阅读说明：本技术 一种合成烯丙基脂肪醇聚氧乙烯醚羧酸（apea-4）的新方法 (Novel method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-4) ) 是由 卢鑫 赵伟东 王良成 王璐 张昆 苏梅 张强 常立民 于 2019-09-30 设计创作，主要内容包括：本发明提供了一种合成烯丙基脂肪醇聚氧乙烯醚羧酸(APEA-4)的新方法。本发明以四乙二醇(HO(CH<Sub>2</Sub>CH<Sub>2</Sub>O)<Sub>3</Sub>CH<Sub>2</Sub>CH<Sub>2</Sub>OH)、氯丙烯(H<Sub>2</Sub>C＝CHCH<Sub>2</Sub>Cl)、氯乙酸(ClCH<Sub>2</Sub>COOH)和氢氧化钠(NaOH)为原料,合成烯丙基脂肪醇聚氧乙烯醚羧酸钠,经30％盐酸酸化、过滤和减压蒸除溶剂得到目标产物；APEA-4的收率为85～95％,纯度为85～90％；本方法相对于已报道的方法有以下几个优点：(1)操作简便且反应效率高；(2)反应条件温和；(3)APEA-4的收率和纯度均较高；反应过程中没有引入除原料和溶剂以外的其它物质,溶剂没被污染且易于回收再利用；(5)避免因采用传统、低效的合成过程(聚合、萃取、蒸馏等)而造成大量的溶剂和能量损耗,以及环境污染。(The invention provides a new method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-4). The invention uses tetraethylene glycol (HO (CH) 2 CH 2 O) 3 CH 2 CH 2 OH), chloropropene (H) 2 C＝CHCH 2 Cl), chloroacetic acid (ClCH) 2 COOH) and sodium hydroxide (NaOH) as raw materialsAcidifying sodium allyl fatty alcohol polyoxyethylene ether carboxylate with 30% hydrochloric acid, filtering, and removing the solvent by reduced pressure evaporation to obtain a target product; the yield of the APEA-4 is 85-95%, and the purity is 85-90%; the method has the following advantages compared with the reported method: (1) the operation is simple and convenient, and the reaction efficiency is high; (2) the reaction condition is mild; (3) the yield and the purity of the APEA-4 are both high; in the reaction process, other substances except the raw materials and the solvent are not introduced, and the solvent is not polluted and is easy to recycle; (5) avoids large solvent and energy loss and environmental pollution caused by adopting traditional and low-efficiency synthetic processes (polymerization, extraction, distillation and the like).)

1. A process for synthesizing allyl emtrol polyoxyvinethene carboxylate (APEA-4) from tetraethylene glycol (HO (CH)₂CH₂O)₃CH₂CH₂OH), chloroacetic acid (ClCH)₂COOH) and sodium hydroxide (NaOH), chloropropene (H)₂C＝CHCH₂Cl) as raw material, ethanol (CH)₃CH₂OH) as solvent, and synthesizing APEA-4 by two-step reaction of carboxymethylation and allylation under normal pressure, wherein the structural formula is H₂C＝CHCH₂O(CH₂CH₂O)₄CH₂COOH。

2. The novel process for the synthesis of allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-4) according to claim 1, wherein: (a) adding tetraethylene glycol, sodium hydroxide and chloroacetic acid into a three-neck flask with a stirrer and a thermometer according to the molar ratio of 1:2: 1-1: 2.2:1.1 by taking ethanol as a solvent, introducing nitrogen for protection, reacting at the constant temperature of 45-50 ℃ for 10-12 h, and filtering sodium chloride to obtain an intermediate sodium fatty alcohol polyoxyethylene ether monocarboxylate (HO (CH)₂CH₂O)₄CH₂COONa) in ethanol; (b) introducing nitrogen for protection at a constant temperature of 70-75 ℃, adding sodium hydroxide into the ethanol solution of the sodium alcohol polyoxyethylene fatty alcohol ether monocarboxylic acid, activating for 30-40 min under stirring, and then cooling to 40 DEG CAdding chloropropene, controlling the molar ratio of the intermediate sodium fatty alcohol-polyoxyethylene ether monocarboxylate to the sodium hydroxide to the chloropropene to be 1:1: 1-1: 1.1:1.1, carrying out reflux reaction at the constant temperature of 70-75 ℃ for 5-7 h, acidifying by using 30% hydrochloric acid, filtering, and recovering solvent ethanol under reduced pressure to finally obtain a light yellow liquid, wherein the yield is 85-95%, and the purity is 85-90%.

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-4), and particularly relates to a novel preparation method of the allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-4). The ethanol is used as a solvent for synthesis, so that on one hand, the use of toxic solvents is avoided, meanwhile, the solubility of reactants is increased, and the solvent can be recycled; on the other hand, the method avoids a great deal of energy loss and environmental pollution caused by adopting the traditional and low-efficiency synthesis processes (polymerization, extraction, distillation and the like).

Background

Four Ethylene Oxide (EO) groups are embedded between a hydrophobic group and a hydrophilic group (-COO-) in allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA), so that the allyl fatty alcohol polyoxyethylene ether carboxylic acid has water solubility and hard water resistance which are not comparable to those of common anionic surfactants, and has a plurality of excellent performances (such as good foamability, foam stability, excellent biodegradability and the like) of the anionic surfactants and nonionic surfactants; meanwhile, due to the existence of hydrophobic allyl, the compound can be polymerized with other monomers containing allyl or vinyl, so that the compound is an important synthetic organic monomer.

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

(1) carboxylate capping method, laboratory uses Allyl Polyoxyethylene Ether (APEO), chloroacetic acid (ClCH)₂COOH) and sodium hydroxide (NaOH) as raw materials to perform carboxymethylation reaction, cooling to room temperature after the reaction is finished, and performing carboxymethylation reactionExtracting, filtering and distilling under reduced pressure, vacuum drying the obtained product to obtain light red transparent liquid sodium allyl fatty alcohol polyoxyethylene ether carboxylate, acidifying to obtain allyl fatty 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 synthesis of allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-4) by the method is not reported. The raw material of the Allyl Polyoxyethylene Ether (APEO) is scarce and high in price, the allyl polyoxyethylene ether containing different 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 in the process are large, and the harm to the environment is also large, so that the process is feasible for synthesizing the allyl fatty alcohol polyoxyethylene ether (1) carboxylic acid (APEA-1) and the allyl fatty alcohol polyoxyethylene ether (2) carboxylic acid (APEA-2) except the allyl fatty alcohol polyoxyethylene ether (1) and the allyl fatty alcohol polyoxyethylene ether (2), but the synthesis of the allyl fatty alcohol polyoxyethylene ether carboxylic acid (such as APEA-4) with the Ethylene Oxide (EO) number larger than 3 is infeasible;

(2) the polymerization method is used for ring-opening polymerization of allyl alcohol and ethylene oxide under the action of alkaline catalyst to produce glycol allyl ether, and is easy to produce by-product polyethylene glycol and allyl polyethylene glycol ether whose polymerization degree of ethylene oxide is above 1, and its reaction formula is as follows

The reaction is synthesized in an autoclave with a stirring device and N is used₂Replacing air in the autoclave for several times, feeding according to a certain feeding ratio and catalyst dosage, heating to a certain reaction temperature for reaction, introducing cooling water to about 30 ℃ after the reaction is finished, discharging, and rectifying to obtain the ethyl acetateThe product of glycol allyl ether is subjected to carboxymethylation to obtain sodium allyl polyethylene glycol carboxylate, the temperature and pressure required by the reaction are high, the requirements on equipment are high, and the reaction conditions are harsh, the synthesis of the allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-4) by using the method is not reported, the boiling point of the allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-4) is high, the final product obtained by the polymerization method is a mixture, and the separation of the product by adopting a rectification method is infeasible;

(3) the etherification end-capping method adopts a Williamson ether forming method to synthesize alcohol monoallyl ether. Firstly, alcohol and sodium metal react to prepare sodium alkoxide, the generated sodium alkoxide and chloropropene bimolecular nucleophilic substitution generate alcohol monoallyl ether, most of the alcohol monoallyl ether synthesized by the traditional Williamson ether forming method adopts high-price bromopropylene as a raw material, alkali is inflammable, explosive and difficult-to-operate sodium metal, and a large amount of salt is generated in the reaction process, and high-toxicity organic solvents such as tetrahydrofuran, dioxane, toluene and the like are introduced as reaction media to ensure the reaction fluidity, so that the alcohol monoallyl ether is generated and then carboxymethylated to obtain the sodium allyl polyalcohol carboxylate.

Disclosure of Invention

The synthesis method of the allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-4) is subjected to a large number of experiments and industrial feasibility researches in a laboratory, and the novel method for synthesizing the allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-4) has the advantages of high technological content, mature and simple process, mild reaction conditions, high product yield and purity, low equipment requirements, easily available raw materials required by the product, low cost due to the fact that the reaction is carried out in an ethanol solvent, capability of effectively realizing separation of the solvent and the product, no 'three wastes' generated in the reaction process, greenness and high efficiency.

The invention takes tetraethylene glycol, chloroacetic acid, sodium hydroxide and chloropropene as raw materials, and the raw materials are subjected to carboxymethylation in an ethanol solvent to generate an intermediate sodium fatty alcohol-polyoxyethylene ether monocarboxylate, and then allylation reaction is carried out to finally synthesize the allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-4).

The specific preparation method comprises the following process steps: (a) adding tetraethylene glycol, sodium hydroxide and chloroacetic acid into a three-neck flask with a stirrer and a thermometer according to the molar ratio of 1:2: 1-1: 2.2:1.1 by taking ethanol as a solvent, introducing nitrogen for protection, reacting at the constant temperature of 45-50 ℃ for 10-12 h, and filtering sodium chloride to obtain an ethanol solution of an intermediate sodium fatty alcohol polyoxyethylene ether monocarboxylate; (b) and introducing nitrogen for protection at a constant temperature of 70-75 ℃, adding sodium hydroxide into the ethanol solution of the sodium alcohol polyoxyethylene ether monocarboxylate, activating for 30-40 min under stirring, cooling to below 40 ℃, adding chloropropene, controlling the molar ratio of the sodium alcohol polyoxyethylene ether monocarboxylate to the intermediate, sodium hydroxide and chloropropene to be 1: 1-1: 1.1, carrying out reflux reaction for 5-7 h at the constant temperature of 70-75 ℃, acidifying with 30% hydrochloric acid, filtering, and recovering ethanol as a solvent under reduced pressure to finally obtain a light yellow liquid, wherein the yield is 85-95%, and the purity is 85-90%.

The reaction equation is shown below

ClCH₂COOH+NaOH→ClCH₂COONa+H₂O

HO(CH₂CH₂O)₃CH₂CH₂OH+NaOH→HO(CH₂CH₂O)₃CH₂CH₂ONa+H₂O

HO(CH₂CH₂O)₃CH₂CH₂ONa+ClCH₂COONa→HO(CH₂CH₂O)₃CH₂CH₂OCH₂COONa+NaCl

HO(CH₂CH₂O)₄CH₂COONa+H₂C＝CHCH₂Cl+NaOH→H₂C＝CHCH₂HO(CH₂CH₂O)₄CH₂COONa+NaCl

H₂C＝CHCH₂O(CH₂CH₂O)₄CH₂COONa+HCl→H₂C＝CHCH₂O(CH₂CH₂O)₄CH₂COOH+NaCl

The invention aims to provide a novel method for synthesizing allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-4).

The invention is a new method for synthesizing allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-4) by an asymmetric synthesis method.

APEA-4 Infrared Spectroscopy (FTIR), sampling the dried product, measuring the infrared spectrum on a Fourier Infrared spectrometer with a resolution of 4cm^-1Wave number range of 400-4000 cm^-1And scanning 30 times. FIG. 1 is a FTIR spectrum of allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-4), which is observed at 1745cm in FIG. 1^-1The vibration absorption of C ═ O appears to be stronger and stronger, 1647cm^-1Is H₂Absorption peak of C ═ CH-2878 cm^-1Is used for absorbing stretching vibration of saturated C-H bonds and is 1352-1456 cm^-1Is C-H bending vibration, 1213cm^-1Stretching vibration for C-O, 3371em^-11116em for O-H telescopic vibration absorption^-1Is- (CH)₂CH₂O) asymmetric stretching vibration.

Drawings

FIG. 1 shows an IR spectrum of allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-4).

Detailed Description