CN110655645B - Application of strong-base anion exchange resin in preparation of hydroxyl-terminated polyether quaternary ammonium salt - Google Patents
Application of strong-base anion exchange resin in preparation of hydroxyl-terminated polyether quaternary ammonium salt Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
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- C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
- C07C239/08—Hydroxylamino compounds or their ethers or esters
- C07C239/12—Hydroxylamino compounds or their ethers or esters having nitrogen atoms of hydroxylamino groups further bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
Abstract
The hydroxyl-terminated polyether quaternary ammonium salt, namely the alpha-hydroxyl polyether quaternary ammonium salt can be used for preparing various functional polymer materials such as cationic polyurethane, cationic antibacterial hydrogel, cationic-nonionic surfactant, functional ionic liquid and the like. The invention provides a method for preparing alpha-hydroxy polyether quaternary ammonium salt by ring-opening polymerization reaction of alkylene oxide by taking beta-hydroxyethyl ammonium salt as an initiator and strong-base anion exchange resin as an alkali reagent. The product containing the hydroxyl-terminated polyether quaternary ammonium salt obtained by the preparation method has high purity, high yield and small polydispersity.
Description
Technical Field
The invention relates to a preparation method of polyether quaternary ammonium salt, in particular to application of strong-basicity anion exchange resin in preparation of hydroxyl-terminated polyether quaternary ammonium salt, belonging to the field of organic functional materials.
Technical Field
The hydroxyl-terminated polyether quaternary ammonium salt, namely the alpha-hydroxyl polyether quaternary ammonium salt, belongs to a class of functional polymer materials, has some special physical, chemical and biological properties, can be used for preparing the functional polymer materials in multiple fields such as cationic polyurethane, cationic antibacterial hydrogel, cationic/nonionic surfactant, functional ionic liquid and the like, and has wide application prospect, so that the research and development of synthesis and production technology and process with practical application value have significance.
The general preparation method of the alpha-hydroxy polyether quaternary ammonium salt can be specifically shown by the following reaction formulas:
the alpha-hydroxy polyether quaternary ammonium salt prepared by the five reaction formulas has the characteristics of the technology, the process and the product. According to the reaction formula 1 and the reaction formula 2, the polyethylene glycol is used as a starting material, the alpha-hydroxy polyether secondary amine or the alpha-hydroxy polyether quaternary ammonium salt with the specific polyether chain length can be prepared, but the prepared product also contains impurities of which alpha-groups and omega-groups are secondary amine groups or quaternary ammonium salts. The technical processes of the reaction formula 1 and the reaction formula 2 are alternative methods for preparing the gemini quaternary ammonium salt with the polyether chain as the spacer.
The method adopts the principle and the steps of a reaction formula 3, generally adopts N, N-dialkyl ethanolamine as an initiator, adopts sodium hydroxide, potassium hydroxide, sodium hydride, sodium alkoxide, sodium naphthalene or butyl lithium and the like as catalysts, and prepares R by ring-opening polymerization of ethylene oxide1～R3The alkyl is selected according to the requirement, and the chain length of the polyether is uncertain. The alpha-hydroxy polyether secondary amine prepared by the step of the reaction formula 3 needs to be acidified to further carry out quaternary ammonium salinization reaction with halogenated hydrocarbon to prepare the needed alpha-hydroxy polyether quaternary ammonium salt. In addition, the alpha-hydroxy polyether secondary amine and the alpha-hydroxy polyether quaternary ammonium salt products prepared by the method have darker colors.
The method of the reaction formula 4 for preparing the alpha-hydroxy polyether quaternary ammonium salt has the simplest process, R1～R3The alkyl can be freely selected according to the requirement, the polymerization degree of the polyether chain can be controlled according to the addition amount of the ethylene oxide, and the prepared alpha-hydroxy polyether tertiary amine or alpha-hydroxy polyether quaternary ammonium salt product has high purity and light color. However, the preparation of the alpha-hydroxy polyether tertiary amine from low-boiling point secondary amine such as dimethylamine or diethylamine usually uses water as a solvent, so that the solvent water can also be used as an initiator, and the polyethylene glycol synthesized by polymerization of ethylene oxide is a byproduct, so that the separation of the alpha-hydroxy polyether tertiary amine is not easy.
R can be prepared by the procedure of reaction formula 51～R3The alkyl is selected according to the requirement, and the polyether chain length is specified. But the process is complex and the product is not easy to purify.
In view of the foregoing, it is well known to those skilled in the art that quaternization of tertiary alpha-hydroxy polyether amines with halohydrocarbons, alkyl sulfates, or propane sultone is currently the usual method for preparing hydroxyl terminated polyether containing quaternary ammonium salts. However, recently CN105801831A provides a method for preparing unsaturated hydroxy polyether quaternary ammonium salt, which is to prepare unsaturated poly β -hydroxyethyl quaternary ammonium salt by quaternization reaction between poly β -hydroxyethyl amine and unsaturated halohydrocarbon, and using potassium acetate, sodium hydroxide, sodium hydride or sodium methoxide as catalyst; then the ring-opening polymerization reaction of ethylene oxide or propylene oxide catalyzed by sodium hydride is carried out to prepare the alpha-hydroxy polyether unsaturated quaternary ammonium salt. The present inventors have conducted the quaternary ammonification reaction between N, N-dimethylethanolamine and chloropropene according to the method and procedure provided in CN105801831A, using sodium hydroxide as a catalyst, and have not high yield of the product of N-allyl-N, N-dimethyl-N- (. beta. -hydroxyethyl) ammonium chloride. It was found by analysis that several by-products of allyl alcohol, diallyl ether, N-allyl-N, N-dimethylammonium-N- (. beta. -hydroxyethyl) ammonium hydroxide and N, N-dimethyl-N-allyl-N- (2-allyloxyethyl) ammonium chloride were also present in the N-allyl-N, N-dimethyl-N- (. beta. -hydroxyethyl) ammonium chloride product. And then the ring-opening polymerization reaction of the alkylene oxide is carried out, and more by-products in the prepared N, N-dimethyl-N-allyl-N- (hydroxyl-terminated polyether) ammonium chloride product also comprise omega-chloro hydroxyl-terminated polyether, polyethylene glycol and the like.
Disclosure of Invention
As the professional is familiar with, the ring-opening reaction of secondary amine and ethylene oxide to prepare the N, N-dialkyl ethanolamine is mature technology and process, and the purity of the prepared product is high, so the N, N-dialkyl ethanolamine is a common commercial product; the N, N-dialkyl ethanolamine reacts with the halohydrocarbon to prepare halogenated N, N, N-trialkyl-N- (beta-hydroxyethyl) ammonium salt, and the method is simple in process, safe and reliable in technology and convenient in product separation and purification. The inventor designs N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium hydroxide by using halogenated N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium salt as a starting material and using strongly basic anion exchange resin as an alkali reagent; then the N, N, N-trialkyl-N- (beta-hydroxyethyl) ammonium hydroxide is subjected to azeotropic dehydration to prepare N, N, N-trialkyl-N- (beta-negative oxyethyl) ammonium inner salt; the N, N, N-trihydrocarbyl-N- (beta-negative oxyethyl) ammonium inner salt can perform ring-opening polymerization reaction with alkylene oxide, and then is subjected to acidification treatment to prepare the hydroxyl-terminated polyether quaternary ammonium salt with the structure shown in the general formula I.
The hydroxyl-terminated polyether quaternary ammonium salt has a structure shown in a general formula (I):
wherein R in the general formula (I)1、R2And R3Are respectively selected from substituted or unsubstituted C1～C18One of the hydrocarbon radicals, R4Selected from H, methyl or ethyl, n is selected from natural numbers between 1 and 200, and X is selected from F, Cl, Br and CH3COO、C3F7COO、BF4、PF6、SbF6、CH3SO3、CF3SO3、C4F9SO3、(CF3SO2)3C or (CF)3SO2)2One of N;
the halogenated N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium salt has a structure shown by a general formula (II):
wherein R in the general formula (II)1、R2And R3Are respectively selected from substituted or unsubstituted C1～C18And Y is selected from Cl, Br or I.
The alkali reagent refers to a strongly basic anion exchange resin.
The alkylene oxide refers to one or more than two of ethylene oxide, propylene oxide or butylene oxide.
The method takes halogenated N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium salt as a starting material, and applies strong-base anion exchange resin as an alkali reagent to ring-opening polymerization reaction of alkylene oxide to prepare the alpha-hydroxy polyether quaternary ammonium salt with the structure shown in the general formula I, and the beneficial effects are as follows:
(1) the method utilizes N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium salt as a starting material and strong-base anion exchange resin as an alkali reagent for double decomposition reaction to prepare N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium hydroxide, and can completely separate the N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium hydroxide from the ion exchange resin by filtering, so that the residual ion exchange resin is prevented from participating in the subsequent ring opening reaction of alkylene oxide, the byproducts of omega-chloro-terminated hydroxyl polyether and polyethylene glycol are avoided, the utilization rate of the alkylene oxide is ensured, the subsequent alpha-hydroxy polyether quaternary ammonium salt product has high purity and small polydispersity, and the separation technology is simplified.
(2) The N, N, N-trialkyl-N- (beta-hydroxyethyl) ammonium hydroxide is refluxed and azeotropically dehydrated in a solvent to prepare N, N, N-trialkyl-N- (beta-negative oxyethyl) ammonium, the negative oxygen in the trialkyl-N- (beta-negative oxyethyl) ammonium is used as the only initiator in a reaction system to perform ring-opening polymerization reaction initiated by negative oxygen ions with alkylene oxide, and the alpha-hydroxy polyether quaternary ammonium salt product prepared by multiple acidification treatments has high purity and light color.
The design purpose, the preparation method and the technical process of the invention are expressed by a reaction formula.
(3) The preparation method of the alpha-hydroxy polyether quaternary ammonium salt provided by the invention has the advantages that the needed raw materials are mostly commercial products, the adopted reaction technology belongs to the classical chemical synthesis principle, the side reaction of each step is less, and the product separation technology of each step is simple and easy to implement.
The application process and the specific operation for realizing the purpose of the invention are as follows:
Detailed Description
Dissolving N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium halide in a solvent, adding strong-base ion exchange resin, stirring at room temperature to complete ion exchange, and filtering to remove the ion exchange resin to obtain a solution of N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium hydroxide; feeding the solution of the N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium hydroxide into a distillation kettle, adding an organic solvent, and heating for distillation; distilling to remove water completely to obtain N, N, N-trialkyl-N- (beta-negative oxygen ethyl) ammonium solution; feeding the N, N, N-trialkyl-N- (beta-negative oxyethyl) ammonium solution into a high-pressure reaction kettle, feeding 5-20% of alkylene oxide by mass percent into the high-pressure reaction kettle after nitrogen is filled in the high-pressure reaction kettle and oxygen is removed, controlling the temperature of reaction materials in the high-pressure reaction kettle to 90-120 ℃ to initiate ring-opening polymerization reaction, increasing the pressure in the high-pressure reaction kettle to 0.1-4.0 MPa, continuously feeding the rest alkylene oxide into the high-pressure reaction kettle after the polymerization reaction temperature is constant to 90-110 ℃, continuing curing reaction for 0.5-2 hours, reducing the temperature of the reaction materials in the high-pressure reaction kettle to room temperature after the pressure in the high-pressure reaction kettle is not reduced, adding acid to regulate the pH value of the materials in the high-pressure reaction kettle to 5.5-6.5, transferring the reaction materials in the high-pressure reaction kettle into a distillation kettle, performing rotary distillation to remove unreacted alkylene oxide, Cyclopolyalkylene oxide, solvent or organic solvent to obtain hydroxyl terminated polyether quaternary ammonium salt with the structure shown in the general formula I.
Wherein, the hydroxyl-terminated polyether quaternary ammonium salt has a structure shown in a general formula (I):
wherein R in the general formula (I)1、R2And R3Are respectively selected from substituted or unsubstituted C1～C18One of the hydrocarbon radicals, R4Selected from H, methyl or ethyl, n is selected from natural numbers between 1 and 2000, and X is selected from F, Cl, Br and CH3COO、C3F7COO、BF4、PF6、SbF6、CH3SO3、CF3SO3、C4F9SO3、(CF3SO2)3C or (CF)3SO2)2One of N;
the halogenated N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium has a structure shown by a general formula (II):
wherein R in the general formula (II)1、R2And R3Are respectively selected from substituted or unsubstituted C1～C18One of hydrocarbyl, wherein Y is selected from Cl, Br or I;
the solvent is selected from one or more of water, methanol, ethanol, propanol, butanol, cyclohexanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, acetophenone, methyl benzoate, anisole and phenetole, and the dosage of the solvent is 0-200% of the mass of halogenated N, N, N-trialkyl-N- (beta-hydroxyethyl) ammonium.
The strongly basic anion exchange resin refers to polystyrene quaternary ammonium base type anion exchange resin, polyvinyl pyridinium (OH) type anion exchange resin, polyallylamine (OH) type anion exchange resin or acrylic acid (OH) type anion exchange resin, and the dosage of the strongly basic anion exchange resin is 5-500% of the mass of N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium halide.
The organic solvent is one or more of pentane, hexane, cyclohexane, octane, benzene, toluene, xylene, decalin, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether or petroleum ether with a boiling range of 60-120 ℃, and the amount of the organic solvent is 0-200% of the mass of halogenated N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium.
The alkylene oxide refers to one or more than two of ethylene oxide, propylene oxide or butylene oxide. The dosage of the alkylene oxide is 0.5 to 500 times of the mass of the halogenated N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium;
the acid refers to HF, HCl, HBr and CH3COOH、C3F7COOH、HBF4、HPF6、HSbF6、CH3SO3H、CF3SO3H、C4F9SO3H、(CF3SO2)3CH or (CF)3SO2)2And one of NH, wherein the dosage of the acid is 1.0 to 1.05 times of the molar quantity of the halogenated N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium.
The preparation method of the alpha-hydroxy polyether quaternary ammonium salt provided by the invention has the following characteristics:
(1) the strong-base anion exchange resin is applied to the preparation of the hydroxyl-terminated polyether quaternary ammonium salt, the side reaction is less, the product separation and purification technology is simplified, and the ion exchange resin can be recycled and regenerated.
(2) The quaternary ammonium salt product containing the hydroxyl-terminated polyether prepared by the preparation method provided by the invention has high purity and high yield.
(3) The hydroxyl-terminated polyether quaternary ammonium salt prepared by the preparation method has small polydispersity index by using halogenated N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium salt as a starting material.
(4) The length of the polyether chain in the hydroxyl-terminated polyether quaternary ammonium salt or the average molecular weight of the hydroxyl-terminated polyether quaternary ammonium salt can be regulated and controlled according to the requirements by the dosage ratio of the alkylene oxide and the halogenated N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium.
Example 1
21 g of N-benzyl-N, N-dimethyl-N- (. beta. -hydroxyethyl) ammonium chloride and 40 g of dehydrated strongly basic anion exchange resin (201X 7) in the form of (B) sodium chloride were weighed outShanghai Lanrun chemical Co., Ltd) Dispersing in a mixed solvent of 50 g of ethanol and 50 g of ethylene glycol diethyl ether, stirring for 30 minutes at room temperature, and filtering to recover the ion exchange resin; feeding the obtained filtrate into a distillation kettle, carrying out temperature-controlled reflux distillation, cooling and transferring into a high-pressure reaction kettle after removing water and ethanol by azeotropic distillation, filling nitrogen and deoxidizing for 3 minutes, pressing 5 g of ethylene oxide, controlling the temperature of reaction materials in the high-pressure reaction kettle to be 100 ℃, initiating ring-opening polymerization reaction, raising the pressure in the high-pressure reaction kettle to be 0.26MPa, when the polymerization temperature is constant at 100-110 ℃, starting to reduce the pressure in the high-pressure reaction kettle, continuously feeding 50 g of ethylene oxide into the high-pressure reaction kettle, continuing curing reaction for 0.5 hour after continuous feeding is finished, reducing the temperature of the reaction materials in the high-pressure reaction kettle to room temperature after the pressure in the high-pressure reaction kettle is not reduced any more, regulating the pH value of the materials in the high-pressure reaction kettle to be about 4-6 by using 6.0 g of acetic acid, transferring the materials in the high-pressure reaction kettle into the distillation kettle, carrying out rotary evaporation, removing unreacted alkylene oxide, recovering ethylene glycol diethyl ether and acetic acid, the obtained yellowish viscous N-benzyl-N, N-dimethyl-N- (alpha-hydroxy polyether) ammonium acetate has a hydroxyl value of 67.83mgKOH/g (calculated according to the amount of ethylene oxide, the hydroxyl value should be about 77.8 mgKOH/g) according to the analysis and measurement method of GB/T30915-.
Example 2
By changing the amount of N-benzyl-N, N-dimethyl-N- (. beta. -hydroxyethyl) ammonium chloride to 33 g of N-dodecyl-N, N-dimethyl-N- (. beta. -hydroxyethyl) ammonium bromide in accordance with the procedure and operation of example 1, a pale yellow waxy N-dodecyl-N, N-dimethyl-N- (. alpha. -hydroxy polyether) ammonium acetate was obtained, which had a hydroxyl value of 84.73mgKOH/g (about 88mgKOH/g, calculated on the amount of ethylene oxide) as determined by analysis in accordance with GB/T30915-.
Example 3
By changing the amount of N-benzyl-N, N-dimethyl-N- (. beta. -hydroxyethyl) ammonium chloride to 30 g of N-benzyl-N, N-di-N-butyl-N- (. beta. -hydroxyethyl) ammonium chloride and increasing the amount of ethylene oxide to 120 g in accordance with the procedure and operation of example 1, a pale yellow waxy N-benzyl-N, N-di-N-butyl-N- (. alpha. -hydroxypolyether) ammonium acetate was obtained, which had a hydroxyl value of 146.21mgKOH/g (about 150mgKOH/g, calculated on the amount of ethylene oxide) according to GB/T30915-A-Si method).
Example 4
By changing the amount of N-benzyl-N, N-dimethyl-N- (. beta. -hydroxyethyl) ammonium chloride to 42 g of N-dodecyl-N, N-di-N-butyl-N- (. beta. -hydroxyethyl) ammonium bromide and increasing the amount of ethylene oxide to 120 g in accordance with the procedure and procedure of example 1, a pale yellow waxy ammonium N-dodecyl-N, N-di-N-butyl-N- (. alpha. -hydroxypolyether) acetate was obtained, which had a hydroxyl value of 160.33mgKOH/g (about 162 mgKOH/g, calculated on the amount of ethylene oxide) according to GB/T30915-A-Si method).
Example 5
By changing the N-benzyl-N, N-dimethyl-N- (. beta. -hydroxyethyl) ammonium chloride to 42 g of N-dodecyl-N, N-di-N-butyl-N- (. beta. -hydroxyethyl) ammonium bromide, the ethylene oxide content to 120 g, and the acetic acid to trifluoromethanesulfonic acid in accordance with the procedure and procedure of example 1, a pale yellow waxy ammonium N-dodecyl-N, N-di-N-butyl-N- (. alpha. -hydroxypolyether) trifluoromethanesulfonate was prepared, which had a hydroxyl value of 160.33mgKOH/g (about 162 mgKOH/g, calculated on the basis of the ethylene oxide content) by analysis in accordance with GB/T30915-2014.
Claims (6)
1. The application of the strong-base anion exchange resin in the preparation of the hydroxyl-terminated polyether quaternary ammonium salt is characterized by comprising the following steps:
dissolving N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium halide in a solvent, adding strong-base anion exchange resin, stirring at room temperature to complete ion exchange, filtering, separating and recovering the ion exchange resin to prepare a solution of N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium hydroxide;
feeding the solution of the N, N, N-trialkyl-N- (beta-hydroxyethyl) ammonium hydroxide into a distillation kettle, adding an organic solvent, and heating for reflux distillation; distilling to remove water completely to obtain N, N, N-trialkyl-N- (beta-negative oxyethyl) ammonium solution;
step three, feeding the N, N, N-trialkyl-N- (beta-negative oxyethyl) ammonium solution into a high-pressure reaction kettle, feeding 5-20% by mass of alkylene oxide into the high-pressure reaction kettle after filling nitrogen and removing oxygen in the high-pressure reaction kettle, controlling the temperature of reaction materials in the high-pressure reaction kettle to be 90-120 ℃ to initiate ring-opening polymerization reaction of the alkylene oxide, increasing the pressure in the high-pressure reaction kettle to 0.1-4.0 MPa, continuously feeding the rest alkylene oxide into the high-pressure reaction kettle after the polymerization reaction temperature is constant to be 90-110 ℃, feeding the alkylene oxide, continuing curing reaction for 0.5-2 hours, reducing the temperature of the reaction materials in the high-pressure reaction kettle to room temperature after the pressure in the high-pressure reaction kettle is not reduced, adding acid to regulate the pH value of the materials in the high-pressure reaction kettle to be 5.5-6.5, transferring the reaction materials in the high-pressure reaction kettle into a distillation kettle, performing rotary evaporation, removing unreacted cyclopolyalkylene oxide by-products, solvents or organic solvents to obtain hydroxyl-terminated polyether quaternary ammonium salt with the structure shown in the general formula I;
wherein the hydroxyl-terminated polyether quaternary ammonium salt has a structure shown in a general formula (I):
wherein R in the general formula (I)1、R2And R3Are respectively selected from substituted or unsubstituted C1～C18One of the hydrocarbon radicals, R4Selected from H, methyl or ethyl, n is selected from natural numbers between 1 and 2000, and X is selected from F, Cl, Br and CH3COO、C3F7COO、BF4、PF6、SbF6、CH3SO3、CF3SO3、C4F9SO3、(CF3SO2)3C or (CF)3SO2)2And one of N.
2. The use of a strongly basic anion exchange resin in the preparation of a hydroxyl terminated polyether quaternary ammonium salt according to claim 1, wherein the N, N-trialkyl-N- (β -hydroxyethyl) ammonium halide has the general formula (i):
wherein R in the general formula (II)1、R2And R3Are respectively selected from substituted or unsubstituted C1～C18And Y is selected from Cl, Br or I.
3. The use of the strongly basic anion exchange resin according to claim 1 in the preparation of hydroxyl-terminated polyether quaternary ammonium salt, wherein the solvent is one or more of water, methanol, ethanol, propanol, butanol, cyclohexanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, acetophenone, methyl benzoate, anisole or phenetole, and the amount of the solvent is 0-200% by mass of the halogenated N, N-trihydrocarbyl-N- (β -hydroxyethyl) ammonium.
4. The use of the strongly basic anion exchange resin according to claim 1 in the preparation of hydroxyl-terminated polyether quaternary ammonium salt, wherein the organic solvent is one or more of pentane, hexane, cyclohexane, octane, benzene, toluene, xylene, decalin, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether or petroleum ether with a boiling range of 60-120 ℃, and the amount of the organic solvent is 0-200% by mass of N, N, N-trihydrocarbyl-N- (β -hydroxyethyl) ammonium halide.
5. The use of a strong base anion exchange resin in the preparation of hydroxyl terminated polyether quaternary ammonium salt according to claim 1, wherein the alkylene oxide refers to one or more of ethylene oxide, propylene oxide or butylene oxide, and the amount of the alkylene oxide is 0.5-500 times of the mass of the N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium halide.
6. Use of strongly basic anion exchange resin according to claim 1 for the preparation of hydroxyl terminated polyether quats, characterized in that the acid is HF, HCl, HBr, CH3COOH、C3F7COOH、HBF4、HPF6、HSbF6、CH3SO3H、CF3SO3H、C4F9SO3H、(CF3SO2)3CH or (CF)3SO2)2And one of NH, wherein the dosage of the acid is 1.0 to 1.05 times of the molar quantity of the halogenated N, N, N-trihydrocarbyl-N- (beta-hydroxyethyl) ammonium.
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| US5756604A (en) * | 1995-08-31 | 1998-05-26 | Hodogaya Chemical Co., Ltd. | Process for producing polyether, and process for recycling and reusing herteropolyacid |
| CN105801831A (en) * | 2014-12-30 | 2016-07-27 | 辽宁奥克化学股份有限公司 | Unsaturated quaternary ammonium salt polyether, preparation method and application thereof |
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