CN109126485A - A kind of filling-modified polyurethane film and preparation method thereof - Google Patents
A kind of filling-modified polyurethane film and preparation method thereof Download PDFInfo
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- CN109126485A CN109126485A CN201811096127.2A CN201811096127A CN109126485A CN 109126485 A CN109126485 A CN 109126485A CN 201811096127 A CN201811096127 A CN 201811096127A CN 109126485 A CN109126485 A CN 109126485A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/54—Polyureas; Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
- B01D2323/345—UV-treatment
Abstract
The invention discloses a kind of filling-modified polyurethane films and preparation method thereof, belong to infiltration evaporation technical field of membrane separation；This method comprises the following steps: (1) preparation of ZIF-8 nanoparticle；(2) preparation of amination ZIF-8 particle；(3) preparation of the compound particle of amination ZIF-8 and silica；(4) preparation of the compound particle filled polyurethane film of amination ZIF-8 and silica.Filling-modified polyurethane film of the invention and preparation method thereof has the features such as permeation flux is high, selectivity is good, low in cost, preparation process is easy to operate.In filling-modified polyurethane film preparation method of the invention, when the temperature of water etching reaction is 90 DEG C, the porous, inorganic complex particle filled polyurethane film that the loading of silicon substrate compound particle is prepared when being 1%, the phenol/water mixture that mass percent for phenol is 1%, in the case where operation temperature is 60 DEG C, PSI can achieve 810.139kg μm of m‑2·h‑1, than under the same terms, pure polyurethane film (523.23) improves 1.54 times.
Description
Technical field
The present invention relates to a kind of polyurethane film and preparation method thereof, in particular to a kind of filling-modified polyurethane film and its system
Preparation Method belongs to infiltration evaporation technical field of membrane separation.
Background technique
Infiltration evaporation membrane separation technique is a new and high technology, be in liquid mixture component steam pressure difference push under,
The process separated is realized with the difference of diffusion rate by the dissolution of film using component.It is difficult to point especially suitable for the way of distillation
From or indissociable nearly boiling point, constant boiling point mixture and isomer separation, to organic solvent and in the mixed solvent
The separation of a small amount of organic pollutant has apparent technical and economically advantage in the removing of minor amount of water and waste water.
The core of membrane separation technique is membrane material, and wherein polyurethane (polyurethane, PU) has good film forming
And chemical resistance.In polyurethane (PU) membrane separating process, the soft segment of polyurethane (PU) communicate often with have good permeability and
To the absorption property of organic matter, and the hydrogen bonding action between its hard section can mutually rely on forms rigid physical crosslinking point,
Although cannot function as the permeable region of small molecule, can play the role of inhibiting membrane swelling, so that it is whole to improve membrane material
The mechanical performance and thermal stability of body, guarantee the stable operation of separation process.Single polyurethane material can reach certain separation
Purpose, but the range of its application is limited.Filling-modified is a kind of simple and easy method of modifying, can make film thermostabilization and
Mechanical stability is enhanced, and many fillers can play the role of promoting mass transfer, there is the separating property of film substantially
The raising of degree.
(Kusakabe K, Yoneshige S, the Morooka S.Separation of such as such as Kusakabe
benzene/cyclohexane mixtures using polyurethane–silica hybrid membranes[J]
J.Membr.Sci., 1998,149 (1): 29-37.) it discloses and a kind of prepares polyurethane-silica with sol-gel method
(PU-SiO2) hybridized film, non-porous silica (SiO can be fairly evenly formed in situ in this method in film2) grain
Son avoids direct additional SiO2When particle aggregation problem.As a result, it has been found that the content increase of silica can inhibit film
Swelling, and the selectivity of film is improved, the permeation flux and separation factor to benzol-cyclohexane system can respectively reach 108g/
(m2And 19 h)；Soft segment phase of the polypropylene glycol as polyurethane (PU), ensure that good diffusion of the small molecule in film.?
It is joyfully equal that (Zhang Xinran, ZIF-8 fill ethyl acetate [D] in the preparation and infiltration evaporation separation water of PEBA hybridized film, and Jiangnan is big
Learn, 2014) it is prepared for ZIF-8 (zeolite imidazole skeleton material) particle using solvent-thermal method, then it is added to polyethers copolymerization
In amide (PEBA) film, the influence of ZIF-8 particle morphology, specific surface area to PEBA film infiltration evaporation performance is had studied, studies table
Bright, ZIF-8 particle made from different Hmim/Zn2+ molar ratios is uniformly dispersed in PEBA film, made from differential responses temperature
ZIF-8 particle disperses unevenly in PEBA film；The high-specific surface area of ZIF-8 particle improves infiltration component in PEBA/ZIF-8
Dissolubility in film, but it is reduction of diffusivity of the component in film；Meanwhile also having extensively studied the additive amount of ZIF-8 particle
Influence to PEBA/ZIF-8 film infiltration evaporation performance, the results showed that ZIF-8 particle and the compatibility of PEBA film are fine, addition
After ZIF-8 particle, the thermal stability of PEBA film increases；With the increase of ZIF-8 particle additive amount, the infiltration of ethyl acetate
Coefficient increases, and the infiltration infiltration coefficient of water is constant, and the selectivity of the two increases.
In conclusion SiO2The particle properties of inorganic particulate itself extremely has Research Prospects, to infiltration evaporation membrane material
The modification of material has feasibility in field of membrane material and obtains certain research achievement；ZIF-8 is as zeolite imidazole ester skeleton
One of material (ZIFs), is a kind of metallo-organic framework material of current most application potential, it has high hole
The advantages of gap rate, high-specific surface area, thus there is stronger adsorption capacity to organic molecule.But the two respectively has disadvantage, dioxy
SiClx can only be prepared into non-porous or mesoporous particle, to complex without selective, and ZIF-8 surface group and polyurethane
(PU) material affinity is weaker, it is difficult to disperse.
Therefore, how two kinds of particles to be combined and forms composite material ZIF-8@SiO2Particle can be used as filler and fill in right amount
Improving its separating property in infiltration evaporation membrane material just becomes the technical field technical problem urgently to be solved.
Summary of the invention
, selectivity good, low in cost, preparation process high with permeation flux that one of the objects of the present invention is to provide one kind
The filling-modified polyurethane film of the features such as easy to operate.
Above-mentioned purpose of the invention reaches by the following technical programs:
A kind of filling-modified polyurethane film, it is characterised in that: the filling-modified polyurethane film is amination ZIF-8 and two
The polyurethane film of the compound particle filling of silica.
Preferably, the loading of the compound particle of the amination ZIF-8 and silica is 0.5-5.0 weight %.
Preferably, the loading of the compound particle of the amination ZIF-8 and silica is 1.0-3.0 weight %.
Preferably, amination ZIF-8 particle and silica in the compound particle of the amination ZIF-8 and silica
The mass ratio of silicon source tetraethyl orthosilicate be 1:200-1:67.
It is a further object of the present invention to provide a kind of preparation methods of above-mentioned filling-modified polyurethane film.
Above-mentioned purpose of the invention reaches by the following technical programs:
A kind of preparation of filling-modified polyurethane film, its step are as follows:
(1) preparation of ZIF-8 nanoparticle
By a certain amount of Zn (NO3)2·6H2The methanol solution of O is quickly poured into the methanol solution of 2-methylimidazole and stirs
It mixes, mixture slowly becomes cloudy, and stands, centrifugation, separates nanoparticle from milky dispersion, and with fresh methanol rinses, obtain
ZIF-8 nanoparticle；
(2) preparation of amination ZIF-8 particle
ZIF-8 nanoparticle made from a certain amount of step (1) is weighed, ammonia spirit is impregnated in, mixture is placed in container
In, said vesse is placed in thermostatic container, is vibrated at room temperature, then, container is transferred in heating dish, is heated,
Until ammonia spirit all volatilizees, finally, above-mentioned product is washed with deionized water, filters, obtain amination ZIF-8 particle；
(3) amination ZIF-8@SiO2The preparation of compound particle (compound particle of amination ZIF-8 and silica)
Amination ZIF-8 particle made from a certain amount of step (2) is weighed, is put into the mixed liquor of ethyl alcohol, water, ammonium hydroxide, is surpassed
Sound stirring, is added in water-bath, stirs evenly, and cetyl trimethylammonium bromide is added, and positive silicic acid four is added in two portions in stirring
Ethyl ester (tetraethoxysilane, abbreviation TEOS), continues to stir, mixed liquor centrifugation, and with ethanol washing, obtains interior packet amination
The solid SiO of ZIF-82Particle, product are added to the water, after carrying out water etching reaction under high temperature, mixed liquor centrifugation, and use ethyl alcohol
Washing, obtains the hollow SiO of interior packet amination ZIF-82Particle, product, which is added in ethanol solution, to react, in a conventional oven and
Vacuum oven is separately dried, and obtains amination ZIF-8@SiO2Compound particle (the compound grain of amination ZIF-8 and silica
Son)；
(4) amination ZIF-8@SiO2Compound particle (compound particle of amination ZIF-8 and silica) fills poly- ammonia
The preparation of ester film
Polyurethane particles are dissolved in n,N-dimethylacetamide (DMAC), polyurethane solutions are obtained, then by step
(3) amination ZIF-8@SiO is obtained in2Compound particle (compound particle of amination ZIF-8 and silica) is added to above-mentioned
In polyurethane solutions, by stirring, ultrasonic disperse, vacuum defoamation, casting solution is formed；Casting solution casting film-forming solidifies, drying,
It places into vacuum oven, obtains amination ZIF-8@SiO2Compound particle (the compound grain of amination ZIF-8 and silica
Son) filled polyurethane film.
Preferably, Zn (NO described in the step (1)3)2·6H2Mass ratio between O and 2-methylimidazole is 1:1-1:
4。
Preferably, Zn (NO described in the step (1)3)2·6H2Mass ratio between O and 2-methylimidazole is 1:2.
Preferably, the mass ratio described in the step (3) between amination ZIF-8 particle and tetraethyl orthosilicate is 1:
200-1:67.
Preferably, it is added twice described in the step (3): 25 weight %-75 weight % being added for the first time, stirring half is small
Shi Hou adds remaining 75-25%.
Preferably, time of repose described in the step (1) is 0.5-2 hours, preferably 1 hour.
Preferably, the concentration of ammonia spirit described in the step (1) is 2mol/L-4mol/L, preferably 3mol/L.
Preferably, heating temperature described in the step (2) is 120-160 DEG C, preferably 140 DEG C；The duration of oscillation is
12-48 hours, preferably 24 hours；It is filtered described in the step (2), until pH value is 7 in filtrate；The drying temperature is
100-120 DEG C, preferably 110 DEG C, drying time are 12-48 hours, preferably for 24 hours.
Preferably, the ultrasonic agitation time described in the step (3) is 5-15min, preferably 10min；The water-bath is set
Setting temperature is 30-40 DEG C, preferably 35 DEG C；The mixing time is 20-40min, preferably 30min；It is described to continue stirring setting turn
Number 400-550r, preferably 505r, react 12-48 hours, preferably 24 hours；The amount that water is added is 300-400ml, preferably
320ml；The temperature of the water etching reaction is 70-90 DEG C, and the reaction time is 6-18 hours, preferably 12 hours；The ethyl alcohol is molten
The additional amount of liquid is 200-300ml, preferably 240ml；The reaction temperature of the ethanol solution is 50-70 DEG C, preferably 60 DEG C, is reacted
Time is 3-10 hours, preferably 5 hours；The drying temperature is 60-100 DEG C, and preferably 80 DEG C, drying time is 2-5 hours, excellent
It selects 3 hours.
Preferably, casting film-forming described in the step (4) is on polyfluortetraethylene plate；The solidification is to pass through ultraviolet lamp
Irradiation solidification；The drying temperature is 60-100 DEG C, and preferably 80 DEG C, the time is 2-10 hours, preferably 5 hours；The vacuum is dry
Dry temperature is 120-180 DEG C, and preferably 150 DEG C, the time is 2-10 hours, preferably 5 hours.
Preferably, the loading of the compound particle of amination ZIF-8 described in the step (4) and silica is 0.5-
5.0 weight %, preferably 1.0-3.0 weight %.
The utility model has the advantages that
Silica-coated is prepared for both a kind of compound particle except ZIF-8 and is used for infiltrating and vaporizing membrane by the present invention
It is modified, guarantee the dispersion of compound particle using silica surface group, also ensure that the isolation of ZIF-8 particle simultaneously and divide
It dissipates, guarantees that particle to the selectivity of target molecule, while can carry out water quarter using silicon dioxide granule using the micropore of ZIF-8
The characteristics of erosion, makes to form certain interval between silica and ZIF-8, guarantees the permeability for penetrating molecule.To make compound grain
After son is filled into film, membrane separating property is improved.
In filling-modified polyurethane film preparation method of the invention, when the temperature of water etching reaction is 90 DEG C, silicon substrate is compound
The porous, inorganic complex particle filled polyurethane film that the loading of particle is prepared when being 1%, for the mass percent of phenol
For 1% phenol/water mixture, in the case where operation temperature is 60 DEG C, PSI can achieve 810.139kg μm of m-2·
h-1, than under the same terms, pure polyurethane film (523.23) improves 1.54 times.
Filling-modified polyurethane film preparation method of the invention is high with permeation flux, selectivity is good, low in cost, preparation
The features such as process is easy to operate.
Below by specific embodiment, the present invention is described in detail.It should be understood that the embodiment described is only
It is related to the preferred embodiments of the invention, when not departing from the spirit and scope of the present invention, the change of various composition and content
It is all possible for changing and improving.
Specific embodiment
Term as used in the present invention generally has those of ordinary skill in the art usual unless otherwise specified
The meaning of understanding.
Below in an example, the various processes and method being not described in detail are conventional methods as known in the art.
The source of agents useful for same, trade name and it is necessary to list its constituent person, are indicated on the first occurrence, thereafter phase used
Unless otherwise specified with reagent, identical as the content indicated for the first time.
Embodiment 1
(1) preparation of ZIF-8 nanoparticle
2.933g (9.87mmol) commercially available Zn (NO will be contained3)2·6H2The 200mL methanol solution of O be quickly poured into containing
In the 200mL methanol solution of 6.489g (79.04mmol) commercially available 2-methylimidazole, mixture is slowly become cloudy, and stands 1 hour
Afterwards, by centrifugation, nanocrystal is separated from milky dispersion, and with fresh methanol rinses, obtain ZIF-8 nanoparticle；
(2) preparation of amination ZIF-8 particle
ZIF-8 nanoparticle made from 0.5g step (1) is weighed, the ammonia spirit that 50mL concentration is 3mol/L is impregnated in,
Mixture is obtained, mixture is placed in 100mL glass beaker, beaker is placed in constant temperature water bath, is vibrated at room temperature
For 24 hours, then, beaker is transferred in heating dish, is heated to 140 DEG C, until ammonia spirit all volatilizees, finally, using deionization
It washes above-mentioned product and filters, until pH value is 7 in filtrate, at 110 DEG C, drying for 24 hours, obtains amination ZIF-8 particle；
(3) amination ZIF-8@SiO2The system of compound particle (compound particle of amination ZIF-8 particle and silica)
It is standby
Weigh 40mg amination ZIF-8 particle made from step (2), be put into ethyl alcohol, water, ammonium hydroxide be respectively 50.7830g,
In the mixed liquor of 107.3088g and 1.9320g, ultrasonic 10min is added in the water-bath that setting temperature is 35 DEG C, and stirring is equal
After even, it is added the commercially available cetyl trimethylammonium bromide (CTAB) of 1.2904g, after stirring 30min, 8g (the is added in two portions
Primary that 4g is added, add 4g after stirring half an hour) commercially available tetraethyl orthosilicate (tetraethoxysilane, abbreviation TEOS), if
Set revolution 505r, after reaction for 24 hours, mixed liquor centrifugation, and with ethanol washing, obtain the solid SiO of interior packet amination ZIF-82Grain
Son, product are added in 320ml water, after water etching reaction 12h is carried out under 70 DEG C of bath temperatures, mixed liquor centrifugation, and use ethyl alcohol
Washing, obtains the hollow SiO of interior packet amination ZIF-82Particle, product are added in 240ml ethanol solution, are reacted at 60 DEG C
5h, product are separately dried 3h at a conventional oven and 80 DEG C of vacuum oven, obtain amination ZIF-8@SiO2Compound particle
(compound particle of amination ZIF-8 and silica)；
(4) preparation of silicon substrate compound particle (compound particle of amination ZIF-8 and silica) filled polyurethane film
4.0g commercial polyurethane particle is weighed, is put into and fills the commercially available n,N-dimethylacetamide of 36g,
In the beaker of (Dimethylacetamide, DMAC) solvent, it is stirred at room temperature to dissolution, obtains polyurethane solutions；It weighs
Amination ZIF-8@SiO obtained in 0.02g step (3)2Compound particle is added in above-mentioned polyurethane solutions, agitated, ultrasonic
Dispersion, vacuum defoamation, obtain casting solution；By casting solution on polytetrafluoroethylene (PTFE) ware casting film-forming；Then, 20 are irradiated in the UV lamp
Minute makes its solidification, is put into 80 DEG C drying 5 hours in baking oven, places into 150 DEG C drying 5 hours in vacuum oven；Obtain ammonia
Base ZIF-8@SiO2The filled polyurethane film that (compound particle of amination ZIF-8 and silica) content is 0.5%.
(5) performance of silicon substrate compound particle (compound particle of amination ZIF-8 and silica) filled polyurethane film is surveyed
Examination
Use phenol quality content for 1% phenol/water mixture, testing procedure (4) preparation amination ZIF-8@
SiO2The infiltration evaporation separation for the filled polyurethane film that (compound particle of amination ZIF-8 and silica) content is 0.5%
Performance, at 60 DEG C, permeation flux is 25.64kg μm of m-2·h-1, separation factor 34.48, infiltration evaporation separation finger
Number PSI is up to 858.43kg μm of m-2·h-1。
Embodiment 2
(1) preparation of ZIF-8 nanoparticle
2.933g (9.87mmol) commercially available Zn (NO will be contained3)2·6H2The 200mL methanol solution of O be quickly poured into containing
In the 200mL methanol solution of 6.489g (79.04mmol) commercially available 2-methylimidazole, mixture is slowly become cloudy, and stands 1 hour
Afterwards, by centrifugation, nanocrystal is separated from milky dispersion, and with fresh methanol rinses, obtain ZIF-8 nanoparticle；
(2) preparation of amination ZIF-8 particle
ZIF-8 nanoparticle made from 0.5g step (1) is weighed, the ammonia spirit that 50mL concentration is 3mol/L is impregnated in,
Mixture is placed in 100mL glass beaker, above-mentioned beaker is placed in constant temperature water bath, is vibrated at room temperature for 24 hours, so
Afterwards, beaker is transferred in heating dish, is heated to 140 DEG C, until ammonia spirit all volatilizees；Finally, being washed with deionized water
Product is stated, and is filtered, until pH value is 7 in filtrate, at 110 DEG C, drying for 24 hours, obtains amination ZIF-8 particle；
(3) amination ZIF-8@SiO2The preparation of (compound particle of amination ZIF-8 and silica)
Weigh 40mg amination ZIF-8 particle made from step (2), be put into ethyl alcohol, water, ammonium hydroxide be respectively 50.7830g,
In the mixed liquor of 107.3088g and 1.9320g, ultrasonic 10min is added in the water-bath that setting temperature is 35 DEG C, and stirring is equal
After even, the commercially available cetyl trimethylammonium bromide (CTAB) of 1.2904g is added, after stirring 30min, total 8g is added in two portions
(4g being added for the first time, add 4g after stirring half an hour) commercially available tetraethyl orthosilicate (tetraethoxysilane, abbreviation TEOS), if
Set revolution 505r, after reaction for 24 hours, mixed liquor centrifugation, and with ethanol washing, obtain the solid SiO of interior packet amination ZIF-82Grain
Son, product are added in 320ml water, under 70 DEG C of bath temperatures, after carrying out water etching reaction 12h, and mixed liquor centrifugation, and use second
Alcohol washing, obtains the hollow SiO of interior packet amination ZIF-82Particle, product are added in 240ml ethanol solution, anti-at 60 DEG C
5h is answered, product is separately dried 3h at a conventional oven and 80 DEG C of vacuum oven, obtains amination ZIF-8@SiO2Compound particle
(compound particle of amination ZIF-8 and silica)；
(4) preparation of silicon substrate compound particle (compound particle of amination ZIF-8 and silica) filled polyurethane film:
It weighs 4.0g commercial polyurethane particle and is put into and fill the commercially available n,N-dimethylacetamide of 36g,
In the beaker of (Dimethylacetamide, DMAC) solvent, it is stirred at room temperature to dissolution, obtains polyurethane solutions；It weighs
Amination ZIF-8@SiO obtained in 200mg step (3)2Compound particle is added in above-mentioned polyurethane solutions, agitated, ultrasonic
Dispersion, vacuum defoamation, obtain casting solution；By casting solution on polytetrafluoroethylene (PTFE) ware casting film-forming；Then, 20 are irradiated in the UV lamp
Minute, make its solidification, is put into baking oven, it is 5 hours dry at 80 DEG C, it places into vacuum oven, it is 5 hours dry at 150 DEG C；
Obtain amination ZIF-8@SiO2The filled polyurethane that (compound particle of amination ZIF-8 and silica) content is 5.0%
Film.
(5) performance of silicon substrate compound particle (compound particle of amination ZIF-8 and silica) filled polyurethane film is surveyed
Examination
Use phenol quality content for 1% phenol/water mixture, testing procedure (4) preparation amination ZIF-8@
SiO2The infiltration evaporation separation for the filled polyurethane film that (compound particle of amination ZIF-8 and silica) content is 5.0%
Performance, at 60 DEG C, permeation flux is 40.13kg μm of m-2·h-1, separation factor 23.66, infiltration evaporation separation finger
Number PSI is up to 909.14kg μm of m-2·h-1。
Embodiment 3
(1) preparation of ZIF-8 nanoparticle
2.933g (9.87mmol) commercially available Zn (NO will be contained3)2·6H2The 200mL methanol solution of O be quickly poured into containing
In the 200mL methanol solution of 6.489g (79.04mmol) commercially available 2-methylimidazole, mixture is slowly become cloudy, and stands 1 hour
Afterwards, by centrifugation, nanocrystal is separated from milky dispersion, and with fresh methanol rinses, obtain ZIF-8 nanoparticle；
(2) preparation of amination ZIF-8 particle
ZIF-8 nanoparticle made from 0.5g step (1) is weighed, the ammonia spirit that 50mL concentration is 3mol/L is impregnated in
In, mixture is placed in 100mL glass beaker, above-mentioned beaker is placed in constant temperature water bath, is vibrated at room temperature
For 24 hours, then, beaker is transferred in heating dish, is heated to 140 DEG C.Until ammonia spirit all volatilizees；Finally, using deionization
Above-mentioned product is washed, and is filtered, until pH value is 7 in filtrate, drying for 24 hours, obtains amination ZIF-8 particle at 110 DEG C；
(3) amination ZIF-8@SiO2The preparation of compound particle (compound particle of amination ZIF-8 and silica)
Weigh 40mg amination ZIF-8 particle made from step (2), be put into ethyl alcohol, water, ammonium hydroxide be respectively 50.7830g,
In the mixed liquor of 107.3088g and 1.9320g, ultrasonic 10min is added in the water-bath that setting temperature is 35 DEG C, and stirring is equal
After even, it is added the commercially available cetyl trimethylammonium bromide (CTAB) of 1.2904g, after stirring 30min, 8g (the is added in two portions
Primary that 6g is added, 2g is added after stirring half an hour) commercially available tetraethyl orthosilicate (tetraethoxysilane, abbreviation TEOS), setting
Revolution 505r, after reaction for 24 hours, mixed liquor centrifugation, and with ethanol washing, obtain the solid SiO of interior packet amination ZIF-82Particle,
Product is added in 320ml water, after water etching reaction 12h is carried out under 90 DEG C of bath temperatures, mixed liquor centrifugation, and washed with ethyl alcohol
It washs, obtains the hollow SiO of interior packet amination ZIF-82Particle, product are added in 240ml ethanol solution, are reacted at 60 DEG C
5h, product are separately dried 3h at a conventional oven and 80 DEG C of vacuum oven, obtain amination ZIF-8@SiO2Compound particle
(compound particle of amination ZIF-8 and silica)；
(4) preparation of silicon substrate compound particle (compound particle of amination ZIF-8 and silica) filled polyurethane film
It weighs 4.0g commercial polyurethane particle and is put into and fill the commercially available n,N-dimethylacetamide of 36g,
In the beaker of (Dimethylacetamide, DMAC) solvent, it is stirred at room temperature to dissolution, obtains polyurethane solutions；Weigh 40mg
Amination ZIF-8@SiO obtained in step (3)2Compound particle is added in above-mentioned polyurethane solutions, agitated, ultrasonic disperse,
Vacuum defoamation obtains casting solution；By casting solution on polytetrafluoroethylene (PTFE) ware casting film-forming；Then, it irradiates 20 minutes in the UV lamp,
Make its solidification, is put into baking oven, it is 5 hours dry at 80 DEG C, it places into vacuum oven, it is 5 hours dry at 150 DEG C；
Obtain amination ZIF-8@SiO2The filled polyurethane that (compound particle of amination ZIF-8 and silica) content is 1.0%
Film.
(5) performance of silicon substrate compound particle (compound particle of amination ZIF-8 and silica) filled polyurethane film is surveyed
Examination
Use phenol quality content for 1% phenol/water mixture, testing procedure (4) preparation amination ZIF-8@
SiO2The infiltration evaporation separation for the filled polyurethane film that (compound particle of amination ZIF-8 and silica) content is 1.0%
Performance, at 60 DEG C, permeation flux is 26.12kg μm of m-2·h-1, separation factor 32.02, infiltration evaporation separation finger
Number PSI is up to 810.19kg μm of m-2·h-1。
Embodiment 4
(1) preparation of ZIF-8 nanoparticle
2.933g (9.87mmol) commercially available Zn (NO will be contained3)2·6H2The 200mL methanol solution of O be quickly poured into containing
In the 200mL methanol solution of 6.489g (79.04mmol) commercially available 2-methylimidazole, mixture is slowly become cloudy, and stands 1 hour
Afterwards, by centrifugation, nanocrystal is separated from milky dispersion, and with fresh methanol rinses, obtain ZIF-8 nanoparticle；
(2) preparation of amination ZIF-8 particle
ZIF-8 nanoparticle made from 0.5g step (1) is weighed, the ammonia spirit that 50mL concentration is 3mol/L is impregnated in,
Mixture is placed in 100mL glass beaker, above-mentioned beaker is placed in constant temperature water bath, is vibrated at room temperature for 24 hours, so
Afterwards, beaker is transferred in heating dish, is heated to 140 DEG C.Until ammonia spirit all volatilizees；Finally, being washed with deionized water
Product is stated, and is filtered, until pH value is 7 in filtrate, drying for 24 hours, obtains amination ZIF-8 particle at 110 DEG C；
(3) amination ZIF-8@SiO2The preparation of compound particle (compound particle of amination ZIF-8 and silica)
Weigh 120mg amination ZIF-8 particle made from step (2), be put into ethyl alcohol, water, ammonium hydroxide be respectively 50.7830g,
In the mixed liquor of 107.3088g and 1.9320g, ultrasonic 10min is added in the water-bath that setting temperature is 35 DEG C, and stirring is equal
After even, it is added the commercially available cetyl trimethylammonium bromide (CTAB) of 1.2904g, after stirring 30min, 8g (the is added in two portions
Primary that 2g is added, 6g is added after stirring half an hour) commercially available tetraethyl orthosilicate (tetraethoxysilane, abbreviation TEOS), setting
Revolution 505r, after reaction for 24 hours, mixed liquor centrifugation, and with ethanol washing, obtain the solid SiO of interior packet amination ZIF-82Particle,
Product is added in 320ml water, after water etching reaction 12h is carried out under 90 DEG C of bath temperatures, mixed liquor centrifugation, and washed with ethyl alcohol
It washs, obtains the hollow SiO of interior packet amination ZIF-82Particle, product are added in 240ml ethanol solution, are reacted at 60 DEG C
5h, product are separately dried 3h at a conventional oven and 80 DEG C of vacuum oven, obtain amination ZIF-8@SiO2Compound particle
(compound particle of amination ZIF-8 and silica)；
(4) preparation of silicon substrate compound particle (compound particle of amination ZIF-8 and silica) filled polyurethane film
It weighs 4.0g commercial polyurethane particle and is put into and fill the commercially available n,N-dimethylacetamide of 36g,
In the beaker of (Dimethylacetamide, DMAC) solvent, it is stirred at room temperature to dissolution, obtains polyurethane solutions；It weighs
Amination ZIF-8@SiO obtained in 120mg step (3)2Compound particle is added in above-mentioned polyurethane solutions, agitated, ultrasonic
Dispersion, vacuum defoamation, obtain casting solution；By casting solution on polytetrafluoroethylene (PTFE) ware casting film-forming；Then, 20 are irradiated in the UV lamp
Minute, make its solidification, is put into baking oven, it is 5 hours dry at 80 DEG C, it places into vacuum oven, dry 5 at 150 DEG C
Hour；Obtain amination ZIF-8@SiO2The filling that (compound particle of amination ZIF-8 and silica) content is 5.0% is poly-
Urethane film.
(5) performance of silicon substrate compound particle (compound particle of amination ZIF-8 and silica) filled polyurethane film is surveyed
Examination
Use phenol quality content for 1% phenol/water mixture, testing procedure (4) preparation amination ZIF-8@
SiO2The infiltration evaporation separation for the filled polyurethane film that (compound particle of amination ZIF-8 and silica) content is 3.0%
Performance, at 60 DEG C, permeation flux is 40.12kg μm of m-2·h-1, separation factor 22.61, infiltration evaporation separation finger
Number PSI is up to 867.5kg μm of m-2·h-1。
Comparative example 1:
(1) 4.0g commercial polyurethane particle is weighed, is put into and fills the commercially available n,N-dimethylacetamide of 36g (DMAC) solvent
Beaker in, agitated, ultrasonic disperse, vacuum defoamation obtain casting solution；By casting solution on polytetrafluoroethylene (PTFE) ware casting film-forming；
Then, it irradiates 20 minutes in the UV lamp, makes its solidification, be put into 80 DEG C drying 5 hours in baking oven, place into vacuum oven
150 DEG C drying 5 hours；Obtain polyurethane film.
(2) it uses phenol quality content for 1% phenol/water mixture, tests the infiltration evaporation point of the pure polyurethane film
From performance, at 60 DEG C, permeation flux is 25.41kg μm of m-2·h-1, separation factor 23.71, infiltration evaporation separation
Index PSI is up to 577.23kg μm of m-2·h-1。
Comparative example 2 (hybridized film of polyurethane-ZIF-8)
(1) 4.0g commercial polyurethane particle is weighed, is put into and fills the commercially available n,N-dimethylacetamide of 36g (DMAC) solvent
Beaker in, be stirred at room temperature to dissolution, obtain polyurethane solutions；0.04gZIF-8 particle is weighed, it is molten that above-mentioned polyurethane is added
In liquid, agitated, ultrasonic disperse, vacuum defoamation obtain casting solution；By casting solution on polytetrafluoroethylene (PTFE) ware casting film-forming；Then,
It irradiates 20 minutes in the UV lamp, makes its solidification, be put into 80 DEG C drying 5 hours in baking oven, place into vacuum oven 150 DEG C
It is 5 hours dry；Obtain the hybridized film of polyurethane-ZIF-8.
(2) use phenol quality content for 1% phenol/water mixture, when test, less than 5 minutes, polyurethane-ZIF-8
Hybridized film leakage, can not continue to test.
Can be seen that polyurethane film from the above comparative example and embodiment can be realized phenol/water mixing object infiltration vapour
Change separation, compared with pure polyurethane film, passes through amination ZIF-8@SiO2The polyurethane film of particle-filled modification realizes and is increasing
Separation factor is improved while big permeation flux, to effectively increase the infiltration evaporation segregation index of the filling-modified film.With
Pure ZIF-8 filling film is compared, and tolerance greatly improves.
Claims (10)
1. a kind of filling-modified polyurethane film, it is characterised in that: the filling-modified polyurethane film is amination ZIF-8 and dioxy
The polyurethane film of the compound particle filling of SiClx.
2. filling-modified polyurethane film according to claim 1, it is characterised in that: the amination ZIF-8 and titanium dioxide
The loading of the compound particle of silicon is 0.5-5.0 weight %.
3. filling-modified polyurethane film according to claim 1, it is characterised in that: the amination ZIF-8 and titanium dioxide
The loading of the compound particle of silicon is 1.0-3.0 weight %.
4. filling-modified polyurethane film according to claim 1, it is characterised in that: the amination ZIF-8 and titanium dioxide
The mass ratio of the silicon source tetraethyl orthosilicate of amination ZIF-8 particle and silica is 1:200-1 in the compound particle of silicon:
67。
5. the preparation method of filling-modified polyurethane film described in any one of claim 1-4, its step are as follows:
(1) preparation of ZIF-8 nanoparticle
By a certain amount of Zn (NO3)2·6H2The methanol solution of O is quickly poured into the methanol solution of 2-methylimidazole and stirs, and mixes
It closes object slowly to become cloudy, stand, centrifugation separates nanocrystal from milky dispersion, and with fresh methanol rinses, obtains ZIF-8
Nanoparticle；
(2) preparation of amination ZIF-8 particle
ZIF-8 nanoparticle made from a certain amount of step (1) is weighed, ammonia spirit is impregnated in, mixture is placed in container, it will
Said vesse is placed in thermostatic container, is vibrated at room temperature, and then, container is transferred in heating dish, heating, until ammonia
Aqueous solution all volatilizees, finally, above-mentioned product is washed with deionized water, filters, obtains amination ZIF-8 particle；
(3) preparation of the compound particle of amination ZIF-8 and silica
Amination ZIF-8 particle made from a certain amount of step (2) is weighed, is put into the mixed liquor of ethyl alcohol, water, ammonium hydroxide, ultrasound is stirred
It mixes, is added in water-bath, stirs evenly, cetyl trimethylammonium bromide is added, positive silicic acid tetrem is added in two portions in stirring
Ester continues to stir, mixed liquor centrifugation, and with ethanol washing, obtains the solid SiO of interior packet amination ZIF-82Particle, product add
Enter into water, after carrying out water etching reaction under high temperature, mixed liquor centrifugation, and with ethanol washing, obtain interior packet amination ZIF-8's
Hollow SiO2Particle, product, which is added in ethanol solution, to react, and is separately dried in a conventional oven and vacuum oven, obtains amino
Change the compound particle of ZIF-8 and silica；
(4) preparation of the compound particle filled polyurethane film of amination ZIF-8 and silica
Polyurethane particles are dissolved in n,N-dimethylacetamide, polyurethane solutions are obtained, it then will be obtained in step (3)
The compound particle of amination ZIF-8 and silica is added in above-mentioned polyurethane solutions, by stirring, ultrasonic disperse, vacuum
Deaeration forms casting solution；Casting solution casting film-forming, solidify, drying, place into vacuum oven, obtain amination ZIF-8 and
The compound particle filled polyurethane film of silica.
6. the preparation method of filling-modified polyurethane film according to claim 5, it is characterised in that: in the step (1)
The time of repose is 0.5-2 hours；The concentration of ammonia spirit described in the step (1) is 2mol/L-4mol/L；The step
Suddenly heating temperature described in (2) is 120-160 DEG C；The duration of oscillation is 12-48 hours；It is filtered described in the step (2),
Until pH value is 7 in filtrate；The drying temperature is 100-120 DEG C, and drying time is 12-48 hours.
7. the preparation method of filling-modified polyurethane film according to claim 6, it is characterised in that: in the step (1)
Zn (the NO3)2·6H2Mass ratio between O and 2-methylimidazole is 1:1-1:4；Amination described in the step (3)
Mass ratio between ZIF-8 particle and tetraethyl orthosilicate is 1:200-1:67.
8. the preparation method of filling-modified polyurethane film according to claim 7, it is characterised in that: in the step (3)
The ultrasonic agitation time is 5-15min；The water-bath setting temperature is 30-40 DEG C；The mixing time is 20-40min；
It is described to continue stirring setting revolution 400-550r, it reacts 12-48 hours；The amount that water is added is 300-400m；The water is carved
The temperature of erosion reaction is 70-90 DEG C, and the reaction time is 6-18 hours；The additional amount of the ethanol solution is 200-300ml；It is described
The reaction temperature of ethanol solution is 50-70 DEG C, and the reaction time is 3-10 hours；The drying temperature is 60-100 DEG C, when dry
Between be 2-5 hours；
Casting film-forming described in the step (4) is on polyfluortetraethylene plate；The solidification is solidified by ultraviolet light irradiation；Institute
Stating drying temperature is 60-100 DEG C, and the time is 2-10 hours；The vacuum drying temperature is 120-180 DEG C, time 2-10
Hour.
9. the preparation method of filling-modified polyurethane film according to claim 8, it is characterised in that: in the step (4)
The loading of the compound particle of the amination ZIF-8 and silica is 0.5-5.0 weight %.
10. the preparation method of filling-modified polyurethane film according to claim 8, it is characterised in that: step (4) institute
The loading for stating the compound particle of amination ZIF-8 and silica is 1.0-3.0 weight %.
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| CN114522545A (en) * | 2022-02-23 | 2022-05-24 | 浙江大学 | Load type imprinted membrane for selectively removing diclofenac sodium and preparation method thereof |
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