CN112079736A - Quaternary ammonium salt compound of fuel cell anion membrane capable of completely blocking methanol permeation - Google Patents

Quaternary ammonium salt compound of fuel cell anion membrane capable of completely blocking methanol permeation Download PDF

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CN112079736A
CN112079736A CN202010858868.0A CN202010858868A CN112079736A CN 112079736 A CN112079736 A CN 112079736A CN 202010858868 A CN202010858868 A CN 202010858868A CN 112079736 A CN112079736 A CN 112079736A
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quaternary ammonium
ammonium salt
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王永军
王海军
王贝越
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Shanghai Manguanyue Water Treat Co ltd
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Abstract

The quaternary ammonium salt compound of the fuel cell anion membrane and the synthetic method thereof can completely block methanol permeation, because the beta-position of the quaternary ammonium salt ion has no hydrogen and contains fluorine saturated alkyl carbon chains, the quaternary ammonium salt compound has excellent performances of high ion capacity, high ion conductivity, high oxidation resistance, high temperature and strong base stability, no degradation and the like; after two tertiary hydroxyls of the dehydrated quaternary ammonium salt compound are cracked by strong acid, the anionic membrane quaternary ammonium salt compound with double end olefinic bonds can be obtained, and the compound can be polymerized into a compact cross-linked anionic membrane which can completely prevent methanol from permeating by free radicals, thereby meeting various harsh performance requirements of alkaline fuel cells.

Description

Quaternary ammonium salt compound of fuel cell anion membrane capable of completely blocking methanol permeation
Technical Field
The invention relates to a quaternary ammonium salt compound of a high-performance compact cross-linked anion membrane, which is used in the field of new energy of direct methanol alkaline fuel cells.
Background
In recent years, the performance of proton membrane fuel cells has been slowly improved, and it is difficult to apply them on a large scale in the electric automobile industry. Mainly, the membrane electrode is expensive, and the power density cannot be increased to be more than or equal to 1.4W/cm 2; fuel cells employing alkaline anionic membranes have the following great advantages over proton exchange membrane based alkaline fuel cells.
Compared with the acid condition, the oxidation speed of the alkaline fuel cell is higher, which is beneficial to improving the conversion efficiency of the fuel cell; and the major problems of water shortage of the proton membrane hydrogen electrode and water flooding of the oxygen electrode are solved.
The alkaline fuel cell avoids the poisoning of noble metal electrode catalyst, the oxygen electrode can also select common cheap metal electrode materials, such as silver, nickel, chelated manganese and the like, the platinum consumption is greatly reduced compared with that of a proton membrane fuel cell, and the electrode cost is greatly reduced; the ideal anionic membrane of the direct methanol alkaline fuel cell needs to meet a plurality of performance requirements. The main technical performance requirements are as follows:
alkaline stability: in 0.5mol/L NaOH, the operation can be stably carried out for more than 8000 hours, so that the main chain of the membrane polymer cannot contain ester bonds, amido bonds, imide bonds, ether bonds, guanidyl, ketocarbonyl and other groups which are easily broken by strong alkali; the beta-position of the quaternary ammonium salt film compound monomer cannot have active H, otherwise, Hoffman degradation reaction of quaternary ammonium salt can rapidly occur under the strong alkali condition of more than 50 ℃, and the ion capacity is rapidly reduced;
temperature resistance: the ion membrane containing the benzyl quaternary ammonium salt can stably operate at the temperature of more than or equal to 80 ℃, and can be stably used at the temperature of less than or equal to 60 ℃ at most; therefore, benzyl quaternary ammonium salt ions must be avoided, and the temperature resistance can be improved only by dense crosslinking;
③ solvent blocking ability: cannot permeate and swell with methanol, and must be effectively overcome by a densely crosslinked anionic membrane. Because the molecular diameter of the methanol is about 0.45nm, the membrane needs to be densely crosslinked, so that the pore diameter of the membrane is less than or equal to 0.5 nm;
oxidation resistance: the fuel cell operates in a strong oxidation environment for a long time, so that the main chain of the membrane material is prevented from containing easily-oxidized ether bonds or benzyl groups, such as the alpha position of a benzene ring of a styrene polymer structure is easily oxidized and broken, and the membrane material is not suitable;
high ionic conductivity: the conductivity can reach more than or equal to 50mS/cm, and higher generating power can be ensured. In order to keep the high conductivity of the membrane, the quaternary ammonium salt ion content of the membrane needs to be more than or equal to 1.8mmol/g (calculated by 100% anhydrous), and the more the ion passing capacity of the unit membrane area is, the higher the power of the fuel cell is. The content of quaternary ammonium salt of the existing anion membrane is only less than or equal to 1.0mmol/g at most, and the further improvement of the power of the fuel cell is limited. High power fuel cells require dense cross-linked anionic membranes that match high ion content;
high electron resistivity: the ideal state can reach more than or equal to 1000 omega cm2, and the electronic short circuit of the membrane electrode can be effectively prevented; high electron resistivity is achieved only when there is very little water contained within the anion membrane. To reduce the internal water content of the anionic membrane, it is necessary to have a strong hydrophobic alkyl group and a dense cross-linked structure to prevent water from penetrating into the anionic membrane.
The above fuel cells have strict technical requirements on anion membranes, and the existing anion membranes prepared by crosslinking and polymerizing aromatic ring-containing mixed monomers such as styrene, butadiene and the like at home and abroad are difficult to achieve; anionic membranes prepared from mixed monomers containing aromatic hydrocarbons with benzene rings have several significant drawbacks:
1: the normal distribution of the size difference of the ion channels of the anion membrane is very wide: the anionic membrane copolymerized by multiple mono-olefinic monomers cannot prevent methanol from permeating because the competitive polymerization rates among the monomers are greatly different, the crosslinking degree is very uneven, the size difference of membrane ion channels can reach more than 10 times, and the ionic channels can exist from 2 to 20 nm;
2: no oxidation resistance: the benzyl quaternary ammonium salt containing the styrene structure can be degraded and damaged in oxidizing environments such as sodium hypochlorite and hydrogen peroxide within a few weeks, and the service life is too short to be used for a long time;
3: weak resistance to strong base decay: the quaternary ammonium salt with hydrogen at the beta position of the alkyl is heated to be more than or equal to 60 ℃, Hofmann degradation is easily carried out under strong alkali to olefin and tertiary amine, and the quaternary ammonium salt ion attenuation is fast under high temperature and strong alkali;
4: the quaternary ammonium salt ion content is very low, which limits the improvement of the power density of the fuel cell: the content of quaternary ammonium salt ions of the mixed monomer anion membrane at home and abroad is mostly less than or equal to 1.0mmol NaOH/g (100% dry membrane), so that the improvement of anion movement efficiency and the power of a fuel cell membrane is limited, and a high-power-density fuel cell firstly needs to be matched with the anion membrane with high ion content;
5: the degree of crosslinking is far from sufficient: the swelling of the anion membrane is serious in solvents such as methanol, and the ion channel of the anion membrane is rapidly swelled in alcohol solvents and the methanol leakage is serious; the ionic membrane with low crosslinking degree can not be used for a direct methanol fuel cell at all.
CN200910248538 introduces a fluorine-containing anion membrane, which is formed by copolymerizing fluorine-containing monomers and styrene, and then connecting quaternary ammonium salt groups through chloromethyl reaction. The membrane is lack of crosslinking, and since the membrane is cast at 60 ℃ by a solvent method, namely the anion membrane has no crosslinking structure, the membrane can not resist the temperature of more than or equal to 60 ℃ basically, and can not prevent the organic solvent from swelling and breaking through basically, and the membrane can not be used for a direct methanol alkaline fuel cell basically.
CN 2010105632791 describes a cross-linked anionic membrane, which is cross-linked by a nitrogen-containing biguanide using a polymer of styrene or the like structure. Guanidino groups are relatively stable in acid but slowly degrade in strong alkalinity. The guanidine cross-linked membrane can be rapidly broken in the strong alkaline direct methanol fuel cell, so that the membrane is swelled and broken.
CN201510594150 introduces a fuel cell anion membrane prepared from chitosan, which is a fuel cell anion membrane with a main chain rich in unstable ether bonds due to crosslinking of dodecyl morpholine quaternary ammonium salt and glutaraldehyde, and dodecyl can cause the pore diameter of the ion membrane to be larger than 30nm, and methanol permeation cannot be prevented at all.
Manabu Tanaka synthesizes a fluorenylpolyethersulfone ketone anion membrane (Macromolecules 2010,43: 2657-2059) with a structure shown as a formula C, the anion membrane has high quaternary ammonium salt ion content and high conductivity, reaches 50mS/cm at room temperature, and is easy to permeate and swell by methanol due to no crosslinking; in addition, the a site of the electron-rich ether oxygen benzene ring and benzyl is easy to be oxidized, and quaternary ammonium salt falls off, so that the alkali resistance is poor;
Figure 750118DEST_PATH_IMAGE001
CN105884948 introduces a fluorine-containing anionic membrane of polyisobutene, which is prepared by adopting alkyl mixed monomers, although the membrane is very oxidation-resistant and has high quaternary ammonium salt ion content, beta-position of alkyl quaternary ammonium salt has hydrogen, and quaternary ammonium salt is easy to generate Hofmann degradation and fracture under high temperature and strong alkali; meanwhile, the membrane prepared by mixing the monomers has large difference in pore size, and the methanol permeation resistance is not ideal.
The anion membrane of the existing direct methanol fuel cell cannot quantitatively control the crosslinking density because a large amount of rigid structural materials containing aromatic ring, such as polyphenylsulfone, polyphenylether and the like are used; the quaternary ammonium salt is difficult to increase to be more than or equal to 1.0mmol NaOH/g, and the quaternary ammonium salt is firstly formed into pores and then grafted by chloromethylation, so that the quaternary ammonium salt ions can not be uniformly distributed in each pore channel, and the problem is that the high ionic conductivity and compact crosslinking of an anion membrane are difficult to select. The high ionic conductivity needs to increase the content of quaternary ammonium salt ions to be more than or equal to 1.8mmol/g, but the high quaternary ammonium salt content of the multi-mono-olefin monomer copolymerized anion membrane is converged into a water absorption macropore, so that the permeation of methanol is difficult to overcome.
The existing direct methanol fuel cell has a plurality of defects of an anionic membrane, and the core problem is that no dense cross-linked uniform membrane pore channel exists and the alkali resistance of the main chain is stable for a long time;
because the direct methanol alkaline fuel cell anion membrane is just emerging research and development application, and practical key performance requirements comprise strong alkali attenuation resistance, oxidation resistance and high ion content, and the ion channel can be stable, uniform and less than or equal to 0.5nm through compact crosslinking.
Disclosure of Invention
Aiming at various defects of the anion membrane of the direct methanol fuel cell, the invention abandons a method for preparing the anion membrane by copolymerizing a plurality of mono-olefinic bond monomers, and various functional requirements of the anion membrane are intensively designed into a quaternary ammonium salt compound with a double-olefinic bond, thereby ensuring uniform and compact crosslinking and high, stable and uniform performance of the anion membrane.
The invention provides a fluorine-containing anion membrane quaternary ammonium salt compound capable of being uniformly and densely crosslinked and a synthesis method thereof, wherein the fluorine-containing anion membrane quaternary ammonium salt compound has a chemical structure shown in a formula A, and has a chemical name of bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) dimethyl ammonium halide;
Figure 136100DEST_PATH_IMAGE002
wherein: x = chlorine, bromine, iodine, etc.
The quaternary ammonium salt compound of formula A, bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) dimethylammonium halide, is a quaternary ammonium salt compound of a compact cross-linked anionic membrane; the trifluoromethyl tertiary alcohol is dehydrated and cracked under the catalysis of strong acid, converted into 2 free radical active end olefinic bonds, and subjected to free radical polymerization to obtain the uniform and compact crosslinked anionic membrane containing fluorine saturated alkyl carbon chains, and the anion membrane has the following performance advantages:
(1) high temperature and strong alkali degradation resistance: because the beta position has no hydrogen, the quaternary ammonium salt ions are not easy to generate Hoffman degradation, can be very stable under high temperature and strong alkali, and can be stably used under the strong alkali condition of 80-100 ℃ without degradation;
(2) the ion content is high: more than or equal to 1.8mmol NaOH/g; the ions passing through the unit membrane area are greatly increased, and the high-power-density fuel cell can be effectively matched; the higher the power density is, the more ions the membrane needs to pass through, and the low-ion-content anion membrane can block the improvement of the power density of the alkaline fuel cell;
(3) very resistant to oxidation: the polymerized fluorine-containing saturated alkyl carbon chain has no groups which are easy to be oxidized, broken or hydrolyzed;
(4) uniform and compact crosslinking, solvent swelling resistance: because the quaternary ammonium salt compound has 2 polymerized olefinic bonds, other olefinic bond monomers do not need to be doped for copolymerization during polymerization, the membrane ion channel is very uniform and compact and is less than or equal to 0.5nm, and the swelling and permeation of various organic solvents can be prevented; the quaternary ammonium salt is also very uniformly distributed, which is incomparable with the mixed monomer polymerization;
(5) very flexible: the polymeric compact cross-linked anion membrane is not broken when being bent without a rigid aromatic ring;
(6) batch variation in film formation quality is small: because of single compound polymerization, the polymerization quality of each batch is very stable and reliable.
The invention relates to a quaternary ammonium salt compound of formula A, the chemical name is bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) dimethyl ammonium halide, the synthesis method of the quaternary ammonium salt compound of formula A must adopt di-tert-alcohol compound of the chemical structure of formula B as the starting material, the chemical name is 2-methyl-5-trifluoromethyl-2, 5-hexanediol:
Figure 119100DEST_PATH_IMAGE003
the synthesis preparation method of the quaternary ammonium salt compound in the formula A needs six-step synthesis reaction of hydrazino reaction, azo reaction, coupling reaction, halogenation reaction, tertiary amination and quaternary ammonium salt;
Figure 779888DEST_PATH_IMAGE004
wherein: x = chlorine, bromine, iodine; y is chlorine or bromine.
(1) Hydrazine group reaction: chlorinating tertiary alcohol by using a compound in a formula B and excessive concentrated hydrochloric acid at the temperature of 30-50 ℃, washing a separated oil layer to be neutral by using a sodium bicarbonate water solution, dropwise adding the separated oil layer into excessive hydrazine hydrate and methanol mixed solution, and separating to obtain a compound in a formula C, wherein the chemical name of the compound is 2-methyl-5-trifluoromethyl-5-hydroxy-2-hexylhydrazine;
Figure 797523DEST_PATH_IMAGE005
(2) and (3) azo reaction: mixing the compound of the formula C and a methanol solution of 2-isopentenoic acid, reacting at room temperature, adding a catalyst and NaOH after the compound of the formula C disappears, adjusting the pH value to be more than or equal to 10, and then introducing oxygen to oxidize completely to obtain the methanol solution of the compound of the formula D with an azo structure;
Figure 885565DEST_PATH_IMAGE006
(3) coupling reaction: heating the compound of formula D to 120-200 ℃ to release N2The free radical coupling is a compound of formula E, the chemical name is 3,3,4, 4-tetramethyl-7-trifluoromethyl-7-sodium hydroxyoctanoate:
Figure 355860DEST_PATH_IMAGE007
(4) halogenation reaction: dissolving the compound shown in the formula E in water, introducing bromine or chlorine, heating to keep the temperature at 50-80 ℃, performing decarboxylation and halogenation, and separating to obtain 2,2,3, 3-tetramethyl-6-trifluoromethyl-1-halo-6-octanol with a chemical structure shown in the formula F:
Figure 23602DEST_PATH_IMAGE008
wherein: y is chlorine or bromine;
(5) tertiary amination: adding a compound of a formula F and anhydrous methanol into an autoclave, sealing, replacing air, and then adding metered anhydrous monomethylamine gas, wherein the molar ratio of monomethylamine to the compound of the formula F is 0.6-0.7: 1; heating to 60-120 ℃ for complete reaction for 6-10 h, cooling to room temperature, and separating to obtain a compound of formula G, wherein the chemical name of the compound is bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) methyl tertiary amine;
Figure 692481DEST_PATH_IMAGE009
(6) reaction of quaternary ammonium salt: adding anhydrous methanol and a compound shown in a formula G into an autoclave, sealing, replacing air, and introducing metered methyl halide, wherein the molar ratio of the methyl halide to the compound shown in the formula G is 1.5-2.0: 1, heating to 50-90 ℃ to perform quaternary sodium salt reaction for 4-8 h completely, cooling to room temperature, and separating to obtain a quaternary ammonium salt white crystal with a chemical structure shown as a formula A, wherein the chemical name of the quaternary ammonium salt white crystal is bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) dimethyl ammonium halide;
Figure 951424DEST_PATH_IMAGE002
wherein: x = chlorine, bromine, iodine, etc.
Hydrazine group reaction, which is mainly characterized in that the molar ratio of hydrazine hydrate to the compound shown in the formula B is 3-6: 1;
the azo reaction is mainly characterized in that a catalyst is 2, 6-di-tert-butyl-4-methylphenol or 4-hydroxy-TEMPO with a chemical structure shown as a formula H, and the adding proportion of the catalyst is 0.5-3 wt% of the compound shown as the formula C;
Figure 909015DEST_PATH_IMAGE010
the specific implementation mode is as follows:
in order to better understand the synthesis of the quaternary ammonium salt compound of the structure of formula a of the present invention, the following examples are given to better understand the present invention.
Example 1:
1. hydrazine group reaction: adding 802g of a compound (4 mol) of a formula B and 400g of pure water into a 2000ml three-necked bottle at room temperature, stirring and mutually dissolving, keeping the room temperature, slowly dropwise adding 420g of concentrated hydrochloric acid (4.2 mol), quickly carrying out tertiary alcohol chlorination reaction, continuously separating out a chloride oil layer, gradually heating to 30-40 ℃ after dropwise adding, completely reacting, collecting the oil layer in a layered manner, and washing the obtained chloride oil layer to be neutral by using a proper amount of sodium bicarbonate aqueous solution;
adding 950g of anhydrous methanol and 950g of 85% hydrazine hydrate (16 mol) into a 3000ml three-necked bottle, dropwise adding the chloride oil layer at room temperature, continuously substituting tertiary chlorine by hydrazine hydrate for reaction, analyzing chloride by GC, and finishing the hydrazine group reaction; recovering methanol and hydrazine hydrate by reduced pressure distillation, adding 540g (4.1 mol) of 30% NaOH liquid alkali into the residual material, separating out an organic layer, and collecting 105-108 ℃/10mmHg by reduced pressure rectification to obtain 674g of the compound C with the purity of 98.3%;
2: and (3) azo reaction:
adding 430g of the compound (2 mol) of the formula C and 600g of anhydrous methanol into a 2000ml three-necked bottle, mutually dissolving and transparent, slowly dropwise adding a solution of 220g of 2-isopentenoic acid (2.2 mol) and 100g of anhydrous methanol at room temperature, stirring overnight at room temperature, analyzing the disappearance of the compound of the formula C by GC, and finishing the reaction; 6g of 4-hydroxy-TEMPO and 100g of solid NaOH are added and O is introduced at room temperature2The catalytic oxidation is complete, and the compound of the formula D is not required to be separated, and is directly used for the next coupling reaction;
3: coupling reaction: distilling the methanol solution of the azo compound in the formula D, heating to 160 ℃ in an oil bath, and continuously generating N in the tail gas of a reflux condenser pipe2Discharging until no tail gas is discharged, finishing the coupling reaction, and adding 1200g of water to dissolve the compound of the formula E for the next halogenation reaction;
4: halogenation reaction: heating the water solution of the compound E in the coupling reaction to 60-70 ℃, slowly introducing chlorine, absorbing tail gas with water, and continuously releasing CO2Continuously separating out a gas oil layer, supplementing a 10% NaOH aqueous solution, keeping the pH of the material alkaline = 7-8 until carboxyl disappears, finishing the reaction, and collecting the oil layer to obtain 483.2g of 2,2,3, 3-tetramethyl-6-trifluoromethyl-1-chloro-6-octanol with the chemical structure of the formula F, wherein the purity is 97.6%;
5: tertiary amination: adding 276G of a compound (1 mol) of a formula F, 55G of sodium carbonate (0.5 mol) and 500G of anhydrous methanol into a 2000ml stainless steel autoclave, sealing at room temperature, replacing air, introducing 18.5G (0.6 mol) of anhydrous monomethylamine gas, heating and keeping at 110-120 ℃ for reaction for 10 hours, cooling to room temperature, adding 10% sodium methoxide solution, keeping the pH = 12-14, separating out a disodium salt solid of a compound of a formula G and NaCl crystals, performing suction filtration to collect a disodium salt solid of the compound of the formula G, and recovering filtrate;
pouring the disodium salt solid of the compound of the formula G into water, acidifying with acetic acid until the pH is = 8.5-9, separating out a tertiary amine compound solid of the formula G, and performing suction filtration to collect an organic layer solid to obtain 214.6G of the compound of the formula G with the purity of 97.8%;
6: reaction of quaternary ammonium salt: adding 214G of tertiary amine compound shown in formula G and 300G of anhydrous methanol into a 1000ml stainless steel autoclave, sealing, replacing air, introducing 50G of methyl chloride, heating, keeping the internal temperature at 85-90 ℃, reacting for 6 hours, and finishing the reaction;
and (2) cooling to room temperature, heating in a water bath, carrying out reduced pressure distillation to recover methanol, pouring the solid with methanol removed into water, separating out unreacted tertiary amine compound solid in the formula G in the water, carrying out suction filtration to collect the aqueous solution of the quaternary ammonium salt compound in the formula A, adding cyclohexane for azeotropic dehydration, and separating to obtain 201.5G of bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) dimethyl ammonium chloride crystal with the chemical structure in the formula A, wherein the purity is 98.9%.
Example 2:
1. hydrazine group reaction: adding 802g of a compound (4 mol) of a formula B and 400g of pure water into a 2000ml three-necked bottle at room temperature, stirring and mutually dissolving, keeping the room temperature, slowly dropwise adding 420g of concentrated hydrochloric acid (4.2 mol), quickly carrying out tertiary alcohol chlorination reaction, continuously separating out a chloride oil layer, gradually heating to 30-40 ℃ after dropwise adding, completely reacting, collecting the oil layer in a layered manner, and washing the obtained chloride oil layer to be neutral by using a proper amount of sodium bicarbonate aqueous solution;
adding 1100g of anhydrous methanol and 1200g of 85% hydrazine hydrate (20 mol) into a 5000ml three-necked bottle, dropwise adding the chloride oil layer at room temperature, continuously substituting tertiary chlorine by hydrazine hydrate for reaction, analyzing chloride by GC, and finishing the hydrazine group reaction; distilling under reduced pressure to recover methanol and hydrazine hydrate, adding 550g (4.1 mol) of 30% NaOH solution alkali into the residual material, separating out an organic layer, and carrying out rectification under reduced pressure to collect 105-108 ℃/10mmHg to obtain 718g of a compound shown in the formula C, wherein the purity is 98.7%;
2: and (3) azo reaction:
718g of the compound of the formula C (3.35 mol) and 1000g of anhydrous methanol are added into a 5000ml three-necked bottle, the mixture is mutually dissolved and transparent, a solution of 400g of 2-isopentenoic acid (4.0 mol) and 400g of anhydrous methanol is slowly dripped into the bottle at room temperature, the mixture is stirred at room temperature overnight, the compound of the formula C disappears through GC analysis, and the reaction is finished; 10g of 4-hydroxy-TEMPO and 180g of solid NaOH are added and O is introduced at room temperature2The catalytic oxidation is complete, and the azo compound of the formula D is not required to be separated, and is directly used for the next coupling reaction;
3: coupling reaction: reacting azo-reacted methanol of azo compound of formula DDistilling the solution, heating in oil bath to 160 deg.C, and continuously generating N in the tail gas of reflux condenser2Discharging until no tail gas is discharged, finishing the coupling reaction, adding 2000g of water to dissolve the solid compound of the formula E, and using the solid compound of the formula E for the next halogenation reaction;
4: halogenation reaction: heating the water solution of the compound E in the coupling reaction to 50-60 ℃, slowly introducing 290g of chlorine, absorbing tail gas with water, and continuously releasing CO2And (3) continuously separating out a gas oil layer, supplementing a 10% NaOH aqueous solution, keeping the alkaline pH of the material = 7-8 until the carboxyl disappears, finishing the reaction, and collecting the oil layer to obtain 811.5g of 2,2,3, 3-tetramethyl-6-trifluoromethyl-1-chloro-6-octanol with the chemical structure shown in the formula F, wherein the purity is 97.4%. (ii) a
5: tertiary amination: adding 277G of a compound (1 mol) of a formula F, 58G of sodium carbonate (0.5 mol) and 500G of anhydrous methanol into a 2000ml stainless steel autoclave, sealing at room temperature, replacing air, introducing 51G (1.6 mol) of anhydrous monomethylamine gas, heating and keeping at 110-120 ℃ for reaction for 10 hours, cooling to room temperature, adding 10% sodium methoxide solution, keeping the pH = 12-14, separating out a disodium salt solid of a compound of a formula G and NaCl crystals, performing suction filtration to collect a disodium salt solid of the compound of the formula G, and recovering filtrate;
pouring the disodium salt solid of the compound of the formula G into water, acidifying with acetic acid until the pH is = 8.5-9, separating out a tertiary amine compound solid of the formula G, and performing suction filtration to collect an organic layer solid to obtain 205G of the compound of the formula G with the purity of 97.2%;
6: reaction of quaternary ammonium salt: adding 205G of tertiary amine compound shown in formula G and 250G of anhydrous methanol into a 1000ml stainless steel autoclave, sealing, replacing air, introducing 75G of methyl bromide, heating, keeping the internal temperature at 65-75 ℃, reacting for 6 hours, and finishing the reaction;
and (2) cooling to room temperature, carrying out reduced pressure distillation under water bath heating to recover methanol, pouring the solid with methanol removed into water, separating out unreacted tertiary amine compound solid of the formula G in the water, carrying out suction filtration to collect the aqueous solution of the quaternary ammonium salt compound of the formula A, adding cyclohexane for azeotropic dehydration, and separating to obtain 231G of bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) dimethylammonium bromide crystal with the chemical structure of the formula A, wherein the purity is 97.9%.
Example 3:
5: tertiary amination: adding 278G (1 mol) of 2,2,3, 3-tetramethyl-6-trifluoromethyl-1-chloro-6-octanol with a chemical structure of a halogenation reaction formula F in example 2, 56G of sodium carbonate (0.5 mol) and 502G of anhydrous methanol into a 2000ml stainless steel autoclave, sealing at room temperature, replacing air, introducing 20.6G (0.67 mol) of anhydrous monomethylamine gas, heating and keeping at 110-120 ℃ for reaction for 10 hours, cooling to room temperature, adding 10% sodium methoxide solution, keeping pH = 12-14, separating out a disodium salt solid and NaCl crystals of a compound of a formula G, carrying out suction filtration to collect the disodium salt solid of the compound of the formula G, and recycling filtrate;
pouring the disodium salt solid of the compound of the formula G into water, dropwise adding acetic acid to acidify until the pH is = 8.5-9, separating out the solid of the tertiary amine compound of the formula G, and performing suction filtration to collect the solid of an organic layer to obtain 193G of the tertiary amine compound of the formula G with the purity of 97.6%;
6: reaction of quaternary ammonium salt: adding 193G of tertiary amine compound shown in the formula G and 250G of anhydrous methanol into a 1000ml stainless steel autoclave, sealing, replacing air, introducing 80G of methyl iodide, heating to keep the internal temperature at 50-60 ℃, reacting for 6 hours, and finishing the reaction;
and (2) cooling to room temperature, carrying out reduced pressure distillation under water bath heating to recover methanol, pouring the solid with methanol removed into water, separating out unreacted tertiary amine compound solid of the formula G in the water, carrying out suction filtration to collect the aqueous solution of the quaternary ammonium salt compound of the formula A, adding cyclohexane for azeotropic dehydration, and separating to obtain 226G of bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) dimethylammonium iodide crystal with the chemical structure of the formula A, wherein the purity is 96.3%.
Example 4:
1. hydrazine group reaction: adding 805g of a compound (4 mol) of a formula B and 400g of pure water into a 2000ml three-necked bottle at room temperature, stirring and mutually dissolving, keeping slowly dropwise adding 420g of concentrated hydrochloric acid (4.2 mol) at room temperature, enabling the tertiary alcohol chlorination reaction to be rapid, continuously separating out a chloride oil layer, gradually heating to 30-40 ℃ after dropwise adding is finished, completely reacting, collecting the oil layer in a layered manner, and washing the obtained chloride oil layer to be neutral by using a proper amount of sodium bicarbonate aqueous solution;
adding 1200g of anhydrous methanol and 1400g of 85% hydrazine hydrate (24 mol) into a 5000ml three-necked bottle, dropwise adding the chloride oil layer at room temperature, continuously substituting tertiary chlorine by hydrazine hydrate for reaction, analyzing chloride by GC, and finishing the hydrazine group reaction; distilling under reduced pressure to recover methanol and hydrazine hydrate, adding 540g (4.0 mol) of 30% NaOH liquid alkali into the residual material, separating out an organic layer, and carrying out rectification under reduced pressure to collect 105-108 ℃/10mmHg to obtain 748g of the compound shown in the formula C with the purity of 98.4%;
2: and (3) azo reaction:
adding 748g of the compound shown in the formula C (3.5 mol) and 1000g of anhydrous methanol into a 5000ml three-necked bottle, mutually dissolving and transparent, slowly dropwise adding a solution of 400g of 2-isopentenoic acid (4.0 mol) and 400g of anhydrous methanol at room temperature, stirring at room temperature overnight, analyzing the disappearance of the compound shown in the formula C by GC, and finishing the reaction; 10g of 4-hydroxy-TEMPO and 170g of solid NaOH (4.2 mol) are added and O is bubbled in at room temperature2The catalytic oxidation is complete, and the azo compound of the formula D is not required to be separated, and is directly used for the next coupling reaction;
3: coupling reaction: distilling the methanol solution of azo compound of formula D in azo reaction, heating in oil bath to 160 deg.C, and continuously generating N in the tail gas of reflux condenser tube2Discharging until no tail gas is discharged, finishing the coupling reaction, adding 2000g of water to dissolve the solid compound of the formula E, and using the solid compound of the formula E for the next halogenation reaction;
4: halogenation reaction: heating the water solution of the compound E in the coupling reaction to 50-60 ℃, slowly introducing 660g (4.1 mol) of bromine, absorbing tail gas with water, and continuously releasing CO2Continuously separating out a gas oil layer, supplementing a 10% NaOH aqueous solution, keeping the pH of the material alkaline = 7-8 until carboxyl disappears, finishing the reaction, and collecting the oil layer to obtain 893.4g of 2,2,3, 3-tetramethyl-6-trifluoromethyl-1-bromo-6-octanol with the chemical structure of the formula F, wherein the purity is 98.1%;
5: tertiary amination: adding 893.4G (2.8 mol) of 2,2,3, 3-tetramethyl-6-trifluoromethyl-1-bromo-6-octanol with a chemical structure of formula F, 151G of sodium carbonate (1.42 mol) and 1500G of anhydrous methanol into a 2000ml stainless steel autoclave, sealing at room temperature, displacing air, introducing 51G (1.64 mol) of anhydrous monomethylamine gas, heating and keeping at 70-80 ℃ for reaction for 10 hours, cooling to room temperature, adding 10% sodium methoxide solution, keeping pH = 12-14, separating out a disodium salt solid of a compound of formula G and a NaBr crystal, carrying out suction filtration to collect a disodium salt solid of the compound of formula G, and recovering a filtrate;
pouring the disodium salt solid of the compound of the formula G into water, acidifying with acetic acid until the pH is = 8.5-9, separating out a tertiary amine compound solid of the formula G, and performing suction filtration to collect an organic layer solid to obtain 629G of the compound of the formula G with the purity of 97.6%;
6: reaction of quaternary ammonium salt: adding 629G of tertiary amine compound (1.24 mol) of formula G and 800G of anhydrous methanol into a 3000ml stainless steel autoclave, sealing, replacing air, introducing 96G of chloromethane (1.9 mol), heating to keep the internal temperature at 85-90 ℃, reacting for 8 hours, and finishing the reaction;
and (3) cooling to room temperature, carrying out reduced pressure distillation under water bath heating to recover methanol, pouring the solid with methanol removed into water, separating out unreacted tertiary amine compound solid of the formula G in the water, carrying out suction filtration to collect the aqueous solution of the quaternary ammonium salt compound of the formula A, adding cyclohexane for azeotropic dehydration, and separating to obtain 658G of bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) dimethyl ammonium chloride crystal with the chemical structure of the formula A, wherein the purity is 97.5%.
Example 5:
1: hydrazine group reaction: the feeding operation is the same as that of the embodiment 4, and the compound with the formula C of 756g and the purity of 98.6 percent is obtained by rectification under reduced pressure and collection at the temperature of 105-108 ℃/10 mmHg;
2: and (3) azo reaction:
adding 756g of compound (3.5 mol) of formula C and 1000g of anhydrous methanol into a 5000ml three-necked bottle, dissolving and transparent mutually, keeping the mixture at room temperature, slowly dropwise adding a solution of 400g of 2-isopentenoic acid (4.0 mol) and 400g of anhydrous methanol, stirring at room temperature overnight, analyzing the disappearance of the compound of formula C by GC, and finishing the reaction; 15g of 4-hydroxy-TEMPO and 170g of solid NaOH (4.2 mol) are added and O is bubbled in at room temperature2The catalytic oxidation is complete, and the azo compound of the formula D is not required to be separated, and is directly used for the next coupling reaction;
3: coupling reaction: the feeding operation was the same as in example 4, and the aqueous solution was used for the next halogenation reaction;
4: halogenation reaction: heating the water solution of the compound E in the coupling reaction to 50-60 ℃, slowly introducing 291g (4.1 mol) of chlorine, absorbing tail gas with water, and continuously releasing CO2Separating out gas and oil layer continuously, supplementing a small amount of 10% NaOH aqueous solution, keeping the pH of the material alkaline = 7-8 until carboxyl disappears, finishing the reaction, and collectingAn oil layer, to obtain 841.9g of 2,2,3, 3-tetramethyl-6-trifluoromethyl-1-chloro-6-octanol with a chemical structure of formula F and a purity of 97.1%;
5: tertiary amination: adding 841.9G (3.0 mol) of 2,2,3, 3-tetramethyl-6-trifluoromethyl-1-chloro-6-octanol with a chemical structure of formula F, 165G of sodium carbonate (1.55 mol) and 1500G of anhydrous methanol into a 2000ml stainless steel autoclave, sealing at room temperature, replacing air, introducing 52G (1.65 mol) of anhydrous monomethylamine gas, heating and keeping at 110-120 ℃ for reaction for 10 hours, cooling to room temperature, adding 10% sodium methoxide solution, keeping pH = 12-14, separating out a disodium salt solid and NaCl crystals of a compound of formula G, carrying out suction filtration to collect the disodium salt solid of the compound of formula G, and recovering filtrate;
pouring the disodium salt solid of the compound shown in the formula G into water, acidifying with acetic acid until the pH is = 8.5-9, separating out a tertiary amine compound solid shown in the formula G, and performing suction filtration to collect an organic layer solid to obtain 676G of the compound shown in the formula G, wherein the purity is 97.8%;
6: reaction of quaternary ammonium salt: adding 676G of tertiary amine compound (1.33 mol) of formula G and 800G of anhydrous methanol into a 3000ml stainless steel autoclave, sealing, replacing air, introducing 101G of chloromethane (1.9 mol), heating to keep the internal temperature at 85-90 ℃, reacting for 8h, and finishing the reaction.
And (2) after the temperature is reduced to room temperature, carrying out reduced pressure distillation under water bath heating to recover methanol, pouring the solid with methanol removed into water, separating out unreacted tertiary amine compound solid of the formula G in the water, carrying out suction filtration to collect the aqueous solution of the quaternary ammonium salt compound of the formula A, adding cyclohexane for azeotropic dehydration, and separating to obtain the bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) dimethyl ammonium chloride crystal of the chemical structure of the formula A in 695G with the purity of 97.8%.
Example 6:
1: hydrazine group reaction: the feeding operation is the same as that of the embodiment 4, and the compound with the formula C is obtained by rectification under reduced pressure at the temperature of 105-108 ℃/10mmHg, and 752g of the compound with the formula C and the purity of 98.4 percent;
2: and (3) azo reaction:
752g of the compound of formula C (3.5 mol) and 1000g of anhydrous methanol are added into a 5000ml three-necked flask, dissolved and transparent with each other, a solution of 400g of 2-isopentenoic acid (4.0 mol) and 400g of anhydrous methanol is slowly dropped into the flask at room temperature, the mixture is stirred at room temperature overnight, and the solution is subjected to GC analysisThe compound disappears and the reaction is finished; 15g of 2, 6-di-tert-butyl-4-methylphenol and 170g of solid NaOH (4.2 mol) were added thereto, and O was introduced at room temperature2The catalytic oxidation is complete, and the azo compound of the formula D is not required to be separated, and is directly used for the next coupling reaction;
3: coupling reaction: the feeding operation was the same as in example 4, the water-insoluble solids were removed by filtration, and the aqueous solution was used for the next halogenation reaction;
4: halogenation reaction: heating the water solution of the compound E in the coupling reaction to 50-60 ℃, slowly introducing 294g (4.1 mol) of chlorine, absorbing tail gas with water, and continuously releasing CO2Continuously separating out gas with an oil layer, supplementing a small amount of 10% NaOH aqueous solution, keeping the alkaline pH of the material = 7-8 until the carboxyl disappears, finishing the reaction, and collecting the oil layer to obtain 846g of 2,2,3, 3-tetramethyl-6-trifluoromethyl-1-chloro-6-octanol with the chemical structure of the formula F, wherein the purity is 97.9%;
5: tertiary amination: adding 846G (3.0 mol) of 2,2,3, 3-tetramethyl-6-trifluoromethyl-1-chloro-6-octanol with a chemical structure of formula F, 165G of sodium carbonate (1.55 mol) and 1500G of anhydrous methanol into a 2000ml stainless steel autoclave, sealing at room temperature, replacing air, then introducing 52G (1.65 mol) of anhydrous monomethylamine gas, heating and keeping the temperature at 110-120 ℃ for reaction for 10 hours, cooling to room temperature, and then carrying out other feeding operations in the same way as in example 5 to obtain 683G of the compound with the formula G and the purity of 98.2 percent;
6: reaction of quaternary ammonium salt: adding 683G of a tertiary amine compound (1.34 mol) of a formula G and 800G of anhydrous methanol into a 3000ml stainless steel autoclave, sealing, replacing air, introducing 101G of chloromethane (2.0 mol), heating, keeping the internal temperature at 85-90 ℃, reacting for 8 hours, and finishing the reaction;
and (2) cooling to room temperature, carrying out reduced pressure distillation under water bath heating to recover methanol, pouring the solid with methanol removed into water, separating out unreacted tertiary amine compound solid of the formula G in the water, carrying out suction filtration to collect the aqueous solution of the quaternary ammonium salt compound of the formula A, adding cyclohexane for azeotropic dehydration, and separating to obtain 706G of bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) dimethyl ammonium chloride crystal with the chemical structure of the formula A, wherein the purity is 97.5%.
Example 7:
1: hydrazine group reaction: the feeding operation is the same as that of the embodiment 4, and the mixture is rectified and collected under reduced pressure at the temperature of 105-108 ℃/10mmHg to obtain 758g of the compound shown in the formula C with the purity of 98.6%;
2: and (3) azo reaction:
adding 758g of a compound (3.5 mol) of the formula C and 1000g of anhydrous methanol into a 5000ml three-necked bottle, mutually dissolving and transparent, slowly dropwise adding a solution of 400g of 2-isopentenoic acid (4.0 mol) and 400g of anhydrous methanol at room temperature, stirring at room temperature overnight, analyzing the disappearance of the compound of the formula C by GC, and finishing the reaction; 22g of 2, 6-di-tert-butyl-4-methylphenol and 170g of solid NaOH (4.2 mol) were added thereto, and O was introduced at room temperature2The catalytic oxidation is complete, and the azo compound of the formula D is not required to be separated, and is directly used for the next coupling reaction;
3: coupling reaction: the feeding operation was the same as in example 4, the water-insoluble solids were removed by filtration, and the aqueous solution was used for the next halogenation reaction;
4: halogenation reaction: the feeding operation was the same as in example 6, and the oil layer was collected to obtain 843g of 2,2,3, 3-tetramethyl-6-trifluoromethyl-1-chloro-6-octanol of the chemical structure of formula F with a purity of 98.2%;
5: tertiary amination: adding 843g (3.0 mol) of 2,2,3, 3-tetramethyl-6-trifluoromethyl-1-chloro-6-octanol with a chemical structure of formula F, 165g of sodium carbonate (1.55 mol) and 1500g of anhydrous methanol into a 2000ml stainless steel autoclave, sealing at room temperature, replacing air, introducing 50g (1.6 mol) of anhydrous monomethylamine gas, heating to keep at 110-120 ℃, reacting for 10 hours, cooling to room temperature, and then carrying out the same feeding operation as in example 5; separating out a G tertiary amine compound solid, and performing suction filtration to collect an organic layer solid to obtain 687G of the compound of the formula G with the purity of 97.6%;
6: reaction of quaternary ammonium salt: adding 687G of a tertiary amine compound (1.35 mol) of a formula G and 800G of anhydrous methanol into a 3000ml stainless steel autoclave, sealing, replacing air, introducing 101G of chloromethane (2.0 mol), heating, keeping the internal temperature at 85-90 ℃, reacting for 8 hours, and finishing the reaction;
and (3) cooling to room temperature, carrying out reduced pressure distillation under water bath heating to recover methanol, pouring the solid with methanol removed into water, separating out unreacted tertiary amine compound solid of the formula G in the water, carrying out suction filtration to collect the aqueous solution of the quaternary ammonium salt compound of the formula A, adding cyclohexane for azeotropic dehydration, and separating to obtain 712G of bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) dimethyl ammonium chloride crystal with the chemical structure of the formula A, wherein the purity is 97.8%.

Claims (5)

1. A quaternary ammonium salt compound of an anionic membrane of a fuel cell capable of completely blocking methanol permeation, chemically named bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) dimethylammonium halide, having the chemical structure of formula a:
Figure 355892DEST_PATH_IMAGE001
wherein: x = chlorine, bromine, iodine, etc.
2. A quaternary ammonium salt compound of a fuel cell anion membrane for blocking methanol permeation is mainly characterized in that a synthesis preparation method of the quaternary ammonium salt compound needs to adopt a di-tert-alcohol compound with a chemical structure shown as a formula B as a starting raw material, and the chemical name of the compound is 2-methyl-5-trifluoromethyl-2, 5-hexanediol:
Figure 273033DEST_PATH_IMAGE002
。
3. a preparation method of a fuel cell anion membrane quaternary ammonium salt compound for blocking methanol permeation is mainly characterized in that six steps of hydrazine reaction, azo reaction, coupling reaction, halogenation reaction, tertiary amination and quaternary ammonium salt synthesis reaction are required:
(1) hydrazine group reaction: and (2) chlorinating tertiary alcohol by using a compound shown in the formula B and excessive concentrated hydrochloric acid at the temperature of 30-50 ℃, washing a separated oil layer to be neutral by using a sodium bicarbonate water solution, dropwise adding the separated oil layer into a mixed solution of excessive hydrazine hydrate and methanol, and separating to obtain a compound shown in the formula C, wherein the chemical name of the compound is 2-methyl-5-trifluoromethyl-5-hydroxy-2-hexylhydrazine:
Figure 787191DEST_PATH_IMAGE003
(2) and (3) azo reaction: mixing the compound of the formula C and a methanol solution of 2-isopentenoic acid, reacting at room temperature, adding a catalyst and NaOH after the compound of the formula C disappears, adjusting the pH value to be more than or equal to 10, introducing oxygen, completely oxidizing, and separating to obtain a compound of a formula D with an azo structure:
Figure 415356DEST_PATH_IMAGE004
(3) coupling reaction: heating the compound of formula D to 120-200 ℃ to release N2The free radical coupling is a compound of formula E, the chemical name is 3,3,4, 4-tetramethyl-7-trifluoromethyl-7-sodium hydroxyoctanoate:
Figure 964149DEST_PATH_IMAGE005
(4) halogenation reaction: dissolving the compound shown in the formula E in water, introducing bromine or chlorine, heating to keep the temperature at 50-80 ℃, performing decarboxylation and halogenation, and separating to obtain 2,2,3, 3-tetramethyl-6-trifluoromethyl-1-halo-6-octanol with a chemical structure shown in the formula F:
Figure 786611DEST_PATH_IMAGE006
wherein: y is chlorine or bromine;
(5) tertiary amination: adding a compound of a formula F and anhydrous methanol into an autoclave, sealing, replacing air, and then adding metered anhydrous monomethylamine gas, wherein the molar ratio of monomethylamine to the compound of the formula F is 0.6-0.7: 1; heating to 60-120 ℃ for complete reaction for 6-10 h, cooling to room temperature, and separating to obtain a compound of formula G, wherein the chemical name of the compound is bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) methyl tertiary amine;
Figure 788065DEST_PATH_IMAGE007
(6) reaction of quaternary ammonium salt: adding anhydrous methanol and a compound shown in a formula G into an autoclave, sealing, replacing air, and introducing metered methyl halide, wherein the molar ratio of the methyl halide to the compound shown in the formula G is 1.5-2.0: 1, heating to 50-90 ℃ to perform quaternary sodium salt reaction for 4-8 h completely, cooling to room temperature, and separating to obtain a quaternary ammonium salt white crystal with a chemical structure shown as a formula A, wherein the chemical name of the quaternary ammonium salt white crystal is bis (2, 2,3, 3-tetramethyl-6-trifluoromethyl-6-heptanol) dimethyl ammonium halide;
Figure 721386DEST_PATH_IMAGE001
wherein: x = chlorine, bromine, iodine, etc.
4. The hydrazino reaction of claim 3, characterized in that the molar ratio of hydrazine hydrate to the compound of formula B is 3-6: 1.
5. The azo reaction of claim 3, wherein the catalyst is 2, 6-di-tert-butyl-4-methylphenol or 4-hydroxy-TEMPO of formula H, and the proportion of the catalyst is 0.5-3 wt% of the compound of formula C
Figure 124686DEST_PATH_IMAGE008
。
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CN102479962A (en) * 2010-11-29 2012-05-30 中国科学院大连化学物理研究所 Cross-linked anion membrane, preparation method thereof and application
JP2013186989A (en) * 2012-03-07 2013-09-19 Japan Atomic Energy Agency Anion conducting electrolyte membrane and method for producing the same
CN105985475A (en) * 2015-02-13 2016-10-05 上海漫关越水处理有限公司 Diluted hydrochloric acid concentration anion membrane
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Application publication date: 20201215