CN114656356A - Spiro-indane tetraacylchloride and preparation method thereof, and composite membrane and preparation method thereof - Google Patents
Spiro-indane tetraacylchloride and preparation method thereof, and composite membrane and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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Abstract
The invention provides spiro-biindane tetraacyl chloride which has a structure shown as a formula I. The spiro-biindane tetraacylchloride provided by the invention has a three-dimensional twisted structure, and the generated polymer has a microporous characteristic, so that the spiro-biindane tetraacylchloride can be used for a separation membrane material to show higher permeability.
Description
Technical Field
The invention relates to the technical field of synthetic chemistry, in particular to spiro-diindane tetraacylchloride and a preparation method thereof, and a composite membrane and a preparation method thereof.
Background
The polybasic acyl chloride is an important chemical raw material, is mainly used for preparing materials or films such as polyamide, polyester, polyimide and the like, and is widely applied in the fields of separation and adsorption, such as gas separation membranes, organic solvent nanofiltration membranes, microporous adsorption media and the like.
The synthesis method of the polybasic acyl chloride monomer comprises the step of reacting polybasic carboxylic acid with an acylation reagent to obtain the acyl chloride monomer. The selected acylating agent is one or more of thionyl chloride, oxalyl chloride, triphosgene and phosphorus pentachloride. In 2005, acid chloride monomers such as 5-oxoformyl chloride-isopeptide acid chloride (CFIC) and 5-isocyanate isopeptide acid chloride (ICIC) were synthesized by Zhouyong et al using triphosgene (e.g., Desalination,2005,180, 189-196; Journal of Membrane Science,2006,270, 162-168; Desalination,2006,192, 182-189). In 2009, lie was prepared by Suzuki coupling, Ni (0) catalytic coupling and thionyl chloride method to obtain various polyacyl chlorides containing biphenyl structures: 3,4, 5-biphenyltriacyl chloride, 3,3', 5,5' -biphenyltetracarbonyl chloride, 2,2 ', 4, 4' -biphenyltetracarbonyl chloride (for example, in the Journal of Membrane Science 2007,289(1/2): 258-. In 2013, 2,4,4 ', 6-biphenyltetracarbonyl, 2, 3', 4, 5', 6-biphenylpentacyloyl chloride and 2, 2', 4,4 ',6,6' -biphenylhexacarbonyl chloride were synthesized by Wantun Yu (for example, Journal of Membrane Science,2013,440: 48-57).
However, the existing polymers generated by polyacyl chloride (such as trimesoyl chloride and biphenylyl tetrachloride) do not have micropore characteristics, molecular chains of the polymers are effectively stacked, the free volume of the polymers is small, and the dense stacking structure of a polymer film prevents gas and organic solvents from passing through the polymer film.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a spiro-indane tetraacylchloride and a preparation method thereof, and a composite membrane and a preparation method thereof, wherein the prepared spiro-indane tetraacylchloride is used as a separation membrane material, which can improve the permeability of the separation membrane.
The invention provides spiro-biindane tetraacylchloride which has a structure shown in a formula I:
wherein R is H, CH3-、CH3CH2-or CH3(CH2)nCH2-；
n is an integer of 1 to 20.
Preferably, the spiro-biindane tetrachloride has a structure shown in formula I-a:
wherein R is H, CH3-、CH3CH2-or CH3(CH2)nCH2-；
n is an integer of 1 to 20.
Further preferably, R is CH3-。
The invention discloses a preparation method of the spiro-biindane tetraacylchloride, which comprises the following steps:
A) benzene or dialkyl benzene is used as a raw material and is subjected to condensation reaction with 2-halopropene under the condition that metal halide is used as a catalyst to obtain an intermediate shown in a formula 1;
B) carrying out oxidation reaction on the intermediate shown in the formula 1 by using an oxidant to obtain an intermediate shown in a formula 2;
C) carrying out acylation reaction on carboxyl of the intermediate shown in the formula 2 to obtain spiro-biindane tetraacylchloride shown in the formula I;
preferably, the metal halide is a chloride, bromide or iodide of the metal. Further preferably, the metal halide is aluminum bromide.
Preferably, the 2-halopropene is selected from one or more of 2-iodopropene, 2-bromopropene and 2-chloropropene.
Preferably, the condensation reaction in the step A) is carried out at the temperature of 25-60 ℃ for 48-72 h.
Preferably, after the reaction in the step A) is finished, the system is quenched by ice water, the organic phase is extracted by diethyl ether, and after drying, the crude product is obtained by reduced pressure distillation. Preferably, the crude product is purified, preferably by recrystallization from acetone to obtain a pure intermediate of formula 1.
Preferably, the oxidant in the step B) is potassium permanganate or hydrogen peroxide. The solvent for the oxidation reaction is preferably pyridine. The temperature of the oxidation reaction is preferably 80-140 ℃, and the reaction time is preferably 48-72 h. Preferably, after the reaction is finished, manganese dioxide is removed by hot filtration, the pH of the filtrate is adjusted to 1 by concentrated hydrochloric acid, and white solid is precipitated by cooling, so that the intermediate product represented by the formula 2 is a pure product.
In the present invention, the preferred acylating agent for the acylation reaction in the step C) is thionyl chloride, triphosgene, phosphorus pentachloride or oxalyl chloride.
In the preferred embodiment of the present invention, the acylation reaction in step C) may use thionyl chloride as an acylating agent. Specifically, the intermediate spirocyclic indantetracarboxylic acid shown in formula 2 and thionyl chloride are mixed and reacted, and the molar ratio of the spirocyclic indantetracarboxylic acid to the thionyl chloride is preferably 1: 1-20, more preferably 1: 1-14, most preferably 1: 8, the reaction temperature is preferably 40-150 ℃, more preferably 60-120 ℃, and most preferably 80-100 ℃, and the reaction time is preferably 2-24 hours, more preferably 3-12 hours, and most preferably 4-8 hours. The reaction of the present invention preferably includes refining steps such as reduced pressure distillation and filtration, which are not particularly limited in the present invention and can be selected and adjusted by those skilled in the art according to actual conditions and product requirements.
The reaction equation is as follows:
preferably, the step C) may also adopt a triphosgene method, specifically, under the protection of nitrogen, adding triphosgene and a solvent into a reaction vessel, slowly dropping the spiro biindane tetracarboxylic acid represented by formula 2 into a bottle in an ice bath, and preferably, slowly adding a proper amount of a catalyst. And after dripping is finished, reacting for 1-3 h in ice bath, then heating to 30-50 ℃ for reacting for a period of time, standing, filtering, and recovering the solvent to obtain the spiro-biindane tetraacylchloride product.
The reaction equation is as follows:
preferably, the step C) can also adopt a phosphorus pentachloride method, and specifically, the same amount of phosphorus pentachloride and spiro-ring diindane tetracarboxylic acid sodium shown in the formula 2 are placed in a 500mL single-neck flask; carrying out condensation reflux reaction at 170-180 ℃ for 12-15 h; and cooling, adding 1-1.5L of water and 1-1.5 kg of crushed ice, separating, washing with water once, extracting with diethyl ether, and performing reduced pressure rotary evaporation to remove the diethyl ether to obtain the product spiro-biindane tetraacylchloride.
The reaction equation is as follows:
preferably, the step C) may also adopt an oxalyl chloride method, specifically, diethyl ether is used as a solvent, a trace amount of DMF is used as a catalyst, the mixture and the spiro-biindane tetracarboxylic acid shown in formula 2 are placed in a three-neck flask, stirred at room temperature, excessive oxalyl chloride is dropwise added, the reaction is continued for 24 hours after the dropwise addition is finished, and diethyl ether and oxalyl chloride are recovered at normal pressure to obtain the spiro-biindane tetraacylchloride product.
The reaction equation is as follows:
the invention can also take spiro-biindane tetraphenol as a raw material, in particular to the spiro-biindane tetraphenol which is taken as a raw material and is processed by trifluoromethanesulfonic anhydride (Tf)2O) protection of phenolic hydroxyl group, followed by ferrocene palladium dichloride complex catalyst (Pd)2(dba)3Reaction with Zinc cyanide (Zn (CN))2) Reacting to obtain corresponding spiro-bis-indan tetracyano compound, hydrolyzing cyano group, and obtaining the final productTo form a carboxyl group by reacting a spirocyclic indane tetracarboxylic acid compound with thionyl chloride (SOCl)2) Reacting to synthesize spiro-diindane tetrachloride. Or preparing the spiro-biindane tetrachloride by any method (triphosgene method, phosphorus pentachloride method and oxalyl chloride method).
The equation for the above reaction is as follows:
the spiro-biindane tetraacylchloride prepared by the method has a three-dimensional twisted structure, and the generated polymer has a microporous characteristic, so that the spiro-biindane tetraacylchloride can be used for a separation membrane material to show higher permeability.
The invention also provides a high-flux nanofiltration composite membrane, which comprises a supporting layer and a polyamide active separation layer and/or a polyimide active separation layer compounded on the surface of the supporting layer;
the polyamide active separation layer is obtained by carrying out interfacial polymerization on the spiro-indane tetraacylchloride or the spiro-indane tetraacylchloride prepared by the preparation method and m-phenylenediamine monomers;
the polyimide active separation layer is obtained by imidizing the polyamide active separation layer.
The support layer is not particularly limited in the present invention, and may be a nanofiltration composite membrane support layer well known to those skilled in the art, and the present invention is preferably a polyetheretherketone support layer.
Preferably, the thickness of the support layer is 50 μm.
Preferably, the thickness of the polyamide active separation layer and/or the polyimide active separation layer is 80-100 nm.
The invention provides a preparation method of the high-flux nanofiltration composite membrane, which comprises the following steps:
s1) covering the surface of the supporting layer film with the aqueous solution of the m-phenylenediamine monomer, then removing the redundant aqueous solution of the m-phenylenediamine monomer, and airing to obtain a composite film;
s2) covering the surface of the composite membrane with the organic solution of the spiro-indane tetraacylchloride monomer or the spiro-indane tetraacylchloride monomer prepared by the preparation method, carrying out interfacial polymerization, and then carrying out heat treatment to obtain a polyamide composite membrane;
s3) carrying out imidization treatment on the polyamide composite membrane to obtain the high-flux nanofiltration composite membrane.
The high-flux nanofiltration composite membrane is a polyimide nanofiltration composite membrane with high flux performance.
The mass volume concentration of the m-phenylenediamine monomer aqueous solution is preferably 0.1-8%, more preferably 0.5-6%, and most preferably 1-4%; the time for covering is preferably 1min to 8min, more preferably 2min to 6min, and most preferably 4min to 5min, the covering is not particularly limited in the present invention, and the covering is defined as covering known to those skilled in the art, and can be a full covering or a partial covering film, and can be poured, soaked, smeared, or sprayed. The method also comprises the steps of removing the redundant aqueous solution of the m-phenylenediamine monomer on the surface and airing, wherein the airing time is preferably 5-10 min, more preferably 6-9 min, and most preferably 7-8 min.
The mass volume concentration of the organic solution of the spiro-biindane tetraacyl monomer is preferably 0.05-4%, more preferably 0.1-2%, and most preferably 0.2-1%, and the covering time is preferably 20 s-10 min, more preferably 1-8 min, and most preferably 2-5 min.
The temperature of the heat treatment according to the present invention is preferably 75 to 110 ℃, more preferably 80 to 100 ℃, and most preferably 85 to 95 ℃, and other conditions of the heat treatment according to the present invention are not particularly limited, and may be conditions for heat treatment of a composite film, which are well known to those skilled in the art.
The method of imidization in the present invention is not particularly limited, and may be any method known to those skilled in the art.
The imidization method is classified into a thermal imide method and a chemical imide method. The thermal imide method was to program the temperature of the film sample to 300 ℃ under nitrogen atmosphere for 2 h. When the polyimide composite membrane is prepared by the chemical imide method, a polyamide membrane is soaked in a proper amount of dehydrating agent and catalyst solution. The dehydrating agent is any one or a combination of acetic anhydride, propionic anhydride, butyric anhydride, trifluoroacetic anhydride, benzoic anhydride, 1, 3-dichlorohexylcarbodiimide, N-dicyclohexylcarbodiimide, lower aliphatic halide, halogenated lower aliphatic anhydride, arylsulfonic acid dihalide, thionyl halide and phosphorus halide. The imidization catalyst can be selected from one or more of heterocyclic tertiary amine, aliphatic tertiary amine and aromatic tertiary amine; the heterocyclic tertiary amine is preferably one or more of quinoline, isoquinoline, pyridine and the like; the aliphatic tertiary amine is preferably one or more of 1, 3-dichlorohexylcarbodiimide, triethylamine and the like; the aromatic tertiary amine is preferably N, N-dimethylaniline or the like. The dehydrating agent and the catalyst may be used alone or in combination.
The method preferably adopts a chemical imide method, specifically, a dehydrating agent and a catalyst are used for preparing an imidization solution, then a nascent composite nanofiltration membrane is immersed in the imidization solution, and after imidization is completed, the solvent-resistant composite nanofiltration membrane is obtained.
The subsequent steps of washing and the like are preferably included in the present invention, and the present invention is not particularly limited to this, and the washing method known to those skilled in the art may be adopted, and the present invention preferably washes several times with deionized water at 25-80 ℃, more preferably 30-65 ℃, and the finally obtained nanofiltration composite membrane is stored in deionized water for later use.
Compared with the prior art, the invention provides spiro-biindane tetraacylchloride which has a structure shown in a formula I. The spiro-biindane tetraacylchloride provided by the invention has a three-dimensional twisted structure, and the generated polymer has a microporous characteristic, so that the spiro-biindane tetraacylchloride can be used for a separation membrane material to show higher permeability.
Drawings
FIG. 1 is an infrared spectrum of the monomer prepared in example 1;
figure 2 is a nuclear magnetic hydrogen spectrum of the spirocyclic indane tetraacylchloride (product 3) prepared in example 1.
Detailed Description
In order to further illustrate the present invention, the following examples are provided to describe the spiro-biindane tetrachloride and the preparation method thereof, and the composite membrane and the preparation method thereof in detail.
Pure solvent flux: the volume of pure solvent per unit time per unit membrane area at a specific pressure. Can be represented by the following formula:
In the following examples, pure solvent flux test conditions were as follows: operating temperature 25 ℃, 50ppm of methanol dye solution, operating pressure 10 bar. The permeate flux of the nanofiltration membrane is expressed as the pure solvent flux at this pressure. Before the permeation flux of the nanofiltration membrane is tested, the composite membrane is pre-pressed for 8 hours under 10bar, so that the stability of test data is ensured. The composite films for each formulation were tested for 6 data and averaged.
Example 1
3,3,3',3' -tetramethyl-5, 5',6,6' -tetrachloroformyl-1, 1' -spirobiindane
The synthesis method comprises the following steps:
(1) to a three-necked flask were added o-xylene (40ml) and aluminum bromide (6.7mmol,1.8g), and the mixture was dissolved with stirring. 2-bromopropene (25.7mmol,3.1g) was added dropwise and reacted at 60 ℃ for 72 h. After the reaction was complete, it was quenched with ice water, the organic phase was extracted with diethyl ether, dried and distilled under reduced pressure to give a crude product as a brown powder, which was recrystallized from acetone to give colorless crystals 1 in 31.4% yield.
(2) 1(3mmol,1g), pyridine (27.17ml), purified water (25ml) were added to a three-necked flask. Stirring for dissolving, refluxing at 80-90 deg.C for two hours, adding potassium permanganate (10g) in batches, heating to boil, and reacting for 24 h. Manganese dioxide was removed by hot filtration, the filtrate was adjusted to pH 1 with concentrated hydrochloric acid and cooled to precipitate a white solid 2 which was weighed 1.3g after drying in 93% yield.
(3) Reacting the mixture 2 and thionyl chloride (10ml) at 80 ℃ for 3 hours; after the reaction is finished, cooling to the temperature of 25 ℃, removing most of thionyl chloride under normal pressure, distilling under reduced pressure to remove residual thionyl chloride, and recrystallizing with o-xylene to obtain 3, wherein the yield of the obtained product is 90%, and the purity is 95%.
The infrared spectrum and nuclear magnetic hydrogen spectrum detection are carried out on the obtained target product, the result is shown in figures 1-2, and figure 1 is the infrared spectrum of the monomer prepared in the embodiment 1 of the invention. As is clear from fig. 1, the product 2 is 3,3,3',3' -tetramethyl-5, 5',6,6' -tetracarboxyl-1, 1 '-spirobiindane, and the product 3 is the desired product, 3,3',3 '-tetramethyl-5, 5',6,6 '-tetrachloroformyl-1, 1' -spirobiindane. FIG. 2 shows the nuclear magnetic hydrogen spectrum of 3,3,3',3' -tetramethyl-5, 5',6,6' -tetrachloroformyl-1, 1' -spirobiindane.
Example 2
3,3,3',3' -tetramethyl-5, 5',6,6' -tetrachloroformyl-1, 1' -spirobiindane
Compound 2 prepared in example 1 was reacted with thionyl chloride (15ml) in admixture, one drop of DMF was added dropwise at a reaction temperature of 100 ℃ for 1 hour; after the reaction is finished, cooling to the temperature of 25 ℃, removing most of thionyl chloride under normal pressure, distilling under reduced pressure to remove residual thionyl chloride, and recrystallizing with o-xylene to obtain 3, wherein the yield of the obtained product is 92% and the purity is 96%.
Example 3
3,3,3',3' -tetramethyl-5, 5',6,6' -tetrachloroformyl-1, 1' -spirobiindane
Compound 2 prepared in example 1 was reacted with thionyl chloride (20ml) in admixture, one drop of DMF was added dropwise at a reaction temperature of 60 ℃ for 6 hours; after the reaction is finished, cooling to the temperature of 25 ℃, removing most of thionyl chloride under normal pressure, distilling under reduced pressure to remove residual thionyl chloride, and recrystallizing with o-xylene to obtain 3, wherein the yield of the obtained product is 87%, and the purity is 95%.
Example 4
Description of the procedure for preparing an interfacial polymerization film by reacting the acid chloride monomer prepared in example 1 with m-phenylenediamine
An aqueous solution of m-phenylenediamine with a mass volume concentration (g/ml) of 2% was poured onto the surface of a polyetheretherketone support film and held for 4 min. Then pouring off the redundant m-phenylenediamine solution on the surface of the support membrane, wiping off obvious water drops on the surface of the membrane by using filter paper, and airing for 7min in the air. Then, Isopar G/o-xylene solution of 3,3,3',3' -tetramethyl-5, 5',6,6' -tetrachloroformyl-1, 1' -spirobiindane with a mass volume concentration (G/ml) of 0.1% was poured onto the membrane surface to carry out interfacial polymerization, wherein Isopar G/o-xylene was 1, and the reaction time was 5 min. And finally, the prepared composite membrane is placed in a blowing oven at 90 ℃ for treatment for 6 min. Soaking the prepared polyamide composite membrane in a mixed solvent of a proper amount of acetic anhydride, 1, 3-dichlorohexylcarbodiimide and triethylamine for 2 hours to obtain the polyimide composite membrane, and washing with ethanol and clean water for later use.
Example 5
A nanofiltration membrane was prepared by reacting 3,3,3',3' -tetramethyl-5, 5',6,6' -tetrachloroformyl-1, 1' -spirobiindane obtained in example 1 with m-phenylenediamine. The mass concentration (g/ml) of the spiro-biindane tetraacyl chloride monomer is 0.2%. Other films were prepared under the same conditions as in example 4.
Example 6
The nanofiltration membrane is prepared by reacting the 3,3,3',3' -tetramethyl-5, 5',6,6' -tetrachloroformyl-1, 1' -spirobiindane prepared in example 1 with m-phenylenediamine. The mass concentration (g/ml) of the spiro-biindane tetraacyl chloride monomer is 0.3%. Other films were prepared under the same conditions as in example 4.
Example 7
A nanofiltration membrane was prepared by reacting 3,3,3',3' -tetramethyl-5, 5',6,6' -tetrachloroformyl-1, 1' -spirobiindane obtained in example 1 with m-phenylenediamine. The mass concentration (g/ml) of the spiro-biindane tetraacyl monomer is 0.4%. Other films were prepared under the same conditions as in example 4.
Example 8
A nanofiltration membrane was prepared by reacting 3,3,3',3' -tetramethyl-5, 5',6,6' -tetrachloroformyl-1, 1' -spirobiindane obtained in example 1 with m-phenylenediamine. The mass concentration (g/ml) of the spiro-biindane tetraacyl chloride monomer is 0.5%. Other films were prepared under the same conditions as in example 4.
Example 9
A nanofiltration membrane was prepared by reacting 3,3,3',3' -tetramethyl-5, 5',6,6' -tetrachloroformyl-1, 1' -spirobiindane obtained in example 1 with m-phenylenediamine. The mass concentration (g/ml) of the spiro-biindane tetraacyl chloride monomer is 0.6%. Other films were prepared under the same conditions as in example 4.
Example 10
A nanofiltration membrane was prepared by reacting 3,3,3',3' -tetramethyl-5, 5',6,6' -tetrachloroformyl-1, 1' -spirobiindane obtained in example 1 with m-phenylenediamine. The mass concentration (g/ml) of the spiro-biindane tetraacyl chloride monomer is 0.8%. Other films were prepared under the same conditions as in example 4.
Comparative example 1
An aqueous solution of m-phenylenediamine with a mass volume concentration (g/ml) of 2% was poured onto the surface of a polyetheretherketone support film and held for 4 min. Then pouring off the redundant m-phenylenediamine solution on the surface of the support membrane, wiping off obvious water drops on the surface of the membrane by using filter paper, and airing for 7min in the air. Then Isopar G solution of 1% by mass/volume (G/ml) of trimesoyl chloride was poured onto the membrane surface for interfacial polymerization for 40 s. And finally, the prepared composite membrane is placed in a blowing oven at 90 ℃ for treatment for 5 min. Washing with 40 deg.C deionized water for several times, and storing in deionized water for use.
The following reaction formula 2 is a structure of polyamide generated by reacting spiro-dichloroindane tetrachloride with m-phenylenediamine, and the reaction formula 1 is a molecular structure of polyamide generated by reacting trimesoyl chloride with m-phenylenediamine, and it can be seen that compared with the structure of conventional polyamide (PA/TMC), PA/TAC-TSBI and PI/TAC-TSBI have large space distortion degree, strong rigidity, large free volume and microporous characteristics.
1.
2.
The nanofiltration membranes prepared in examples 4 to 10 and comparative example 1 were subjected to permeability detection, and the results are shown in table 1:
TABLE 1 organic solvent permeation performance of Polyamide and polyimide membranes prepared based on the interfacial polymerization of Spirocyclic indane tetrachloride with m-phenylenediamine
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A spiro-biindane tetraacyl chloride has a structure shown in formula I:
wherein R is H, CH3-、CH3CH2-or CH3(CH2)nCH2-；
n is an integer of 1 to 20.
2. The spirocyclic indane tetraacylchloride according to claim 1, characterized by the structure of formula i-a:
wherein R is H, CH3-、CH3CH2-or CH3(CH2)nCH2-；
n is an integer of 1 to 20.
3. A process for the preparation of a spirocyclic indane tetraacyl chloride according to any one of claims 1-2, comprising the steps of:
A) benzene or dialkyl benzene is used as a raw material and is subjected to condensation reaction with 2-halopropene under the condition that metal halide is used as a catalyst to obtain an intermediate shown in a formula 1;
B) carrying out oxidation reaction on the intermediate shown in the formula 1 by using an oxidant to obtain an intermediate shown in a formula 2;
C) carrying out acylation reaction on carboxyl of the intermediate shown in the formula 2 to obtain spiro-biindane tetraacylchloride shown in the formula I;
wherein R is H, CH3-、CH3CH2-or CH3(CH2)nCH2-；
n is an integer of 1 to 20.
4. The method of claim 3, wherein the metal halide is selected from the group consisting of aluminum bromide;
the 2-halopropene is selected from one or more of 2-iodopropene, 2-bromopropene and 2-chloropropene;
the oxidant in the step B) is potassium permanganate or hydrogen peroxide.
5. The method according to claim 3, wherein the acylating agent used in the step C) is thionyl chloride, triphosgene, phosphorus pentachloride or oxalyl chloride.
6. Use of the spirocyclic indane tetraacylchloride according to any one of claims 1 to 2 or the spirocyclic indane tetraacylchloride prepared by the preparation method according to any one of claims 3 to 5 as a polymerization monomer for preparing microporous polymers and separation membrane materials.
7. A high flux nanofiltration composite membrane comprises a supporting layer and a polyamide active separation layer and/or a polyimide active separation layer compounded on the surface of the supporting layer;
the polyamide active separation layer is obtained by carrying out interfacial polymerization on the spiro-indane tetrachloride as defined in any one of claims 1 to 2 or the spiro-indane tetrachloride prepared by the preparation method as defined in any one of claims 3 to 5 and m-phenylenediamine monomers;
the polyimide active separation layer is obtained by imidizing the polyamide active separation layer.
8. The high-throughput nanofiltration composite membrane according to claim 7, wherein the support layer is a polyetheretherketone support layer.
9. The preparation method of the high-flux nanofiltration composite membrane of any one of claims 7 to 8, comprising the following steps:
s1) covering the surface of the supporting layer film with the aqueous solution of the m-phenylenediamine monomer, removing the redundant aqueous solution of the m-phenylenediamine monomer, and airing to obtain a composite film;
s2) covering the organic solution of the spiro-indane tetraacylchloride monomer prepared by the preparation method of any one of claims 1 to 2 or 3 to 5 on the surface of the composite film, carrying out interfacial polymerization, and then carrying out heat treatment to obtain a polyamide composite film;
s3) carrying out imidization treatment on the polyamide composite membrane to obtain the high-flux nanofiltration composite membrane.
10. The preparation method according to claim 9, wherein the organic solvent in the organic solution of the spirocyclic indane tetraacylchloride monomer is Isopar G/o-xylene mixed solution;
the temperature of the heat treatment is 75-110 ℃.
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