CN106902652B - Gas separation membrane with shape memory performance - Google Patents
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- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Abstract
The invention discloses a gas separation membrane with shape memory performance, which is characterized in that dianhydride 4, 4'- (hexafluoroisopropylidene) diphthalic anhydride, diamine 4, 4' -diaminodiphenyl ether and 2- (4-aminophenyl) -5-aminobenzoxazole are firstly used to form a copolymerized linear oligomer, then the linear oligomer is gradually reacted with 2,4, 6-triaminopyrimidine to form hyperbranched macromolecules, and finally the hyperbranched polyimide membrane is obtained through thermal imidization. The hyperbranched polyimide film has a large specific surface area, and can realize the adsorption of gas; the rigidity and flexibility of the polyimide structure are adjusted, so that different gases have different adsorption characteristics, and the gas separation characteristic is realized. In addition, the hyperbranched polyimide has obvious glass transition temperature, the transition can be used as a reversible phase of shape memory, and the mutual entanglement of macromolecular chains and strong interaction force among molecules in the polyimide structure can be used as a stationary phase to endow the hyperbranched polyimide with shape memory performance.
Description
Technical Field
The invention relates to a gas separation membrane with shape memory performance, which has good shape memory performance, gas separation and thermal stability.
Background
Shape Memory Polymers (SMPs) are a class of smart materials that can set a temporary shape under certain external conditions and return to the original shape when an external stimulus such as heat, light, electricity, magnetism, etc. is applied again. SMP has wide application prospect in the fields of flexible electronic devices, biomedicine, aerospace and the like. One of the most common classes of SMPs is the thermotropic SMP, including: polyurethane, polystyrene, epoxy, and a variety of SMP materials. However, vitrification of shape memory polymer materials is now commonTransition temperature (T)g) Most of the materials are lower than 120 ℃, so that the application of the shape memory polymer material in harsh environments such as aerospace and the like is limited. In order to broaden the applications of shape memory polymers in complex environments, shape memory properties based on aromatic heterocyclic Polyimides (PI) have been reported in recent years. Research shows that the chain structure of PI is properly regulated, the performance is adjustable, and the glass transition temperature is high>250 ℃) and has excellent shape memory properties [ Macromolecules, 2015, 48(11): 3582-.]。
Polyimide-based gas separation membranes have been widely used in gas separation membrane research [ Macromolecules 2012, 45(8), 3298-. In the middle of the 80 s, the company of the Ministry of Japan developed a biphenyl type copolymerized polyimide gas membrane separator, which was successfully used in industrial processes such as hydrogen recovery, gas dehumidification and ethanol gas phase dehydration. DuPont later developed a membrane separator of fluorinated polyimide for air nitrogen enrichment [ Polymer bulletin, 1998 (3): 1-8 ]. At present, various methods have been used to improve the overall performance of polyimide, such as gas separation. For example, polymer chain forging with micropores, rigid structural unit containing imidazole or oxazole, bridging group, and hyperbranched polyimide structure design are introduced into the main chain [ Macromolecules 2015, 48 (7), 2194-. However, many polyimide-based gas separation membranes are difficult to change their intrinsic shape to achieve multi-functionalization.
There is no report on a polyimide gas separation membrane having shape memory properties. The polyimide material with gas separation characteristic and shape memory performance is expected to further widen the application of the polyimide gas separation membrane in the fields of gas separation and shape memory.
Disclosure of Invention
The invention aims to provide a gas separation membrane with shape memory performance.
The gas separation membrane is a polyimide material with shape memory performance and gas separation characteristic, and the polyimide material has large specific surface area, good gas separation performance and good shape fixing rate (R)f) And recovery ratio (R)r). The gas separation membrane is prepared by the steps of firstly forming a linear copolymerized oligomer by dianhydride 4, 4'- (hexafluoroisopropylidene) diphthalic anhydride, diamine 4, 4' -diaminodiphenyl ether and 2- (4-aminophenyl) -5-aminobenzoxazole, then gradually reacting with 2,4, 6-triaminopyrimidine to form a hyperbranched structure, and finally obtaining a hyperbranched polyimide film through thermal imidization. The hyperbranched polyimide has a large specific surface area due to a special three-dimensional macromolecular structure, so that adsorption of different gases can be realized. In addition, the rigidity and flexibility of the polyimide structure are adjusted, so that different gases have different adsorption characteristics, and the gas separation characteristic is realized. The hyperbranched polyimide has obvious glass transition temperature, the transition can be used as a reversible phase of shape memory, and the mutual entanglement of macromolecular chains and strong interaction force among molecules in the polyimide structure can be used as a stationary phase to endow the hyperbranched polyimide with shape memory performance. The hyperbranched polyimide has a high glass transition temperature (T)g=296 to 348 ℃), good gas separation selectivity (S)CO2/N2= 66.3) and shape memory properties (R)f>99%,Rr>85%)。
A gas separation membrane having shape memory properties, characterized in that it is prepared by the steps of:
1) preparation of diamine solution: mixing 4, 4' -diaminodiphenyl ether, 2- (4-aminophenyl) -5-aminobenzoxazole and an organic solvent, stirring at room temperature under a dry nitrogen atmosphere until the mixture is completely dissolved, then adding 2,4, 6-triaminopyrimidine, and stirring for 5-20 min to obtain a diamine solution;
2) preparation of a polyamic acid solution: adding 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride into a diamine solution in several times, and stirring at room temperature in a nitrogen atmosphere for 24-72 hours to obtain a polyamic acid solution with a certain viscosity;
3) thermal imidization: vacuumizing and degassing the polyamic acid solution at normal temperature for 0.5-1 h, then pouring the polyamic acid solution onto a glass substrate, heating the polyamic acid solution from room temperature to 60-80 ℃, and preserving the heat for 2-8 h at the temperature of 60-80 ℃; then the temperature is raised to 100-140 ℃, and the temperature is kept for 1-3 h; continuously raising the temperature to 200-240 ℃, and keeping the temperature for 1-3 h; continuously raising the temperature to 300-340 ℃, and keeping the temperature for 1-3 h;
4) demoulding and post-treatment: putting the glass substrate of the polyimide into hot water to enable the polyimide to fall off from the substrate, washing the polyimide by using distilled water, and completely drying at 120 ℃.
The 2,4, 6-triaminopyrimidine is a chemical branching point, and the molar weight of the 2,4, 6-triaminopyrimidine is 1-17.7 percent of the total molar weight of 4, 4' -diaminodiphenyl ether and 2- (4-aminophenyl) -5-aminobenzoxazole.
The molar ratio of the 4, 4' -diaminodiphenyl ether to the 2- (4-aminophenyl) -5-aminobenzoxazole is 0: 1-1: 0.
the organic solvent is one of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide or trichloromethane.
The ratio of the molar amount of the 4, 4'- (hexafluoroisopropylidene) diphthalic anhydride to the total molar amount of the 4, 4' -diaminodiphenyl ether and the 2- (4-aminophenyl) -5-aminobenzoxazole was 1: 1-1.27: 1, and adding the mixture in 5-10 times.
The solid content of the polyamic acid solution is 5-20%.
The invention has the following advantages:
1. the polyimide gas separation membrane with the shape memory performance has the glass transition temperature of 296-348 ℃, and can be applied to harsh environments such as high temperature and the like.
2. The polyimide gas separation membrane with the shape memory performance has a large specific surface area and good gas separation performance.
3. The polyimide gas separation membrane with the shape memory performance has good shape fixation rate and recovery rate.
4. The polyimide gas separation membrane with the shape memory performance has high thermal stability and mechanical performance.
Drawings
FIG. 1 is a graph of the thermomechanical properties of a shape memory gas separation membrane prepared in example 1 of the present invention.
FIG. 2 is a shape memory performance curve of the shape memory gas separation membrane prepared in example 1 of the present invention.
FIG. 3 is a CO of the shape memory gas separation membrane prepared in example 1 of the present invention2/N2Adsorption selectivity curve.
Detailed Description
In order that the invention may be better understood, reference will now be made to the following examples.
Example 1
A preparation method of a gas separation membrane with shape memory performance comprises the following steps:
1.4, 4' -diaminodiphenyl ether (4.4mmol) was charged into a 250mL three-necked flask, 36mL of N, N-dimethylacetamide was added, and after dissolution, 2- (4-aminophenyl) -5-aminobenzoxazole (4.4mmol) was added and dissolved with stirring under a nitrogen atmosphere. Then 2,4, 6-triaminopyrimidine (0.8 mmol) was added and mechanically stirred for 10 min.
2. 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (10 mmol) is weighed and slowly added into the diamine solution in the step 1 for 5 times, and stirred for 36 hours at room temperature under the protection of nitrogen to obtain a polyamic acid solution with certain viscosity.
3. Vacuumizing and degassing the polyamic acid solution at normal temperature for 0.5h, then pouring the polyamic acid solution onto a glass substrate, heating the polyamic acid solution to 60 ℃ from the room temperature, and keeping the temperature for 8 h; then the temperature is raised to 100 ℃, and the temperature is kept for 1 h; continuously heating to 200 ℃, and keeping the temperature for 1 h; finally, the temperature is raised to 300 ℃ and the temperature is kept for 1 h.
4. Putting the glass substrate of the polyimide into hot water to enable the polyimide to fall off from the substrate, washing the polyimide clean by using distilled water, and completely drying at 120 ℃.
The shape memory gas separation membrane prepared in example 1 was subjected to a glass transition temperature test using a dynamic mechanical analyzer, as shown in fig. 1. Fig. 1 is a graph of the thermomechanical properties of the shape memory gas separation membrane prepared in example 1. It can be seen that the glass transition temperature is 336 ℃.
The shape memory performance of the shape memory gas separation membrane prepared in example 1 was characterized by using a dynamic mechanical analyzer, and the results are shown in fig. 2. FIG. 2 shows that the prepared shape memory gas separation membrane has good shape memory cycle performance and high shape fixation rate and recovery rate (R)f>99%,Rr>85%)。
The specific surface area and the gas selective adsorption performance of the shape memory gas separation membrane prepared in example 1 were measured using a BET tester, and the results are shown in fig. 3. The specific surface area of the shape-memory gas separation membrane prepared in example 1 was 314.4m2G, selectivity (CO)2/N2) Was 66.3.
Example 2
1.4, 4' -diaminodiphenyl ether (4.25mmol) was charged into a 250mL three-necked flask, 36mL of N, N-dimethylacetamide and 2- (4-aminophenyl) -5-aminobenzoxazole (4.25mmol) were added thereto, and the mixture was dissolved with stirring under a nitrogen atmosphere. Then 2,4, 6-triaminopyrimidine (1.0 mmol) was added and mechanically stirred for 10 min.
2. 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (10 mmol) is weighed and slowly added into the diamine solution in the step 1 by 10 times, and stirred for 72 hours at room temperature under the protection of nitrogen to obtain a polyamic acid solution with certain viscosity.
3. Vacuumizing and degassing polyamic acid at normal temperature for 0.5h, pouring the polyamic acid on a glass substrate, heating the polyamic acid to 80 ℃ from the room temperature, and preserving the heat for 6 h; then the temperature is raised to 120 ℃, and the temperature is kept for 1 h; continuously heating to 220 ℃, and keeping the temperature for 1 h; finally, the temperature is raised to 320 ℃, and the temperature is kept for 1 h.
4. As in example 1.
The performance characterization test was performed in the same manner as in example 1.
Example 3
1.4, 4' -diaminodiphenyl ether (3.95mmol) was charged in a 250mL three-necked flask, 36mL of N, N-dimethylacetamide and 2- (4-aminophenyl) -5-aminobenzoxazole (3.95mmol) were added thereto, and the mixture was dissolved with stirring under a nitrogen atmosphere. Then 2,4, 6-triaminopyrimidine (1.4 mmol) was added and mechanically stirred for 20 min.
2. 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (10 mmol) is weighed and slowly added into the diamine solution in the step 1 for 3 times, and stirred for 48 hours at room temperature under the protection of nitrogen to obtain a polyamic acid solution with certain viscosity.
3. Vacuumizing and degassing polyamic acid at normal temperature for 1.0 h, then pouring the polyamic acid onto a glass substrate, heating the polyamic acid to 60 ℃ from the room temperature, and preserving the heat for 8 h; then the temperature is raised to 130 ℃, and the temperature is kept for 1 h; continuously heating to 230 ℃, and keeping the temperature for 1 h; the temperature is continuously raised to 330 ℃ and kept for 1 h.
4. As in example 1.
The performance characterization test was performed in the same manner as in example 1.
Example 4
1.4, 4' -diaminodiphenyl ether (4.25mmol) was charged into a 250mL three-necked flask, 26 mL of N-methylpyrrolidone was added, and after dissolution, 2- (4-aminophenyl) -5-aminobenzoxazole (4.25mmol) was added and dissolved with stirring under a nitrogen atmosphere. Then 2,4, 6-triaminopyrimidine (1.0 mmol) was added and mechanically stirred for 10 min.
2. 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (10 mmol) is weighed and slowly added into the diamine solution in the step 1 by 10 times, and stirred for 72 hours at room temperature under the protection of nitrogen to obtain a polyamic acid solution with certain viscosity.
3. Vacuumizing and degassing polyamic acid at normal temperature for 0.5h, pouring the polyamic acid on a glass substrate, heating the polyamic acid to 80 ℃ from the room temperature, and preserving the heat for 6 h; then the temperature is raised to 100 ℃, and the temperature is kept for 1 h; continuously heating to 200 ℃, and keeping the temperature for 1 h; the temperature is continuously raised to 300 ℃ and kept for 1 h.
4. As in example 1.
The performance characterization test was performed in the same manner as in example 1.
Example 5
1.4, 4' -diaminodiphenyl ether (8.8mmol) was charged into a 250mL three-necked flask, 26 mL of N-methylpyrrolidone was added, and the mixture was dissolved with stirring under a nitrogen atmosphere. Then 2,4, 6-triaminopyrimidine (0.8 mmol) was added and mechanically stirred for 10 min.
2. 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (10 mmol) is weighed and slowly added into the diamine solution in the step 1 for 5 times, and stirred for 60 hours at room temperature under the protection of nitrogen to obtain a polyamic acid solution with certain viscosity.
3. Vacuumizing and degassing polyamic acid at normal temperature for 0.5h, then pouring the polyamic acid onto a glass substrate, heating the polyamic acid to 60 ℃ from the room temperature, and preserving the heat for 8 h; then the temperature is raised to 120 ℃, and the temperature is kept for 1 h; continuously heating to 220 ℃, and keeping the temperature for 1 h; the temperature is continuously raised to 320 ℃ and kept for 1 h.
4. As in example 1.
The performance characterization test was performed in the same manner as in example 1.
Example 6
1. 2- (4-aminophenyl) -5-aminobenzoxazole (8.8mmol) was added to a 250mL three-necked flask, 26 mL of N-methylpyrrolidone was added thereto, and the mixture was dissolved with stirring under a nitrogen atmosphere. Then 2,4, 6-triaminopyrimidine (0.8 mmol) was added and mechanically stirred for 10 min.
2. 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (10 mmol) is weighed and slowly added into the diamine solution in the step 1 by 10 times, and stirred for 72 hours at room temperature under the protection of nitrogen to obtain a polyamic acid solution with certain viscosity.
3. Vacuumizing and degassing polyamic acid at normal temperature for 0.5h, then pouring the polyamic acid onto a glass substrate, heating the polyamic acid to 60 ℃ from the room temperature, and preserving the heat for 8 h; then the temperature is raised to 120 ℃, and the temperature is kept for 1 h; continuously heating to 220 ℃, and keeping the temperature for 1 h; the temperature is continuously raised to 320 ℃ and kept for 1 h.
4. As in example 1.
The performance characterization test was performed in the same manner as in example 1.
Claims (1)
1. A gas separation membrane having shape memory properties, characterized in that it is prepared by the steps of:
1) preparation of diamine solution: adding 4.4mmol of 4, 4' -diaminodiphenyl ether into a 250mL three-neck flask, adding 36mL of N, N-dimethylacetamide, adding 4.4mmol of 2- (4-aminophenyl) -5-aminobenzoxazole after dissolution, stirring and dissolving under a nitrogen atmosphere, adding 0.8mmol of 2,4, 6-triaminopyrimidine, and mechanically stirring for 10 min;
2) preparation of a polyamic acid solution: weighing 10mmol of 4, 4'- (hexafluoroisopropylidene) diphthalic anhydride, slowly adding the weighed 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride into the diamine solution in the step 1 for 5 times, and stirring the mixture for 36 hours at room temperature under the protection of nitrogen to obtain a polyamic acid solution with certain viscosity;
3) thermal imidization: vacuumizing and degassing the polyamic acid solution at normal temperature for 0.5h, then pouring the polyamic acid solution onto a glass substrate, heating the polyamic acid solution to 60 ℃ from the room temperature, and keeping the temperature for 8 h; then the temperature is raised to 100 ℃, and the temperature is kept for 1 h; continuously heating to 200 ℃, and keeping the temperature for 1 h; finally, the temperature is increased to 300 ℃, and the temperature is kept for 1 h;
4) demoulding and post-treatment: putting a glass substrate of polyimide into hot water to make the polyimide fall off from the substrate, washing the polyimide clean by using distilled water, and completely drying at 120 ℃;
the glass transition temperature of the gas separation membrane is 336 ℃, and the shape fixation rate of the gas separation membrane is 336 DEG C>99% recovery rate>85 percent and the specific surface area is 314.4m2/g。
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CN103980492A (en) * | 2014-05-23 | 2014-08-13 | 哈尔滨工业大学 | High-temperature-resistant thermoplastic shape memory polyimide and preparation method thereof |
CN105254888A (en) * | 2015-11-23 | 2016-01-20 | 厦门理工学院 | Polyimide ionomer and preparation method thereof |
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