CN114656356B - Spiro biindane tetraacyl chloride and preparation method thereof, and composite membrane and preparation method thereof - Google Patents
Spiro biindane tetraacyl chloride and preparation method thereof, and composite membrane and preparation method thereof Download PDFInfo
- Publication number
- CN114656356B CN114656356B CN202210310154.5A CN202210310154A CN114656356B CN 114656356 B CN114656356 B CN 114656356B CN 202210310154 A CN202210310154 A CN 202210310154A CN 114656356 B CN114656356 B CN 114656356B
- Authority
- CN
- China
- Prior art keywords
- composite membrane
- chloride
- biindane
- monomer
- phenylenediamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/33—Polycyclic acids
- C07C63/49—Polycyclic acids containing rings other than six-membered aromatic rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/93—Spiro compounds
- C07C2603/94—Spiro compounds containing "free" spiro atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides spiro biindane tetraacyl chloride which has a structure shown in a formula I. The spiro biindane tetraacyl chloride provided by the invention has a three-dimensional torsion structure, and the generated polymer has self-contained micropore characteristics and can show higher permeability when used for separation membrane materials.
Description
Technical Field
The invention relates to the technical field of synthetic chemistry, in particular to spiro biindane tetraacyl chloride, a preparation method thereof, a composite membrane and a preparation method thereof.
Background
The polyacyl chloride is an important chemical raw material, is mainly used for preparing polyamide, polyester, polyimide and other materials or films, and has wide application in the separation and adsorption fields, such as gas separation membranes, organic solvent nanofiltration membranes, microporous adsorption media and the like.
The method for synthesizing the polybasic acyl chloride monomer comprises the step of reacting polybasic carboxylic acid with an acylating agent to obtain the acyl chloride monomer. The acylating agent is selected from one or more of thionyl chloride, oxalyl chloride, triphosgene and phosphorus pentachloride. In 2005, zhou Yong et al synthesized 5-oxo-isopeptidoyl chloride (CFIC), 5-isocyanatoisopeptidoyl chloride (ICIC) and other acyl chloride monomers using triphosgene (e.g., desalination,2005,180,189-196;Journal of Membrane Science,2006,270,162-168; desalination,2006,192, 182-189). In 2009, li Lei, a plurality of polybasic acyl chlorides containing biphenyl structures were prepared by a method of Suzuki coupling and Ni (0) catalytic coupling and thionyl chloride: 3,4, 5-biphenyltriacyl chloride, 3', 5' -biphenyltetra-acyl chloride, 2', 4' -biphenyltetra-acyl chloride (e.g., document Journal of Membrane Science,2007,289 (1/2): 258-267;Journal of Membrane Science,2008,315 (1-2): 20-27;Journal of Membrane Science,2009,335 (1-2): 133-139). Wang Tun in 2013, 2, 4', 6-biphenyltetra-acyl chloride, 2,3',4,5', 6-biphenylpenta-acyl chloride, and 2,2', 4', 6' -biphenylhexa-acyl chloride were synthesized (e.g., document Journal of Membrane Science,2013,440: 48-57).
However, the polymers generated by the existing polybasic acyl chlorides (such as trimesic chloride and biphenyl tetra-acyl chloride) have no micropore characteristic, and the molecular chains are effectively stacked, and the free volume is smaller, so that the densely stacked structure of the polymer film prevents gas and organic solvent from passing through.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a spiro biindane tetraacyl chloride, a preparation method thereof, a composite membrane and a preparation method thereof, wherein the prepared spiro biindane tetraacyl chloride is used as a separation membrane material, and the permeability of the separation membrane can be improved.
The invention provides spiro biindane tetraacyl chloride which has a structure shown in a formula I:
wherein R is H, CH 3 -、CH 3 CH 2 -or CH 3 (CH 2 ) n CH 2 -；
n is an integer of 1 to 20.
Preferably, the spiro biindane tetraacyl chloride has the structure shown in formula I-a:
wherein R is H, CH 3 -、CH 3 CH 2 -or CH 3 (CH 2 ) n CH 2 -；
n is an integer of 1 to 20.
Further preferably, said R is CH 3 -。
The invention discloses a preparation method of the spiro biindane tetraacyl chloride, which comprises the following steps:
a) Benzene or dialkylbenzene is used as a raw material, and condensation reaction is carried out with 2-halopropene under the condition of taking metal halide as a catalyst, so as to obtain an intermediate shown in a formula 1;
b) Oxidizing the intermediate shown in the formula 1 by adopting an oxidant to obtain an intermediate shown in the formula 2;
c) Acylating the carboxyl of the intermediate shown in the formula 2 to obtain spiro biindane tetraacyl chloride shown in the formula I;
preferably, the metal halide is chloride, bromide or iodide of metal. Further preferably, the metal halide is aluminum bromide.
Preferably, the 2-halopropene is selected from one or more of 2-iodopropylene, 2-bromopropene and 2-chloropropene.
In the preferred embodiment of the present invention, the temperature of the condensation reaction in the step A) is 25-60 ℃ and the reaction time is 48-72 hours.
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 the crude product is obtained by reduced pressure distillation after drying. Preferably, the crude product is purified, preferably by recrystallization from acetone, to yield the 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 be 1 by concentrated hydrochloric acid, and white solid is separated out by cooling, so that the intermediate pure product shown in the formula 2 is obtained.
Preferably, the acylating agent for the acylation reaction in the step C) is thionyl chloride, triphosgene, phosphorus pentachloride or oxalyl chloride.
In a preferred embodiment of the present invention, the acylation reaction in the step C) may use thionyl chloride as an acylating agent. Specifically, the intermediate of spiro biindane tetracarboxylic acid shown in formula 2 and thionyl chloride are mixed for reaction, and the molar ratio of spiro biindane tetracarboxylic acid to thionyl chloride is preferably 1:1 to 20, more preferably 1:1 to 14, most preferably 1:8, the reaction temperature is preferably 40 to 150 ℃, more preferably 60 to 120 ℃, most preferably 80 to 100 ℃, and the reaction time is preferably 2 to 24 hours, more preferably 3 to 12 hours, most preferably 4 to 8 hours. The reaction of the present invention is preferably followed by purification steps such as distillation under reduced pressure and filtration, and the present invention is not particularly limited thereto, and those skilled in the art can select and adjust the reaction according to the actual conditions and the requirements of the product.
The reaction equation is as follows:
in the preferred embodiment of the present invention, the step C) may be performed by a triphosgene method, specifically, triphosgene and a solvent are added into a reaction vessel under the protection of nitrogen, and the spirocyclic biindane tetracarboxylic acid represented by formula 2 is slowly dropped into a bottle in an ice bath, preferably, a proper amount of catalyst is slowly added. After dripping, the mixture reacts for 1 to 3 hours in ice bath, then the temperature is raised to 30 to 50 ℃ for reacting for a period of time, standing and filtering are carried out, and the solvent is recovered to obtain the spirobiindane tetraacyl chloride product.
The reaction equation is as follows:
in the preferred embodiment of the present invention, the step C) may be performed by a phosphorus pentachloride method, specifically, placing equal amounts of phosphorus pentachloride and sodium spirobiindane tetracarboxylic acid represented by formula 2 in a 500mL single-neck flask; condensing and refluxing at 170-180 ℃ for 12-15 h; 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 removing diethyl ether by reduced pressure rotary evaporation to obtain the product spirocyclic biindan tetraacyl chloride.
The reaction equation is as follows:
in the preferred embodiment of the invention, the step C) can also adopt a oxalyl chloride method, specifically, diethyl ether is adopted as a solvent, a trace of DMF is adopted as a catalyst, the spirobiindan tetracarboxylic acid shown in the formula 2 and the spirobiindan tetracarboxylic acid are placed in a three-mouth bottle, stirred at room temperature, dropwise added with excessive oxalyl chloride, continuously reacted for 24 hours after the dropwise addition is finished, and diethyl ether and oxalyl chloride are recovered at normal pressure to obtain the spirobiindan tetrachloride product.
The reaction equation is as follows:
the invention can also take spiro biindane tetraphenol as raw material, concretely, takes spiro biindane tetraphenol as raw material, and uses trifluoro methanesulfonic anhydride (Tf) 2 O) protection of phenolic hydroxyl groups, followed by ferrocene palladium dichloride complex catalyst (Pd 2 (dba) 3 Under the action of dppf, with zinc cyanide (Zn (CN) 2 ) The corresponding spirobiindane tetracyano compound can be prepared by reaction, cyano groups can be hydrolyzed to generate carboxyl groups, and the spirobiindane tetracarboxyl compound and thionyl chloride (SOCl) 2 ) And (3) reacting to synthesize the spiro biindane tetraacyl chloride. Or preparing the spiro biindane tetraoyl chloride by any method (triphosgene method, phosphorus pentachloride method and oxalyl chloride method).
The equation for the above reaction is as follows:
the spiro biindane tetraacyl chloride prepared by the invention has a three-dimensional torsion structure, and the generated polymer has self-microporous characteristics and can show higher permeability when used for separation membrane materials.
The invention also provides a high-flux nanofiltration composite membrane, which comprises a support layer and a polyamide active separation layer and/or a polyimide active separation layer which are compounded on the surface of the support layer;
the polyamide active separation layer is prepared from the spiro biindane tetraacyl chloride or the spiro biindane tetraacyl chloride prepared by the preparation method and m-phenylenediamine monomer through interfacial polymerization;
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 polyether ether ketone support layer.
In the present invention, the thickness of the support layer is preferably 50 μm.
In the present invention, the thickness of the polyamide active separation layer and/or the polyimide active separation layer is preferably 80 to 100nm.
The invention provides a preparation method of the high-flux nanofiltration composite membrane, which comprises the following steps:
s1) covering the surface of a support layer film with an aqueous solution of m-phenylenediamine monomer, removing the excessive aqueous solution of m-phenylenediamine monomer, and airing to obtain a composite film;
s2) covering the surface of the composite film with an organic solution of the spiro biindane tetraacyl chloride or the spiro biindane tetraacyl chloride monomer prepared by the preparation method, performing interfacial polymerization, and then performing 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.
The high-flux nanofiltration composite membrane provided by the invention is a polyimide nanofiltration composite membrane with high flux performance.
The mass volume concentration of the aqueous solution of the m-phenylenediamine monomer is preferably 0.1-8%, more preferably 0.5-6%, and most preferably 1-4%; the covering time is preferably 1min to 8min, more preferably 2min to 6min, and most preferably 4min to 5min, and the covering is not particularly limited, and the covering is defined by covering known to those skilled in the art, and may be a full covering or a partial covering of the surface of the film, and may be pouring, soaking, smearing or spraying. The method also removes the superfluous aqueous solution of m-phenylenediamine monomer on the surface and dries the m-phenylenediamine monomer for 5 to 10 minutes, more preferably 6 to 9 minutes and most preferably 7 to 8 minutes.
The mass volume concentration of the organic solution of the spirobiindane tetraacyl chloride monomer is preferably 0.05% -4%, more preferably 0.1% -2%, most preferably 0.2% -1%, the covering time is preferably 20 s-10 min, more preferably 1 min-8 min, most preferably 2 min-5 min, the solvent of the organic solution is not particularly limited, the solvent for mixing the acyl chloride monomer is well known to those skilled in the art, the mixing ratio of the organic solution is preferably Isopar G/o-xylene mixed solution, and the mixing ratio can be adjusted according to practical situations by those skilled in the art.
The temperature of the heat treatment in the present invention is preferably 75 to 110 ℃, more preferably 80 to 100 ℃, and most preferably 85 to 95 ℃, and the other conditions of the heat treatment are not particularly limited in the present invention, and the conditions of the heat treatment of the composite film known to those skilled in the art may be used.
The method of imidization according to the present invention is not particularly limited, and may be imidization methods well known to those skilled in the art.
Imidization methods are classified into a thermal imidization method and a chemical imidization method. The thermal imide method was to program the film sample to 300 ℃ under nitrogen atmosphere and hold for 2 hours. When preparing the polyimide composite film by the chemical imide method, the polyamide film 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-dicyclohexylcarbodiimide, N-dicyclohexylcarbodiimide, lower aliphatic halide, halogenated lower aliphatic acid anhydride, aryl sulfonic acid dihalide, thionyl halide and phosphorous 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-dichloro-hexyl-carbodiimide, triethylamine and the like; the aromatic tertiary amine is preferably N, N-dimethylaniline or the like. The above-mentioned dehydrating agent and catalyst may be used alone or in combination.
The invention preferably adopts a chemical imidization method, specifically uses a dehydrating agent and a catalyst to prepare imidization solution, and then immerses the nascent composite nanofiltration membrane into the imidization solution to obtain the solvent-resistant composite nanofiltration membrane after imidization is completed.
The subsequent steps of cleaning and the like are also preferably included, the method is not particularly limited, the method is carried out in a cleaning mode well known to a person skilled in the art, deionized water with the temperature of 25-80 ℃ is preferably adopted for cleaning for a plurality of times, more preferably 30-65 ℃, and finally the obtained nanofiltration composite membrane is stored in the deionized water for standby.
Compared with the prior art, the invention provides spiro biindane tetraacyl chloride which has a structure shown in a formula I. The spiro biindane tetraacyl chloride provided by the invention has a three-dimensional torsion structure, and the generated polymer has self-contained micropore characteristics and can show higher permeability when used for separation membrane materials.
Drawings
FIG. 1 is an infrared spectrum of the monomer prepared in example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of spiro biindane tetraacyl chloride (product 3) prepared in example 1.
Detailed Description
In order to further illustrate the present invention, the spiro biindane tetraacyl chloride and the preparation method thereof, the composite membrane and the preparation method thereof provided by the present invention are described in detail below with reference to examples.
Pure solvent flux: at a specific pressure, a unit of time passes through a unit of volume of pure solvent per membrane area. Can be represented by the following formula:
volume of (V (L) -penetrating solvent, A (m) 2 ) Effective area of the membrane, t (h) -time, P (bar) -pressure
In the following examples, the pure solvent flux test conditions are as follows: operating temperature 25 ℃,50ppm methanol dye solution, operating pressure 10 bar. The flux of permeation of nanofiltration membranes is expressed as the flux of pure solvent at that 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 film for each formulation was tested for 6 data and averaged.
Example 1
3,3 '-tetramethyl-5, 5',6 '-tetrachloroformyl-1, 1' -spirobiindane
The synthesis method comprises the following steps:
(1) To a three-necked flask was added o-xylene (40 ml), aluminum bromide (6.7 mmol,1.8 g) and dissolved by stirring. 2-bromopropene (25.7 mmol,3.1 g) was added dropwise thereto and reacted at 60℃for 72 hours. After the reaction, quenching with ice water, extracting the organic phase with diethyl ether, drying, distilling under reduced pressure to obtain crude product brown powder, and recrystallizing with acetone to obtain colorless crystal 1 with a yield of 31.4%.
(2) 1 (3 mmol,1 g), pyridine (27.17 ml) and purified water (25 ml) were added to a three-necked flask. Stirring and dissolving, refluxing for two hours at 80-90 ℃, adding potassium permanganate (10 g) in batches, heating to boiling, and reacting for 24 hours. Manganese dioxide is removed by hot filtration, the pH of the filtrate is adjusted to 1 by concentrated hydrochloric acid, white solid 2 is separated out by cooling, 1.3g of the white solid is weighed after drying, and the yield is 93%.
(3) Mixing 2 with thionyl chloride (10 ml) for reaction at 80 ℃ for 3 hours; after the reaction is completed, cooling to 25 ℃, removing most thionyl chloride at normal pressure, removing residual thionyl chloride by reduced pressure distillation, and recrystallizing with o-xylene to obtain 3, wherein the yield of the obtained product is 90% and the purity is 95%.
The obtained target product is subjected to infrared spectrum and nuclear magnetic hydrogen spectrum detection, the results are shown in figures 1-2, and figure 1 is an infrared spectrum of the monomer prepared in the embodiment 1 of the invention. As can be seen from FIG. 1, product 2 is 3,3 '-tetramethyl-5, 5',6 '-tetracarboxylic-1, 1' -spirobiindane, the product 3 is the target product 3,3 '-tetramethyl-5, 5',6 '-tetrachloroformyl-1, 1' -spirobiindane. FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of 3,3 '-tetramethyl-5, 5',6 '-tetrachloroformyl-1, 1' -spirobiindane.
Example 2
3,3 '-tetramethyl-5, 5',6 '-tetrachloroformyl-1, 1' -spirobiindane
The compound 2 prepared in example 1 was reacted with thionyl chloride (15 ml) in a mixture, and one drop of DMF was added dropwise at a temperature of 100℃for 1 hour; after the reaction is completed, cooling to 25 ℃, removing most thionyl chloride at normal pressure, removing residual thionyl chloride by reduced pressure distillation, 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 '-tetramethyl-5, 5',6 '-tetrachloroformyl-1, 1' -spirobiindane
The compound 2 prepared in example 1 was reacted with thionyl chloride (20 ml) in a mixture, and one drop of DMF was added dropwise at a temperature of 60℃for 6 hours; after the reaction is completed, cooling to 25 ℃, removing most thionyl chloride at normal pressure, removing residual thionyl chloride by reduced pressure distillation, 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 having a mass volume concentration (g/ml) of 2% was poured onto the surface of the polyether-ether-ketone support layer membrane and held for 4 minutes. And then pouring out 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 the membrane in the air for 7min. Thereafter, an Isopar G/o-xylene solution of 3,3 '-tetramethyl-5, 5',6 '-tetrachloroformyl-1, 1' -spirobiindane having a mass volume concentration (G/ml) of 0.1% was poured onto the membrane surface for interfacial polymerization, wherein Isopar G/o-xylene=1, and the reaction time was 5min. Finally, the prepared composite film is placed in a blast oven at 90 ℃ for 6min. And (3) soaking the prepared polyamide composite membrane in a proper amount of mixed solvent of acetic anhydride, 1, 3-dichloro-hexyl carbodiimide and triethylamine for 2 hours to obtain the polyimide composite membrane, and flushing the polyimide composite membrane with ethanol and clear water for later use.
Example 5
Nanofiltration membranes were prepared by reacting 3,3 '-tetramethyl-5, 5',6 '-tetrachloroformyl-1, 1' -spirobiindane prepared in example 1 with m-phenylenediamine. The mass concentration (g/ml) of the spirocyclic biindane tetraacyl chloride monomer is 0.2%. Other films were prepared under the same conditions as in example 4.
Example 6
Nanofiltration membranes were prepared by reacting 3,3 '-tetramethyl-5, 5',6 '-tetrachloroformyl-1, 1' -spirobiindane prepared in example 1 with m-phenylenediamine. The mass concentration (g/ml) of the spirocyclic biindane tetraacyl chloride monomer is 0.3%. Other films were prepared under the same conditions as in example 4.
Example 7
Nanofiltration membranes were prepared by reacting 3,3 '-tetramethyl-5, 5',6 '-tetrachloroformyl-1, 1' -spirobiindane prepared in example 1 with m-phenylenediamine. The mass concentration (g/ml) of the spirocyclic biindane tetraacyl chloride monomer is 0.4%. Other films were prepared under the same conditions as in example 4.
Example 8
Nanofiltration membranes were prepared by reacting 3,3 '-tetramethyl-5, 5',6 '-tetrachloroformyl-1, 1' -spirobiindane prepared in example 1 with m-phenylenediamine. The mass concentration (g/ml) of the spirocyclic biindane tetraacyl chloride monomer is 0.5%. Other films were prepared under the same conditions as in example 4.
Example 9
Nanofiltration membranes were prepared by reacting 3,3 '-tetramethyl-5, 5',6 '-tetrachloroformyl-1, 1' -spirobiindane prepared in example 1 with m-phenylenediamine. The mass concentration (g/ml) of the spirocyclic biindane tetraacyl chloride monomer is 0.6%. Other films were prepared under the same conditions as in example 4.
Example 10
Nanofiltration membranes were prepared by reacting 3,3 '-tetramethyl-5, 5',6 '-tetrachloroformyl-1, 1' -spirobiindane prepared in example 1 with m-phenylenediamine. The mass concentration (g/ml) of the spirocyclic 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 having a mass volume concentration (g/ml) of 2% was poured onto the surface of the polyether-ether-ketone support layer membrane and held for 4 minutes. And then pouring out 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 the membrane in the air for 7min. Thereafter, isopar G solution of trimesic chloride having a mass/volume concentration (G/ml) of 1% was poured onto the film surface for interfacial polymerization for 40 seconds. Finally, the prepared composite film is placed in a blast oven at 90 ℃ for 5min. Washing with 40deg.C deionized water for several times, and storing in deionized water for use.
The following reaction formula 2 is the structure of polyamide generated by the reaction of spiro biindane tetraacyl chloride and m-phenylenediamine, and the reaction formula 1 is the molecular structure of polyamide generated by the reaction of trimesoyl chloride and m-phenylenediamine, and it can be seen that compared with the structure of traditional polyamide (PA/TMC), the spatial distortion degree of PA/TAC-TSBI and PI/TAC-TSBI is large, the rigidity is strong, the free volume is large, and the microporous characteristic is provided.
1.
2.
The nanofiltration membranes prepared in examples 4 to 10 and comparative example 1 were subjected to permeation performance measurement, and the results are shown in table 1:
TABLE 1 organic solvent permeation Properties of Polyamide films and polyimide films prepared based on the interfacial polymerization of spirobiindane tetraoyl chloride with m-phenylenediamine
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (4)
1. A high-flux nanofiltration composite membrane comprises a support layer and a polyamide active separation layer and/or a polyimide active separation layer which are compounded on the surface of the support layer;
the polyamide active separation layer is prepared by interfacial polymerization of spiro biindane tetraoyl chloride with a structure shown in a formula I-a and m-phenylenediamine monomers;
the polyimide active separation layer is obtained by imidizing the polyamide active separation layer;
wherein R is CH 3 -；
The preparation method of the high-flux nanofiltration composite membrane comprises the following steps:
s1) covering the surface of a support layer film with an aqueous solution of m-phenylenediamine monomer, removing the excessive aqueous solution of m-phenylenediamine monomer, and airing to obtain a composite film;
s2) covering an organic solution of a spiro biindane tetraacyl chloride monomer on the surface of the composite membrane, performing interfacial polymerization, and then performing heat treatment to obtain a polyamide composite membrane;
s3) carrying out imidization treatment on the polyamide composite membrane to obtain a high-flux nanofiltration composite membrane;
the concentration of the aqueous solution of the m-phenylenediamine monomer is 2%g/mL;
the concentration of the organic solution of the spirocyclic biindane tetraacyl chloride monomer is 0.1% or 0.2% g/mL.
2. The high flux nanofiltration composite membrane of claim 1, wherein the support layer is a polyetheretherketone support layer.
3. The method for preparing the high-flux nanofiltration composite membrane according to any one of claims 1 to 2, comprising the following steps:
s1) covering the surface of a support layer film with an aqueous solution of m-phenylenediamine monomer, removing the excessive aqueous solution of m-phenylenediamine monomer, and airing to obtain a composite film;
s2) covering an organic solution of a spiro biindane tetraacyl chloride monomer on the surface of the composite membrane, performing interfacial polymerization, and then performing heat treatment to obtain a polyamide composite membrane;
s3) carrying out imidization treatment on the polyamide composite membrane to obtain a high-flux nanofiltration composite membrane;
the concentration of the aqueous solution of the m-phenylenediamine monomer is 2%g/mL;
the concentration of the organic solution of the spirocyclic biindane tetraacyl chloride monomer is 0.1% or 0.2% g/mL.
4. A process according to claim 3, wherein the organic solvent in the organic solution of the spirocyclic biindane tetraacyl chloride monomer is Isopar G/o-xylene mixed solution;
the temperature of the heat treatment is 75-110 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210310154.5A CN114656356B (en) | 2022-03-28 | 2022-03-28 | Spiro biindane tetraacyl chloride and preparation method thereof, and composite membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210310154.5A CN114656356B (en) | 2022-03-28 | 2022-03-28 | Spiro biindane tetraacyl chloride and preparation method thereof, and composite membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114656356A CN114656356A (en) | 2022-06-24 |
| CN114656356B true CN114656356B (en) | 2023-10-13 |
Family
ID=82033444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210310154.5A Active CN114656356B (en) | 2022-03-28 | 2022-03-28 | Spiro biindane tetraacyl chloride and preparation method thereof, and composite membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114656356B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09143146A (en) * | 1995-11-24 | 1997-06-03 | Mitsui Toatsu Chem Inc | Spiroindanephenolsufonic ester and its use |
| CN101332415A (en) * | 2008-07-31 | 2008-12-31 | 中国科学院长春应用化学研究所 | Polyamide reverse osmosis composite membrane containing biphenyl structure and production method thereof |
| WO2013057492A1 (en) * | 2011-10-18 | 2013-04-25 | Imperial Innovations Limited | Membranes for separation |
| CN103143271A (en) * | 2013-03-20 | 2013-06-12 | 中国科学院长春应用化学研究所 | Reverse osmosis complex membrane and preparation method thereof |
| CN104470628A (en) * | 2012-07-19 | 2015-03-25 | 陶氏环球技术有限责任公司 | Thin film composite membrane derived from tetrafunctional acyl halide monomer |
| CN105566383A (en) * | 2015-12-25 | 2016-05-11 | 中国科学院长春应用化学研究所 | Acyl chloride monomer and preparation method thereof and reverse osmosis composite membrane and preparation method thereof |
| CN107176963A (en) * | 2017-07-04 | 2017-09-19 | 中国科学院长春应用化学研究所 | A kind of preparation method of phosphonic chloride monomer, Nano filtering composite membrane and Nano filtering composite membrane |
| CN111821861A (en) * | 2020-08-21 | 2020-10-27 | 烟台大学 | Method for preparing high-flux organic solvent nanofiltration membrane by star-shaped molecular compound |
| CN113634136A (en) * | 2020-05-11 | 2021-11-12 | 中国石油化工股份有限公司 | Nanofiltration membrane and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108452689A (en) * | 2017-03-06 | 2018-08-28 | 青岛致用新材料科技有限公司 | Highly selective full alicyclic polyamide NF membrane of one kind and preparation method thereof |
-
2022
- 2022-03-28 CN CN202210310154.5A patent/CN114656356B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09143146A (en) * | 1995-11-24 | 1997-06-03 | Mitsui Toatsu Chem Inc | Spiroindanephenolsufonic ester and its use |
| CN101332415A (en) * | 2008-07-31 | 2008-12-31 | 中国科学院长春应用化学研究所 | Polyamide reverse osmosis composite membrane containing biphenyl structure and production method thereof |
| WO2013057492A1 (en) * | 2011-10-18 | 2013-04-25 | Imperial Innovations Limited | Membranes for separation |
| CN104010718A (en) * | 2011-10-18 | 2014-08-27 | 帝国创新有限公司 | Membranes for separation |
| CN108176258A (en) * | 2011-10-18 | 2018-06-19 | 帝国创新有限公司 | For the film of separation |
| CN104470628A (en) * | 2012-07-19 | 2015-03-25 | 陶氏环球技术有限责任公司 | Thin film composite membrane derived from tetrafunctional acyl halide monomer |
| CN103143271A (en) * | 2013-03-20 | 2013-06-12 | 中国科学院长春应用化学研究所 | Reverse osmosis complex membrane and preparation method thereof |
| CN105566383A (en) * | 2015-12-25 | 2016-05-11 | 中国科学院长春应用化学研究所 | Acyl chloride monomer and preparation method thereof and reverse osmosis composite membrane and preparation method thereof |
| CN107176963A (en) * | 2017-07-04 | 2017-09-19 | 中国科学院长春应用化学研究所 | A kind of preparation method of phosphonic chloride monomer, Nano filtering composite membrane and Nano filtering composite membrane |
| CN113634136A (en) * | 2020-05-11 | 2021-11-12 | 中国石油化工股份有限公司 | Nanofiltration membrane and preparation method and application thereof |
| CN111821861A (en) * | 2020-08-21 | 2020-10-27 | 烟台大学 | Method for preparing high-flux organic solvent nanofiltration membrane by star-shaped molecular compound |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis and gas permeation properties of novel spirobisindane-based polyimides of intrinsic microporosity;Yulia Rogan et al.;《Polymer Chemistry》;20131231;第4卷;第3813–3820页 * |
| 詹茂盛等.公知常识1.《聚酰亚胺泡沫材料》.北京：国防工业出版社,2018,第302页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114656356A (en) | 2022-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Synthesis and properties of novel organosoluble polyimides derived from 1, 4-bis [4-(3, 4-dicarboxylphenoxy)] triptycene dianhydride and various aromatic diamines | |
| US10619009B2 (en) | Ortho-substituted triptycene-based diamines, monomers, and polymers, methods of making and uses thereof | |
| US6689899B2 (en) | Diamine and acid anhydride | |
| US5336409A (en) | Composite reverse osmosis membrane and novel acid chloride | |
| JP3053462B2 (en) | 9,9-bis (perfluoroalkyl) xanthene, 9-aryl-9-perfluoroalkylxanthene, monomers and polymers derived therefrom | |
| WO2001032749A1 (en) | Novel diamine, novel acid dianhydride, and novel polyimide composition formed therefrom | |
| Bara et al. | Synthesis and characterization of ionene-polyamide materials as candidates for new gas separation membranes | |
| Mallakpour et al. | Synthesis and characterization of novel optically active poly (amide‐imide) s | |
| CN114656356B (en) | Spiro biindane tetraacyl chloride and preparation method thereof, and composite membrane and preparation method thereof | |
| Huang et al. | Synthesis and characterization of a highly soluble aromatic polyimide from 4, 4′‐methylenebis (2‐tert‐butylaniline) | |
| US4987238A (en) | Process for the preparation of high-purity 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)-ethylidene]bis-1,3-isobenzofurandione | |
| KR101197116B1 (en) | Method of making halophthalic acids and halophthalic anhydrides | |
| JPH0257057B2 (en) | ||
| KR20200066446A (en) | BCDA-based semi-alicyclic polyimide membrane materials for gas separation and the preparation method thereof | |
| WO2022030447A1 (en) | Fluorinated diamine or salt thereof, method for producing fluorinated diamine or salt thereof, polyamide, method for producing polyamide, polyamide solution, cyclized polyamide, method for producing cyclized polyamide, insulating material for high-frequency electronic component, method for producing insulating material for high-frequency electronic component, high-frequency electronic component, high-frequency appliance, and insulating material for producing high-frequency electronic component | |
| JP2971324B2 (en) | Method for converting macrocyclic polyimide oligomer to linear polyimide | |
| KR20230035390A (en) | Polybenzoxazole, polyamide, polyamide solution, insulating material for high frequency electronic parts, high frequency electronic parts, high frequency equipment, insulating material for manufacturing high frequency electronic parts, manufacturing method of polyamide, manufacturing method of polybenzoxazole, for high frequency electronic parts Method for producing insulating material, and diamine or salt thereof | |
| JP2001040089A (en) | Polyimide resin, its production and gas separation membrane composed thereof | |
| CN115746299B (en) | Cross-linked membrane, carbon molecular sieve membrane, preparation method and application | |
| Zhu et al. | A new synthetic route of 4, 4′-hexafluoroisopropylidene-2, 2-bis-(phthalic acid anhydride) and characterization of 4, 4′-hexafluoroisopropylidene-2, 2-bis-(phthalic acid anhydride)-containing polyimides | |
| JPH02235842A (en) | Alicyclic tetracarboxylic acid and derivative thereof | |
| JP2883769B2 (en) | Polyimide copolymer and method for producing the same | |
| JP2002275185A (en) | Spiro diacid anhydride having optical activity, method for producing the same, polyimide having optical activity and method for producing the same | |
| CN116023277A (en) | Diamine monomer containing dicyclo side group structure, and preparation method and application thereof | |
| KR20100015813A (en) | 3,3'-diamino-5,5'-diphenyl-4,4'-biphenyldiol, raw material therefor, and polybenzoxazole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |