when the canvas is just completely immersed in the bottom of the container. The experimental results are shown in Table 5:

Table 5 Wetting performance test results of surfactants

The settling time of Example 1 and Example 3 obtained after modification has been reduced, which means that the canvas sheet is more easily wetted, so it is compatible with the unmodified surfactant M2070 polyetheramine nonionic surfactant. In comparison, the wetting properties of the modified polyetheramine nonionic surfactants prepared in Example 1 and Example 3 were significantly improved.

To sum up, the modified polyetheramine type nonionic surfactant prepared by the present invention has significantly improved emulsifying performance, foaming performance and wetting performance compared with the traditional polyetheramine type nonionic surfactant. Therefore, the modified polyetheramine nonionic surfactant prepared by the present invention can be applied to the fields of daily chemical industry, textile washing, food, pesticide preparation, medicine preparation, etc. Use requirements for foam properties and wetting properties.

Since the modified polyetheramine nonionic surfactant prepared by the invention has excellent surface properties, it can be used as the main component of detergents to improve the decontamination performance of existing detergents.

The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other modifications, changes, substitutions, combinations, The simplification should be equivalent replacement methods, and should be included in the protection scope of the present invention.

Claims (10)

1. a modified polyetheramine class nonionic surfactant, is characterized in that, its molecular structure is as shown in the following formula:

where R= is

2. a method for preparing the modified polyetheramine nonionic surfactant of claim 1, characterized in that, comprising the steps: Dissolving polyetheramines in organic solvent A to obtain polyetheramines solution; Dissolving reducing sugars in water to obtain reducing sugars aqueous solution; After ultrasonically mixing the polyetheramine solution and the reducing sugar aqueous solution, heating and stirring to fully react to obtain a crude product; The crude product was dissolved in organic solvent B, and then the modified polyetheramine nonionic surfactant was obtained by cooling, recrystallization and rotary evaporation. 3 . The method according to claim 2 , wherein the polyetheramine substance is polyetheramine M2070. 4 . 4. The method according to claim 3, wherein the molar ratio of the reducing sugar substance to the polyetheramine M2070 is 1:(1-3). 5. The method according to any one of claims 2-4, wherein the temperature of the heating reaction is 50-100°C. 6. method according to claim 2 is characterized in that, the time of heating reaction is 6～48h. 7. The method according to any one of claims 2, 3, 4, and 6, wherein the organic solvent A is at least one of methanol, ethanol, isopropanol, n-butanol, and isoamyl alcohol kind. 8. The method according to claim 2, wherein the organic solvent B is ethanol. 9. Application of the modified polyetheramine nonionic surfactant of claim 1 in textile washing, food, pesticide preparation, and pharmaceutical preparation. 10 . A detergent comprising the modified polyetheramine type nonionic surfactant according to claim 1 . 11 .

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