CN110642704A - Novel method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-4) - Google Patents
Novel method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-4) Download PDFInfo
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- 229940051841 polyoxyethylene ether Drugs 0.000 title claims abstract description 49
- 229920000056 polyoxyethylene ether Polymers 0.000 title claims abstract description 49
- -1 allyl fatty alcohol Chemical class 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 29
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 99
- 239000011734 sodium Substances 0.000 claims abstract description 28
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 16
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 13
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940106681 chloroacetic acid Drugs 0.000 claims abstract description 11
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 72
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005937 allylation reaction Methods 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 238000007039 two-step reaction Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NNQDMQVWOWCVEM-UHFFFAOYSA-N 1-bromoprop-1-ene Chemical group CC=CBr NNQDMQVWOWCVEM-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000012658 bimolecular nucleophilic substitution Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention provides a new method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-4). The invention uses tetraethylene glycol (HO (CH)2CH2O)3CH2CH2OH), chloropropene (H)2C＝CHCH2Cl), chloroacetic acid (ClCH)2COOH) 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).
Description
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
The first embodiment is as follows: 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 by taking ethanol as a solvent, introducing nitrogen for protection, reacting at the constant temperature of 45 ℃ for 12 hours, and filtering sodium chloride to obtain an ethanol solution of an intermediate sodium fatty alcohol polyoxyethylene ether monocarboxylate; 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, controlling the molar ratio of the intermediate alcohol monocarboxylate to the sodium hydroxide to the chloropropene to be 1:1, carrying out reflux reaction for 7h at the constant temperature of 75 ℃, then acidifying by 30% hydrochloric acid, filtering, and removing the solvent under reduced pressure to obtain a light yellow liquid, wherein the yield is 86%, and the purity is 85%.
Example two: 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: 1.05 by taking ethanol as a solvent, introducing nitrogen for protection, reacting at the constant temperature of 45 ℃ for 10 hours, and filtering sodium chloride to obtain an ethanol solution of the intermediate sodium fatty alcohol polyoxyethylene ether monocarboxylate; 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, controlling the molar ratio of the intermediate alcohol sodium monoallyl carboxylate, the sodium hydroxide and the chloropropene to be 1:1.1, carrying out reflux reaction for 7h at the constant temperature of 75 ℃, then acidifying by 30% hydrochloric acid, filtering, and removing the solvent under reduced pressure to obtain a light yellow liquid, wherein the yield is 85%, and the purity is 86%.
Example three: 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 1:2.2:1.1 by taking ethanol as a solvent, introducing nitrogen for protection, reacting at the constant temperature of 50 ℃ for 12 hours, and filtering sodium chloride to obtain an ethanol solution of the intermediate sodium fatty alcohol polyoxyethylene ether monocarboxylate; 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, controlling the molar ratio of the sodium alcohol polyoxyethylene ether monocarboxylate to the intermediate sodium hydroxide to chloropropene to be 1: 1.05, carrying out reflux reaction for 6h at the constant temperature of 75 ℃, then acidifying by 30% hydrochloric acid, filtering, and removing the solvent under reduced pressure to obtain a light yellow liquid, wherein the yield is 85%, and the purity is 87%.
Example four: 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: 1.05 by taking ethanol as a solvent, introducing nitrogen for protection, reacting at the constant temperature of 50 ℃ for 12 hours, and filtering sodium chloride to obtain an ethanol solution of the intermediate sodium fatty alcohol polyoxyethylene ether monocarboxylate; 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, controlling the molar ratio of the sodium alcohol polyoxyethylene ether monocarboxylate to the intermediate sodium hydroxide to chloropropene to be 1:1.1, carrying out reflux reaction for 7h at the constant temperature of 70 ℃, then acidifying by 30% hydrochloric acid, filtering, and removing the solvent under reduced pressure to obtain a light yellow liquid, wherein the yield is 86%, and the purity is 86%.
Example five: 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: 1.05 by taking ethanol as a solvent, introducing nitrogen for protection, reacting at the constant temperature of 45 ℃ for 12 hours, and filtering sodium chloride to obtain an ethanol solution of the intermediate sodium fatty alcohol polyoxyethylene ether monocarboxylate; 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, controlling the molar ratio of the sodium alcohol polyoxyethylene ether monocarboxylate to the intermediate sodium hydroxide to chloropropene to be 1:1, carrying out reflux reaction for 7h at the constant temperature of 75 ℃, acidifying by 30% hydrochloric acid, filtering, and removing the solvent under reduced pressure to obtain a light yellow liquid, wherein the yield is 90%, and the purity is 92%.
Claims (2)
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%.
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