CN110759824B - Method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-3) - Google Patents

Abstract

The invention provides a novel method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-3). The invention provides a method for preparing a target product APEA-3 by using triethylene glycol, chloropropene, chloroacetic acid and sodium hydroxide as raw materials, obtaining allyl fatty alcohol polyoxyethylene ether sodium carboxylate (APEC-3) through reaction, acidifying a crude product by 30% hydrochloric acid, filtering and evaporating a solvent under reduced pressure. APEA-3 has a yield of 85-90% and a purity of 80-86%. The method has the following advantages relative to the reported process: (1) the operation is simple and convenient, and the reaction efficiency is higher; (2) the reaction condition is mild; the conversion rate of APEA-3 is higher; (4) No other substances except raw materials and solvents are introduced in the reaction process, and the solvents are not polluted and are easy to recycle; (5) Avoiding a great deal of energy loss and environmental pollution caused by adopting traditional and low-efficiency synthesis processes (polymerization, extraction, distillation and the like); (6) The waste residue (sodium chloride) generated in the synthesis process can be recycled, and the negative influence on the environment is avoided.

Description

Method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-3)

Technical Field

The invention belongs to the technical field of synthesis of organic monomers, relates to preparation of allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-3), and particularly relates to a novel preparation method of allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-3). Ethanol is used as a solvent for synthesis, so that on one hand, the use of toxic solvents is avoided, and meanwhile, the solubility of reactants is increased, and the solvents can be recycled; on the other hand, the method avoids a great deal of energy loss and environmental pollution caused by adopting traditional and low-efficiency synthesis processes (polymerization, extraction, distillation and the like).

Background

The allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-3) is embedded with three Ethylene Oxides (EO) between a hydrophobic group and a hydrophilic group (-COO-) so that the allyl fatty alcohol polyoxyethylene ether carboxylic acid has water solubility and hard water resistance which are difficult to compare with common anionic surfactants, has many excellent performances (such as good foamability, foam stability, excellent biodegradability and the like) of the anionic surfactants and nonionic surfactants, and can have different surface characteristics by adjusting the hydrophobic chain length and EO addition number; meanwhile, due to the existence of hydrophobic allyl, the allyl can be polymerized with other monomers containing allyl or vinyl, so that the allyl is an important organic monomer.

According to the reports of domestic and foreign documents, the synthesis methods of the allyl fatty alcohol polyoxyethylene ether carboxylic acid comprise the following three methods:

(1) Carboxylate capping process, in laboratory, using Allyl Polyoxyethylene Ether (APEO), chloroacetic acid and sodium hydroxide as raw materials to carry out carboxymethylation reaction, cooling to room temperature after the reaction is completed, extracting, filtering and distilling under reduced pressure to obtain a product, vacuum drying the product to obtain light red transparent liquid sodium allylfatty alcohol polyoxyethylene ether carboxylate, and acidifying to obtain allylfatty alcohol polyoxyethylene ether carboxylic acid (APEA), wherein the reaction equation is as follows

CH₂＝CHCH₂O(CH₂CH₂O)_nH+NaOH→CH₂＝CHCH₂O(CH₂CH₂O)_nNa

CH₂＝CHCH₂O(CH₂CH₂O)_nNa+ClCH₂COOH+NaOH→CH₂＝CHCH₂O(CH₂CH₂O)_nCH₂COONa However, the method for synthesizing the allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-3) has no report, the raw materials of the Allyl Polyoxyethylene Ether (APEO) are scarce, the price is very high, the allyl polyoxyethylene ether containing different numbers of Ethylene Oxide (EO) groups can be obtained in the process of synthesizing the APEO, the separation process is quite complicated, the energy consumption and the material consumption of the process are large, and the damage to the environment is also large. Therefore, the process is feasible for synthesizing allyl fatty alcohol polyoxyethylene ether (1) carboxylic acid (APEA-1) and allyl fatty alcohol polyoxyethylene ether (2) carboxylic acid (APEA-2), but is not feasible for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (such as APEA-3) with the quantity of Ethylene Oxide (EO) being more than 3;

(2) The polymerization method is used for ring-opening polymerization of allyl alcohol and ethylene oxide under the condition of alkaline catalyst to generate ethylene glycol allyl ether, and polyethylene glycol and allyl polyethylene glycol ether with the polymerization degree of the ethylene oxide being more than 1 are easy to generate byproducts, and the reaction equation is as follows

The reaction is carried out in an autoclave with a stirring device, the air in the autoclave is replaced by N₂ for a plurality of times, then the materials are added according to a certain material adding ratio and a certain catalyst dosage, the materials are heated to a certain reaction temperature for reaction, cooling water is introduced to about 30 ℃ for discharging after the reaction is finished, ethylene glycol allyl ether products are obtained through rectification, sodium allyl polyethylene glycol carboxylate can be obtained through carboxymethylation of the products, the reaction temperature and pressure are higher, the equipment requirements are higher, the reaction condition is more severe, the method is not reported for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-3), the boiling point of the allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-3) is high, the final product obtained through a polymerization method is a mixture, and the separation of the products through a rectification method is not feasible;

(3) The etherification end-capping method adopts a Williamson ether formation method to synthesize alcohol monoallyl ether, and is commonly used for synthesizing diethylene glycol monoallyl ether and ethylene glycol monoallyl ether. Firstly, alcohol reacts with metal sodium or sodium hydride to prepare sodium alkoxide, and the generated sodium alkoxide is subjected to nucleophilic substitution with bimolecular chloropropene to generate alcohol monoallyl ether. The traditional Williamson ether method for synthesizing alcohol monoallyl ether mostly adopts relatively high-price bromopropene as a raw material, alkali is inflammable and explosive metal sodium or sodium hydride which is difficult to operate, and because a large amount of salt is generated in the reaction process, high-toxicity organic solvents such as tetrahydrofuran, dioxane, toluene and the like are introduced as reaction media to ensure the fluidity of the reaction, and the allyl polyalcohol sodium carboxylate can be obtained after carboxymethylation of the generated alcohol monoallyl ether.

Disclosure of Invention

The method for preparing the allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-3) has the advantages of higher technological content, mature and simple process, mild reaction conditions, low equipment requirements, readily available raw materials required by the product, low cost, capability of effectively realizing separation of the solvent from the product, no generation of three wastes in the reaction process, and environment friendliness and high efficiency.

According to the invention, triethylene glycol, chloroacetic acid and sodium hydroxide are taken as raw materials, subjected to carboxymethylation reaction in an ethanol solvent, and subjected to allylation reaction, so that allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-3) is finally synthesized.

The specific preparation method comprises the following process steps: (a) Ethanol is taken as a solvent, triethylene glycol, sodium hydroxide and chloroacetic acid are added into a three-neck flask with a stirrer and a thermometer according to the molar ratio of 1:2:1-1:2.1:1.05, nitrogen is filled for protection, the mixture reacts for 10-12 hours at the constant temperature of 40-45 ℃, and sodium chloride is filtered out to obtain an ethanol solution of an intermediate fatty alcohol polyoxyethylene ether sodium monocarboxylate; (b) At the constant temperature of 70-75 ℃, charging nitrogen for protection, adding sodium hydroxide into the fatty alcohol polyoxyethylene ether sodium monocarboxylate ethanol solution, activating for 30-40 min under stirring, then cooling to below 40 ℃, adding chloropropene, controlling the molar ratio of the intermediate fatty alcohol polyoxyethylene ether sodium monocarboxylate to sodium hydroxide to chloropropene to be 1:1-1:1.05:1.05, carrying out reflux reaction for 6-8 h at the constant temperature of 70-75 ℃, and then acidifying with 30% hydrochloric acid, filtering and removing the solvent under reduced pressure to obtain light yellow liquid with the yield of 85-90% and the purity of 80-86%.

The reaction equation is shown below

ClCH₂COOH+NaOH→ClCH₂COONa+H₂O

HO(CH₂CH₂O)₂CH₂CH₂OH+NaOH→HO(CH₂CH₂O)₂CH₂CH₂ONa+H₂O

HO(CH₂CH₂O)₂CH₂CH₂ONa+ClCH₂COONa→HO(CH₂CH₂O)₂CH₂CH₂OCH₂COONa+NaCl

HO(CH₂CH₂O)₃CH₂COONa+H₂C＝CHCH₂Cl+NaOH→H₂C＝CHCH₂HO(CH₂CH₂O)₃CH₂COONa+NaCl

H₂C＝CHCH₂O(CH₂CH₂O)₃CH₂COONa+HCl→H₂C＝CHCH₂O(CH₂CH₂O)₃CH₂COOH+NaCl

The invention aims to provide a novel method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-3).

The invention provides an innovative point of synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-3) by an asymmetric synthesis method.

APEA-3 infrared spectroscopy (FTIR), the dried product was sampled and subjected to infrared spectroscopy on a Fourier infrared spectrometer with a resolution of 4cm^-1 and a wavenumber range of 400-4000 cm^-1, scanned 30 times. The FTIR spectrum of APEA-3 allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-3) is shown in figure 1, and the vibration absorption of C=O is stronger and stronger in 1745cm^-1, 1674cm^-1 is the absorption peak of H₂ C=CH-, 2878cm^-1 is the telescopic vibration absorption of saturated C-H bond, 1352-1454 cm^-1 is the C-H bending vibration, 1213cm^-1 is the telescopic vibration of C-O, 3383cm^-1 is the O-H telescopic vibration absorption, and 1120cm^-1 is the asymmetric telescopic vibration of-CH₂CH₂ O-.

Drawings

FIG. 1 is an infrared spectrum of allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-3).

Detailed Description

Embodiment one: ethanol is taken as a solvent, triethylene glycol, sodium hydroxide and chloroacetic acid are added into a three-neck flask with a stirrer and a thermometer according to the molar ratio of 1:2:1, nitrogen is filled for protection, the mixture is reacted for 12 hours at the constant temperature of 40 ℃, and sodium chloride is filtered out to obtain an ethanol solution of an intermediate fatty alcohol polyoxyethylene ether sodium monocarboxylate; (b) At the constant temperature of 72 ℃, charging nitrogen for protection, adding sodium hydroxide into the fatty alcohol polyoxyethylene ether sodium monocarboxylate ethanol solution, activating for 30-40 min under stirring, then cooling to below 40 ℃, adding chloropropene, controlling the mole ratio of the intermediate fatty alcohol polyoxyethylene ether sodium monocarboxylate, sodium hydroxide and chloropropene to be 1:1:1, carrying out reflux reaction for 8h at the constant temperature of 75 ℃, and then acidifying with 30% hydrochloric acid, filtering and removing the solvent under reduced pressure to obtain light yellow liquid with the yield of 90% and the purity of 82%.

Embodiment two: ethanol is used as a solvent, triethylene glycol, sodium hydroxide and chloroacetic acid are added into a three-neck flask with a stirrer and a thermometer according to the molar ratio of 1:2.1:1.05, nitrogen is filled for protection, the mixture reacts for 10 hours at the constant temperature of 40 ℃, and sodium chloride is filtered out to obtain an ethanol solution of an intermediate fatty alcohol polyoxyethylene ether sodium monocarboxylate; (b) At the constant temperature of 75 ℃, nitrogen is filled for protection, sodium hydroxide is added into the fatty alcohol polyoxyethylene ether sodium monocarboxylate ethanol solution, the mixture is activated for 30 to 40 minutes under stirring, then the temperature is reduced to below 40 ℃, chloropropene is added, the molar ratio of the intermediate fatty alcohol polyoxyethylene ether sodium monocarboxylate to sodium hydroxide to chloropropene is controlled to be 1:1:1, reflux reaction is carried out for 8 hours at the constant temperature of 75 ℃, and then 30 percent hydrochloric acid is used for acidification, filtration and decompression solvent removal are carried out, so that light yellow liquid is obtained, the yield is 86 percent, and the purity is 83 percent.

Embodiment III: ethanol is taken as a solvent, triethylene glycol, sodium hydroxide and chloroacetic acid are added into a three-neck flask with a stirrer and a thermometer according to the molar ratio of 1:2.1:1.05, nitrogen is filled for protection, the mixture reacts for 12 hours at the constant temperature of 45 ℃, and sodium chloride is filtered out to obtain an ethanol solution of an intermediate fatty alcohol polyoxyethylene ether sodium monocarboxylate; (b) At the constant temperature of 75 ℃, nitrogen is filled for protection, sodium hydroxide is added into the fatty alcohol polyoxyethylene ether sodium monocarboxylate ethanol solution, the mixture is activated for 30 to 40 minutes under stirring, then the temperature is reduced to below 40 ℃, chloropropene is added, the molar ratio of the intermediate fatty alcohol polyoxyethylene ether sodium monocarboxylate to sodium hydroxide to chloropropene is controlled to be 1:1:1, reflux reaction is carried out for 6 hours at the constant temperature of 75 ℃, and then 30 percent hydrochloric acid is used for acidification, filtration and decompression solvent removal are carried out, so that a pale yellow liquid is obtained, the yield is 88 percent, and the purity is 81 percent.

Embodiment four: ethanol is taken as a solvent, triethylene glycol, sodium hydroxide and chloroacetic acid are added into a three-neck flask with a stirrer and a thermometer according to the molar ratio of 1:2.1:1.05, nitrogen is filled for protection, the mixture reacts for 12 hours at the constant temperature of 45 ℃, and sodium chloride is filtered out to obtain an ethanol solution of an intermediate fatty alcohol polyoxyethylene ether sodium monocarboxylate; (b) At the constant temperature of 70 ℃, nitrogen is filled for protection, sodium hydroxide is added into the fatty alcohol polyoxyethylene ether sodium monocarboxylate ethanol solution, the mixture is activated for 30 to 40 minutes under stirring, then the temperature is reduced to below 40 ℃, chloropropene is added, the molar ratio of the intermediate fatty alcohol polyoxyethylene ether sodium monocarboxylate to sodium hydroxide to chloropropene is controlled to be 1:1:1, reflux reaction is carried out for 8 hours at the constant temperature of 70 ℃, and then 30 percent hydrochloric acid is used for acidification, filtration and decompression solvent removal are carried out, so that a pale yellow liquid is obtained, the yield is 87 percent, and the purity is 80 percent.

Fifth embodiment: ethanol is taken as a solvent, triethylene glycol, sodium hydroxide and chloroacetic acid are added into a three-neck flask with a stirrer and a thermometer according to the molar ratio of 1:2.1:1.05, nitrogen is filled for protection, the mixture reacts for 12 hours at the constant temperature of 40 ℃, and sodium chloride is filtered out to obtain an ethanol solution of an intermediate fatty alcohol polyoxyethylene ether sodium monocarboxylate; (b) At the constant temperature of 75 ℃, filling nitrogen for protection, adding sodium hydroxide into the fatty alcohol polyoxyethylene ether sodium monocarboxylate ethanol solution, activating for 30-40 min under stirring, then cooling to below 40 ℃, adding chloropropene, controlling the mole ratio of triethylene glycol, sodium hydroxide and chloropropene to be 1:1:1.05, carrying out reflux reaction for 8h at the constant temperature of 75 ℃, and then acidifying with 30% hydrochloric acid, filtering and removing the solvent under reduced pressure to obtain light yellow liquid with the yield of 88% and the purity of 87%.

Claims (1)

1. A method of synthesizing APEA-3, characterized by: triethylene glycol, chloroacetic acid, sodium hydroxide and H₂C＝CHCH₂ Cl are used as raw materials, ethanol is used as a solvent, and the raw materials are subjected to two-step reactions of carboxymethylation and allylation at normal pressure to synthesize APEA-3, wherein the structure of APEA-3 is H₂C＝CHCH₂O(CH₂CH₂O)₃CH₂ COOH; the method specifically comprises the following steps: (a) Adding triethylene glycol, sodium hydroxide and chloroacetic acid into a three-mouth flask with a stirrer and a thermometer according to the molar ratio of 1:2:1-1:2.1:1.05, filling nitrogen for protection, reacting for 10-12 hours at the constant temperature of 40-45 ℃, filtering sodium chloride to obtain an intermediate HO (ethanol solution of CH₂CH₂O)₃CH₂ COONa), filling nitrogen for protection at the constant temperature of 70-75 ℃, adding sodium hydroxide into the ethanol solution of HO (CH₂CH₂O)₃CH₂ COONa and activating for 30-40 minutes under stirring, cooling to below 40 ℃, adding H₂C＝CHCH₂ Cl, controlling the molar ratio of the intermediate HO (CH₂CH₂O)₃CH₂ COONa, sodium hydroxide and H₂C＝CHCH₂ Cl to be 1:1:1.05:1.05, refluxing for reacting for 6-8 hours at the constant temperature of 70-75 ℃, acidifying with 30% hydrochloric acid, filtering and removing the solvent under reduced pressure to obtain a pale yellow liquid, wherein the yield of APEA-3 is 85-90%, and the purity is 80-86%.