CN106902652A - A kind of gas separation membrane with shape-memory properties - Google Patents

A kind of gas separation membrane with shape-memory properties Download PDF

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CN106902652A
CN106902652A CN201710171015.8A CN201710171015A CN106902652A CN 106902652 A CN106902652 A CN 106902652A CN 201710171015 A CN201710171015 A CN 201710171015A CN 106902652 A CN106902652 A CN 106902652A
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separation membrane
gas separation
temperature
shape
incubated
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CN106902652B (en
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王齐华
杨增辉
王廷梅
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • 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
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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    • B01D—SEPARATION
    • B01D53/00—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
    • 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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—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
    • 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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    • 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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    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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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    • C08G73/10—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
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract

The invention discloses a kind of gas separation membrane with shape-memory properties, the gas separation membrane is first with dianhydride 4,4 ' (hexafluoro isopropyl alkene) two anhydride phthalic acids and diamines 4,4 ' diaminodiphenyl ethers and 2 (4 aminophenyl) 5 amino benzoxazoles form the linear oligomerization thing of copolymerization, then gradually with 2,4,6 Triaminopyrimidines are reacted to form hyperbranched macromolecular, and hyperbranched polyimide film is obtained eventually through hot imidization.Super-branched polyimide film of the present invention has larger specific surface area, can realize the absorption of gas；By the hard and soft for adjusting polyimide structures so that there are different characterization of adsorptions to gas with various, so as to realize Molecular Sieving Properties.In addition, the hyperbranched polyimides has obvious glass transition temperature, this transformation can be as shape memory can anti-phase, and the strong interaction force entangled to each other and intermolecular of macromolecular chain can assign super-branched polyimide shape-memory properties as fixing phase in polyimide structures.

Description

A kind of gas separation membrane with shape-memory properties
Technical field
The present invention relates to a kind of gas separation membrane with shape-memory properties, the gas separation membrane has good shape Memory performance, gas are separated and heat endurance.
Background technology
Shape-memory polymer (shape memory polymer, SMP) is that one kind can be consolidated under certain external condition Determine temporary shapes and the intelligent material of a class of original shape can be returned to when environmental stimuli such as heat, light, electricity, magnetic is applied again Material.SMP is with a wide range of applications in fields such as flexible electronic device, biomedical and Aero-Space.Most common one Class SMP is thermotropic SMP, including：Various SMP materials such as polyurethane, polystyrene, epoxy resin.But shape common at present The glass transition temperature of shape memory polymer material（Tg）Below 120 DEG C mostly, therefore limit shape-memory polymer Material is in severe rugged environment, such as application in terms of Aero-Space.In order to widen shape-memory polymer answering in complex environment With in recent years based on heteroaromatic polyimides（PI）Shape-memory properties be constantly reported.Research shows suitably to regulate and control PI Chain structure, it is adjustable to obtain performance, with high glass-transition temperature（>250 ℃）Shape-memory material, and have Excellent shape-memory properties [Macromolecules, 2015,48 (11):3582-3589. Polymer 2016,88, 19-28.]。
Polyimide-based gas separation membrane, due to mechanical strength high, modulus high, low thermal coefficient of expansion and The advantages of excellent heat endurance and be widely used in the research [Macromolecules 2012,45 of gas separation membrane (8), 3298-3311.].The mid-80, company of Ube Industries Ltd. develops biphenyl type copolyimide gas film point From device, the industrial process such as hydrogen retrieval, gas dehumidification and gas-phase dehydration of alcohol have been successfully used to.Du pont company opens again afterwards Fluorinated polyimide gaseous jet simulation device [the macromolecule circular, 1998 (3) for air richness nitrogen are sent out: 1-8.].At present, People have improved the combination properties such as the gas separation of polyimides using various methods.Introduced for example in main chain from tool micropore Polymer chain forging, introduce the rigid structure unit containing imidazoles or oxazole, introduce bridge linkage group, design hyperbranched polyimides Structure etc. [Macromolecules 2015,48 (7), 2194-2202. Macromolecules 2013,46 (20), The ACS Macro Letters of 8179-8189. Journal of Membrane Science 2014,450,138-146. 2014,3 (7), 597-601.], to keep good mechanical performance while gas separating property is improved.But it is many Number polyimides gas separation membrane be difficult to change its intrinsic shape realize multifunction.
There is no the report on the polyimide gas separating film with shape-memory properties at present.It is this to divide with gas From characteristic, while have the polyimide material of shape-memory properties concurrently, it is expected to further to widen polyimide gas separating film and exists Gas separation and the application in shape memory field.
The content of the invention
It is an object of the invention to provide a kind of gas separation membrane with shape-memory properties.
Gas separation membrane of the present invention be it is a kind of with shape-memory properties and have concurrently Molecular Sieving Properties polyamides it is sub- Amine material, the polyimide material has larger specific surface area, good gas separating property and preferable shape fixed rate （Rf）And response rate（Rr）.Gas separation membrane of the present invention is before this with dianhydride 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids and diamines 4,4 '-diaminodiphenyl ether and 2- (4- aminophenyls) -5- amino benzoxazoles form the linear oligomerization thing of copolymerization, then gradually With 2,4,6- Triaminopyrimidines react to form hyperbranched structure, and it is thin to obtain hyperbranched polyimides eventually through hot imidization Film.The hyperbranched polyimides due to special three-dimensional macromolecular structure, therefore with larger specific surface area such that it is able to Realize the absorption of gas with various.Additionally, the hard and soft by adjusting polyimide structures so that have to gas with various different Characterization of adsorption, so as to realize Molecular Sieving Properties.The hyperbranched polyimides has obvious glass transition temperature, this turn Become can as shape memory can anti-phase, and in polyimide structures macromolecular chain it is entangled to each other and intermolecular by force it is mutual Active force can assign super-branched polyimide shape-memory properties as fixing phase.This hyperbranched polyimides has Glass transition temperature high（Tg=296~348 DEG C）, good gas separation selectivity（SCO2/N2=66.3）And shape memory Performance（Rf>99%, Rr>85%）.
A kind of gas separation membrane with shape-memory properties, it is characterised in that the gas separation membrane comes through the following steps Prepare：
1) diamine solution is prepared：By 4,4 '-diaminodiphenyl ether, 2- (4- aminophenyls) -5- amino benzoxazoles and organic Solvent mixes, and stirring is complete to dissolving under room temperature, dry nitrogen atmosphere, and 2,4,6- Triaminopyrimidines, stirring 5 are added afterwards ~20 min obtain final product diamine solution；
2) polyamic acid solution is prepared：4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids are added in diamine solution by several times, in room 24~72 h are stirred under temperature, nitrogen atmosphere and obtains the polyamic acid solution with certain viscosity；
3) hot imidization：Polyamic acid solution is vacuumized into 0.5 h~1 h of degassing in normal temperature, is subsequently poured on glass substrate, From room temperature to 60 DEG C~80 DEG C, and 2h~8h is incubated in the case where temperature is for 60 DEG C~80 DEG C；Again by temperature rise to 100 DEG C~ 140 DEG C, it is incubated 1h~3h；Continue for temperature to rise to 200 DEG C~240 DEG C, be incubated 1h~3h；Continue by temperature rise to 300 DEG C~ 340 DEG C, it is incubated 1h~3h；
4) demoulding and post processing：The glass substrate of polyimides is put into hot water, polyimides is come off from substrate, made Polyimides is rinsed well with distilled water, it is complete in 120 DEG C of dryings.
Described 2,4,6- Triaminopyrimidines are chemical branch point, and its mole is 4,4 '-diaminodiphenyl ether and 2- (4- ammonia Base phenyl) -5- amino benzoxazoles integral molar quantities 1%~17.7%.
Described 4,4 '-diaminodiphenyl ether is 0 with the mol ratio of 2- (4- aminophenyls) -5- amino benzoxazoles：1~1： 0。
The organic solvent is 1-METHYLPYRROLIDONE, DMF, DMA or trichlorine One kind in methane.
The mole and 4 of described 4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids, 4 '-diaminodiphenyl ether and 2- (4- aminobenzenes Base) -5- amino benzoxazoles integral molar quantities ratio be 1：1~1.27：1, and point 5~10 additions.
The solid content of the polyamic acid solution is 5~20%.
The present invention has the following advantages that：
1st, the glass transition temperature of the polyimide gas separating film with shape-memory properties of the present invention be 296 DEG C~ 348 DEG C, can be applied to the severe rugged environments such as high temperature.
2nd, the polyimide gas separating film with shape-memory properties of the present invention have larger specific surface area and Good gas separating property.
3rd, the polyimide gas separating film with shape-memory properties of the present invention has good shape fixed rate And response rate.
4th, the polyimide gas separating film with shape-memory properties of the present invention has heat endurance and machine high Tool performance.
Brief description of the drawings
Fig. 1 is the thermomechanical property curve of shape memory gas separation membrane prepared by the embodiment of the present invention 1.
Fig. 2 is the shape-memory properties curve of shape memory gas separation membrane prepared by the embodiment of the present invention 1.
Fig. 3 is the CO of shape memory gas separation membrane prepared by the embodiment of the present invention 12/N2Adsorptive selectivity curve.
Specific embodiment
In order to be better understood from the present invention, it is illustrated with the following examples.
Embodiment 1
A kind of preparation method with shape-memory properties gas separation membrane：
1st, 4,4 '-diaminodiphenyl ether (4.4mmol) is added in the there-necked flask of 250 mL, adds 36 mL N, N- Dimethylacetylamide, it is to be dissolved after add 2- (4- aminophenyls) -5- amino benzoxazoles（4.4mmol）, in nitrogen atmosphere Lower stirring and dissolving.It is subsequently adding 2,4,6- Triaminopyrimidines（0.8 mmol）And the min of mechanical agitation 10.
2nd, 4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids are weighed（10 mmol）The diamines for points for 5 being times slowly added to step 1 is molten In liquid, in room temperature and stirred under nitrogen atmosphere 36h, the polyamic acid solution of certain viscosity is obtained.
3rd, by polyamic acid solution normal temperature vacuumize degassing 0.5 h, be subsequently poured on glass substrate, from room temperature to 60 DEG C, and it is incubated 8h；Temperature is risen to 100 DEG C again, 1h is incubated；Continue for temperature to rise to 200 DEG C, be incubated 1h；Finally by temperature 300 DEG C are risen to, 1h is incubated.
4th, the glass substrate of polyimides is put into hot water, polyimides is come off from substrate, will using distilled water Polyimides is rinsed well, is dried at 120 DEG C complete.
Glass transition temperature is carried out to shape memory gas separation membrane prepared by embodiment 1 using dynamic mechanical analyzer Test, as shown in Figure 1.Fig. 1 is the thermomechanical property curve of shape memory gas separation membrane prepared by embodiment 1.It can be seen that Glass transition temperature is 336 DEG C.
Shape-memory properties table is carried out to shape memory gas separation membrane prepared by embodiment 1 using dynamic mechanical analyzer Levy, as a result as shown in Figure 2.Fig. 2 shows, the shape memory gas separation membrane of preparation have good memory cycle performance and Shape fixed rate higher and response rate（Rf>99%, Rr>85%）.
The specific surface area and gas of the shape memory gas separation membrane prepared using BET testers testing example 1 are selected Selecting property absorption property, as a result as shown in Figure 3.The specific surface area of shape memory gas separation membrane prepared by embodiment 1 is 314.4 m2/ g, selectivity（CO2/N2）It is 66.3.
Embodiment 2
4,4 '-diaminodiphenyl ether (4.25mmol) the 1st, is added to the there-necked flask of 250 mL, 36 mL N, N- bis- are added Methylacetamide, adds 2- (4- aminophenyls) -5- amino benzoxazoles（4.25 mmol）, stir in a nitrogen atmosphere molten Solution.It is subsequently adding 2,4,6- Triaminopyrimidines（1.0mmol）And the min of mechanical agitation 10.
2nd, 4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids are weighed（10 mmol）The diamines for points for 10 being times slowly added to step 1 is molten In liquid, in room temperature and the h of stirred under nitrogen atmosphere 72, the polyamic acid solution of certain viscosity is obtained.
3rd, polyamic acid is vacuumized into 0.5 h of degassing in normal temperature, is subsequently poured on glass substrate, from room temperature to 80 DEG C, and it is incubated 6h；Temperature is risen to 120 DEG C again, 1h is incubated；Continue for temperature to rise to 220 DEG C, be incubated 1h；Finally by temperature liter To 320 DEG C, 1h is incubated.
4th, with example 1.
Performance characterization test is carried out with the method for example 1.
Embodiment 3
4,4 '-diaminodiphenyl ether (3.95mmol) the 1st, is added to the there-necked flask of 250 mL, N, N- dimethyl second is added The mL of acid amides 36, adds 2- (4- aminophenyls) -5- amino benzoxazoles（3.95 mmol）, stir in a nitrogen atmosphere molten Solution.It is subsequently adding 2,4,6- Triaminopyrimidines（1.4mmol）And the min of mechanical agitation 20.
2nd, 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids are weighed（10 mmol）The diamines for points for 3 being times slowly added to step 1 is molten In liquid, in room temperature and the h of stirred under nitrogen atmosphere 48, the polyamic acid solution of certain viscosity is obtained.
3rd, polyamic acid is vacuumized into 1.0 h of degassing in normal temperature, is subsequently poured on glass substrate, from room temperature to 60 DEG C, and it is incubated 8h；Temperature is risen to 130 DEG C again, 1h is incubated；Continue for temperature to rise to 230 DEG C, be incubated 1h；Continue temperature liter To 330 DEG C, 1h is incubated.
4th, with example 1.
Performance characterization test is carried out with the method for example 1.
Embodiment 4
1st, 4,4 '-diaminodiphenyl ether (4.25 mmol) is added to the there-necked flask of 250 mL, adds 26 mLN- methyl Pyrrolidones, it is to be dissolved after add 2- (4- aminophenyls) -5- amino benzoxazoles（4.25mmol）, stir in a nitrogen atmosphere Mix dissolving.It is subsequently adding 2,4,6- Triaminopyrimidines（1.0 mmol）And the min of mechanical agitation 10.
2nd, 4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids are weighed（10 mmol）The diamines for points for 10 being times slowly added to step 1 is molten In liquid, in room temperature and the h of stirred under nitrogen atmosphere 72, the polyamic acid solution of certain viscosity is obtained.
3rd, polyamic acid is vacuumized into 0.5 h of degassing in normal temperature, is subsequently poured on glass substrate, from room temperature to 80 DEG C, and it is incubated 6h；Temperature is risen to 100 DEG C again, 1h is incubated；Continue for temperature to rise to 200 DEG C, be incubated 1h；Continue temperature 300 DEG C are risen to, 1h is incubated.
4th, with example 1.
Performance characterization test is carried out with the method for example 1.
Embodiment 5
4,4 '-diaminodiphenyl ether (8.8mmol) the 1st, is added to the there-necked flask of 250 mL, 26 mL N- methyl pyrroles are added Pyrrolidone, in a nitrogen atmosphere stirring and dissolving.It is subsequently adding 2,4,6- Triaminopyrimidines（0.8 mmol）And mechanical agitation 10 min。
2nd, 4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids are weighed（10 mmol）The diamines for points for 5 being times slowly added to step 1 is molten In liquid, in room temperature and the h of stirred under nitrogen atmosphere 60, the polyamic acid solution of certain viscosity is obtained.
3rd, polyamic acid is vacuumized into 0.5 h of degassing in normal temperature, is subsequently poured on glass substrate, from room temperature to 60 DEG C, and it is incubated 8h；Temperature is risen to 120 DEG C again, 1h is incubated；Continue for temperature to rise to 220 DEG C, be incubated 1h；Continue temperature 320 DEG C are risen to, 1h is incubated.
4th, with example 1.
Performance characterization test is carried out with the method for example 1.
Embodiment 6
1st, by 2- (4- aminophenyls) -5- amino benzoxazoles（8.8 mmol）The there-necked flask of 250 mL is added to, 26 are added ML 1-METHYLPYRROLIDONEs, in a nitrogen atmosphere stirring and dissolving.It is subsequently adding 2,4,6- Triaminopyrimidines（0.8 mmol）And machine Tool stirs 10 min.
2nd, 4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids are weighed（10 mmol）The diamines for points for 10 being times slowly added to step 1 is molten In liquid, in room temperature and the h of stirred under nitrogen atmosphere 72, the polyamic acid solution of certain viscosity is obtained.
3rd, polyamic acid is vacuumized into 0.5 h of degassing in normal temperature, is subsequently poured on glass substrate, from room temperature to 60 DEG C, and it is incubated 8h；Temperature is risen to 120 DEG C again, 1h is incubated；Continue for temperature to rise to 220 DEG C, be incubated 1h；Continue temperature 320 DEG C are risen to, 1h is incubated.
4th, with example 1.
Performance characterization test is carried out with the method for example 1.

Claims (6)

1. a kind of gas separation membrane with shape-memory properties, it is characterised in that the gas separation membrane is made through the following steps It is standby：
1) diamine solution is prepared：By 4,4 '-diaminodiphenyl ether, 2- (4- aminophenyls) -5- amino benzoxazoles and organic Solvent mixes, and stirring is complete to dissolving under room temperature, dry nitrogen atmosphere, and 2,4,6- Triaminopyrimidines, stirring 5 are added afterwards ~20 min obtain final product diamine solution；
2) polyamic acid solution is prepared：4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids are added in diamine solution by several times, in room 24~72 h are stirred under temperature, nitrogen atmosphere and obtains the polyamic acid solution with certain viscosity；
3) hot imidization：Polyamic acid solution is vacuumized into 0.5 h~1 h of degassing in normal temperature, is subsequently poured on glass substrate, From room temperature to 60 DEG C~80 DEG C, and 2 h~8 h are incubated in the case where temperature is for 60 DEG C~80 DEG C；Temperature is risen to 100 again DEG C~140 DEG C, it is incubated 1 h~3 h；Continue for temperature to rise to 200 DEG C~240 DEG C, be incubated 1 h~3 h；Continue temperature 300 DEG C~340 DEG C are risen to, 1 h~3 h is incubated；
4) demoulding and post processing：The glass substrate of polyimides is put into hot water, polyimides is come off from substrate, made Polyimides is rinsed well with distilled water, it is complete in 120 DEG C of dryings.
2. gas separation membrane as claimed in claim 1, it is characterised in that described 2,4,6- Triaminopyrimidines are chemical branch point, Its mole is 4,4 '-diaminodiphenyl ether and 2- (4- aminophenyls) -5- amino benzoxazoles integral molar quantities 1%~ 17.7%。
3. gas separation membrane as claimed in claim 1, it is characterised in that described 4,4 '-diaminodiphenyl ether and 2- (4- amino Phenyl) -5- amino benzoxazoles mol ratio be 0：1~1：0.
4. gas separation membrane as claimed in claim 1, it is characterised in that the organic solvent is 1-METHYLPYRROLIDONE, N, N- One kind in dimethylformamide, DMA or chloroform.
5. gas separation membrane as claimed in claim 1, it is characterised in that described 4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids rub The ratio of that amount and 4,4 '-diaminodiphenyl ether and 2- (4- aminophenyls) -5- amino benzoxazoles integral molar quantities is 1：1~ 1.27：1, and point 5~10 additions.
6. gas separation membrane as claimed in claim 1, it is characterised in that the solid content of the polyamic acid solution is 5~20%.
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CN111303425A (en) * 2020-04-20 2020-06-19 中国科学院兰州化学物理研究所 Photo-thermal response three-dimensional shape memory polyimide and preparation method and application thereof

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CN102838745A (en) * 2012-09-19 2012-12-26 中国科学院长春应用化学研究所 Preparation method of polyimide foam
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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CN102838745A (en) * 2012-09-19 2012-12-26 中国科学院长春应用化学研究所 Preparation method of polyimide foam
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111303425A (en) * 2020-04-20 2020-06-19 中国科学院兰州化学物理研究所 Photo-thermal response three-dimensional shape memory polyimide and preparation method and application thereof

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