CN109293523A - A kind of ionic cross-linking monomer, Its Preparation Method And Use - Google Patents

A kind of ionic cross-linking monomer, Its Preparation Method And Use Download PDF

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CN109293523A
CN109293523A CN201810820739.5A CN201810820739A CN109293523A CN 109293523 A CN109293523 A CN 109293523A CN 201810820739 A CN201810820739 A CN 201810820739A CN 109293523 A CN109293523 A CN 109293523A
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compound
salt
alkyl
ion exchange
aryl
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郑长风
杨辉
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Shengbo (shenzhen) Technology Co Ltd
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Shengbo (shenzhen) Technology Co Ltd
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    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
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    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
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    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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Abstract

The invention discloses a kind of ionic cross-linking monomer, preparation method and its purposes for being used to prepare homogeneous ion-exchange membrane.The method have the characteristics that vinyl three-level aminated compounds and vinylglycidyl ester compounds ring-opening reaction, form the cross-linking monomer with ion-exchange capacity, to improve dissolubility of the crosslinkers monomers in water and other solvents.Ionic cross-linking monomer according to the present invention realizes the integration of ion exchange and crosslinked action, has the advantages that safety and cost is lower.The present invention also provides compositions and Electrochemical separation device comprising the ionic cross-linking monomer.

Description

Ionic crosslinking monomer, preparation method and application thereof
Technical Field
The present invention relates to the field of ion exchange membranes. In particular to an ionic crosslinking monomer for preparing an ion exchange membrane, a preparation method and application thereof.
Background
The electrodialysis technology, the electrodeionization technology and the related membrane separation technology which are developed by taking the ion exchange membrane as an important core element can be used for water recovery and advanced treatment, treatment of acid-base waste liquid and waste gas, green synthesis for realizing organic reaction, fuel cells or flow batteries and the like, and have wide prospects in the application fields of industry, food, pharmacy, seawater desalination and the like. At present, the country pays more attention to environmental protection, and zero discharge of high-salinity wastewater, coal chemical wastewater, flue gas and the like is expected by society and country and is also an important task of the current chemical industry and environmental protection industry.
Ion exchange membranes can be generally classified into heterogeneous ion exchange membranes and homogeneous ion exchange membranes according to phase states. The heterogeneous ion exchange membrane mainly comprises ion exchange resin, a thermoplastic adhesive and a supporting cloth net, and has the advantages of large membrane forming resistance, high energy consumption, poor quality and short service life. Unlike heterogeneous ion exchange membranes, homogeneous ion exchange membranes mostly realize the crosslinking of ion exchange groups through polymerization reaction, the ion exchange functional groups are connected with the membrane matrix through chemical bonds, and the membranes have uniform chemical structures, small membrane resistance, low energy consumption and long service life. Over the years of development, homogeneous ion exchange membrane preparation technology is becoming mature, and gradually replacing heterogeneous ion exchange membranes, and has already occupied an important position in membrane separation and related technical fields.
Homogeneous ion exchange membranes are generally made from ion exchange monomers containing ion exchange functional groups, cross-linking agents, solvents, and initiators. Commonly used ion exchange monomers include trimethyl ammonium ethyl acrylate chloride (TMAEMC), 2-acrylamide-2-methyl-1-propanesulfonic Acid (AMPS), 3-potassium methacrylate sulfonate, sodium styrene sulfonate, lithium styrene sulfonate, 2-sulfoethyl methacrylate and other vinyl monomers capable of realizing ion exchange. Commonly used crosslinking agents include diene compounds having a crosslinking effect, such as Divinylbenzene (DVB), Ethylene Glycol Dimethacrylate (EGDM), and the like.
Since the preparation of homogeneous ion exchange membranes requires the use of crosslinkers and ion exchange monomers of widely differing polarity, large amounts of solvent (up to 50% by weight or more of the mixture) are typically required to prepare homogeneous solutions. Furthermore, the choice of suitable solvents for dissolving the ion exchange monomers and the cross-linking agents is also very limited. Finally, the ion exchange membrane needs to be made and the solvent removed, which greatly increases the cost of disposal and the cost of the environment.
With the continuous development of separation technology, the performance requirements of ion exchange membranes are continuously increased, including increasing the ion exchange capacity of homogeneous ion exchange membranes and reducing the membrane resistance, and in some applications, ion exchange membranes with lower water content are required.
In order to solve the above problems, it is necessary to prepare a crosslinking agent having higher water solubility while increasing the ion exchange capacity of a homogeneous ion exchange membrane. US patent US 5,118,717 discloses a process for preparing conventional anion exchange membranes wherein water and an alcohol-water solution are used as solvents. In the method, dimethylamine ethyl methacrylate and vinylbenzyl chloride (VBC) are adopted to react to form the water-soluble quaternary ammonium salt divinyl cross-linking agent. However, the vinyl benzyl chloride used in this process is highly toxic, which greatly increases the environmental cost. Further, the use of dimethylaminoethyl methacrylate reduces the film hydrolyzability to some extent, limiting the use of film formation. Also, it is difficult to increase the ion exchange capacity of the resulting membrane by forming vinylbenzyl chloride (VBC) into a quaternary ammonium salt.
U.S. Pat. No. 4, 4,617,321 discloses a method for preparing a homogeneous ion-exchange membrane, which comprises subjecting N-methylolacrylamide to dealdehydizing reaction under acid catalysis in the polymerization process to obtain the homogeneous ion-exchange membrane. Although N-methylol acrylamide has high solubility in water, formaldehyde is removed in the process of generating the cross-linking agent, and the application of film forming is limited in production and application.
US patent No. 4,310,631 discloses a method for preparing an ion-exchange membrane, in which water-soluble ionic crosslinking monomers are prepared under acidic conditions using dimethylaminoethyl methacrylate (DMAEMA) and glycidyl methacrylate, and thus used to prepare an ion-exchange membrane. This process effectively links two vinyl groups to form an ionic crosslinking monomer that can be dissolved in water. Such methods achieve integration of the crosslinking agent and ion exchange monomer functions, but the use of dimethylamine ethyl methacrylate (DMAEMA) reduces the hydrolysis resistance of the film to some extent.
Therefore, there is a need for a highly water-soluble, safe, hydrolysis-resistant crosslinking monomer to improve the quality of ion exchange membranes, i.e., to improve the ion exchange capacity of homogeneous ion exchange membranes, and to control the water content of the ion exchange membranes as desired. Meanwhile, the invention can directly use water and other conventional solvents, thereby reducing the production cost in the production process of the ion exchange membrane.
Disclosure of Invention
The invention discloses an ionic crosslinking monomer, a preparation method thereof and application thereof in preparing a homogeneous phase ion exchange membrane. Specifically, the invention adopts vinyl tertiary amine and vinyl glycidyl ester compound to react to form divinyl cross-linking monomer with anion exchange capacity. On one hand, the solubility of the crosslinking monomer in water and other solvents is improved, the water content of a formed film can be controlled in a large range, on the other hand, the crosslinking monomer has ion exchange capacity, the integration of ion exchange and crosslinking is realized, and the crosslinking monomer can be used for preparing a film with high ion exchange capacity. Thirdly, compared with the prior art, the crosslinking monomer of the invention can also improve the hydrolysis resistance of the ion exchange membrane. The invention is characterized in that the vinyl tertiary amine compound and the vinyl glycidyl ester compound are subjected to ring-opening reaction to form a crosslinking monomer with ion exchange capacity, thereby improving the solubility of the crosslinking agent monomer in water and other solvents. Moreover, the reaction does not affect the electronic structure of the vinyl group, so the water-soluble crosslinking monomer can also be used as an ion exchange monomer for preparing homogeneous phase ion exchange membranes, such as high-performance ion exchange membranes with ultrahigh ion exchange capacity and low water content. In addition, the ionic crosslinking monomer can effectively avoid the use of a large amount of solvents, so that the preparation process of the ion exchange membrane is more environment-friendly and has lower cost.
Accordingly, in a first aspect, the present invention provides a compound having the following formula (I) or a salt thereof, which can be used as an ionic crosslinking monomer:
wherein B is selected from:
wherein R is1、R2、R4、R5、R6、R8、R11、R12、R13、R15、R16、R19Each independently selected from H, C1-C22Alkyl, aryl and heteroaryl;
R9、R14、R17and R18Each independently selected from C1-C22Alkyl, aryl and heteroaryl;
R3、R7and R10Each independently selected from C1-C22An alkylene group;
a is selected from O or N-Ra, wherein Ra is selected from H, C1-C22Alkylene, arylene, and heteroarylene;
x is the anion of a protic acid.
In one embodiment, B isMore preferably, in this embodiment, R17And R18Each independently is C1-C22Alkyl or aryl, even more preferably C1-C6Alkyl or phenyl.
In another embodiment, B isMore preferably, in this embodiment, R11Is H or C1-22Alkyl or aryl, even more preferably H, C1-C6Alkyl or phenyl.
In another embodiment, B isMore preferably, in this embodiment, R16Is H or C1-C22Alkyl or aryl, even more preferably H, C1-C6Alkyl or phenyl.
In another embodiment, B isMore preferably, in this embodiment, R12And R13Each independently is H or C1-C22Alkyl or aryl, even more preferably H, C1-C6Alkyl or phenyl.
In another embodiment, B isMore preferably, in this embodiment, R14Is C1-C22Alkyl or aryl, even more preferably C1-C6Alkyl or phenyl; r15Is H or C1-C22Alkyl or aryl, even more preferably H, C1-C6Alkyl or phenyl.
In another embodiment, B isMore preferably, in this embodiment, R19Is H or C1-C22Alkyl or aryl, even more preferably H, C1-C6Alkyl or phenyl; r9Is C1-C22Alkyl or aryl, even more preferably C1-C6Alkyl or phenyl; r10Is C1-C22Alkylene, even more preferably C1-6An alkylene group.
In one embodiment, a is O. In another embodiment, A is N-Ra, wherein Ra is selected from H or C1-C22Alkylene, preferably H or C1-C6An alkylene group.
In one embodiment, examples of X include, but are not limited to, F-、Cl-、Br-、I-、SO4 2-、PO4 3-、C2O4 2-、CH3CO2 -、CF3SO3 -、CF3CO2 -、CH3SO3 -And the like. In a preferred embodiment, X is Cl-。
In one embodiment, the ionic crosslinking monomer of the present invention has the following formula (I-1):
in one embodiment, examples of the ionic crosslinking monomer of the present invention further include, but are not limited to, the structures represented by the following formulas (I-2) to (I-21):
as used herein, the term "alkyl" refers to a straight or branched chain saturated monovalent hydrocarbon radical. In certain embodiments, the alkyl group contains 1 to 22 carbon atoms. For example, "C1-C22Alkyl "means an alkyl group containing only 1 carbon atom, 2 carbon atoms, 3 carbon atoms, and the like, up to 22 carbon atoms. E.g. C1-C22The alkyl group containing C1-C6An alkyl group. C1-C6Alkyl refers to an alkyl group containing 1, 2,3, 4, 5, or 6 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-pentyl, hexyl, heptyl, octyl, and the like. In the present invention, the term includes substituted or unsubstituted alkyl groups.
As used herein, the term "substituted or unsubstituted" means that the group may be unsubstituted or that H in the group is substituted with one or more substituents.
As used herein, the term "substituted" means that the group has one or more substituents selected from: halogen, hydroxy, C1-C4Alkyl radical, C1-C4Haloalkyl, -NH2Nitro, -CN.
As used herein, the term "halogen" or "halo" includes fluorine, chlorine, bromine and iodine.
As used herein, the term "alkylene" refers to a straight or branched chain saturated divalent hydrocarbon radical. In certain embodiments, the alkyl group contains 1 to 22 carbon atoms. For example, "C1-C22Alkylene "means an alkyl group containing only 1 carbon atom, 2 carbon atoms, 3 carbon atoms, and the like, up to 22 carbon atoms. E.g. C1-C22Alkylene contains C1-C6An alkylene group. C1-C6Alkylene means an alkylene group containing 1, 2,3, 4, 5 or 6 carbon atoms. Examples of alkyl groups include, but are not limited to, methylene, ethyleneN-propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-pentylene, hexylene, heptylene, octylene and the like. In the present invention, the term includes substituted or unsubstituted alkylene groups.
As used herein, the term "aryl" includes monovalent monocyclic aromatic radicals and/or monovalent polycyclic aromatic radicals of at least one aromatic carbon ring. In certain embodiments, aryl has 6 to 20 (C)6-20) 6 to 15 (C)6-15) Or 6 to 10 (C)6-10) A ring atom. Examples of aryl groups include, but are not limited to: phenyl, naphthyl, fluorenyl, azulenyl, anthracenyl, phenanthryl, pyrenyl, biphenyl, and terphenyl. Aryl also refers to bicyclic or tricyclic carbocycles, wherein one ring is aromatic and the other ring may be saturated, partially saturated or aromatic, for example, dihydronaphthyl, indenyl, indanyl or tetrahydronaphthyl (tetralinyl). The term includes substituted and unsubstituted forms wherein the substituents are as defined above.
As used herein, the term "arylene" refers to a divalent monocyclic aromatic radical and/or a divalent polycyclic divalent aromatic radical comprising at least one aromatic carbocyclic ring. In certain embodiments, the arylene group has 6 to 20 (C)6-20) 6 to 15 (C)6-15) Or 6 to 10 (C)6-10) A ring atom. Examples of arylene groups include, but are not limited to: phenylene, naphthylene, fluorenylene, oxinylene, anthracenylene, phenanthrenylene, pyrenylene, biphenylene, and terphenylene. Arylene also refers to bicyclic or tricyclic carbocycles in which one ring is aromatic and the other ring may be saturated, partially saturated or aromatic, for example dihydronaphthylene, indenylene, indanylene or tetrahydronaphthylene. The term includes substituted and unsubstituted forms wherein the substituents are as defined above.
As used herein, the term "heteroaryl" refers to a monovalent monocyclic aromatic radical and/or a monovalent polycyclic aromatic radical comprising at least one aromatic ring, wherein the at least one aromatic ring comprises one or more heteroatoms independently selected from O, S and N in the ring. The heteroaryl group is bonded to the rest of the molecule via an aromatic ring. Each ring of the heteroaryl group can contain one or two O atoms, one or two S atoms, and/or one to four N atoms, provided that the total number of heteroatoms in each ring is four or less, and each ring contains at least one carbon atom. In certain embodiments, heteroaryl has 5 to 20, 5 to 15, 5 to 10, or 5-6 ring atoms. Examples of heteroaryl groups include, but are not limited to: pyridyl, pyrrolyl, indolyl, thienyl, phenazinyl and furyl. The term includes substituted and unsubstituted forms wherein the substituents are as defined above.
As used herein, the term "heteroarylene" refers to a divalent monocyclic aromatic radical and/or a divalent polycyclic aromatic radical comprising at least one aromatic ring, wherein at least one of the aromatic rings comprises one or more heteroatoms independently selected from O, S and N in the ring. Each ring of a heteroarylene group may contain one or two O atoms, one or two S atoms, and/or one to four N atoms, provided that the total number of heteroatoms in each ring is four or less, and each ring contains at least one carbon atom. In certain embodiments, the heteroarylene group has 5 to 20, 5 to 15, 5 to 10, or 5-6 ring atoms. Examples of heteroarylenes include, but are not limited to: pyridylidene, pyrrolylidene, indoliylidene, thienylidene, phenazinylidene, and furanylidene. The term includes substituted and unsubstituted forms wherein the substituents are as defined above.
As used herein, the term "protic acid" refers to any compound capable of releasing a proton (H +). Examples of protic acids include, but are not limited to: HF. HCl, HBr, HI, H2SO4、H3PO4、C2H2O4、CH3SO3H、CH3CO2H、CF3SO3H、CF3CO2H. In a preferred embodiment, the suitable protic acid is HCl or CH3SO3H。
In a second aspect, the present invention provides a method for preparing an ionic crosslinking monomer, comprising reacting a vinyl tertiary amine compound having the following formula (III) with a vinyl glycidyl ester compound having the following formula (IV) in the presence of a protic acid and a solvent:
wherein,
y is selected from
R20、R21、R27、R28、R29、R31、R32、R33、R35、R36、R37And R38Each independently selected from H, C1-C22Alkyl, aryl and heteroaryl;
R23、R24、R26and R30Each independently selected from C1-C22Alkyl, aryl or heteroaryl;
R22、R25and R34Each independently selected from C1-C22An alkylene group;
z is selected from O and N-R39Wherein R is39Selected from H, C1-C22Alkylene, arylene and heteroarylene, wherein each group is as defined above.
In one embodiment, formula (III) has a structure selected from the following formulae (III-1) to (III-6):
in one embodiment, formula (IV) has a structure selected from the following formulae (IV-1) to (IV-3):
the vinyl tertiary amine compound and the vinyl glycidyl ester compound react in the presence of protonic acid, the oxygen ring of the tertiary amine compound is opened to form quaternary ammonium salt, and the bonding of two vinyl groups is realized. The polymerization of the tertiary amine and glycidyl ester can be carried out by heating the reactants to a suitable temperature and for a time sufficient to quaternize and crosslink the tertiary amine. In one embodiment, the temperature of the reaction ranges from about 50 ℃ to 105 ℃, most preferably 75 ℃. In one embodiment, the time of reaction is about 0.5 to 10 hours, such as 2 to 5 hours. The reaction temperature and reaction time can be adjusted by the person skilled in the art by routine experimentation, as desired.
The ionic crosslinking monomer of the invention can be synthesized from a wide range of molar ratios of vinyl tertiary amine compounds and vinyl glycidyl ester compounds. In one embodiment, the molar ratio is 1:1 to 2.5.
The ionic crosslinking monomer has an ion exchange function and has high solubility in water and other polar solvents. Other polar solvents useful in the present invention include, but are not limited to: alcohol solvents and ether solvents as aprotic polar solvents. Water and alcohol solvents are preferred. Examples of the alcohol solvent are, for example, methanol, ethanol, isopropanol, n-butanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and the like. Among the alcohol solvents, ethanol, isopropanol, n-butanol, and ethylene glycol are more preferable. In the present invention, one or more solvents may be used, and it is preferable to use water alone or water and a polar solvent, particularly an alcohol solvent, at the same time.
Meanwhile, the product also has the function of a cross-linking agent, so that the product can be directly used for preparing an ion exchange membrane. Because the ionic crosslinking monomer can be dissolved in various solvents with higher solubility and has ion exchange capacity, when the ionic crosslinking monomer is directly used for preparing an ion exchange membrane, the ion exchange membrane with high performance can be obtained, for example, the ion exchange membrane with low resistance, high ion exchange capacity, low water content and hydrolysis resistance can be obtained, and the wide-range control of the membrane performance can be realized. It is noted that the present invention employs an amide-type tertiary amine, and thus the resulting ion-exchange membrane has higher hydrolysis resistance, as compared with US patent US 4,310,631.
In one embodiment, the method for preparing the ionic crosslinking monomer of the present invention further comprises adding a polymerization inhibitor.
As used herein, the term "polymerization inhibitor" refers to a compound that completely terminates the radical polymerization reaction of an ethylenic monomer. Suitable polymerization inhibitors include, but are not limited to: hydroquinone, methylhydroquinone, p-hydroxyanisole, hydroquinone monomethyl ether, 2, 6-di-tert-butyl-4-methylphenol, 4-tert-butylcatechol, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, phenothiazine, 4-oxo-2, 2,6, 6-tetramethyl-1-piperidinyloxy, 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinyloxy, 2, 6-dinitro-sec-butylphenol, tris (N-nitroso-N-phenylhydroxylamine) aluminum salt, and mixtures thereof. In one embodiment, a suitable polymerization inhibitor is p-hydroxyanisole.
In one embodiment, the inhibitor content is from 10 to 3000 ppm.
Accordingly, the present invention also provides an ionic crosslinking monomer prepared by the above method.
As used herein, the term "tertiary amine" refers to a tertiary amine, specific examples including, but not limited to, pyridine, branched tertiary amines, cyclic tertiary amines, and the like. In one embodiment, suitable vinyl tertiary amine compounds include, but are not limited to: n- [ (dimethylamino) methyl ] acrylamide, N- [ (diethylamino) methyl ] methacrylamide, 4- (2-methacrylamide) methylpyridine, 2- (2-methacrylamide) methylpyrimidine, 2- (2-methacrylamide) methylimidazole, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and mixtures thereof. In a preferred embodiment, the vinyl tertiary amine compound is dimethylaminopropyl methacrylamide.
In one embodiment, examples of suitable vinyl glycidyl ester compounds include, but are not limited to: glycidyl methacrylate, 3, 4-epoxy butyl methacrylate, N- (2, 3-epoxypropyl) methacrylamide.
In one embodiment, the vinyl tertiary amine compound and the vinyl glycidyl ester compound may be added to the solvent simultaneously or in portions.
The amount of solvent is any amount suitable to dissolve the components. In one embodiment, the amount of solvent is from about 10 to about 90 weight percent based on the total weight of the reactant mixture. In another embodiment, the amount of solvent is from about 20 to about 70 weight percent based on the total weight of the reactant mixture. Suitable solvents include, but are not limited to, water and other polar solvents, such as dipropylene glycol.
In one embodiment, the molar ratio of the vinyl tertiary amine compound to the proton ionized by the protonic acid is from 1:1 to 1.5.
In a third aspect, the present invention provides the use of an ionic crosslinking monomer in the preparation of an ion exchange membrane. Furthermore, the inventors have found that the ionic crosslinking monomers prepared according to the present invention can also be widely used in other fields where good hydrolytic stability is required, such as in the preparation of coatings, adhesives, ion exchange resins, and the like.
In a fourth aspect, the present invention provides a composition for preparing an ion exchange membrane comprising an ionic crosslinking monomer according to the present invention and optionally an initiator.
As described above, the ionic crosslinking monomer of the present invention has both functions of a crosslinking agent and an ion exchange monomer. Thus, in one embodiment, the composition for preparing an ion exchange membrane comprises an ionic crosslinking monomer according to the invention and an initiator without further anion exchange monomers.
In another embodiment, the composition for preparing an ion exchange membrane comprises an ionic crosslinking monomer according to the invention, an initiator and at least one further anion exchange monomer.
As used herein, the term "anion exchange monomer" refers to a monomer having a positively charged ionic group or having a basic primary, secondary, tertiary amine, pyridine, etc. that can effect anion exchange. In one embodiment, the anion exchange monomer is a vinyl anionic monomer or a vinyl monomer having a basic nature. Examples of suitable anion exchange monomers include, but are not limited to, one or more selected from the group consisting of: trimethylethacrylic acid ammonium chloride (TMAMCC), 3-acrylamidopropyltrimethylammonium chloride, 2-acryloxyethyltrimethylammonium chloride, 2-methacryloxyethyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride (MAPTAC), dimethylaminoethyl methacrylate, dimethylbenzyl-2-methylammonium methacrylate chloride, N- (3-dimethylaminopropyl) methacrylamide, N, N, N-trimethyl-3- (2-methylallylamido) -1-propylamine chloride, dimethylaminopropylacrylamide, (3-acrylamidopropyl) -trimethylammonium chloride, diallyldimethylammonium chloride, tetraallylammonium chloride, dimethylaminoethyl acrylate, and vinylbenzyltrimethylammonium chloride (TMAVAC), Vinylpyridine, dimethylaminopropyl methacrylamide, dimethylaminoethyl methacrylate, and the like.
As used herein, the term "initiator" refers to a substance that can generate a radical polymerization active center, including, but not limited to, 2 ' -azacyclo (2-imidazoline) dihydrochloride, 2 ' -azobisisobutyramidine dihydrochloride, 2 ' -azo (2-methyl-N- (2-hydroxyethyl) propionamide).
In one embodiment, the initiator is present in an amount of 0.1 to 10% by weight based on the total weight of the composition for preparing an ion-exchange membrane according to the present invention.
In a fifth aspect, the present invention provides a method of preparing an ion exchange membrane, an ion exchange membrane made thereby, and uses of the ion exchange membrane. The method for preparing the ion exchange membrane comprises the steps of coating the composition on the reinforced fabric, and curing the composition into a membrane. The coating may be carried out by any coating technique known to those skilled in the art. In addition, the method of preparing an ion exchange membrane of the present invention further comprises curing the composition of the present invention directly to a film without a reinforcing fabric. Curing may be carried out by any curing technique known to those skilled in the art, for example, by heat, light, radiation, plasma, microwave, and the like. The ion-exchange membrane prepared according to the method of the present invention can be used for various electrochemical devices, such as an electrodialyzer, a battery, etc.
As used herein, the term "reinforcing fabric" refers to a reinforcing support layer made of fibers, or a reinforcing support layer having a porous structure. Suitable reinforcing fabrics include, but are not limited to, fibrous cloth and porous membrane materials. Examples of reinforcing fabrics include: glass fiber, polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile, polyester, polycarbonate, polymethyl methacrylate, polytetrafluoroethylene or other polymer alloy fiber or porous membrane material.
The composition is based on the polymerization reaction process of free radicals, and is directly polymerized by adopting the ionic crosslinking monomer (or polymerized after being mixed with the anion exchange monomer), so that less organic solvent or even organic solvent polluting the environment is used, the pollution is effectively reduced, the cost is saved, and the preparation process is simplified. Meanwhile, the invention can form stable homogeneous solution, so that the membrane formed by polymerization has a more uniform physical structure, and the problem that in the prior art, because the reinforced high polymer material is difficult to be sulfonated or chloromethylated, the membrane is basically a semi-homogeneous membrane and defects are easily formed on the membrane is effectively solved. Compared with the ion exchange membrane in the prior art, the ion exchange membrane has the ion exchange capacity of 2-4meq/g resin, the water content of 20-40 percent, and lower water content can be obtained on the basis of keeping high ion exchange capacity. Finally, the ion-exchange membranes of the invention are paired with monovalent anions such as Cl-Has high selective permeability.
Detailed Description
Example 1 preparation of Ionic crosslinking monomers of the invention
126.35g of dimethylaminopropyl methacrylamide was added to 70.7g of 34% aqueous hydrochloric acid solution and reacted at 75 ℃ for 30 minutes, whereby the solution became pale yellow. 100.63g of glycidyl methacrylate and 0.0374g of p-hydroxyanisole were added to the solution, whereupon the solution became cloudy. The temperature was raised to 85 ℃ and reacted at that temperature for 2 hours until the solution system appeared to be a uniform transparent pale yellow. The resulting solution did not precipitate at room temperature. It was rotary evaporated under vacuum and then crystallized. NMR data of the crystals confirmed that the obtained product was 2-hydroxy-N- (3-methacrylamidopropyl) -3- (methacryloyloxy) -N, N-dimethylpropane-1-ammonium chloride (i.e., the compound of formula I-1 of the present invention).
Example 2 preparation of a homogeneous anion exchange Membrane according to the invention
The solution obtained in example 1 was cooled to room temperature, 76.3g of water and 1.496g of azobisisobutyramidine hydrochloride were added, mixed uniformly, and then the mixture was uniformly impregnated on a polyester knitted fabric, insulated with a polyester film to exclude air, and kept at 75 ℃ for 1 hour to obtain a homogeneous anion exchange membrane. Then the ion exchange capacity and the water content of the anion exchange membrane are measured according to the marine industry standard HY/T166.1-2013 of the people's republic of China, and the results are as follows: the ion exchange capacity was 2.71meq/g resin, and the water content was 31%.
Example 3 preparation of a homogeneous anion exchange Membrane according to the invention
177.2g of p-hydroxyanisole was added to 177.2g N- [ (diethylamino) methyl ] methacrylamide, after dissolution, 105g of a 36% pure aqueous hydrochloric acid solution was added, and the mixture was reacted at 65 ℃ for 0.5 hour to obtain an aqueous hydrochloride solution of dimethylaminopropyl methacrylamide. Then 163g of (3, 4-epoxy) butyl methacrylate was added dropwise, reacted at 75 ℃ for 1 hour, and 90g of deionized water was added to obtain a solution of the ionic crosslinking monomer represented by the formula (I-2).
After the solution of the ionic crosslinking monomer represented by the formula (I-2) was cooled to room temperature, 2.2g of azobisisobutyrimidazoline hydrochloride (12g dissolved in deionized water) was added. After being stirred uniformly, the mixture is evenly dipped on polyester knitted fabric, and a polyester film is adopted to isolate air, and the temperature is kept for 1 hour at 75 ℃, so that the homogeneous anion exchange membrane is obtained. The ion exchange capacity and the water content of the anion exchange membrane are measured according to the marine industry standard HY/T166.1-2013 of the people's republic of China, and the results are as follows: the ion exchange capacity was 2.75meq/g resin, and the water content was 32%.
Example 4 preparation of a homogeneous anion exchange Membrane according to the invention
0.5g of p-hydroxyanisole was added to 130g N- [ (dimethylamino) methyl ] acrylamide, after dissolution, 105g of a hydrochloric acid aqueous solution with a purity of 36% was added, and the mixture was reacted at 65 ℃ for 0.5 hour to obtain a hydrochloric acid aqueous solution of dimethylaminopropyl methacrylamide, then 148g of glycidyl methacrylate was added dropwise, and after reaction at 75 ℃ for 1 hour, 70g of deionized water was added to obtain a solution of the ionic crosslinking monomer represented by formula (I-3).
After the solution of the ionic crosslinking monomer represented by the formula (I-3) was cooled to room temperature, 1.9g of azobisisobutyrimidazoline hydrochloride (10g dissolved in deionized water) was added. After being stirred uniformly, the mixture is evenly dipped on polyester knitted fabric, and a polyester film is adopted to isolate air, and the temperature is kept for 1 hour at 75 ℃, so that the homogeneous anion exchange membrane is obtained. The ion exchange capacity and the water content of the anion exchange membrane are measured according to the marine industry standard HY/T166.1-2013 of the people's republic of China, and the results are as follows: the ion exchange capacity was 3.12meq/g resin, and the water content was 30%.
Example 5 preparation of a homogeneous anion exchange Membrane according to the invention
10.9g of tetramethlyaminopyridine and 20ml of acetonitrile (which was refluxed for three hours with addition of phosphorus pentoxide and then distilled to dryness) were placed in a 100ml three-necked flask, and N was passed through2Under protection, a methacrylic chloride acetonitrile solution (10.6g of methacrylic chloride dissolved in 20ml of acetonitrile) was added dropwise at normal temperature, and then the temperature was raised to 60 ℃ to react for 2 hours. The reaction was monitored by TLC and was complete if the spot of starting material (i.e., the location where the tetraminopyridine and methacryloyl chloride were developed on the TLC plate) disappeared. Excess solvent was removed under reduced pressure to give a pale yellow oil, i.e., 4- (2-methacrylamide) picoline. Adding 0.3g of p-hydroxyanisole, adding 10.5g of hydrochloric acid aqueous solution with the purity of 36% after dissolving the p-hydroxyanisole, reacting at 65 ℃ for 0.5h to obtain 4- (2-methacrylamide) methylpyridine hydrochloride aqueous solution, then dropwise adding 14.8g of glycidyl methacrylate, reacting at 75 ℃ for 1h, and then adding 11.2g of deionized water to obtain the solution of the ionic crosslinking monomer shown in the formula (I-4).
After the solution of the ionic crosslinking monomer represented by the formula (I-4) was cooled to room temperature, 0.22g of azobisisobutyrimidazoline hydrochloride (1.1g dissolved in deionized water) was added. After stirring uniformly, it was poured into a PET cavity with a depth of 0.35 mm. Vacuum defoamation was carried out at 20 ℃ for 3 minutes, and then a PET cover plate was covered. And placing the obtained assembly in an oven preheated to 80 ℃ for heat preservation for 100 minutes, taking out and cooling, then placing the composition in water, and removing a cover plate to obtain the homogeneous phase anion exchange membrane with flat and smooth appearance. The ion exchange capacity and the water content of the anion exchange membrane are measured according to the marine industry standard HY/T166.1-2013 of the people's republic of China, and the results are as follows: the ion exchange capacity was 2.8meq/g resin, and the water content was 33%.
Example 6 preparation of a homogeneous anion exchange Membrane according to the invention
11.01g of tetramethypyridine and 20ml of acetonitrile (obtained by adding phosphorus pentoxide P2O5, refluxing for three hours, and then carrying out distillation and drying treatment) are placed in a 100ml three-neck flask, under the protection of N2, an acetonitrile solution of methacryloyl chloride (10.6g of methacryloyl chloride is dissolved in 20ml of acetonitrile) is dropwise added at normal temperature, then the temperature is raised to 60 ℃ for reaction for 2 hours, the reaction is monitored by TLC, if the raw material point disappears, the reaction is finished, and excess solvent is removed under reduced pressure, so that a light yellow oily substance, namely 2- (2-methacrylamide) methylpyrimidine is obtained. Adding 0.3g of p-hydroxyanisole, adding 10.5g of hydrochloric acid aqueous solution with the purity of 36% after dissolving the p-hydroxyanisole, reacting at 65 ℃ for 0.5h to obtain 2- (2-methacrylamide) methylpyrimidine hydrochloride aqueous solution, then dropwise adding 14.8g of glycidyl methacrylate, reacting at 75 ℃ for 1h, and then adding 11.2g of deionized water to obtain the solution of the ionic crosslinking monomer shown in the formula (I-5).
After the solution of the ionic crosslinking monomer represented by the formula (I-5) was cooled to room temperature, 0.22g of azobisisobutyrimidazoline hydrochloride (1.1g dissolved in deionized water) was added. After stirring uniformly, it was poured into a PET cavity with a depth of 0.35 mm. Vacuum defoamation was carried out at 20 ℃ for 3 minutes, and then a PET cover plate was covered. And placing the obtained assembly in an oven preheated to 80 ℃ for heat preservation for 100 minutes, taking out and cooling, then placing the composition in water, and removing a cover plate to obtain the homogeneous phase anion exchange membrane with flat and smooth appearance. The ion exchange capacity and the water content of the anion exchange membrane are measured according to the marine industry standard HY/T166.1-2013 of the people's republic of China, and the results are as follows: the ion exchange capacity was 2.75meq/g resin, and the water content was 33%.
Example 7 preparation of a homogeneous anion exchange Membrane according to the invention
12.75g of 2-aminomethylimidazole and 20ml of acetonitrile (obtained by adding phosphorus pentoxide P2O5, refluxing for three hours, then carrying out distillation and drying treatment) are placed in a 100ml three-neck flask, under the protection of N2, an acetonitrile solution of methacryloyl chloride (10.6g of methacryloyl chloride is dissolved in 20ml of acetonitrile) is dropwise added at normal temperature, then the temperature is raised to 60 ℃ for reaction for 2 hours, the reaction is monitored by TLC, if the raw material point disappears, the reaction is finished, and excess solvent is removed under reduced pressure to obtain a pale yellow oily substance, namely-2- (2-methacrylamide) methylimidazole. Adding 0.3g of p-hydroxyanisole, adding 10.5g of hydrochloric acid aqueous solution with the purity of 36% after dissolving the p-hydroxyanisole, reacting at 65 ℃ for 0.5h to obtain 2- (2-methacrylamide) methylimidazole hydrochloride aqueous solution, then dropwise adding 14.8g of glycidyl methacrylate, reacting at 75 ℃ for 1h, and then adding 11.2g of deionized water to obtain the solution of the ionic crosslinking monomer shown in the formula (I-6).
After the solution of the ionic crosslinking monomer represented by the formula (I-6) was cooled to room temperature, 0.22g of azobisisobutyrimidazoline hydrochloride (1.1g dissolved in deionized water) was added. Stirring uniformly, then uniformly soaking the mixture on polyester knitted fabric, isolating the air by adopting a polyester film, and preserving the heat at 75 ℃ for 1 hour to obtain the homogeneous anion exchange membrane. The ion exchange capacity and the water content of the anion exchange membrane are measured according to the marine industry standard HY/T166.1-2013 of the people's republic of China, and the results are as follows: the ion exchange capacity was 2.7meq/g resin, and the water content was 33%.
Example 8 preparation of a homogeneous anion exchange Membrane according to the invention
0.064g of p-hydroxyanisole was added to 17.72g of dimethylaminopropyl methacrylamide, after dissolution, 10.5g of a hydrochloric acid aqueous solution with a purity of 36% was added, and the mixture was reacted at 65 ℃ for 0.5 hour to obtain a hydrochloride aqueous solution of dimethylaminopropyl methacrylamide, 14.3g N- (2, 3-epoxypropyl) methacrylamide was added dropwise, and after reaction at 75 ℃ for 1 hour, 8.3g of deionized water was added to obtain a solution of the ionic crosslinking monomer represented by the formula (I-7).
After the solution of the ionic crosslinking monomer represented by the formula (I-7) was cooled to room temperature, 0.21g of azobisisobutyrimidazoline hydrochloride (1.1g dissolved in deionized water) was added. Stirring uniformly, then uniformly soaking the mixture on polyester knitted fabric, isolating the air by adopting a polyester film, and preserving the heat at 75 ℃ for 1 hour to obtain the homogeneous anion exchange membrane. The ion exchange capacity and the water content of the anion exchange membrane are measured according to the marine industry standard HY/T166.1-2013 of the people's republic of China, and the results are as follows: the ion exchange capacity was 2.9meq/g resin, and the water content was 33%.
Example 9 preparation of a homogeneous anion exchange Membrane according to the invention
10.9g of tetramethy laminopyridine and 20ml of acetonitrile (after being added with phosphorus pentoxide and refluxed for three hours and then distilled and dried) are placed in a 100ml three-neck flask, under the protection of N2, an acetonitrile solution of methacrylic chloride (10.6g of methacrylic chloride is dissolved in 20ml of acetonitrile) is dripped at normal temperature, then the temperature is raised to 60 ℃ for reaction for 2 hours, the reaction is monitored by TLC, if the raw material point disappears, the reaction is finished, and redundant solvent is removed under reduced pressure, so that light yellow oily matter, namely 4- (2-methacrylamide) methylpyridine is obtained. 0.3g of p-hydroxyanisole is added, 10.5g of hydrochloric acid aqueous solution with the purity of 36% is added after the p-hydroxyanisole is dissolved, the 4- (2-methacrylamide) methylpyridine hydrochloride aqueous solution is obtained after reaction at 65 ℃ for 0.5h, then 14.6g N- (2,3 epoxypropyl) methacrylamide is added dropwise, reaction at 75 ℃ is carried out for 1h, and 11.2g of deionized water is added, thus obtaining the solution of the ionic crosslinking monomer shown in the formula (I-8).
After the solution of the ionic crosslinking monomer represented by the formula (I-8) was cooled to room temperature, 0.22g of azobisisobutyrimidazoline hydrochloride (1.1g dissolved in deionized water) was added. Stirring uniformly, then uniformly soaking the mixture on polyester knitted fabric, isolating the air by adopting a polyester film, and preserving the heat at 75 ℃ for 1 hour to obtain the homogeneous anion exchange membrane. The ion exchange capacity and the water content of the anion exchange membrane are measured according to the marine industry standard HY/T166.1-2013 of the people's republic of China, and the results are as follows: the ion exchange capacity was 2.8meq/g resin, and the water content was 33%.
EXAMPLE 10 determination of acid resistance of the homogeneous anion exchange Membrane of the present invention
The homogeneous anion exchange membrane prepared according to example 1 above was cut to a size of 10cm x 15cm, soaked in deionized water overnight, and then the homogeneous anion exchange membrane was transferred to a 0.1N or 1N sulfuric acid solution for soaking, sampled at intervals and weighed. The results are shown in table 1 below.
TABLE 1 acid resistance assay results for homogeneous anion exchange membranes of the invention
From the above results, it can be seen that the quality of the homogeneous anion exchange membrane of the present invention remains stable and no swelling occurs after soaking in 0.1N or 1N sulfuric acid solution for up to 72 hours. This shows that the homogeneous anion exchange membranes of the present invention have good acid resistance.
It should be noted that the above-mentioned embodiments illustrate only preferred specific embodiments of the invention, and are not to be construed as limiting the invention, and any embodiment falling within the scope of the invention, which is defined by the features of the claims or the equivalents thereof, constitutes a violation of the patent right of the invention. Various other modifications can be made by those skilled in the art from the above disclosure and spirit, and all such modifications are intended to be included within the scope of the invention as defined in the appended claims.

Claims (35)

1. A compound having the following formula (I):
(I)
wherein B is selected from:
wherein R is1、R2、R4、R5、R6、R8、R11、R12、R13、R15、R16、R19Each independently selected from H, C1-C22Alkyl, aryl and heteroaryl;
R9、R14、R17and R18Each independently selected from C1-C22Alkyl, aryl and heteroaryl;
R3、R7and R10Each independently selected from C1-C22An alkylene group; a is selected from O or N-Ra, wherein Ra is selected from H, C1-C22Alkylene, arylene, and heteroarylene;
x is the anion of a protic acid.
2. The compound of claim 1 or salt thereof, wherein X is selected from Cl-、Br-、I-、SO4 2-、PO4 3-、C2O4 2-、CH3CO2 -、CF3SO3 -、CF3CO2 -And CH3SO3 -。
3. The compound or salt thereof according to claim 1, wherein B is
4. The compound of claim 3 or a salt thereof, wherein R is17And R18Each independently selected from C1-C22Alkyl or aryl.
5. The compound or salt thereof according to claim 1, wherein B is
6. A compound or salt thereof according to claim 5, wherein R11Is H or C1-22Alkyl or aryl.
7. The compound or salt thereof according to claim 1, wherein B is
8. The compound of claim 7 or a salt thereof, wherein R16Is H or C1-22Alkyl or aryl.
9. The compound or salt thereof according to claim 1, wherein B is
10. The compound of claim 9, or a salt thereof, wherein R12And R13Each independently is H or C1-22Alkyl or aryl.
11. The compound or salt thereof according to claim 1, wherein B is
12. The compound of claim 11, or a salt thereof, wherein R14Is C1-22Alkyl or aryl, R15Is H or C1-22Alkyl or aryl.
13. The compound or salt thereof according to claim 1, wherein B is
14. The compound of claim 13, or a salt thereof, wherein R19Is H or C1-22Alkyl or aryl, R9Is C1-22Alkyl or aryl, R10Is C1-22An alkylene group.
15. The compound of claim 1, or a salt thereof, wherein R3And R7Each independently is C1-C6An alkylene group.
16. The compound of claim 1, or a salt thereof, wherein R1、R2、R4、R5、R6And R8Each independently is H or C1-C22Alkyl or aryl.
17. The compound of claim 1, or a salt thereof, having a structure selected from the group consisting of:
(I-1)
(I-2)
(I-3)
(I-4)
(I-5)
(I-6)
(I-7)
(I-8)
(I-9)
(I-10)
(I-11)
(I-12)
(I-13)
(I-14)
(I-15)
(I-16)
(I-17)
(I-18)
(I-19)
(I-20)
(I-21)
(I-22)
(I-23)
18. a compound prepared by reacting a compound of a vinyl tertiary amine having the following formula (III) with a vinyl glycidyl ester compound having the following formula (IV) in the presence of a protic acid and a solvent:
(III)
(IV)
wherein,
y is selected from
R20、R21、R27、R28、R29、R31、R32、R33、R35、R36、R37And R38Each independently selected from H, C1-C22Alkyl, aryl and heteroaryl;
R23、R24、R26and R30Each independently selected from C1-C22Alkyl, aryl or heteroaryl;
R22、R25and R34Each independently selected from C1-C22An alkylene group;
z is selected from O and N-R39Wherein R is39Selected from H, C1-C22Alkylene, arylene and heteroarylene.
19. A process for preparing a compound of any one of claims 1 to 18 or a salt thereof, comprising reacting a vinyl tertiary amine compound having the following formula (III), a vinyl glycidyl ester compound having the following formula (IV), and a protonic acid in the presence of a solvent:
(III)
(IV)
wherein,
y is selected from
R20、R21、R27、R28、R29、R31、R32、R33、R35、R36、R37And R38Each independently selected from H, C1-C22Alkyl, aryl and heteroaryl;
R23、R24、R26and R30Each independently selected from C1-C22Alkyl, aryl or heteroaryl;
R22、R25and R34Each independently selected from C1-C22An alkylene group;
z is selected from O and N-R39Wherein R is39Selected from H, C1-C22Alkylene, arylene and heteroarylene.
20. The method of claim 19, wherein the solvent is water and/or an alcohol solvent.
21. The method of claim 19, further comprising adding a polymerization inhibitor.
22. The process of claim 19, wherein the vinyl tertiary amine compound is N- [ (dimethylamino) methyl ] acrylamide, N- [ (diethylamino) methyl ] methacrylamide, 4- (2-methacrylamide) picoline, 2- (2-methacrylamide) methylpyrimidine, 2- (2-methacrylamide) methylimidazole, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, or mixtures thereof.
23. The method of claim 19, wherein the vinyl glycidyl ester compound is glycidyl methacrylate, (3, 4-epoxy) butyl methacrylate, or N- (2, 3-epoxypropyl) methacrylamide.
24. The method of claim 19, wherein the protic acid is at least one selected from the group consisting of: HF. HCl, HBr, HI, H2SO4, H3PO4, C2H2O4, CH3SO3H, CH3CO2H, CF3SO3H, CF3CO 2H.
25. The method of claim 19, wherein the molar ratio of the vinyl tertiary amine compound to the vinyl glycidyl ester compound is 1: 1-2.5.
26. Use of a compound according to any one of claims 1 to 18 or a salt thereof or a compound prepared according to the process of any one of claims 19 to 25 as a cross-linking agent and/or ion exchange monomer.
27. Use of a compound according to any one of claims 1 to 18 or a salt thereof or a compound prepared according to the process of any one of claims 19 to 25 in the preparation of ion exchange membranes, coatings, adhesives and ion exchange resins.
28. A composition comprising a compound according to any one of claims 1 to 18 or a salt thereof or a compound prepared according to the process of any one of claims 19 to 25 and optionally an initiator.
29. The composition of claim 28, further comprising at least one anion exchange monomer.
30. The composition of claim 29, wherein the anion exchange monomer is a vinyl anion monomer or a vinyl monomer having a basicity.
31. A process for preparing an ion exchange membrane comprising applying the composition of any one of claims 28 to 30 to a reinforcement fabric and allowing it to cure to a film.
32. A process for preparing an ion exchange membrane comprising curing the composition of any one of claims 28-30 directly to a film without a reinforcing fabric.
33. An ion exchange membrane comprising a polymer layer obtained by curing the composition of any one of claims 28-30.
34. An ion exchange membrane obtained by the method of any one of claims 31-32.
35. An electrochemical separation device, comprising: at least one ion exchange membrane according to claim 33 or 34.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110075811A (en) * 2019-04-01 2019-08-02 天津大学 Dimethylamino-propyl acrylamide graft Ago-Gel chromatographic media and preparation method and application
CN115073349A (en) * 2022-08-09 2022-09-20 江苏蓝固新能源科技有限公司 Acrylic ester pyrrole compound and preparation method thereof
CN115232050A (en) * 2022-08-09 2022-10-25 江苏蓝固新能源科技有限公司 Acrylate pyrrole compound rich in unsaturated functional group and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110075811A (en) * 2019-04-01 2019-08-02 天津大学 Dimethylamino-propyl acrylamide graft Ago-Gel chromatographic media and preparation method and application
CN115073349A (en) * 2022-08-09 2022-09-20 江苏蓝固新能源科技有限公司 Acrylic ester pyrrole compound and preparation method thereof
CN115232050A (en) * 2022-08-09 2022-10-25 江苏蓝固新能源科技有限公司 Acrylate pyrrole compound rich in unsaturated functional group and preparation method thereof

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