CN110668933A - Novel method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-7) - Google Patents
Novel method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-7) 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
- 238000000034 method Methods 0.000 title claims abstract description 30
- -1 allyl fatty alcohol Chemical class 0.000 title claims abstract description 28
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 102
- 239000011734 sodium Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 16
- 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
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 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
- 238000001914 filtration Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 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
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000005937 allylation reaction Methods 0.000 claims description 2
- 238000007039 two-step reaction Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 150000007942 carboxylates Chemical class 0.000 abstract description 5
- 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
- 239000000463 material Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000012043 crude product Substances 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 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
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 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
- DIOZVWSHACHNRT-UHFFFAOYSA-N 2-(2-prop-2-enoxyethoxy)ethanol Chemical compound OCCOCCOCC=C DIOZVWSHACHNRT-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-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
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 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
- 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
- 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
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000020477 pH reduction Effects 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
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- 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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- Organic Chemistry (AREA)
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Abstract
The invention provides a new method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-7). The invention provides a polyethylene glycol (PEG-300) and chloropropene (H)2C＝CHCH2Cl), chloroacetic acid (ClCH)2COOH) and sodium hydroxide (NaOH) are used as raw materials to react to obtain sodium allyl fatty alcohol polyoxyethylene ether carboxylate (APEC-7), the crude product is acidified by 30% hydrochloric acid, filtered and subjected to reduced pressure evaporation to remove the solvent to obtain a target product APEA-7, the yield of the APEA-7 is 85-90%, and the purity of the APEA-7 is 87-92%. The method has the following advantages compared with the reported process: (1) the operation is simple and convenient, and the reaction efficiency is higher; (2) the reaction condition is mild; (3) the conversion rate of APEA-7 is high; (4) no other substances except raw materials and solvent are introduced in the reaction process, and the solvent is not polluted and is easy to be usedThen the materials are recycled; (5) avoiding 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); (6) waste residue (sodium chloride) generated in the synthesis process can be recycled, and no negative influence on the environment is generated.
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-7), and particularly relates to a novel preparation method of the allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-7). 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
The allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-7) is embedded with seven Ethylene Oxide (EO) between a hydrophobic group and a hydrophilic group (-COO-), so that the anionic surfactant 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 surfactant and a nonionic surfactant, and the anionic surfactant and the nonionic surfactant can have different surface characteristics by adjusting the length of the hydrophobic chain and the addition number of the EO; meanwhile, the existence of hydrophobic allyl can be polymerized with other monomers containing allyl or vinyl, so that the allyl is an important 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) are taken as raw materials to carry out carboxymethylation reaction, the reaction product is cooled to room temperature after the reaction is finished, the reaction product is extracted, filtered and distilled under reduced pressure, the obtained product is dried in vacuum to obtain light red transparent liquid sodium allyl fatty alcohol polyoxyethylene ether carboxylate, and the allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA) is obtained after acidification, and 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-7) is not reported. The raw material of the Allyl Polyoxyethylene Ether (APEO) is scarce, the price is very high, 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 (EO), but the synthesis of the allyl fatty alcohol polyoxyethylene ether carboxylic acid (such as APEA-7) with the Ethylene Oxide (EO) number more 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 the amount of the catalyst, heating to a certain reaction temperature for reaction, introducing cooling water to about 30 ℃ after the reaction is finished, discharging, rectifying to obtain a glycol allyl ether product, and performing carboxymethylation on the product to obtain the sodium allyl polyethylene glycol carboxylate. The temperature and pressure required by the reaction are high, the requirements on equipment are high, the reaction conditions are harsh, the method for synthesizing the allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-7) is not reported, the boiling point of the allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-7) is high, and the final product obtained by the polymerization methodThe product is a mixture, and the product is not feasible to be separated by a rectification method;
(3) the etherification end-capping method adopts Williamson ether forming method to synthesize alcohol monoallyl ether, which is commonly used for synthesizing diethylene glycol monoallyl ether and ethylene glycol monoallyl ether. Firstly, alcohol reacts with sodium hydroxide to prepare sodium alkoxide, the generated sodium alkoxide is then subjected to bimolecular nucleophilic substitution with chloropropene to generate alcohol monoallyl ether, most of the alcohol monoallyl ether synthesized by the traditional Williamson ether formation method adopts high-price bromopropylene as a raw material, alkali is flammable and explosive metal sodium or sodium hydride which is difficult to operate, and a large amount of salt is generated in the reaction process, so that toxic organic solvents such as tetrahydrofuran, dioxane, toluene and the like are introduced as reaction media to ensure the reaction fluidity, and the generated alcohol monoallyl ether is subjected to carboxymethylation to obtain the sodium allyl polyalcohol carboxylate.
Disclosure of Invention
The synthesis method of the allyl fatty alcohol-polyoxyethylene ether carboxylic acid is subjected to a large number of experiments and industrial feasibility researches in laboratories, the method for preparing the allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-7) has high technological content, mature and simple process, mild reaction conditions, low requirements on equipment, easily available raw materials required by products, low cost and no three wastes in the reaction process, and the method is carried out in an ethanol solvent, can effectively realize the separation of the solvent and the products, is green and efficient.
According to the method, polyethylene glycol (PEG-300), chloroacetic acid and sodium hydroxide are used as raw materials, and are subjected to carboxymethylation reaction in an ethanol solvent, and then allylation reaction is carried out, so that the allyl fatty alcohol-polyoxyethylene ether carboxylic acid (APEA-7) is finally synthesized.
The specific preparation method comprises the following process steps: (a) adding PEG-300, 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 40-45 ℃ for 8-10 h, and filtering sodium chloride to obtain an intermediate sodium fatty alcohol polyoxyethylene ether monocarboxylate (HOCH)2CH2O(CH2CH2O)6CH2COONa) 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 ether monocarboxylate, activating for 30-40 min under stirring, then cooling to below 40 ℃, adding chloropropene, controlling the molar ratio of the sodium alcohol polyoxyethylene ether monocarboxylate to the intermediate, the sodium hydroxide and the chloropropene to be 1: 1-1: 1.1, carrying out reflux reaction for 6-8 h at the constant temperature of 70-75 ℃, then acidifying with 30% hydrochloric acid, filtering, and removing the solvent under reduced pressure to obtain a light yellow liquid, wherein the yield is 85-90%, and the purity is 87-92%.
The reaction equation is shown in the following figure
ClCH2COOH+NaOH→ClCH2COONa+H2O
HO(CH2CH2O)6CH2CH2OH+NaOH→HO(CH2CH2O)6CH2CH2ONa+H2O
HO(CH2CH2O)6CH2CH2ONa+ClCH2COONa→HO(CH2CH2O)6CH2CH2OCH2COONa+NaCl
HO(CH2CH2O)7CH2COONa+H2C＝CHCH2Cl+NaOH→H2C＝CHCH2HO(CH2CH2O)7CH2COONa+NaCl
H2C＝CHCH2O(CH2CH2O)7CH2COONa+HCl→H2C＝CHCH2O(CH2CH2O)7CH2COOH+NaCl
The invention aims to provide a novel method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-7).
The invention is an innovation point of synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-7) by an asymmetric synthesis method.
Infrared Spectroscopy (FTIR) of APEA-7, sampling the dried product, and measuring the infrared light on a Fourier Infrared spectrometerSpectrum, resolution 4cm-1Wave number range of 400-4000 cm-1And scanning 30 times. The FTIR spectrum of allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-7) is shown in FIG. 1, which is seen to be 1745cm-1The vibration strong absorption peak of C ═ O, 1674cm-1Is H2Absorption peak of C ═ CH-2878 cm-1Is used for absorbing stretching vibration of saturated C-H bonds and is 1352-1454 cm-1Is C-H bending vibration, 1213cm-1Is C-O stretching vibration, 3383cm-11120cm for O-H stretching vibration absorption-1is-CH2CH2And O, asymmetrical stretching vibration.
Drawings
FIG. 1 shows an IR spectrum of allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-7).
Detailed Description
The first embodiment is as follows: adding PEG-300, sodium hydroxide and chloroacetic acid into a three-neck flask with a stirrer and a thermometer according to a molar ratio of 1:2:1 by taking ethanol as a solvent, introducing nitrogen for protection, reacting at a constant temperature of 40 ℃ for 10 hours, 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 72 ℃, adding sodium hydroxide into the ethanol solution of the sodium alcohol polyoxyethylene ether monocarboxylate, activating for 30-40 min under stirring, then cooling to below 40 ℃, adding chloropropene, controlling the molar ratio of the sodium alcohol polyoxyethylene ether monocarboxylate to the sodium hydroxide as an intermediate to the chloropropene to be 1:1:1, carrying out reflux reaction for 6h at a 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 85%, and the purity is 87%.
Example two: adding PEG-300, sodium hydroxide and chloroacetic acid into a three-neck flask with a stirrer and a thermometer according to a molar ratio of 1:2.1:1.05 by taking ethanol as a solvent, introducing nitrogen for protection, reacting at a constant temperature of 40 ℃ for 10 hours, 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 75 ℃, adding sodium hydroxide into the ethanol solution of the sodium alcohol polyoxyethylene ether monocarboxylate, activating for 30-40 min under stirring, then cooling to below 40 ℃, adding chloropropene, controlling the molar ratio of the sodium alcohol polyoxyethylene ether monocarboxylate to the sodium hydroxide as an intermediate to the chloropropene to be 1:1:1, 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 86% and the purity is 90%.
Example three: adding PEG-300, sodium hydroxide and chloroacetic acid into a three-neck flask with a stirrer and a thermometer according to a molar ratio of 1:2.1:1.05 by taking ethanol as a solvent, introducing nitrogen for protection, reacting at a constant temperature of 45 ℃ for 8 hours, 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 75 ℃, adding sodium hydroxide into the ethanol solution of the sodium alcohol polyoxyethylene ether monocarboxylate, activating for 30-40 min under stirring, then cooling to below 40 ℃, adding chloropropene, controlling the molar ratio of the sodium alcohol polyoxyethylene ether monocarboxylate to the sodium hydroxide as an intermediate to the chloropropene to be 1:1:1, carrying out reflux reaction for 6h 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 87%, and the purity is 90%.
Example four: adding PEG-300, sodium hydroxide and chloroacetic acid into a three-neck flask with a stirrer and a thermometer according to a molar ratio of 1:2.1:1.05 by taking ethanol as a solvent, introducing nitrogen for protection, reacting at a constant temperature of 45 ℃ for 10 hours, 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 ℃, adding sodium hydroxide into the ethanol solution of the sodium alcohol polyoxyethylene ether monocarboxylate, activating for 30-40 min under stirring, then cooling to below 40 ℃, adding chloropropene, controlling the molar ratio of the sodium alcohol polyoxyethylene ether monocarboxylate to the sodium hydroxide as an intermediate to the chloropropene to be 1:1:1, carrying out reflux reaction for 7h at the constant temperature of 70 ℃, 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 five: adding PEG-300, sodium hydroxide and chloroacetic acid into a three-neck flask with a stirrer and a thermometer according to a molar ratio of 1:2.1:1.05 by taking ethanol as a solvent, introducing nitrogen for protection, reacting at a constant temperature of 40 ℃ for 10 hours, 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 75 ℃, adding sodium hydroxide into the sodium alcohol solution of the fatty alcohol-polyoxyethylene ether monocarboxylic acid, activating for 30-40 min under stirring, then cooling to below 40 ℃, adding chloropropene, controlling the molar ratio of triethylene glycol to sodium hydroxide to chloropropene to be 1:1:1.05, 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 89%, and the purity is 91%.
Claims (2)
1. A new method for synthesizing allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-7) is prepared from polyethylene glycol (PEG-300) and chloroacetic acid (ClCH)2COOH) and sodium hydroxide (NaOH), chloropropene (H)2C＝CHCH2Cl) as raw material, ethanol (CH)3CH2OH) as solvent, and synthesizing APEA-7 by two-step reaction of carboxymethylation and allylation under normal pressure, wherein the structural formula is H2C＝CHCH2O(CH2CH2O)7CH2COOH。
2. The process for the preparation of allyl fatty alcohol polyoxyethylene ether carboxylic acid (APEA-7) according to claim 1, wherein: (a) adding PEG-300, 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 40-45 ℃ for 6-9 hours, and filtering sodium chloride to obtain an ethanol solution (HOCH) of intermediate sodium fatty alcohol polyoxyethylene ether monocarboxylate2CH2O(CH2CH2O)6CH2COONa); (b) 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, then cooling to below 40 ℃, adding chloropropene, controlling the molar ratio of the sodium alcohol polyoxyethylene ether monocarboxylate to the intermediate, the sodium hydroxide and the chloropropene to be 1:1: 1-1: 1.1:1.1, carrying out reflux reaction for 5-7 h at the constant temperature of 70-75 ℃, then acidifying with 30% hydrochloric acid, filtering, and removing the solvent under reduced pressure to obtain a light yellow liquid, wherein the yield is 85-90%,the purity is 87-92%.
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| Application Number | Priority Date | Filing Date | Title |
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| WO1999034833A1 (en) * | 1998-01-07 | 1999-07-15 | Shearwater Polymers, Incorporated | Degradable heterobifunctional poly(ethylene glycol) acrylates and gels and conjugates derived therefrom |
| CN102485771A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | Fatty alcohol polyoxypropylene polyoxyethylene ether carboxylate, preparation thereof and application thereof |
| CN102627773A (en) * | 2012-03-19 | 2012-08-08 | 江苏飞翔化工股份有限公司 | Polyoxyethylene fatty alcohol ether-siloxane copolymer and its preparation method and use |
| WO2013181597A2 (en) * | 2012-05-31 | 2013-12-05 | Synchem, Inc. | Thiol-ene click chemistry for drug conjugates |
| CN108738321A (en) * | 2015-11-16 | 2018-11-02 | 豪夫迈·罗氏有限公司 | GalNAc cluster phosphoramidites |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999034833A1 (en) * | 1998-01-07 | 1999-07-15 | Shearwater Polymers, Incorporated | Degradable heterobifunctional poly(ethylene glycol) acrylates and gels and conjugates derived therefrom |
| CN102485771A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | Fatty alcohol polyoxypropylene polyoxyethylene ether carboxylate, preparation thereof and application thereof |
| CN102627773A (en) * | 2012-03-19 | 2012-08-08 | 江苏飞翔化工股份有限公司 | Polyoxyethylene fatty alcohol ether-siloxane copolymer and its preparation method and use |
| WO2013181597A2 (en) * | 2012-05-31 | 2013-12-05 | Synchem, Inc. | Thiol-ene click chemistry for drug conjugates |
| CN108738321A (en) * | 2015-11-16 | 2018-11-02 | 豪夫迈·罗氏有限公司 | GalNAc cluster phosphoramidites |
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