阅读说明：本技术 一种聚酰胺VOCs截留型聚合物分离膜在氮气/VOCs分离方面的应用 (Application of polyamide VOCs (volatile organic compounds) interception type polymer separation membrane in nitrogen/VOCs separation ) 是由 周浩力 金万勤 于 2017-05-17 设计创作，主要内容包括：本发明公开了一种聚酰胺VOCs截留型聚合物分离膜在氮气/VOCs分离方面的应用,属于有机合成和膜分离领域。该方法是将化合物A在相转移催化剂季铵盐催化下,经氧化生成化合物B；生成的化合物B与含有胺基的化合物单体,在缚酸剂和催化剂亚磷酸三苯酯的作用下进行聚合反应,反应结束后得到的聚合物溶液倒入去离子水中沉降,抽滤,真空干燥后得到寡聚物,将寡聚物溶于有机极性溶剂中,经超声破碎后,得到膜液涂；将所得膜液涂覆于耐溶剂聚砜底膜上,真空交联干燥,得到三蝶烯基VOCs截留型聚合物分离膜。本发明制备出一种聚酰胺VOCs截留型聚合物分离膜,此种聚酰胺VOCs截留型聚合物分离膜可用于氮气/VOCs的分离。<Image he="976" wi="700" file="DDA0002195871690000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention discloses an application of a polyamide VOCs (volatile organic compounds) retention type polymer separation membrane in nitrogen/VOCs separation, belonging to the field of organic synthesis and membrane separation.A compound A is oxidized to generate a compound B under the catalysis of a phase transfer catalyst quaternary ammonium salt, the generated compound B and a compound monomer containing amino are subjected to polymerization reaction under the action of an acid binding agent and a catalyst triphenyl phosphite, a polymer solution obtained after the reaction is finished is poured into deionized water for sedimentation, suction filtration and vacuum drying to obtain an oligomer, the oligomer is dissolved in an organic polar solvent and is subjected to ultrasonic crushing to obtain a membrane liquid coating, the obtained membrane liquid coating is coated on a solvent-resistant polysulfone bottom membrane and is subjected to vacuum crosslinking drying to obtain a triptycenyl VOCs retention type polymer separation membrane)

1. The application of a polyamide VOCs interception type polymer separation membrane in the aspect of nitrogen/VOCs separation is characterized in that: the polyamide VOCs interception type polymer separation membrane is prepared by the following method:

The first step is as follows: using water as a solvent, and oxidizing the compound A under the catalysis of a phase transfer catalyst quaternary ammonium salt to generate a compound B;

The second step is that: carrying out polymerization reaction on the generated compound B and a compound monomer containing amino under the action of an acid-binding agent and a catalyst triphenyl phosphite, pouring a polymer solution obtained after the reaction into deionized water for settling, carrying out suction filtration, carrying out vacuum drying to obtain an oligomer, dissolving the oligomer into an organic polar solvent, and carrying out ultrasonic crushing to obtain a membrane liquid coating;

The third step: coating the obtained membrane liquid on a solvent-resistant polysulfone base membrane, and performing vacuum crosslinking and drying to obtain a triptycenyl VOCs interception type polymer separation membrane;

Wherein, R ₁ and R ₂ are respectively and independently any one of H, Cl, Br, I and COOH;

In the second step, the compound monomer containing amino is selected from diamine compounds or tetraamine compounds;

The diamine compound is selected from 5,5' -diamino-2, 2' -bipyridine, 2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether, 2-bis [4- (4-aminooxyphenyl) ] hexafluoropropane, 2',5,5' -tetrachlorodiphenylamine, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, 2,3,5, 6-tetrafluoro-p-xylylenediamine, 3',5,5' -tetramethyl-benzidine, m-phenylenediamine, p-phenylenediamine, benzidine, bi-o-toluidine, 3' -dimethoxy benzidine, p-xylylenediamine, o-xylylenediamine, 5-chloro-m-phenylenediamine, 1, 3-xylylenediamine, 4-methoxy-m-phenylenediamine, benzo [1 ], 2-d; 4,5-D ] bis-thiazole-1, 6-diamine, 2-nitro-1, 4-phenylenediamine, 2, 5-di-chloro-1, 4-phenylenediamine, 4,4' -diaminobenzanilide, toluene-2, 5-diamine, 4-nitro-1, 3-phenylenediamine, 2-chloro-4-nitro-1, 3-phenylenediamine, oxydianiline, tetrafluoroisophthalimide, pyromellitic diamine, 2,4, 4-tetramethyl-1, 3-cyclobutanediamine, 4, 6-diaminopyrimidine or 3, 5-diamino-1, 2, 4-triazole;

the tetramine compound is selected from 3,3' -diaminobenzidine, 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 1,2,4, 5-benzene tetramine, 1,2,4, 5-benzene tetraamide, N, N, N ', N ' -tetra (p-aminophenyl) p-phenylenediamine, penta tetramine or N, N, N, N-tetra (3-aminopropyl) -1, 4-butanediamine.

2. The method of claim 1 for preparing a polyamide VOCs rejection polymer separation membrane, wherein: the quaternary ammonium salt in the first step is selected from methyl trioctyl ammonium chloride, methyl trinonyl ammonium chloride or methyl tridecyl ammonium chloride; the oxidant used for oxidation is selected from potassium permanganate, benzophenone, vanadium pentoxide, triethylamine, vanadyl sulfate or pyridinium chlorochromate; preferably, the quaternary ammonium salt in the first step is selected from methyl trioctyl ammonium chloride, and the oxidant used for oxidation is selected from potassium permanganate.

3. the method of claim 1 for preparing a polyamide VOCs rejection polymer separation membrane, wherein: in the first step, the molar ratio of the compound A to the solvent water to the phase transfer catalyst quaternary ammonium salt is 2-8: 600-1500: 1; preferably: in the first step, the molar ratio of the compound A to the solvent water to the phase transfer catalyst quaternary ammonium salt is 4-6: 800-1300: 1.

4. the method of claim 1 for preparing a polyamide VOCs rejection polymer separation membrane, wherein: the acid-binding agent in the second step is selected from triethylamine, pyridine, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide or potassium hydroxide; preferably: in the second step, the acid binding agent is pyridine.

5. The method of claim 1 for preparing a polyamide VOCs rejection polymer separation membrane, wherein: the diamine compound is selected from 2,2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether, 2-bis [4- (4-aminooxyphenyl) ] hexafluoropropane, 2,3,5, 6-tetrafluorop-xylylenediamine or tetrafluoro isophthalimide;

The tetramine compound is 3,3' -diaminobenzidine, 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 1,2,4, 5-benzene tetramine or 1,2,4, 5-benzene tetraamide.

6. the method of claim 1 for preparing a polyamide VOCs rejection polymer separation membrane, wherein: in the second step, the molar ratio of the compound B, the compound monomer containing amino, the acid-binding agent and the catalyst triphenyl phosphite is 1: 1-2.5: 30-70: 8 to 10.

7. The method of claim 1 for preparing a polyamide VOCs rejection polymer separation membrane, wherein: the temperature of the polymerization reaction in the second step is 10-200 ℃; preferably: the temperature of the polymerization reaction is 95-120 ℃.

8. the method of claim 1 for preparing a polyamide VOCs rejection polymer separation membrane, wherein: the polymerization reaction of the second step is carried out under a double salt solution system of anhydrous lithium chloride and anhydrous calcium chloride.

9. The method of claim 1 for preparing a polyamide VOCs rejection polymer separation membrane, wherein: the organic polar solvent in the second step is any one selected from 1-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, acetonitrile, dioxane and acetone.

10. The method of claim 1 for preparing a polyamide VOCs rejection polymer separation membrane, wherein: the concentration of the membrane liquid coating in the second step is 0.1-20 wt%; preferably: the concentration of the membrane liquid coating in the second step is 4 wt% -10 wt%.

11. The method for preparing a separation membrane of a polyamide VOCs retaining polymer according to claim 1, wherein R ₁ and R ₂ are each independently H.

Technical Field

the invention belongs to the field of organic synthesis and membrane separation, and particularly relates to a polyamide VOCs (volatile organic compounds) interception type polymer separation membrane and a preparation method thereof.

Background

Volatile organic compounds are a class of substances with relatively high volatility. The volatile organic waste gas is discharged into the atmosphere, which affects the physical and mental health of people and pollutes the environment. Various laws and regulations are promulgated for the country to control the emission concentration of volatile organic compounds, such as the "comprehensive emission standard of atmospheric pollutants". In order to meet the national emission requirements, researchers have developed various treatment technologies, such as adsorption, absorption, condensation, membrane separation, catalytic combustion, plasma oxidation, etc., to eliminate organic waste gas pollution. The membrane separation technology has the advantages of high efficiency, low energy consumption, compact equipment, environmental friendliness, no secondary pollution and the like. At present, a membrane which is permeable to organic substances preferentially is used, and the membrane can adsorb, permeate and selectively permeate the organic substances to intercept air so as to realize the separation of the organic substances and the air. However, the organic-substance-permeable membrane cannot be used alone in the use process and must be used together with other equipment such as a vacuum pump, so that the equipment process is complex, the energy consumption is high, and the use of the organic-substance-permeable membrane is limited to a certain extent.

Disclosure of Invention

The invention provides a polyamide VOCs (volatile organic compounds) interception type polymer separation membrane as well as a preparation method and application thereof aiming at the existing technical problems.

The purpose of the invention can be realized by the following technical scheme:

A preparation method of a polyamide VOCs (volatile organic compounds) retention type polymer separation membrane comprises the following steps:

The first step is as follows: using water as a solvent, and oxidizing the compound A under the catalysis of a phase transfer catalyst quaternary ammonium salt to generate a compound B;

The second step is that: carrying out polymerization reaction on the generated compound B and a compound monomer containing amino under the action of an acid-binding agent and a catalyst triphenyl phosphite, pouring a polymer solution obtained after the reaction into deionized water for settling, carrying out suction filtration, carrying out vacuum drying to obtain an oligomer, dissolving the oligomer into an organic polar solvent, and carrying out ultrasonic crushing to obtain a membrane liquid coating;

The third step: coating the obtained membrane liquid on a solvent-resistant polysulfone base membrane, and performing vacuum crosslinking and drying to obtain a triptycenyl VOCs interception type polymer separation membrane;

Wherein R ₁ and R ₂ are respectively and independently any one of H, Cl, Br, I and COOH, and preferably R ₁ and R ₂ are respectively and independently H.

The technical scheme of the invention is as follows: the quaternary ammonium salt in the first step is selected from methyl trioctyl ammonium chloride, methyl trinonyl ammonium chloride or methyl tridecyl ammonium chloride; preferably, the quaternary ammonium salt is selected from methyl trioctyl ammonium chloride.

The technical scheme of the invention is as follows: the oxidant used in the oxidation in the first step is selected from potassium permanganate, benzophenone, vanadium pentoxide, triethylamine, vanadyl sulfate or pyridinium chlorochromate; preferably, the oxidizing agent used for the oxidation is selected from potassium permanganate.

The technical scheme of the invention is as follows: in the first step, the molar ratio of the compound A to the solvent water to the phase transfer catalyst quaternary ammonium salt is 2-8: 600-1500: 1, preferably 4 to 6: 800-1300: 1.

the technical scheme of the invention is as follows: the acid-binding agent in the second step is selected from triethylamine, pyridine, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide or potassium hydroxide; preferably, the acid scavenger is selected from pyridine.

The technical scheme of the invention is as follows: in the second step, the compound monomer containing amino is selected from diamine compounds or tetraamine compounds;

the diamine compound is selected from 5,5' -diamino-2, 2' -bipyridyl, 2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether, 2-bis [4- (4-aminooxyphenyl) ] hexafluoropropane, 2',5,5 '-tetrachlorodiphenylamine, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, 3',5,5 '-tetramethylbenzidine, m-phenylenediamine, p-phenylenediamine, benzidine, orthotoluidine, 3' -dimethoxybenzidine, 2,3,5, 6-tetrafluoro-p-xylylenediamine, o-xylylenediamine, 5-chloro-m-phenylenediamine, 1, 3-xylylenediamine, 4-methoxy-m-phenylenediamine, benzo [1, 2-d; 4,5-D ] bis-thiazole-1, 6-diamine, 2-nitro-1, 4-phenylenediamine, 2, 5-di-chloro-1, 4-phenylenediamine, 4,4' -diaminobenzanilide, toluene-2, 5-diamine, 4-nitro-1, 3-phenylenediamine, 2-chloro-4-nitro-1, 3-phenylenediamine, oxydianiline, tetrafluoroisophthalimide, pyromellitic diamine, 2,4, 4-tetramethyl-1, 3-cyclobutanediamine, triethylene tetramine, 4, 6-diaminopyrimidine or 3, 5-diamino-1, 2, 4-triazole.

Preferably, the method comprises the following steps: the diamine compound is selected from 2,2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether, 2-bis [4- (4-aminooxyphenyl) ] hexafluoropropane, 2,3,5, 6-tetrafluoro-p-xylylenediamine or tetrafluoro-m-phthalimide.

Most preferred are: the diamine compound is selected from 2,2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether or 2, 2-bis [4- (4-aminooxyphenyl) ] hexafluoropropane.

The tetramine compound is selected from 3,3' -diaminobenzidine, 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 1,2,4, 5-benzene tetramine, 1,2,4, 5-benzene tetraamide, N, N, N ', N ' -tetra (p-aminophenyl) p-phenylenediamine, penta tetramine or N, N, N, N-tetra (3-aminopropyl) -1, 4-butanediamine.

Preferably, the method comprises the following steps: the tetraamine compound is selected from 3,3' -diaminobenzidine, 5,10,15, 20-tetra (4-aminophenyl) porphyrin, 1,2,4, 5-benzene tetramine or 1,2,4, 5-benzene tetraamide.

Most preferred are: the tetraamine compound is selected from 3,3' -diaminobenzidine.

The technical scheme of the invention is as follows: in the second step, the molar ratio of the compound B, the compound monomer containing amino, the acid-binding agent and the catalyst triphenyl phosphite is 1: 1-2.5: 30-70: 8 to 10.

The technical scheme of the invention is as follows: the temperature of the polymerization reaction in the second step is 10-200 ℃, and the preferable temperature of the polymerization reaction is 95-120 ℃.

The technical scheme of the invention is as follows: the polymerization reaction of the second step is carried out under a double salt solution system of anhydrous lithium chloride and anhydrous calcium chloride.

The technical scheme of the invention is as follows: the organic polar solvent in the second step is any one selected from 1-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, acetonitrile, dioxane and acetone. Preferably, the organic polar solvent is selected from dimethyl sulfoxide.

The technical scheme of the invention is as follows: the concentration of the membrane liquid coating in the second step is 0.1-20 wt%, preferably 4-10 wt%.

The invention has the beneficial effects that:

The invention prepares a polyamide VOCs (volatile organic compounds) interception type polymer separation membrane, and the polyamide VOCs interception type polymer separation membrane can be used for separating nitrogen/VOCs. Because the membrane is of a plane net structure, the transmission path of gas in the membrane can be reduced, and the purpose of improving flux is achieved.

Drawings

FIG. 1 is an ¹ H-NMR chart of triptycene 2,3,6, 7-tetracarboxylic acid in example of the present invention;

FIG. 2 is a digital photograph of a polysulfone base film in an embodiment of the present invention;

FIG. 3 is a ¹ H-NMR chart of tetraamine-tetraformic acid triptycenyl polyamide in example 1 of the present invention;

FIG. 4 is a ¹ H-NMR chart of a diamine-tetracarboxylic acid triptycenyl polyamide in example 2 of the present invention;

FIG. 5 is a photograph of a tetramine-tetracarboxylic acid triptycene-polyamide VOCs trapping polymer separation membrane in example 1 of the present invention;

FIG. 6 is an SEM image of the surface of a tetramine-tetracarboxylic acid triptycene-based polyamide VOCs trapping polymer separation membrane in example 1 of the present invention;

FIG. 7 is an SEM image of a cross section of a tetramine-tetracarboxylic acid triptycene-based polyamide VOCs trapping polymer separation membrane in example 1 of the present invention.

Detailed Description

The invention is further illustrated by the following examples, without limiting the scope of the invention: