CN106588706B - The synthetic method of castor oil acid formicester ethoxylate sulfonates - Google Patents

Abstract

A kind of synthetic method of methyl ricinoleic acid ethoxylate sulfonate is that methyl ricinoleic acid ethoxylate, sodium bisulfite, catalyzer, deionized water, low-carbon alcohol are added in the reactor, strongly Under stirring, reaction, wherein the mol ratio of ricinoleic acid methyl ethoxylate and sodium bisulfite is 1:1.5-2.5; The consumption of catalyst is 1.5-2.5% of ricinoleic acid ethoxylate quality, Low-carbon alcohol, the mass ratio of deionized water and ricinoleic acid methyl ester ethoxylate is 0.9-3:0.9-3:1, after the reaction finishes, decompression distillation removes water and low-carbon alcohol, uses excessive anhydrous Ethanol was dissolved, unreacted sodium bisulfite and generated sodium sulfite were removed, and ethanol was distilled off under reduced pressure to obtain the product. The invention has the advantages of simple and safe synthesis process and no waste acid and alkali.

Description

The synthetic method of ricinoleic acid methyl ester ethoxylate sulfonate

technical field

The present invention relates to a kind of preparation method of anionic surface active agent, relate in particular to a kind of synthetic method of ricinoleic acid methyl ester ethoxylate sulfonate.

Background technique

In recent years, as people pay more and more attention to environmental issues, the development of new green and multifunctional surfactants has attracted more and more attention. Methyl ricinoleate ethoxylate is a typical nonionic surfactant, which has the characteristics of low cost, easy biodegradation, good environmental compatibility and little skin irritation. Its molecular structure is quite special. Compared with ordinary fatty acid methyl ester ethoxylate, it has a structure similar to fatty alcohol polyoxyethylene ether on the branch chain. In addition, there is a carbon-carbon double bond in the molecule, so it is subject to widespread attention of the people.

Ricinoleic acid methyl ester ethoxylate sulfonate/ricinoleic acid methyl ester ethoxylate sulfate is obtained from ricinoleic acid methyl ester ethoxylate as raw material, sulfonated with sulfur trioxide, and then neutralized with alkali of. Because the sulfonic acid group can replace the α-hydrogen of the ester group and the terminal hydrogen of the branched polyoxyethylene ether, sulfonate and sulfate will be generated. The ricinoleic acid methyl ester ethoxylate sulfonate/ricinoleic acid methyl ester ethoxylate sulfate obtained by the reaction has the advantages of low foaming, strong emulsifying ability, strong detergency, and easy washing (Li Jie, Yang Yi Yi, Sun Yongqiang, Zhi Lifei. Synthesis and physicochemical properties of ricinoleic acid methyl ester ethoxylate sulfonate/sulfate[J]. Printing and Dyeing Auxiliaries, 2016,34(4):7-10.).

Using ricinoleic acid methyl ester ethoxylate as raw material, under the action of catalyst, it can be directly sulfonated with sodium bisulfite to obtain a new type of anionic surfactant----ricinoleic acid methyl ester ethoxylate sulfonate Salt, sodium bisulfite is added on the carbon-carbon double bond in the molecule, and the preparation method of this kind of surfactant has not been reported at home and abroad.

Contents of the invention

The purpose of the present invention is in order to provide a kind of synthetic method of ricinoleic acid methyl ester ethoxylate sulfonate.

The molecular structural formula of the raw material ricinoleic acid methyl ester ethoxylate provided by the invention is as follows:

Among them: x+y=15-20

The reaction synthetic route of the present invention is as follows:

The synthetic method of anionic surfactant methyl ricinoleic acid ethoxylate sulfonate provided by the invention may further comprise the steps:

Add ricinoleic acid methyl ester ethoxylate, sodium bisulfite, catalyst, deionized water, and low-carbon alcohol into the reactor, heat to 60-80°C under strong stirring, and react for 6-8 hours; the castor oil The mol ratio of acid methyl ester ethoxylate and sodium bisulfite is 1:1.5-2.5; The consumption of catalyst is 1.5-2.5% of ricinoleic acid methyl ester ethoxylate quality, low carbon alcohol, deionized water and The mass ratio of ricinoleic acid methyl ester ethoxylate is 0.9-3:0.9-3:1. After the reaction is completed, water and low-carbon alcohols are distilled off under reduced pressure, dissolved in excess ethanol, and unreacted by hot filtration. The sodium bisulfite and the generated sodium sulfite were distilled off under reduced pressure to remove the ethanol to obtain the product.

In the above-mentioned reaction, the average addition number of oxyethane in the ricinoleic acid methyl ester ethoxylate is 15-20, contains unsaturated carbon-carbon double bond in the molecule, because sodium bisulfite adds in the molecule Carbon-carbon double bond, so ricinoleic acid methyl ester ethoxylate sulfonate does not contain carbon-carbon double bond.

The catalyst in the above reaction is azobisisobutyronitrile.

The low-carbon alcohol in the above-mentioned reaction is the alcohol of some short carbon chains such as methyl alcohol, ethanol, propanol, isopropanol or butanol.

In the above-mentioned reaction, the mol ratio of ricinoleic acid methyl ethoxylate and sodium bisulfite is preferably 1:1.8-2.2; The consumption of catalyst is preferably 1.9-2.3 of the quality of ricinoleic acid ethoxylate %, the mass ratio of low carbon alcohol, deionized water and ricinoleic acid methyl ester ethoxylate is preferably 0.9-1.5:0.9-1.5:1.

The product in the above reaction is a mixture of ricinoleic acid methyl ester ethoxylate sulfonate and ricinoleic acid methyl ester ethoxylate, the product is analyzed to prove that the synthesis of ricinoleic acid methyl ester ethoxylate sulfonic acid Salt. The product is separated to obtain ricinoleic acid methyl ester ethoxylate sulfonate, and the ricinoleic acid methyl ester ethoxylate is recycled.

In the above reaction, sodium bisulfite can be dissolved in deionized water in advance, and then ricinoleic acid methyl ester ethoxylate, catalyst and low-carbon alcohol are added to the ionized water, which is conducive to the smooth progress of the reaction.

The purpose of the present invention is to synthesize a kind of new anionic surfactant ricinoleic acid methyl ester ethoxylate sulfonate, it is a kind of anionic surfactant that special anion-nonion is combined, there are three hydrophilic in the molecule The water-based functional group is obtained by the direct addition of sodium bisulfite and ricinoleic acid methyl ester ethoxylate, and the addition position is the carbon-carbon double bond in the molecule.

Compared with the prior art, the present invention has the following advantages:

1 A new type of sulfonate surfactant was synthesized, which has multiple hydrophilic functional groups and has the advantages of low foam, easy washing, and strong alkali resistance.

2. The synthesis process is simple and safe, and waste acid and alkali will not be produced.

Description of drawings

Fig. 1 is the infrared spectrogram after the ricinoleic acid methyl ester ethoxylate sulfonate of synthesis of the present invention purifies

In Figure 1, the absorption peaks at 1178cm ^-1 , 1034cm ^-1 , 620cm ^-1 and 519cm ^-1 indicate that there are sulfonic acid functional groups in the molecule, and the absorption peak at 717cm ^-1 is the absorption peak of the carbon-carbon double bond, because there are Residual methyl ricinoleate ethoxylate was not removed.

Detailed ways

The present invention adopts following test method: (1) confirm that the product contains sulfonic acid functional group by infrared spectrum. (2) Determination of anionic surfactant content by two-phase titration. (3) Measure the iodine value of the product, and compare it with the iodine value of ricinoleic acid methyl ester ethoxylate, and finally determine that sodium bisulfite is added on the carbon-carbon double bond in the molecule through calculation.

Example 1

50g (0.051mol) ricinoleic acid methyl ester ethoxylate (average molecular weight 976, X average value is 10.9, Y average value is 4.2, iodine value is 26.1g/100g), 100g deionized water, 100g isopropanol , 8g (0.077mol) of sodium bisulfite and 1.1g of azobisisobutyronitrile were added to a 500ml four-neck flask, heated to 80°C, and reacted for 6.5h. After the reaction, the water and isopropanol were removed by rotary evaporation, dissolved with excess absolute ethanol, unreacted sodium bisulfite and generated sodium sulfite were removed by hot filtration, and the ethanol was removed by rotary evaporation to obtain the product. The main indicators of the product are as follows: (1) the iodine value is 22.1g/100g; (2) the mass fraction of ricinoleic acid methyl ester ethoxylate sodium sulfonate is 14.7%.

Example 2

30g (0.030mol) ricinoleic acid methyl ester ethoxylate (average molecular weight 976, X average value is 10.9, Y average value is 4.2, iodine value is 26.1g/100g), 60g deionized water, 60g ethanol, 4.8 Add g (0.046mol) sodium bisulfite and 0.6g azobisisobutyronitrile into a 250ml four-neck flask (dissolve sodium bisulfite in deionized water before adding), heat to 78°C, and react for 6h. After the reaction, remove water and ethanol by rotary evaporation, dissolve with excess absolute ethanol, remove unreacted sodium bisulfite and generated sodium sulfite by hot filtration, and remove ethanol by rotary evaporation to obtain the product. The main indicators of the product are as follows: (1) the iodine value is 21.6g/100g; (2) the mass fraction of ricinoleic acid methyl ester ethoxylate sodium sulfonate is 17.9%.

Example 3

30g (0.026mol) ricinoleic acid methyl ester ethoxylate (average molecular weight 1151, X average value is 13.2, Y average value is 5.9, iodine value is 22.5g/100g), 55g deionized water, 55g methanol, 5.4 Add g (0.052mol) sodium bisulfite and 0.5g azobisisobutyronitrile into a 250ml four-neck flask, heat to 60°C, and react for 8h. After the reaction, remove water and methanol by rotary evaporation, dissolve with excess absolute ethanol, remove unreacted sodium bisulfite and generated sodium sulfite by hot filtration, and remove ethanol by rotary evaporation to obtain the product. The main indicators of the product are as follows: (1) the iodine value is 18.5g/100g; (2) the mass fraction of ricinoleic acid methyl ester ethoxylate sodium sulfonate is 18.9%.

Example 4

30g (0.026mol) ricinoleic acid methyl ester ethoxylate (average molecular weight 1151, X average value is 13.2, Y average value is 5.9, iodine value is 22.5g/100g), 80g deionized water, 80g isopropanol , 6.5g (0.064mol) of sodium bisulfite and 0.4g of azobisisobutyronitrile were added to a 500ml four-neck flask (sodium bisulfite was dissolved in deionized water before addition), heated to 78°C, and the reaction 6h. After the reaction, the water and isopropanol were removed by rotary evaporation, dissolved with excess absolute ethanol, unreacted sodium bisulfite and generated sodium sulfite were removed by hot filtration, and the ethanol was removed by rotary evaporation to obtain the product. The main indicators of the product are as follows: (1) the iodine value is 17.6g/100g; (2) the mass fraction of ricinoleic acid methyl ester ethoxylate sodium sulfonate is 20.4%.

Example 5

With 30g (0.029mol) methyl ricinoleic acid ethoxylate (average molecular weight 1037, X mean value is 11.9, Y mean value is 4.5, iodine value is 25g/100g), 70g deionized water, 70g ethanol, 6g ( Add 0.058mol) sodium bisulfite and 0.7g azobisisobutyronitrile into a 500ml four-neck flask, heat to 75°C, and react for 6.5h. After the reaction, remove water and ethanol by rotary evaporation, dissolve with excess absolute ethanol, remove unreacted sodium bisulfite and generated sodium sulfite by hot filtration, and remove ethanol by rotary evaporation to obtain the product. The main indicators of the product are as follows: (1) the iodine value is 18.4g/100g; (2) the mass fraction of ricinoleic acid methyl ester ethoxylate sodium sulfonate is 24.2%.

Example 6

With 30g (0.029mol) methyl ricinoleate ethoxylate (average molecular weight 1037, X average value is 11.9, Y average value is 4.5, iodine value is 25g/100g), 90g deionized water, 90g isopropanol, Add 6g (0.058mol) of sodium bisulfite and 0.7g of azobisisobutyronitrile into a 500ml four-neck flask, heat to 80°C, and react for 6.5h. After the reaction, the water and isopropanol were removed by rotary evaporation, dissolved with excess absolute ethanol, unreacted sodium bisulfite and generated sodium sulfite were removed by hot filtration, and the ethanol was removed by rotary evaporation to obtain the product. The main indexes of the product are as follows: (1) the iodine value is 18.8g/100g; (2) the mass fraction of ricinoleic acid methyl ester ethoxylate sodium sulfonate is 23.1%.

Example 7

30g (0.029mol) ricinoleic acid methyl ester ethoxylate (average molecular weight 1037, X average value is 11.9, Y average value is 4.5, iodine value is 24.6g/100g), 30g deionized water, 30g ethanol, 6g (0.058mol) sodium bisulfite and 0.7g of azobisisobutyronitrile were added to a 250ml four-neck flask, heated to 78°C (sodium bisulfite was dissolved in deionized water before addition), and reacted for 7h. After the reaction, remove water and ethanol by rotary evaporation, dissolve with excess absolute ethanol, remove unreacted sodium bisulfite and generated sodium sulfite by hot filtration, and remove ethanol by rotary evaporation to obtain the product. The main indicators of the product are as follows: (1) the iodine value is 18.2g/100g; (2) the mass fraction of ricinoleic acid methyl ester ethoxylate sodium sulfonate is 25.2%.

Claims (4)

1. a synthetic method of ricinoleic acid methyl ester ethoxylate sulfonate, is characterized in that comprising the steps: Add methyl ricinoleic acid ethoxylate, sodium bisulfite, catalyst, deionized water, and low-carbon alcohol into the reactor, heat to 60-80°C under strong stirring, and react for 6-8 hours; the castor oil The molar ratio of acid methyl ester ethoxylate and sodium bisulfite is 1:1.5-2.5; the consumption of catalyst is 1.5-2.5% of the quality of ricinoleic acid methyl ester ethoxylate, low carbon alcohol, deionized water and The mass ratio of ricinoleic acid methyl ester ethoxylate is 0.9-3:0.9-3:1. After the reaction, the water and lower alcohols are distilled off under reduced pressure, dissolved with excess ethanol, and unreacted by hot filtration. The sodium bisulfite and the sodium sulfite of generation, decompression distillation removes ethanol and obtains product; The molecular structural formula of described raw material ricinoleic acid methyl ester ethoxylate is as follows: Where: x+y=15-20; The catalyst is azobisisobutyronitrile; The low-carbon alcohol is methanol, ethanol, propanol, isopropanol or butanol. 2. the synthetic method of a kind of Ricinoleic acid methyl ester ethoxylate sulfonate as claimed in claim 1, it is characterized in that the mol ratio of Ricinoleic acid methyl ester ethoxylate and sodium bisulfite is 1: 1.8-2.2; The consumption of catalyst is 1.9-2.3% of the quality of ricinoleic acid methyl ester ethoxylate, and the mass ratio of low carbon alcohol, deionized water and ricinoleic acid methyl ethoxylate is 0.9-1.5: 0.9-1.5:1. 3. the synthetic method of a kind of ricinoleic acid methyl ester ethoxylate sulfonate as claimed in claim 1 is characterized in that earlier sodium bisulfite is dissolved in deionized water in advance, then with ricinoleic acid methyl ester Ethoxylates, catalysts and lower alcohols are added to deionized water. 4. the synthetic method of a kind of Ricinoleic acid methyl ester ethoxylate sulfonate as claimed in claim 1 is characterized in that product is Ricinoleic acid methyl ester ethoxylate sulfonate and Ricinoleic acid methyl ester The mixture of ethoxylates, the product is separated to obtain ricinoleic acid methyl ester ethoxylate sulfonate, and the ricinoleic acid methyl ester ethoxylate is recycled.